Data Book On Hydrocarbons. Application To Process Engineering (Maxwell, J. B.)

DATA BOOK ON
HYDROCARBONS
APPLICA TION TO PROCESS ENGINEERING
by
J. B. MAXWELL
NINTH PRINTING
ROBERT E. KRIEGER PUBLISHING COMPANY

MALABAR, FLORIDA
ORIGINAL EDITION 1960

REPRINTED 1977 FROM NINTH PRINTING 1968
Printed and Published by

ROBERT E. KRIEGER PUBLISHING COMPANY, INC.
KRIEGER DRIVE
MALABAR, FLORIDA 32950
Copyright 1950 by
STANDARD OIL DEVELOPMENT COMPANY

Reprinted by Arrangement with
VAN NOSTRAND REINHOLD CoMPANY
All rights reserved. No reproduction in any form

of this book, in while or in part (except for brief
quotation in critical articles or reviews), may be
made without written authorization frOm the
publisher.
PRINTED IN THE UNITED STATES OF AMERICA
Library of Congress Cataloging in Publication Data
Maxwell, J
B
1902Data book on hydrocarbons.
Reprint of the 9th printing published in 1968 by Van
Nostrand, Princeton, N. J., in The Esso series.
Includes bibliographies.
1. Hydrocarbons. I. Title.
TP690.M35 1975
661'.81
74-30163
ISBN 0-88275-257-X
PREFACE
The primary purpose of this book is to provide (1) basic data on hydrocarbons and petroleum fractions, (2) methods of applying these data to process
engineering, including illustrative examples and some fundamental theory, and
(3) applications of a few of the unit operations of chemical engineering uscd
extensively in the petroleum industry.
Earlier editions of the present volume have been used in the Standard Oil
Development Company and other affiliates of the Standard Oil Company (New
.Jersey). Because this book has proved to be quite valuable to technical personnel,
the Standard Oil Development Company has decided to make it available for
practicing engineers and students of petroleum technology.
The author is very much indebted to many associates in the preparation of
thi s book and, in particular, to W. H. Hatch for invaluable assistance in editing
the text and preparing the charts for publication, to C. O. Rbys, Sr., for the
derivation of the .Mollier diagrams and other charts, to C. J. Robrecht (or
constructive criticism and advice during the preparation of the manuscript. Furthermore, any list of acknowledgments would be incomplete without mentioning
R. S. Piroomov who was responsible for the early development of a company
data book.
J. B. MAXWELL
Standard Oil Development Company
Linden, New Jersey
CONTENTS
PHYSICAL DATA
SElCTIOl\
PAGE
1. PHYSICAL CONSTANTS.......................................
Hydrocarbons, 2-Miscellaneous Organic Compounds, 6--MisceIlaneous Gases, 9

2. CHARACTERISTICS OF PETROLEUM FRACTIONS... . . . . . . . ..
10
Average Boiling Point, 14-Characterization Factor, Hi-Gravity, 18

3. MOLECULAR WEIGHT. . . . . . . . . . . . . . . . . .. . . . . .. ... ... . . . . . . . . .
19
Paraffins, 20-Petroleum Fractions, 21

4. VAPOH PRESSURE
24
Paraffins and Olefins, 27-Diolefins and Acetylenes, 35-Aromatics, 37

-Cycloparaffins, 39-Hydrocarbons, 40-Gasolines, 44
5. FUGACITY
45
Fugacity Function of Individual Hydrocarbons, 49-Fugacity Function of Hydrogen, Ol-Fugacity of Hydrocarbon Vapors, 62-Relative
Volatility of LigM Hydrocarbons, 6~-Fugacity Correction Factor for
Light Hydrocarbons in Absorber Oib, 67
6. CRITICAL PROPERTIES.......................................
68
Critical Temperature of Pure Hydrocarbons, 69-Critical Temperature

of Light Hydrocarbon Mixtures, 'i'O-Critical Pressure of K ormal Paraffins, 71-Critical Temperature and Pressure of Petroleum Fractions,
72
7. THEHMAL PHOPERTlES
Specific Heats of Gases and Vapors, 88-Enlhalpy-Presoure Relationship for Hydrocarbon Vapors, 92-Bpecifjr Heats of Liquid Hydrocarbons and Petroleum Fractions, 93-Latenl Ileat of Vaporization of
Light Hydrocarbons and Normal Paraffins, 94-Enthalpy of Individual
Hydrocarbons, 98-Enthalpy of Petroleum Fractions, 114-Mollier
Diagrams for Light Hydrocarbons, 128
VII
75
viii
CONTENTS
PAGE
SECTION
8. DENSITy........................... . . . . . . . . . . . . . . . . . . . . . . . . . . .
136
Conversion Charts for 0 API Gravity, 138-Specific Gravity of Saturated Hydrocarbon Liquids, 14o-Thermal Expamlion of Liquid
Petroleum Fractions, 143-P-V-T Relations of Hydrocarbon Vapors,
148
9. VISCOSITY. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
155
Conversion Charts, 158-Viscosity of Hydrocarbons and Crude Fractions, 161-Viscosity-Temperature Charts, 166--Viscosity Index of
Lubricating Oils, 168-Viscosity Blending Index, 173-Viscosity of
Hydrocarbon Vapors and Miscellaneous Gases, 174
10. COMBUSTION. . .
178
Heat of Combustion of Petroleum Fractions and Hydrocarbon Gases,

18o-Enthalpy of Flue Gas Components, 182-Heat Available from
the Combustion of Refinery Gases and Fuel Oils, 184-Properties of
Flue Gases, 189
UNIT OPERATIONS
11. FLOW OF FLUIDS.............................................
193
Friction Factor for Fluid Flow, 19B-Pressure Drop in Commercial

Pipes, 199-Equivalent Length of Fittings, 202-Friction Loss Due
to Contraction and Enlargement, 204-Discharge Characteristics of
Weirs, 205-Pressure Drop Across Tube Banks, 206
12. FLOW OF HEAT. . . . . . . . . . . . . . . . . . . . . . . . . . .. . .
.. .
207
Heat Loss by Radiation and Natural Convection, 209-Heat Transfer

to Fluids Inside Tubes, 211-Heat Transfcr to Fluids Outside Tubes,
212-Thermal Conductivity of Petroleum Fractions, Water, and
Gases, 213-Logarithmic Mean Temperatme Difference, 217
13. EQUILIBRIUM FLASH VAPORIZATION.. . . . . . . . . . . . . . . . . . . . . ..
222
14. FRACTIONATING TOWERS.. ..
230
Minimum Reflux Ratio and Theoretical Steps, 23O-Correlation of

Theoretical Steps with Reflux Ratio, 244-0verall Plate Efficiency,
245-Packed Towcrs, 246
CONVERSIOX FACTORS. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
249
INDEX............................................................
253
Section I
PHYSICAL CONSTANTS
In the following tables the more common physical constants are given for
hydrocarbons, certain other organic series, and miscellaneous gases. While these
constants, in general, are based upon reliable data, estimated "alues were included
in a few instances where available data were considered questionable. Where no
reasonably good basis was available for either estimating or calculating the constants, they are omitted.
The density, boiling point, melting point, and heat of eo'mbustion for most
of the hydrocarbons are those given in the Burea1t of Standards Circular C461. 1
GENERAL REFERENCES
Annual Tables of Physical Constants, Nat. Research Council (19-11, 1942).
Beattie, Poffenberger and Hadlock, J. Chem. Phys. 3, 96 (1935).
Beattie, Simard and Su, J. Alii. Chem. Soc. 61, 24 (1939); 61,924 (1939).
Cole and Cole, J. Chem. Phys. 9, 341 (1941).
Doss, "Physical ~nstants of the Principal Hydrocarbons," 4th Edition, The Texas Co.,
New York, N.Y. (1943).
Ginnings, J. Am. Cltell/. Soc. 62, 1923 (1940).
Ginnings and Baum, J. Am. Chem. Soc. 59, 1111 (1937).
Ingersoll, Thesis, ~Iass. Inst. Tech. (1930).
International Critical Tables, Vols. I and III.
Kay, Ind. Eng. Chem. 30, 459 (1938).
Kharasch, J. Research Nat. Bur. Standards 2,359 (1929).
Krase and Goodman, Ind. Eng. Chelll. 22, 13 (1930).
Meyers, Scott, Brickwede and RAnds, Unpublished Data, Nat. Bur. Standards.
Pickering, Bur. Standards Sci. Paper 511 (1926).
Rintelen, Gross and Saylor, J. Am. Chelll. Soc. 62, 1923 (19-10).
Tables anntlelles de wnstantes et dunnee nUllteriqlte, Vols. VII to XIII (1925-1939).
I'
"Sclcdcd Values of Propertips of Hydrocarbons," Nal. Bur.
(947).
~lalldards
Circular Cl,61
PHYSICAL CONSTANTS OF HYDROCARBONS
.
FOR~tULA
MOLEC.
WT.
BOILING
POINT
of
:.fELTING
POINT
of
NORMAL PARAFFINS
Methane ...................
Ethane ....................
Propane ...................
Bu~no ....................
CH,
C,H.
C,H,
C,H,o
Pentane ...................
Hexane ....................
Heptane ...................
Octane ...... '" ...........
C,H 12
C,H"
C,H 16
C,H,s
72.1
86.2
100.2
114.2
96.9 -201. 5
155.7 -139.5
209.2 -131. 1
258.2 - 70.3
Nonane ....................
Decane ....................
Undecane ..................
Dodecane .... , .............
C,H,o
C1oH"
C"H,.
C12 H "
128.2
142.3
156.3
170.3
303.4 345.2 384 .4 421.3
ISO-PARAFFINS
Isobutane ..................
C,H 1o
58.1
10.9 -255.0
C,H 12
72.1
82.2 -255.5
C,H"
72.1
49.0
2-Methylpentanc (Isohexane) ,
3-Methylpcnt,ane, ........
2,2-Dimethylbutane ();eohexane) . ' .. , ......... , ...
2,3-Dimethylbutane (Diisopropyl) ...............
C,H"
C,H"
86.2
86.2
140.5 -245
145.9 -180
C,H"
86.2
C.H"
86.2
2-Met,hylhexane (Isoheptane) .
3-Methylhexanc ............
3-Ethylpentane ....
......
2,2-Dimethylpentane ....... '
C,H I6
C,H"
(',H"
(',H"
2,3Dimethylpentane ........
2,4-Dimethylpentane ........
3,3-Dimethylpentane ....... ,
C,H"
C,H"
C,H"
2-Methylbutane (Isopentane),
2,2-Dimeth:dpropane (~eopentane). . ..............
16.0 -258.9 -296.5

30.1 -128.0 -297.8
44.1 - 43.8 -305.7
58.1
31.1 -216.9
DENSITY
API
Sp Gr
60/60 Lb/gal
P
Atm
G/ml
206.3
306
45.8
48.2
42.0
37.4
32.6
29.4
26.8
24.6
of
HEAT OF COMBUSTION
60F-BTU /Ib
Gross
Net
0.162
.203
.226
.225
23,860"
22,300"
21,650"
21,290'
21,500"
20,42019,930"
19,670"
.232
.234
.234
.233
21,070"
20,780
20,670
20,590
19,500"
19,240
19,160
19,100
20,530
20,480
20,450
20,420
19,050
19,020
19,000
18,980
0.30
.374
.508
.584
2.50
3.11
4.23
4.86
92.7
81.6
74.2
6ti,{j
.631
.664
.688
.707
5.25
5.53
5.73
5.89
386.5
455.0
512.5
565
64.5
61.3
58.7
56.4
. -.).)
,- ...
.734
.744
, 753
6.01
6.11
6.19
6.27
612'
654'
695'
731"
.563
4.69
275
36
.234
21,240'
19,610"
.625
5.20
369.5
32.4
.234
21,030"
19,450"
.597
4.97
329"
35'
20,960'
19,330"
o;.:-
83.5
80.0
.658
, 669
5.48
5.57
437'
443'
31'
30"
20,750
20,760
19,210
19,220
tp
121.5 -147 6
84.9
.654
5.44
415'
31'
20,700
19,160
136.4 -198.8
81.0
.666
5.54
441
31
20,740
19,200
100.2
100.2
100.2
100.2
194.1
197.5
200.2
174.6
-180.8
-182.9
-181.5
-190.8
75.i
73.0
69.ti
77.'2
. 68:l
.692
.703
.678
5.68
5.76
5.85
5.64
496
504
508'
475'
28"
28.5"
28.5
28.5
20,650
20,660
20.670
20,600
19,140
19,150
19,160
19,090
100.2
100.2
100.2
193.6
176.9 -183.1
186.9 -211.0
-')
, I ._
70.6
.700
.678
.698
5.83
5.54
5.81
498'
477
487'
29
28.5'
28'
20,540
20,620
20,620
19,130
19,110
19,110
64.5
21.5
14.1
14.7
340
247
147
111
CRITICAL CONSTANTS
-116.3
+ 90.1
23"
22"
20"
lb'
;.:>-3
;.:tp
o
o
o
Z
:I:
2.1
120
94.9
105
71.2
..
. 241
><
S
~
z00
2,2,3-Trimethylbutane (Triptane) ....................
20,620
19,110
25~
25"
20,570
20,570
19,080
19,080
25
0.237
20,550
19,060
515'
27"
20,540
19.050
50
51
.22
21,640"
20,290Q
196.5
45.4
.2:~3
21,040Q
19,690Q
5.00
5.22
5.08
4.99
293'
316'
310'
292.5
39"
37"
37"
39.5
20,840"
20,780"
20,750"
20,720"
19,490Q
19,430Q
19,400"
19,370"
.647
.661
.654
5.38
5.50
5.44
385"
398'
396'
36"
35"
20,710Q
20 ,660Q
19,360"
19,310"
35~
~O,640Q
19,290Q
84.5
.655
5.45
387"
36"
20,610 Q
19,260"
-292.0
-207.0
92.0
80.6
. 6:~3
.667
5.27
5.55
363'
401"
37"
35"
20,660Q
20,570"
19,310"
19,220"
146.4
155.4
154.2
153.7
154.6
-218.0
-231.0
-207.0
-211.0
-171
77.2
73.9
75.7
75.4
76.0
.678
.689
.683
.684
.682
5.64
5.73
5.68
5.69
5.68
463'
473'
472'
4i2'
473'
34"
34"
34"
34"
34"
20,450
20,420
20,400
20,420
20,400
19,100
19,070
19,050
19,070
19,050
30.1
-213.0
.595
4.95
249
70
20,880 Q
19,930"
50.5
24.1
83.5
94.2
.658
.627
5.48
5.22
343'
308
71.5
71.8
76.0
.697
.696
.682
5.80
5.79
5.68
420C
78.9
104
-234.0
-184.0
81. 3
82.9
.665
.685
5.53
5.70
350C
93.3
-231.0
74.8
.686
5.71
13.0
72.1
0.695
5.78
480~
243.8
245.4
-165.1
70.1
65.6
.702
.718
5.84
5.98
549<
551 c
114.2
228.4
-130
71.2
.698
5.81
530
C S H 18
114.2
210.6 -161. 2
71.8
.69u
5.79
OLEFINS
Ethylene .................
C 2H.
28.0
-154.7
-272.5
2n
. ;J;j
2.91
Propylene .................
C 3H s
42.1
-301.4
140
.522
4.35
Butene-I .............
Cis-Butene-2 ............
Trans-Butene-2 .............
Isobutene ........ , ......
C,Hs
C.Hs
C.H s
C.H s
56.1
56.1
56.1
56.1
20.7
38.6 -218.0
33.6 -157.7
19.6 -220.5
104
94.2
100
104
.601
.627
.610
.600
Pentene-1 (Amylene).
Cis-Pentene-2 ............
Trans-Pentene-2 ............
CbH lO
C;H1o
CbH lO
70.1
70.1
70.1
86.2
98.6
96.8
-216.4
-290.2
-211.0
87.2
82.6
84.9
2-Methylbutene-1 ...........
3-Methylbutene-1 (lsoamylene) .......... " .....
2-Methylbutene-2 ...........
C;H 1o
70.1
88.0
C;H lO
C;H lO
70.1 ,
70.1
68.4
101.2
Hexene-1 .............
Cis-Hexene-2 .............
Trans-Hexene-2 .............
Cis-Hexene-3 .............
Trans-Hexene-3 ............
C 6H 12
C 6 H 12
C 6H 12
C SH l2
C aH 12
84.2
84.2
84.2
84.2
84.2
C 3H.
40.1
Butadiene-l ,2 ..............
Butad.iene-1,3 ..............
C.H s
C.H s
54.1
54.1
Pentadiene-1.2 ..... : ..
Cis-Pentadiene- L3 ........
Trans-Pentadiene-l,3 ........
C;H s
C;H s
C;Hs
68.1
68.1
68.1
112.8
111.6
108.1
Pentadiene-I,4 .......
3-Methylbutadiene-l,2 .......
2-Methylbutadiene-l,3 (Isoprene) ...................
CsH s
CsH s
68.1
68.1
C6 H S
68.1
2-Methylheptane (lsooctane) .
3-Ethylhexane ..............
2,5-Dimethylhexane (Diisobutyl) .................
2,2,4-Trimethylpentane ("lsooctane") .................
DIOLEFINS
Propadiene ................
C 7 H 1S
100.2
177.6 -
C SH 18
C sH 18
114.2
114.2
CSHl~
53.9
Heat of combustion as a gas-otherwise as a liquid.

Estimated.
Q
-1.64.0
85.0
106
45
.234
410"
395'
420"
415'
Critical temperature-boiling point correlation.

" Vapor pressure curve or correlation.
29.5
(1
o
Z
lfJ
~
;>
~
lfJ
20,150 Q
20,320Q
-
19,210Q
20,060"
18,950Q
...
;>
t"'i
19,180Q
19,040"
19,04QQ
* Mixture of cis- and

** Sublimes.
-<
....
(1
lfJ
20,230"
20,150"
=:r:
(J,j
trans-isomers.
PHYSICAL CONSTANTS OF HYDROCARBONS (Cont.)
FORMULA
BOILING MELTING
MOLEC.
POINT
POINT
WT.
OF
OF
DIOLEFINS (Cont.)
Hexadiene-1,2 .... : .......
Hexadiene-1,3* ..........
Hexadiene-l,4* ...........
CSH lO
CsH lO
CaRlO
82.1
82.1
82.1
172
163
149
Hexadiene-l.5 ..........
Hexadiene-2,3 ..... : .......
Hexadiene-2,4* .............
CSH lO
CSH lO
CsH lo
82.1
82.1
82.1
139.3 -221.4
154.4
176
-
3-Methylpentadiene-1,2 ......
4-Methylpentadiene-l,2 ......
2-Methylpentadie:le-1,3* .....
3-Methylpentadiene-l.3* .....
CSH lO
CSH lO
CSH lO
CSH 10
82.1
82.1
82.1
82.1
158
158.0
169
171
2-Methylpentadiene-1.4 ......
2,3-Diroethylbutadiene-1,3 ...
2-Ethylbutadiene-1,3 ........
CsH lo
CSH IO
CSH lO
CaRlO
82.1
82.1
82.1
82.1
82.1
169.3 - 94.0
133
162.0
155.7 -105
167
-
ACETYLENES
Acetylene ..................
CzH z
26.0 -119**
Methylacetylene ............
CaH.
40.1
Butyne-1 (Ethylacetylene) ...

Butyne-2 (Dimethylacetylene)
C.H s
C.H s
54.1
54.1
~HIO
DENSITY
API
Sp Gr
60 0 /60 0
CRITICAL CONSTANTS
Lb Igal
OF
P
Atm
64.5
67.8
70.6
0.722
.710
.700
6.01
5.91
5.83
495"
485"
470"
71.8
75.1
63.7
.696
.685
.725
5.79
5.70
6.03
454
475'
500"
65.0
67.0
63.9
59.7
.720
.713
.724
.740
5.99
5.93
6.03
6.16
4W'
480"
490"
495'
63.9
70.9
66.1
62.1
61.0
.724
.699
.716
.731
.735
6.03
5.82
5.96
6.08
6.12
490"
445'
485'
475'
490'
.416
3.46
94.9
.625
86.2
71.2
Gross
Net
--
103.5
62.0
0.231
21,47(}l1
5.20
275'
65~
20.810"
19.8W
.650
.698
5.41
5.81
375
420
65~
20.65QQ
20.51QQ
19,6oog
71.8
66.1
.696
.716
5.79
5.96
429
460"
20,45QQ
19,440g
19,340g
20.5W
19,390"
20,130
18,980
--
19,880
18.730
tj
>
~
c;
o
o
~
Z
::t:
~
-114
9.8 -153
47.7 -188.5
80.4 - 26.0
104.4 -159
132.8 -148
209
60~
Pentyne-1 (Propylacetylene).
Pentyne-2 ..................
3-Methylbutyne-1 (Isopropylacetylene) ................
CsH s
CsH s
68.1
68.1
CsHs
68.1
79.7
.670
5.58
410"
Hexyne-1 (Butylacetylene) ...

Hexyne-2 ..................
Hexyne-3 .................
CsH lo
CSH lO
CsH lO
82.1
82.1
82.1
160.9 -205.6
184.1 -126.4
179.2 -149.8
65.0
60.8
63.1
.720
.736
.727
5.99
6.13
6.05
4-Methylpentyne-1 ..........
4-Methylpentyne-2 ..........
3,3-Diroethylbutyne-1 .......
CSH lO
CSH lO
CaRlO
82.1
82.1
82.1
142.1 -157.1
162
100.0 -114.2
67.5
65.3
78.7
.711
.719
.673
5.92
5.98
5.60
C.H.
52.1
73.9
.689
5.73
365"
OLEFINS-ACETYLENES
Buten-3-yne-1 (VinylAcetylene) ...................
D
G/rol
HEAT OF COMBUSTION
@ 60F-BTU lib
82
42
20,550
20,74~
19,46()Q
75.;
tj
o
o
>
~
c;
en
58.7
0.744
6.19
49.4
.782
6.51
56.4
32.8
.753
.861
6,27
7.17
176.2
41.9
28.6
.884
7.36
231.1
-139.0
30.8
.872
7.26
106.2
106.2
106.2
106.2
292.0 - 13.3
282,4 - 54.2
281.0
55.9
277 .1 -138.9
28.4
31.3
31.9
30.8
.885
.869
.866
.872
C,Hu
120.2
349.0 -
13.8
25.7
C,Hu
120.2
336.5 -
47.3
C,H"
120.2
C9H l2
C9Hn
C,H"
C,H"
C,R"
120.2
120.2
120.2
120.2
120.2
318.6
306.3
329.2
322.7
324.5
CYCLOPARAFFINS
Cyclopropane ... ............
C,H.
42.1
Cyclobutane . ...............
C.H.
56.1
+ 54.7
Cyclopentane . .............
Methylcyc1opentane . ........
1, I-Dimethylcyclopentane ....
CeHlo
CtHn
C,H u
l,2)imethylcyc1opentane-cis.
1,2-Dimethylcyclopentanetrans . ...................
1,3-Dimethylcyclopentanetrans . ...................
Ethylcyclopentane ..........
Cyclohexane ................
Methylcyclohexane . .........
Penten-l-yne-3 . ............
(AllylacetyPenten-l-yne-4
lene) . ...................
2-Methylbutenl-yne3 . .....
C.He
66.1
138.6
C,H e
CoHo
66.1
66.1
107
90
Hexen-l-yne-3 . .............
Hexen-l-yne-5 .. ............
2-Methylpenten-l-yne-3 .....
3--Methylpenten-3-yne-l* .....
C.H.
CoHo
CoHo
CoHo
80.1
80.1
80.1
80.1
185
158
169
156
AROMATICS
Benzene ... .................
CoHo
78,1
Toluene ..... ...............
C,H.
92.1
o-Xylene .... ...............

m-Xylene ................ .
;p-Xylene . .............. , ...
Ethylbenzene .... ...........
C.H IO
CaHlo
CaHlo
CaH lo
1,2,3-Trimethylbenzene . .....
1,2,4-Trimethylbenzene (Pseu
documene) . ..............
1,3,5Trimethyl benzene (Mesitylene) . ................
Propylbenzene . .............
lsopropylbenzene (Cumene) ..
I-Methyl-2-Ethylbenzene ....
---
--
551.3
47.9
0.304
17,990
17.270
609.1
41.6
.292
18,270
17,450
7,37
7.24
7.21
7.26
675
655
652
655
37
36'
35'
38
.288
.288
.270'
18.500
18,500
18,430
18,490
17,610
17,610
17,540
17.600
.900
7.49
72C/'
32'
29.1
.881
7.34
708'
33
18,570
17.620
328.3 - 48.6
31.1
.870
7.24
700'
18,620
17,670
-147,1
-140.8
-126,6
.866
.866
.883
.870
.868
7,21
7.21
7.35
7.24
7.23
690
68C/'
702<
695'
696'
18,660
18.670
17,710
17,720
34'
34'
82.7
31.9
31.9
28.7
31.1
31.5
33
/'
34'
35'
27.0 -196.6
98.6
.615
5.12
256
54
58.0
74.8
.686
5.71
385'
50'
cB
70.1
84.2
98.2
120,7 -136.7
161.3 -224.4
189.5 -105
56,9
56.2
54.7
.751
.754
.760
6.25
6.28
6.33
470'
520'
550'
46'
C7H u
98.2
210.7 -
62
50.4
.778
6.48
570'
40'
C,H u
98.2
197.4 -182
65.4
.757
6.30
560'
41'
C 7H 14
C 7H u
98.2
98.2
195.4 -213
218.2 -217
57.2
52.0
.750
.771
6.24
6.42
555'
580'
41'
40'
20,110
18.760
CeRn
C 7H 14
84.2
98.2
177.3
44
213.6 -195.6
49.0
61.3
.784
.774
6,53
6.44
538
575
40.4
40'
.273
20.030
20.000
18.680
18.650
, Heat of combustion &8 a gas-otherwise &8 a liquid.

Estimated.
Critical temperature-boiling point correlatioil.

., Vapor pressure curve or correlation.
34'
42'
42'
--
20,350'
20,110
18.760
20,020
18,670
20.020
18,670
"'d
~
~
......
19.OO
Mixture of cis- and trans' isomers.

Sublimes.
o:n
PHYSICAL CONSTANTS OF ORGANIC COMPOUNDS

0:.
FORMULA
MOLEC.
WT.
BOILING
POINT
of
MELTING
POINT
of
CRITICAL
CONSTANTS
DENSITY
Sp Gr
600 j600 Lb jgal
of
HEAT OF COMBUSTION
HEAT OF
VAPORIZ.
@B.P.
P
D
Atm Gjml BTU lib
@ 60F-BTU /lb
Gross
Net
-- -ALCOHOLS
Methanol (Methyl Alcohol) .. CHaOH
Ethanol (Ethyl Alcohol) ..... CH aCH20H
Propanol-1 (Normal Propyl
Alcohol) ................. CH aCH2CH20H
Propanol-2 (Isopropyl Alcohoi) ........ , ............ (CHa),CHOH
Butanol-1 (Normal Butyl
Alcohol) .................
Butanol-2 (Sec. Butyl Alcohol)
2-Methylpropanol-l (Isobutyl
Alcohol) .................
2-Methylpropanol-2 (Tert.
Butyl Alcohol) ...........
Pentanol-1 (Normal Amyl
Alcohol) .................
Pentanol-2 (Sec. Amyl Alcohoi) .....................
Pentanol-3 (Diethyl Carbinol)
2-Methylbutanol-l (Sec. Butyl
Carbinol) ................
2-Methylbutanol-2 (Tert.
Amyl Alcohol) ...........
3-Methylbutanol-1 (Isoamyl
Alcohol) ........ , ........
3-Methylbutanol-2 (Methyl
Isopropyl Carbinol) .......
2.2-Dimethylpropanol-l (Tert.
Butyl Carbinol) ..........
474
9760
8580
.794
6.61 469.6 63.1
.275
361
12,780
11,550
207.0 -195
.808
6.73 506.7 50.0 .273
296
14,450
13,190
180.2 -129
.789
6.57
289
14.350
13.090
>
~
148.1 -143.7 0.796
46.1
173.0 -174
60.1
60.1
tj
254
242
15.500
14,220
249
15.450
14.170
(6.60)
235
15,290
14,010
.819
6.82
223*
16,220
14,930
.814
.826
6.78
6.88
213*
211*
...
.820
6.83
- .825 -6.87
218*
77.9
(.793)
280.4 -109.8
(CH ahCHCH 2OH
74.1
226.4 -162
(CHa)aCOH
74.1
180.7
CH a(CH 2) aCH 20H
88.1
CH a(CH2hCH(OH)CH a
(CH.CH 2hCHOH
88.1
88.1
247.1
240
CH aCH2CH(CH a)CHIOH
88.1
264
to
6.71
-129.6
.806
243.9
211.1
o
o
6.78 549
6.75
74.1
74.1
,
.814
.811
CH a(CH 2hCH2OH
CH aCH 2CH(OH)CH a
48
:I:
~
~
o
Z
00
203*
16,030
14,740
216
16.150
14,860
209*
210*
9.31
344
8250
7340
CH aCH 2C(OH) (CHah
88.1
215.8
15
.815
6.79
(CHahCHCH2CH t OH
88.1
269.2 -179
.814
6.78
(CHahCHCH(OmCH.
88.1
233
.825
6.87
(CH a)aCCH20H
88.1
236
62.1
387.5
GLYCOLS AND GLYCEROL

Ethanediol-l,2 (Ethylene Glycol) ..................... CH2(OH)CH 2OH
6.63 464.0 78.7 0.272
32.0
120-125
1.118
..
Propanediol-1,2 (Propylene
Glycol) ................. CH3CH(OH)CH 2OH
Propanediol-1,3 (Trimethy- CH 2 (OH)CH2CH 2(OH)
lene Glycol)
76.1
76.1
371
850
(appr .)
Propanetriol-1,2,3 (Glycerol). CH2(OH)CH(OH)CH 2OH
92.1
554
ETHERS
Methyl Ether .............. CH,OCH 3
Ethyl Ether ............... CH,CH 2OCH 2CH,
46.1
94.1
273*
266*
260
52
5.99 381
35
8.68
65.0 1.265
10.53
-11.5 -217
74.1
1.042
-
-177 .3 0.719
10,350
10,450
9350
9450
7760
6940
0.271
187
13,570u
12,340u
.262
151
15,840
14,560
129
120
16,930
16,870
15,630
15,570
17,560
16,250
Propyl Ether .............. CH 3(CH 2)20(CH 2)2CH 3

Isopropyl Ether ........ '.' .. (CH')2CHOCH(CH,)2
102.2
102.2
194.2 -188
155.3 -122
.752
.729
6.26
6.07
Butyl Ether ............... CH 3(CH 2)30(CH2)3CH 3

Sec. Butyl Ether ........... [CH3CH 2CH (CH,) 120
130.2
130.2
288.0 -144
250
-
.773
.760
6.44
6.33
115*
109*
320*
.786
6.54
257*
11,400
10,540
ALDEHYDES
Methanal (Formaldehyde) ... HCHO
30.0 -
-180
8050U
7420U
P::
~
00
......
(1
>
~
Ethanal (Acetaldehyde) ..... CHaCHO
44.0
Propanal lPropionaldehyde)
58.1
120
-114
.812
6.76
215*'
13,400
12,420
72.1
167.2 -144
.809
6.74
189*
14,640
13,590
00
72.1
142
.799
6.65
180*
14,600
13,550
58.1
133.0 -138.8
.795
6.62
220
13,260
12,280
>
Z
;1
72.1
175.5 -123.5
.810
6.74
190
14,540
13,490
86.1
86.1
216.1 -108.0
215.2 - 40
.812
.820
6.76
6.83
15,430
15,380
14,330
14,280
200.7 -134
.820
6.83
168*
168*
86.1
165*
15,350
14,250
100.2
240.6 -119
.806
6.71
152*
15,980
14,840
CH,CH2CHO
Butanal (Butyraldehyde) .... CH 3CH 2CH2CHO

2-Methylpropanal (Isobutyraldehyde) ............... (CH 3)2CHCHO
KETONES
Propanone (Acetone) ....... CH 3COCH a
Butanone (Methyl Ethyl
Ketone) ................. CH 3COCH 2CH,
Pentanone-2 (Methyl Propyl
Ketone) ................. CH 3COCH 2CH 2CH,
Pentanone-3 (Diethyl Ketone) (CH 3CH 2hCO
3-Methylbutanone-2 (Methyl
Isopropyl Ketone) ........ CH 3COCH (CH a) 2
4-Methyl Pentanone-2
(Methyl Isobutyl Ketone) .
CH,COCH~H(CH,h
68.5 -190.3
87
* Calculated or estimated with a probable accuracy of 2%.
(1
"'-J
u Heat of combustion as a gas-otherwise as a liquid.
..
PHYSICAL CONSTANTS OF GASES
FOn~ULA
MOLEC.
WT.
BOILING
POINT
MELTING
POINT
of
of
CRITICAL CONSTANTS
HEAT OF COMBUSTION
60F-BTU j1b
,~~
P
Atm
D
G /ml
Gross
270.3
111.5
0.235
9670
8000
88.0
73.0
.460
-220.4
34.5
.301
4345
4345
291
76
.57
7.51
369
51.6
.33
-400
12.8
.031
61,100
51,600
124.5
81.6
.42
API
Sp Gr
Lb/gal
60/60
97.5
0.617
5.15
'42.0
.815
6.78
t
of
NH 3
17.0
Carbon Dioxirle ......
COz
44.0
-109.3*
Carbon Monoxirle ....
CO
28.0
-312.7
-::137.0
Chlorine .............
Ch
70.9
30
-151
Ethyl Chloride .......
CzH~CI
64.5
54.1
-214
Hydrogen ...........
Hz
2.0
-423.0
-434.5
Hydrogen Chloride ...
HCl
36.5
-121.0
-173.6
Hydrogen Sulfide .....
H 2S
34.1
76.5
-122.0
46.0
.797
6.64
212.7
88.9
7100
6550
Methyl Chloride .....
CH 3Cl
50.5
11.6
-143.8
20.3
.931
7.76
289.6
65.8
.37
Nitrogen ............
N2
28.0
-320.5
-346.0
-232.8
33.5
.31
Oxygen .............
Oz
32.0
-297.4
-362.0
-181. 9
49.7
.43
Sulfur Dioxide .......
S02
64.1
14.0
315.0
77.7
.52
Ammonia ............
28.1
-107.9
DENSITY
69.9
98.9
25.5
.901
1.394 11.62
"'tl
~
~
~
o
>
~
o
o
U1
"-3
>
"-3
U1
*.Sublimes.
..
Section 2
CHARACTERISTICS OF PETROLEUM
FRACTIONS
Average Boiling Point of Petroleum Fractions
,.
Many physical properties of pure hydrocarbons can be correlated with specific

gravity and normal boiling point as independent variables. However, for use in the
petroleum industry, these correlations must also be applicable to petroleum fractions which are mixtures of a large number of components, usually having a wide
variation in boiling points.
While the average specific gravity is a property of the petroleum fraction
which can be measured directly, just as in the case of pure compounds, there is not
an analogous average normal boiling point for a mixture. By integrating or averaging its distiUation curve (temperature vs. liquid volume percent distilled), a
volume average boiling point can be determined for the mixture. However, as
Watson and Nelson! and Smith and Watson 2 have pointed out, this has no special
significance as a true average boiling point and many physical properties can be
better correlated by the use of some other average boiling point, i.e., weight
average, molal average, etc. Consequently, in all correlations involving boiling
points of petroleum fractions, the proper average should be used. For the following physical properties, these are:
Average Boiling Point
1
2
Physical Property
Volume average
Viscosity
Liquid specific heat
Weight average
True critical temperature
Molal average
Pseudo-critical temperature
Thermal expansion of liquids
Mean average
Molecular weight
Characterization factor
Specific gravity
Pseudo-critical pressure
Heat of combustion
Watson and Nelson, Ind. Eng. Chem. 26, 880 (1933).

Smith and Watson, Ind. Eng. Chem. 29,1408 (1937).
10
CHARACTERISTICS OF PE'l'ROLEUM FRACTIONS
11
Since a distillation curve is usually available and a volume average boiling

point is readily obtained therefrom, the other average boiling points are given as
a function of these data. The chart on page 14 is based on an assay (True Boiling
Point) distillation 3 of the whole crude, while the chart on page 15 refers to the
1070 (or ASTM) distillation of the fraction itself.
The chart on page 14 was derived empirically from crude assay fractions of a
number of crudes. For narrow boiling fractions, all of the average boiling points
approach each other and the volume average boiling point may be used for any of
the others. Then, by appropriately combining the volume average boiling points of
the narrow cuts, the various average boiling points of wider cuts were determined.
The weight and molal average boiling points of the wider cuts were calculated
directly by combining the narrow cuts on the basis of their weight and mole fractions, respectively. The mean average boiling point could not be calculated in the
same manner since it is not a direct average or integral of its fractional parts. As
used herein, mean average boiling point is defined as the boiling point which best
correlates the molecular weight of petroleum fractions. Consequently, the mean
average boiling point for wider cuts was determined indirectly from the generalized
molecular weight chart on page 21.
Although Smith and Watson proposed a cubic average boiling point for the
correlation of characterization factor, specific gravity-boiling point relations forthe different crudes indicate that the present mean average boiling point can be
used for correlating gravity, and consequently characterization factor. Smith and
Watson also used cubic average boiling point for correlating viscosity, but the
present data indicate that the volume average is the proper boiling point.
Since these boiling point correlations were developed directly from crude
assay distillations, this chart should always be used 4 if an assay is available.
Otherwise, the 10% (or ASTM) distillation of the fraction may be used in conjunction with the other chart. The latter was derived from the crude assay chart
and an empirical correlation between the two types of distillation curves. The
difference between the two sets of curves at zero slope represents the thermometer
stem corrections for the 10% distillations.
In the case of light hydrocarbon mixtures, where the analysis is known, the
volume, weight, and molal average boiling points can be calculated directly from
the boiling points of the components and their volume, weight, and mole fractions,
respectively. On the oth~r hand, the mean average boiling point must be determined indirectly from the average molecular weight of the mixture. Up to an
Approximately 15 theoretical plates and 5 to 1 reflux ratio.
Below slopes of 2F/% for low boiling fractions (V.A.B.P. < 500F) and 3F/% for
high boiling fractions (V.A.B.P. > 500F), the volume average may be used for the other
average boiling points with very little error.
3
4
DATA BOOK ON HYDROCARBONS
12
average molecular weight of 80, the molecular weight-boiling point relation for
normal paraffins (page 20) may be used for this purpose, but for higher molecular
weights the generalized chart on page 21 should be employed.
Characterization Factor
Watson and Nelson 1 introduced characterization factor as an index of the
chemical character of pure hydrocarbons and petroleum fractions. The characterization factor of a hydrocarbon is defined as the cube root of its absolute
boiling point in oR divided by its specific gravity (60F/60F), or
Characterization Factor
yt T B/Sp Gr
Characterization factor is given on page 16 as a function of gravity in API

and boiling point in of for hydrocarbons and petroleum fractions.
That characterization factor is only an approximate index of the chemical
nature of hydrocarbons is indicated by its variation with boiling point both for
members of a homologous series and for fractions from the same crude (page 17).
However, it has considerable value in that it can be applied to the entire boiling
range of a crude and it has been generally accepted by the petroleum industry.
Typical Crude Fractions
For approximate use when there are insufficient data, several correlations have
been developed for typical crude fractions grouped according to characterization
factor and viscosity index. 5 These groups are numbered in order of decreasing
paraffinicity and each may be considered representative of the crude fractions
within its characterization factor or viscosity index range. The five groups were
arbitrarily selected as follows:
Group
I
II
III
IV
Characterization
Factor
. 12.1-12.6
. 11.9-12.2
. 11.7-12.0
. 11.5-11.8
. 11.3-11. 6
Viscosity Index of
Lube Fraclions6
80-100
60-80
40-60
20-40
0-20
Fractions from some of the more common crudes are cla5sifil'd in the following
table:
lS
See page 156.

Dewaxed to +20F pour.
CHARACTERISTICS OF PETROLEUM FRACTIONS
13
TYP.lCAL GROUP
White
Products
Pennsylvania
I
Rodessa. . . . . . . . . . . . . . . . . . . . . . . . . . . .. I
Panhandle . . . . . . . . . . . . . . . . . . . . . . . . . . . II
Mid-Continent . . . . . . . . . . . . . . . . . . . . . .. II
Kuwait
I-II
CRUDE
Gas Oils
and Heavier
I
I
I
II
II-III
Iraq
Iranian
East Texas
South Louisiana. . . . . . . . . . . . . . . . . . . . ..
Jusepin
II
II
III
III
III
II-III
II-III
II
II
III
West Texas . . . . . . . . . . . . . . . . . . . . . . . . ..
Tia Juana (Med. and 102)
Colombian
Lagunillas . . . . . . . . . . . . . . . . . . . . . . . . . ..
III
III
IV
V
III
IV
IV
V
Since, in the case of some crudes, the lower boiling fractions belonged in a
different group than the higher boiling fractions, they were classified separatelythat is, into white prorlucts having an average boiling point less than 500F, and
gas oils and heavier having an average boiling point greater than 500F.
+40
+ 30
WEIGHT AVERAGE
+20
+'0
0
- 10
10
Ii
iJ
AVERAGE BOILING POINT

OF PETROLEUM FRACTIONS ~
CRUDE ASSAy DISTILLATION
- 20
MEAN AVERAGE
-30
-40
-50
-60
-70
THE SLOPE AND THE 50% POINT FOR

THE VOL. AV. B.P. UNLESS THE
DISTILLATION FOR THE FRACTION
DEVIATES APPRECIABLY FROM A
STRAIGHT LINE. !N THE LATTER
EVENT THE FOLLOWING FORMUI AS
SHOULD BE USED:
-40 -
_ t7O-t10
S 60
ty = to+4t.50+tIOO
6
-60
In
..
cr....
('~
10
* THE CUT RANGE MAY BE USED FOR
MOLAL AVERAGE
-20
V>
-80
FOR WHOLE CRUDES:
t y = ho
-'00
-120
-'40
14
10
t,50+ teo
t40
WEIGHT AVERAGE
+20
,.L
-20
,~
4
t . t
8
i:J...~t-L_; of
MEAN AVERAGE
i....... .ly.......H-t~.
AVERAGE BOILING POINT
+20
,.
OF PETROLEUM FRACTIONS
0
10 % (A.5.tM.) DISTILLATION
-20
IF AVAILABLE, THE CRUDE ASSAY
DISTILLATION SHOULD BE USED FOR
DETERMINING AVERAGE BOILING POINTS.
-40
r
r-
l/}
<
-60
-eo
cr
(.f-
MOLAL AVERAGE
+-20
THE SLOPE AND AV. B.P. SHOULD

BE DETERMINED FROM THE FOLLOWING
FORMULAS:
t,,70 - tlO
S=
60
.,
-20
tv =
-40
IF THERE ARE INSUFFICIENT DATA

THE 50% POINT MAY BE USED FOR
THE VOL. AV. B.P.
-60
FOR WHOLE CRUDES:
-80
tv:
-100
-120
-140
tlo+2t50 +t 9O
15
'.
t30+t.50+t70
CHARACTERIZATION FACTOR
VS
14.0
BOILING POINT AND GRAVITY
13.0
13.0
12.0
12.0
_ 11.0
11.0
10.0
10.0
90
9.0
100
200
300
400
500
600
800
700
..
900
1000
I
100
..
200
CRUDE
13.6
13.2EEHHl
1 m:aE
3.0
12.1:)
a:m:a
400
.
TYPICAL GROUP
WHITE
PRODUCTS
134HHH1
300
I
I
II
II
I-II
II
II-III
IRAO
IRANIAN
EAST TEXAS
S.LOUISIANA
.lUSEPIN
II
II
II-III
II- III
III
III
WEST TEXAS
TIA .lUANA (NED.
COLOMBIAN
LAGUNILLAS
liI
III
III
III
102)
III
IV
600
700
900
1000
;.t~ 1 I:n __
CHARACTERIZATION FACTOR
~ BOILING
I
I
. .-!{ ~~ili
~ r .1%1+I.l-++J.1=:+I::t1+
POINT
TVPICAL CRUDE
~m
FRACTIONS
13.6
13.4
13.2
II
II
>-
IV
IV
-...
13.0
12.6
800
.,
GAS OILS
HEAVIER
PENNSYLVANIA
RODESSA
PANHANDLf
MID' CONTINENT
KUWAIT
500
:i '.
12.8
12.6
>-
I' .
12.4
12.4
,
.of:
12.2
12.2
.~
12.0
12.0
11.8
11.8
r
11.6
II ~
tt
11.4
TIT
"
d~
..,.+1.t
/00
200
300
400
500
600
., .
800
.
i. _
' 1->-
I~ -I.
700
1/.4
r i
11.2
"
r.
11.6
,J;
_Ir H-I" ;'++1+1-++1 11.2

.,:
900
1000
I
200
100
300
400
500
600
700
800
1300
JOOO
GRAVITY ~ BOILING POINT

TYPICAL CRUDE FRACTIONS
70
60
60
50 IHB111lHlIIII1l1l1J 1111 II tlHIIJIlJI IlIllIIlIIlIHt"KINI!'N:"lIIJilJIIH1I1lIlit11J111 1111111111111111 111I111l"KlOIIJ II i1II1III1II1IJIIJLLIUHlIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIII11II11111111 flll150
....
00
40
40
CRUDE
TYPICAL GROUP
WHITE
PRODUCTS
30 I:fI::i::l:!:1I
20~
10
PENNSYLVANIA
RODESSA
PANHANDLE
MID CONTINENT
KUWAIT
WEST TEXAS
TIA JUANA (MED.
COLOMBIAN
LAGUNILLAS
10J
I
I
II
II
%
II tlllllllllI11tllltul1tlJIlItn1'W"~1i\IM1t1n&J~IIIIIIIIIIIIIIIIIIITI't'l+l>lilJ
II
II III
II
102)
200
GAS OILS
HEAVIER
I
I.
III
IRAO
IRANIAN
EAST TEXAS
S. LOUISIANA
.IUSEPIN
FEIBHtlilMIllllllllllll130
IIIII
II
III
III
III
II-U.I
II
III
III.
IV
V
nI
IV
II
In
II1II111111 i 1IIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIImmmiiIII III IlrmUWOU1l11I1't'ffi!lratJUI:I!li1ln'iJmBTBI20
I1I'
300
400
500
600
700 ..
800
900
1000
Section 3
MOLECULAR WEIGHT
The molecular weight chart for pet.roleum fractions on page 21 was derived
from an empirical correlation of molecular weight and the function, T,,Jso.4o,
where T m i" the mean avcrage boiling point of the fraction in oR, and s, the specific
gravity at 60F/60F. The ayerage deviation for about one hundred petroleum
fractions from 75 to 500 molecular weight is +20/0.
Up to a molecular weight. of about 300 this correlation applies equally well
to pure hydrocarbons, with the exception of normal paraffins, which have lower
molecular \\'eights than predicted by the chart. Above 300 molecular weight most
pure hydrocarbons for which data are available deviate from the correlation in
the same direction as the normal paraffins. An explanation of this incongruity
may be that these particular high molecular weight compounds have relatively
long chains and consequently should fall somewhere between the normal paraffins
and the multibranched and multicyclic hydrocarbons in petroleum fractions.
The molecular weight of crude fractions is given as an independent function
of mean average boiling point, page 22, and also of gravity, page 23, for approximate use when only one of these variables is known. Examination of these charts
shows that the boiling point chart is much less susceptible to variations with type
of crude than the gravity chart and, consequently, will usually give a better
approximation than the latter. However, in general, gravity rather than the
boiling point will be available.
GENERAL REFERENCES
API Research Project 42.
Bridgeman, Proc. API 10, No.2, p. 124 (1929).
Doss, "Physical Properties of the Principal Hydrocarbons," 4th Edition, The Texas Co.,
Fitz imons and Thiele, Ind. Eng. Chem. (Anal. Ed.) 7, 11 (1935).
Francis and Wood, J. Chem. Soc. 48, 1420 (1926).
Kay, Ind. Eng. Chem. 28, 1014 (1936).
Mail' and Schicktanz, J. Research Nat. Bur. Standards 17, 909 (1936).
Mail' and Willingham, .T. Research Nat. Bur. Standards 21, 535, 565, 581 (1938).
Rosenbaum, J. Chern. Phys. 9, 295 (1941).
Shepard, J. Am. Chern. Soc. 53, 1948 (1931).
19
400
600
500
600
700
800
900
1000
1100
MOLECULAR WEIGHT n BOILING POINT
600
NORMAL PARAFFINS AND ISOPARAFFINS
500
500
400
400
200
200
180
160
I - AVERAGE OF ISOMERS CONTAINING
A SINGLE METHYL OR ETHYL BRANCH
2 - AVERAGE OF ALL OTHER ISOMERS
140
120
120
100
100
80
80
60
60
40
40
20
20
-100
100
20
200
300
400
700
800
1000
900
1100
1200
MOLECULAR WEIGHT
Yo! BOILING POINT AND GRAVITY
600
PETROLEUM' FRACTIONS
500
400
300
300
280
260
200
240
220
200
200
180
180
160
160
140
140
120
120
100
100
80
eo
100
200
300
400
500
21
600
700
aoo
200
400
300
500
700
600
800
900
460
460
. MOLECULAR WEIGHT ~ BOILING POI NT

440
TYPICAL CRUDE F RACTIONS
440
420
420
400
400
CRUDE
TYPICAL GROUP
WHITE
'RODUCTS
380
360
340
320
300
PENNSYLVANIA
RODESSA
PANHANDLE
MID - CONTINENT
KUWAIT
GAS 01LS
HEAV lEA
I
I
I
I.
II
360
II
II-III
I I -III
II-III
III
II
II
UI
In
IY
Y
IV
I-II
IRAQ
IRANIAN
UST TEXAS
S. LOUISIANA
JUSEPIN
II
WEST TEXAS
TIA JUANA (NED.
COLOMBIAN
LAGliNILLAS
nI
340
In
III
102)
.,
II
II
380
III
320
IV
300
280
280
260
260
240
240
220
220
CHARACTERIZATION
VISCOSITY
INDEX
200
GROUP
12.1 -12.6
SO-IOO
,eo
II
11.9 -12.2
60-S0
III
11.7-12.0
40-60
IV
11.5 - II.S
20-40
11.3-11.6
0-20
160
FACTOR
* DEWAXEO
OF LUBE FRACTIONS
200
180
160
TO +20 o F POUR
140
140
120
120
100
100
200
300
400
600
500
22
700
800
900
10
20
30
40
50
70
60
MOLECULAR WEIGHT
460
BO
GRAVITY
460
TYPICAL CRUDE FRACTIONS
440
440
CRUDE
TYPICAL GROUP
'WHITE
PRODUCTS
420
360
. WEST TEXAS
TIA .lUANA (NEO.
COLOM81AN
LAGUNILLAS
340
320
GROUP
IX
I-U
II
11
III
IV
280
260
400
II-%II
380
lI-nI
II-XII
II
II
Dr
III
102)
%
:II
:III
II
III
UI
XII
DI
IV
IV
IV
y
360
340
CHARACTERIZATION
VISCOSITY INDEX
FACTOR
OF LU8E FRACTIONS
300
II
420
IRAO
IRANIAN
EAST TEXAS
S. LOUISIANA
.lUSEPIN
380
GAS OILS
HEAVIER
PENNSYLVANIA
RODESSA
PANHANDLE
MID' CONTINENT
KUWAIT
400
320
80-100
12.1 -'2.6
11.9 -12.2
60-80
11.7 - 12.0
1/.5-11.8
1/.3-11.6
40-60
20-40
0-20
300
2BO
DEWAXO TO +20 o F POUR
260
240
240
220
220
200
200
180
180
160
160
140
140
120
120
100
100
110
20
30
40
50
60
23
PIA
PABLO
70
80
o-;n'i L
,
If"
\)
_,_
f.J
. .JJ
t. I.,.
1VI0T'l'A
Section 4
VAPOR PRESSURE
In developing the vapor pressure curves for most of the individual hydrocarbons, the reciprocals of the absolute temperatures were plotted against those of a
reference compound (ethane, butane, or hexane) at the same vapor pressures. 1 With
one or two exceptions, this relation was linear over the entire range of the data,
but if a slight curvature was indicated, as in the case of benzene vs. hexane, a
straight line was not imposed upon the data. The vapor pressure curves for
methane and the reference compounds were developed directly from the data by
plotting vapor pressures against reciprocal temperatures. Most of the reliable
data fell within -I- 1OF of the correlations, and this may be considered as about
the accuracy of solid portions of the vapor pressure curves. Normal boiling points
in all cases were taken from "Selected Values of Properties of Hydrocarbons."2
While vapor pressure is meaningless above the critical temperature, the
curves were extrapolated beyond this point so that other properties in the liquid
phase could be calculated in the absence of any other data. For example, these
extrapolated curves may be used to make rough approximations of the fugacity,
density, and enthalpy of hydrocarbon vapors in solutions at temperatures above
the critical.
The generalized vapor pressure charts for hydrocarbons were also derived
from the linear reciprocal temperature relation with hexane used as the reference
compound. The pressure scales correspond to the vapor pressure of hexane as a
function of reciprocal temperature. The temperature scales were based on the
reciprocal relation up to 700F, but above 700F it was necessary to modify the
scale to secure better agreement with data on high boiling hydrocarbons and
petroleum fractions. 3
The slopes of the normal boiling point lines on the rectilinear chart and the
corresponding points on the alignment charts were based on normal paraffins.
However, with the exception of some of the lowest boiling members of the various
series, there is a good indication that these charts apply to hydrocarbons in
general. In API Research Project 42, the boiling points of a large number of
1 This is the most nearly linear of the simple vapor pressure relations, with the exception
of a similar one where the reciprocal temperatures are plott.ed at the same reduced vapor
pressures.
2Nat. Bur. Standards Circular C461 (1947).
3 Beale and Docksey, J. lnst. Petro Tech. 21, 860 (1935).
24
VAPOR PRESSURE
25
different high boiling hydrocarbons were determined at 0.5 mm, 1.0 mm, and 760
mm, and these were checked against the low-pressure alignment chart. The
average deviation was about 2F over an average extrapolation of around 400F,
and there was no trend between the paraffins and other hydrocarbons.
Thc cxtrapolation of the vapor pressure scale below the hexane data has been
checked indirectly by the Clapeyron equation using thermal data on hexane at
low tempcratures. Also, low-prcssure data (below 0.001 atm) on petroleum fractions are in good agrecment with this correlation.
GENERAL REFERENCES
Aston, Kennedy and Schumann, J. Am. Chem. Soc. 62, 2059 (1940).
Aston and Messerly, J. Am. Chem. Soc. 62,1917 (1940).
Beale, J. Inst. Petro Tech. 22, 311 (1937).
Beattie, Hadlock and Poffenberger, J. Chem. Phys. 3, 93 (1935).
Beattie, Poffenberger and Hadlock, J. Chem. Phys. 3, 96 (1935).
Bea.ttie, Simard and Su, J. Am. Chem. Soc. 61, 24 (1939).
Bea.ttie. Su and Simard, J. Am. Chem. Soc. 61, 924 (1939).
Bekhedahl, Wood and Wojciechowski, J. Research Nat. Bur. Standards 17, 883 (1936).
Benoliel, Thesis, Pelillsylvania State College (1941).
Benson, Ind. Eng. Chern., Anal. Ed. 13, 502 (1941).
Brown and Coa.ts, Univ. of Mich. Res. Circ. Series 2 (1928).
Comrp.unication from The ::\1. W. Kellogg Co., New York, N.Y.
Dana., Jenkins, Burdick and Timm, Refrig. Eng. 12, 387 (1926).
Doss, "Physical Constants of the Principal Hydrocarbons," 4th Edition, The Texas Co.,
Ega.n and Kemp, J. Am. Chem. Soc. 59, 1264 (1937).
Francis and Robbins, J. Am. Chem. Soc. 55, 4339 (1933).
Frolich and Copson, Ind. Eng. Chern. 21, 111G (1929).
Garner, Adams anu Stuchell, Refiner 21, 321 (1942).
Hei ig, J. Am. Chern. Soc. 55, 230-:1: (1933).
Heisig anu Davis, J. Am. Chem. Soc. 57, 339 (1935).
Heisig and Hurd, J. Am. Chem. Soc. 55,3485 (1933).
Ingersoll, Thesis, Mass. Inst. Tech. (1930).
Intel'l1ationa.l Critical T:1bles, Vol. III.
Kassel, J. Am. Chem. Soc. 58, 670 (193G).
Kay, Ind. Eng. Chem. 30, 459 (1938).
Kisti:1kowsky and Ricc, J. Chem. Phys. 8, 610 (1940).
Kistiakowsky, Ruhoff, Smith and Vaughan, J. Am. Chem. Soc. 57,876 (1935); 58,146 (1936).
Krase and Goodman, Ind. Eng. Chem. 22, 13 (1930).
Lamb and Roper, J. Am. Chern. Soc. 62, 806 (1940).
Kinuer, J. Phys. Chem. 35, 531 (1931).
Livingston and Heisig, J. Am. Chem. Soc. 52,2409 (1930).
Loomis and Walters, J. Am. Chem. Soc. 48, 2051 (1926).
Maxwell, Ind. Eng. Chem. 24, 502 (1932).
Morehouse and Maass, Can. J. Research 5, 307 (1931); .11, G37 (1934).
26
DATA BOOK ON HYDROCARBO S
Nieuwland, Calcott, Downing and Carter, J. Am. Chem. Soc. 53,4197 (1931).
Pitzer and Scott, J. Am. Chem. Soc. 65, 803 (1943).
Rintelen, Saylor and Gross, J. Am. Chem. Soc. 59, 1129 (1937).
Sage, Lacey and Schaafsma, Ind. Eng. Chem. 26, 214, 1218 (1934).
Sage, Webster and Lacey, Ind. Eng. Chem. 29, 658 (1937).
Schmidt, Thesis, Paris (1934:).
Stuckey ll,nd Saylor, J. Am. Chem. So:;. G2, 2J~ (1940).
Vaughan, J. Am. Chem. Soc. M, 3863 (1::>2).
Vaughan and Graves, Ind. Eng. Chem. 32, 12.;>2 (1940).
Wiebe and Brcevoort, J. Am. Chem. Soc. 52, 622 (1930).
Wiebe, Hubbard and Breevoort, J. Am. Chem. Soc. 52, 611 (1930) .
_~:
.-- -
4-
::l
HH-
'!' --
80
70
60
50
40
-_.~
30
20
-;-
-300
-200
27
100
200
-2'50
-200
-150
.8
.1
.6
.5
l--:r.
--
-100
.. - , ~
~.-
VAPOR PRESSURE OF
ETHANE AND ETHYLENE
.4
.3
.2
200
.08
80
.07
.06
60
.()5
50
70
.04
40
.-
.O~
30
.02
20
all',
,
II
.1
~
_.
...-
gr
4
3
-200
-tOO
100
28
200
300
400
-100
- ,-;;.,,",
i-
-50
::T:-E.=:io-~:ff-'
~ ::ri..:r--,~f.':'=j-:',
le"",
-,
..6
,,,="
-'
.1
'~7,k
,c.:.~3':!..J
=
VAPOR PRESSURE OF
PROPANE AND PROPYLENE
.5
.4
+- ,
'+:
.3
--H
.2
.1
.09
.08
.07
200
100
r=
90
'''''
" !CA_~{~!
.06
-t-t=f
60
-,.!~
.05
70
''f'
50
.04
40
.03
30
.02
20
II
-'I=.:f.: "
.009
,008
-'
.001
10
9
8
7
IXXJ
.005
=r
100
200
300
29
400
500
50
.4
VAPOR PRESSURE
OF BUTANES AND 8UTENES
:II+-_~,
..3
.2
200
30
I
.
II
II II
.01 ~-====47
I
I
/I
V V 1/
tOO
200
300
30
400
500
-roo
t.O
.9
50
p.
: ::r=tfel. -:-r-:
~-.g:
--
VAPOR PRESSURE OF
.5 ~
PENTANE
-I'
...
::T'
AND ISOPENTANE
.3
.2
'200
11
. ==':.f"_
-=I::
:t=:!-~:.
90
_
!:::f
.07
.06
1=l;.T:,:
80
70
60
.05
50
.()4
40
30
20
.02
.OOQ
Q'
.01
.- -
, .
-',--.
-:.
,008 .007
.006
.:
:~
.'
- ":'::. - .
--
7
6
,=:
l:-
.005
.004
.003
_.
- I::l
.002
It
.00IU-J....l....L.LLL.JLJ...,U.I-......AJ...J...Iu1t.U./-l..'~~I~J.:..z.J,;.W-l...l-J...J.-l...J..J..1..J..J...J...L..J...J..J..J..J...J...IW-L...J.-l....J.-l...J..J..u..J-U...J...J..J..J..1..J..J...J...L-U
100
200
300
400
500
31
l--.
.-.---------
600
-50
-100
100
- 1 I f t i j - -.:.~
.9
.8
..,
';-..::
T.~:
':
="=
.5
50
: .....
'.':~:
ISO
VAPOR PRESSURE
OF HEXANE
.4
.a
200
I~
.1
.09
-t...
-fl
:.~,"'f> :. 'c: :::'.-:x':~ ::~-,.
-17
.07
n-
"
_.
"c't._',_
- _"':4'_ ..-.t
'--J-;,'
:: t~
:'':'
--.
:r.' ,-- '-,-,
, 'f--X:==, T.:i::-'~
~,
.-
..
-'-+-
~.
=- __.---7l~:.
==1':::.
,.. -,-V-FFl
r-- ~-;:=::;=:I
-I:' ' =l:
'
, -
100
90
80
70
.06
60
.05
50
.04
40
.03
30
.02
20
.'
;=;=. ~ 11.,,':.. '.,~':'1.
.008
.OOf
.006
.'f=::i=E j~ --!'
.''=8, !E::-l,=.:l3:: '

--:=;::1:'. :t+= 'r:
- -,
1-..
-- -
,~.
,~f:~T ~.~:~I
_:. ,_ ,. ~ -
,-J.'
~t:.:~
'
-, -. . ,.. =.-1-=!iiC:l 10
9
= -
9
7
6
.00
.003
I
I I
II .
;.,
32
-50
.8
.5
. =-=
::::.C
50
100
150
=--==~~-:'~';'_~c~"==:l~F-=~. .
_--<
200
=:h:b-~.1-'-.
~=t=t::= ~=;::
VAPOR PRESSURE
OF HEPTANE
.4
.3
~t:
.2
200
~~"'~~'t:g~E~ 'fg
-= .
.:
~."
70
60
=t...:
50
40
30
20
H-H-++-H-t--t-++-t-f-fH--f-+-HH-+++!
=f:'~= ~", ~::.~f ~;; -:~-=:.=
'C, E.: ~! :t+' - j:, = ~
- -. '._. ... .-
10
9
,..:::::: 8
:;:::=.;.
.008
.em
.006'
.005
f-:-. :-'~"'-""::l:
.i=i= I/.~ .
.::t t':i::~.
l::::tl"
.0
.003
~-
..:p.
..... :
I-:=:
'-.q::
--l-
'-;- 1-.; ':-i-:'-
";J-
. c;::::=
c-F-+'~f-C.,....=
r_
L:.I ..
.= ..
.1=;""<- H
::-J: :.
tH--
5
4
.
+--'---~"'H
Xt__ 1--
_.-.
.. !-' . ; .
. '--.-1-1- ..
_J
.002
33
50
1.0
.9
200
ISO
100
250
=I-,~-,,::'~,':7~,::I-,-:.-~:: -~~
.8
.7
=F~:::l~+:-
..: .
-f-
.6
.5
VAPOR
:4
OF
PRESSURE
OCTANE
~'.
-I- '
--;
':,::J
.2
,'+'++++++++++++++++H-J-H
"
...:' - t -
.01
100
90
70
60
.06
.05
.04
"
'I
.0/
.009
,
,
-1---J---~--1-I-I-
.009
.007
DOG
.005
I-
J-+-tft-t-H-t-t
f-
"
200
300
500
400
34
600
700'
800
:1..-=
VAPOR PRESSURE
OF C3 UNSATURATES
3
,~-.
-'-"
-,
'-~:j=~~
-Ej
-:1#
.,
-
~I= --,..~
r'
.1-/
_I-~-~.
to
300
t-:~-
j-++
-l-+
++y.j
200
WW-
1- 1
.J
.1'".
II
l'i
100
l'
300
200
35
41)0
500
()
-!'>("}
_'00
1.0
.9
.8
50
.7
.6
.5
VAPOR PRESSURE
.::
OF C4 UNSATURATES
.3
,
-I
200
.2
''1
.1
.09
.-
- =Z:~-E,.;:.
-:'E
~, ~----.
.08
.07
t'-
-~ -~:
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_.
_.-. .
00
..
)/:
-I:
-:J
l" I"
~
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-,
t-
o
o
7o
;:::t::T-
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.os
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r I.~
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t-
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5o
40
_.
_.-
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30
-o
.02
Il"l-II
III
.01
.~
II
.B.P.
of
COMPOUND
11
CRITICAL PT.
of
ATM.
1,3 BUTADIENE
24.1
308
45 .
VINYLACETYLENE
42
365*
75 v
ETHYL ACETYLENE
47.7
DIMETHYL ACETYLENE
80.4
375
420
65 v
60 v
* ESTIMATED
VAPOR PRESSURE CURVE
I
9
8
7
6
5
4
II
100
300
200
36
400
500
-.
1.0
,9
.8
.7
100
.
=r_0-
150
.
..
.5
.4
---
VAPOR PRESSURE OF
BENZENE AND TOLUENE
.6
..
200
.... .
0_
o~
~=
--
.~
.2
.t
.-
..
.09
.08
.07
I
I
I I
.06
~+
0
.04
'0
:t=l=
o.
.05
8o
7o
6o
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...
,~f ~
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5o
~:
...
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4o
.....
I 00
9o
ti
1-4-
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+-
'X
.02
j~rc
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1/
.01
009
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'=' .
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.
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.006
00
9
.8
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6
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0
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4
-Hi
.003
-ti
I
.002
,I
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I I
I
I
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200
Ie
. .
300
400
37
500
600
700
50
1.0
.9
-.- . - .
.8
.7
.6
100
..
..
..
_. .
-~-
.4
B.P.
CRITICAL POINT
ETHYL8ENZENE
p-XYLENE
m-XYLENE
o -XYLENE
.2
250
..
271.1
281.0
655
38
652
35 V
W~
i=1-1=l=1=!.
..
:+
.
--
=.l
..AItL
300
'-
=).
r-'
COMPOUND
.3
2o0
-
'.
VAPOR PRESSURE
OF Ce AROMATICS
..
.5
150
--
--J
282.4 655" 36 V
292.0 675 37
CURVE
*ESnMAlD1 V- VAPOR PRESSURE
.
,
.1
.09
I I I
..--.. ,
.. "
I I
I I
I
I
I
I
I
I
I
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t+
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.03
30
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.
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=T=
.009
..... ,,-:::,
.008 - ~;=.s.
-.
.001
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--
-:.
't:-
til'
-,
..
.,
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~'ffJ$
%.-! '-.
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~_ ~'=T::
'~
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..
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!=1
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.004
..
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'j'
- .. .-
:
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.f-'i F= ' ::':1':=1:2'
'.:\=-1--::
--.-
' 1.-= rot:j;
1_ "
,tfL.~",t--T-i'-=
.... -+,+ H::-
:g I9
.. A
B="-=i::t~::.m -
. :!-r:
-7
=l "f.
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6
~::IS=.$ ,
5
.002
4
~
II
.00I
-= F.[-~
-.' -=to -E-:-:- ;: . j:_-;...~-':'l:LL--..
--l
='
+c -' .-.a:- o
VAPOR PRESSURE OF P - XYLENE

EQUALS VAPOR PRESSURE OF
ETHYLBENZENE MULTIPLIED BY .950
..
.003
.. -1
Ie;
- -l
..
~'I.'1;: o.:,~ :
0-
...
..
':', -,
,}--r:R:: l=f*~
.. . .' - 1-=1-:1=
:",~
IIi
Vl-1-
J: :'i,i 1
... ~'1..:';_:"
i,;
-' ,
....
-
:j~Ii'Jl
i+
!-1-+-
,.. -
.
-;- ~;/
,~"-I::-:.fil-#-
_..
_I::-j,r~.
:.t:
-l
-I-
..
II
'1
.1 I
'1
300
500
00
38
600
700
eoo
100
-50
.9
.'
.8
.7
.6
.3
.2
,H
~:
~. . .
VAPOR PRESSURE
.f"!--1-:-
.5
too
50
OF CYCLOPARAFFlNS
~
.'.
. r--
Ii
I
I
.I~00
.08
80
70
.07
.06
60
.05
50
,04
40
.03
30
.02
20
++-l-l--JTf-++-J.,l;~I)ll-HH-I++-H-++++-H-H-IH-l++++-t++-H-
..1_
:01
.009
.006
.007
COMPOUND
.OO6~
CYCLOPENTANE
I 2 0 .7
tt1'CYCLOPENTANE 161. 3
CYCLOHEXANE
177.3
,005
004
B. P.
of.
'-
CRITICAL POINT
~
ATM.
,g:
10
9
8
7
470*
46 V
520*
538
42 V
40.4
.'
4
*EsrIMATED
V- VAPOR PRESSURE CURVE
003
.002
39
.00001
1200
VAPOR PRESSURE OF HYDROCARBONS
1100
LOW PRESSURE RANGE, 0.00001-1.0 ATMOSPHERES
01
.00002
1000
.00003
.00004
900
.00006
800
.00008
.0001
700
.0002
\'2-00
600
.0003
.0004
.0006
500
.0008
.001
400
u.
w
::>
0=
0..
~
W
f-
250
u0
w
0=
::>
.006
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(f)
(f)
0=
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a0...
19
~
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200
.003
~ .004
0=
300
.Q3
.04
.06
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~
0.2
03
04
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1.0
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0
350
02
.04
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0.1
150
3.0
(j)
(j)
6.0 ~
Q.
8.0 a::
10 ~
~
20
30
40
60
80
100
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100
0.3
0.4
0.6
0.8
1.0
50
40
~I
w
4.0 ~
.02
.03
2.0
200
300
400
600
VAPOR PRESSURE OF HYDROCARBONS
1200
0.1
1.0
HIGH PRESSURE RANGE, 0.1-100.0 ATMOSPHERES
1100
20
1000
\'(..00
900
\ \QO
0.2
3.0
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800
40
9 00
0.3
5.0
700
0.4
0.5
600
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'6
c-
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60
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8.0
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(f)
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vi
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20
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t-
~6.0
250
~ 7.0
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200
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I
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::J
(f)
(f)
w
70 0::
80 a..
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100 a..
8.0
9.0
10
200
150
20
300
400
30
500
40
100
50
60
70
80
90
100
sJ
41
600
700
800
900
1000
1500
fOO&>
' ,
toe
150
200
~O
250
80
60
350
400
PEn'Ll-TURE - OF
VAPOR PRESSURE
OF HYDROCARBONS
40
450
,~_
.,:
-tY.~ "~..." .
'
'!-t _
I,
-ll'
;-r;
3 0 ,
80
,.
60
40
30
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900 1000 1100 ~
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20
aoo
550 600 650'700
500
, . .
' I
''''
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20
lliJd1.LLJL!
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'~
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r 1
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'
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4.0
3.0
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te
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= ~ ~ o~.
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144 """
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........
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'
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::!",~_,-:::
~<-~_
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~
~ ,t+
;,
.4~-::
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_ ~
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=i=rc
~~~.gH-t+I-IIdjctti+b~"
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.
""OB
L:...:..CJ
.06
.008
.006
.004
.003
.002
TE~PERATURE -OF
v
50
100
150
200
250
300
350
400
'/
450
500
tt1
-"
550 ----600 650 700
i I I "
800
900 1000 1100 1200
NORMAL BOILING POINT

.
t. ,
,I
Y! BOILING POINT AT 10 MM
."i,
.1.-
"!
1100
1000
900
800
700
600
500
400
100
200
300
400
500
600
43
oPI
700
r)H,T 1r~T _ TJ)

~ i tV/l. \. J .)
PABLO MOTTA
900
VAPOR
PRESSURE OF GASOLINES
180
.7
.8
.9
1.0
170
2.0
70
80
90
100
3.0
150
4.0
200 ci
J:
* CURVE
SLOPE OF DISTILLATION + LOSS
(A.S.T.M.). F@ 15'>'. - of 54
150
1.5
10
IN THE ABSENCE OF DISTILLATION
DATA THE FOLLOWING AVERAGE
SLOPES MAY 8E USED:
140
LIGHT NAPHTHAS (F.B.P.-300F)

NAPHTHAS (F.B.P.-400F)
AVIATION GASOLINES
MOTOR GASOLINES
130
F/'>'.
2.5
4
2
01234
~
0 2
en
"(Ij 3
Q)
110
:::>
0:
L&J
12
14
Q:"
0 16
Q.
18
20
::E
...
l&.I
70
a:
60
l&J
6
7
8
9
10
UJ II
0..
-J
I
....
u.
0:
6.0
0:
0..
8.0
:::>
...
.4.0 0 F/'Y.
0
COORDINATING RESEARCH
COUNCIL (CRC) HANDBOOK. PP. 244-254 (1946)
44
Q.
~
L&J
Q.
0..
0:
It
It
0:
10
REFERENCE:
400
TRUE VAPOR PRESSURES CORRESPONDING TO A R.V.P. OF 9.0 LBS./

so. IN. AND A SLOPE OF 4.0F/'>'.
ARE READ FROM THE CHART AS
FOLLOWS:
TEMPERATURE TRUE VAPOR PRESS.
OF
LBs/sa. IN.
32
2.8
100
9.9
21.4
150
10
It
(/)
l&J
SLOPEc 160-120
20
300 w
;:)
(/)
EXAMPLE: DETERMINE THE TRUE

VAPOR PRESSURES AT 32F. 100F
AND 15QF OF THE FOLLOWING
GASOLINE:
REID VAPOR PRESS. - 9.0 LBS./SO. IN.
DISTILLATION + LOSS, 5'>'. ~ 120 OF
15'>'. (! 160 OF
30
:::>
12
14
16
18
20
40
(J)
(J)
II
50
~
en 5.0
CD
;;: 4.
0 5
2 6
UJ 7
Q:" 8
:>
en 9
en 10
L&J
0:
80
~
d
...J
l&.
SLOPE
120
90
50
60
160
100
40
II
12
13
14
15
16
17
18
19
20
30
500 ~
us
;:)
600 It
I-
700
800
900
1000
Section 5
FUGACITY
Raoult's Law
If two or more compounds form an ideal solution in the liquid phase, and if
the saturated vapors of the individual components are perfect gases, the system has
been termed an ideal system.! For such a system the partial vapor pressure of
any component may be calculated from the composition of the liquid phase by
Raoult's Law and from the composition of the vapor phase by Dalton's Law. An
equation of these two expressions gives the liquid-vapor equilibrium relation for
any component, i where i = 1, 2, ... , n:
or
Pi = PiXi = 7rYi
(1 )
== P i /7r = Ki
(2)
yi/Xi
where Pi
partial pressure of i
Pi = saturated vapor pressure of i

Xi = mole fraction of i in the liquid phase
Yi
= mole fraction
7r =
Ki
of i in the vapor phase
total (vapor) pressure of the system
= vapor-liquid equilibrium constant for i at the temperature and pressure

of the system
The above equation, usually referred to as the Raoult's Law relation, is true
only for ideal systems, ,as defined above. However, it is usually a good approximation for mixtures of homologues and, in general, for mixtures of chemically similar
compounds, if none of the saturated 'vapors at the equilibrium temperature deviate
too greatly from a perfect gas.
Up to moderate pressures (several atmospheres) hydrocarbon mixtures frequently fall within the scope of the Raoult's Law relation. However, its application to these mixtures is rather limited because of the wide differences usually
encountered between the boiling points of the most volatile and least volatile
components. This results in equilibrium temperatures at which the saturated
vapors of the lowest boiling components deviate considerably from a perfect gas,
even though the equilibrium pressure of the system may be relatively low.
I
Gamson and Watson, Nat. Petroleum News} Technical Section 36, R-258 (1944).
45
46
Fugacity Functions
In order to improve the accuracy in predicting vapor-liquid cquilibrium constants for hydrocarbons at higher pressures, Lewis and Luke 2 and other investigators replaced the pressures in equations (1) and (2) by -analogous fugacities for
any component, i, whereby:
or
Ii = fpiXi = fnYi
(3)
Ki
(4)
Yi/Xi
where fi
fpdf.Tri
fugacity of i in either phase of the system
fpi = fugacity of i as a pure saturated liquid (or vapor) at its vapor pressure
corresponding to the equilibrium temperature of the system

f-rri
= fugacity of i as a pure vapor at the equilibrium temperature and pressure

of the system
Generalized correlations have been developed for the r-atio of fugacity to

pressure for pure hydrocarbons as a function of reduced temperature and reduced
pressure. A correlation of this type (pages 62 and 63) was used in conjunction
with the vapor pressure charts to develop the fugacity function charts for individual hydrocarbons. 3 The fugacity function given by these charts, 7rfp/!-rr, may
be considered a corrected vapor pressure and used in place of the latter in ~ny
equation pertaining to liquid-vapor equiiibrium such as equations (1) and (2).
These simple fugacity relations greatly extend the pressure range for which
liquid-vapor equilibria for hydrocarbon systems may be predicted with confidence, and can be used up to equilibrium pressures of 20 to 25 atm with a fair degree of accuracy. Beyond these pressures and especially as the critical point of the
mixture is approached, serious deviations from true equilibrium conditions are
encountered. Under these circumstances, the assumptions of ideal mixtures no
longer hold and the fugacities of the individual compounds are dependent upon
the compositions of the liquid and vapor phases as well as temperature and
pressure.
In the region where the simple fugacity relations no longer apply and consequently beyond the scope of the present charts, there are data in the literature on
a number of specific binary and multicomponent hydrocarbon systems. Also, The
M. W. Kellogg 00. 4 has published an excellent correlation for lig~1t paraffin and
olefin hydrocarbons in which the fugacities of the individual compounds are
given as a function of the molal average boiling points of the liquid and vapor
2 Lewis
and Luke, Trans. Am. Soc. M echo Engrs. 54, 55 (1932).
a This method was actually used only up to the critical temperature of each compound.
Beyond this point values were calculated from more general fugacity correlations developed
by The M. W. Kellogg Co. to avoid using extrapolated vapor pressure curves.
4"Liquid-Vapor Equilibria in Mixtures of Light Hydrocarbons," The M. W. Kellogg
Co., New York, N. Y. (1950).
FUGA CITY
47
phases in additi on to the equilib rium tempe rature and pressu

re. The Kellogg
correl ation was derive d from the applic ation of exact therm odyna
mic relatio ns to
a comprehensive equati on of state for pure hydro carbon vapors
and liquids and
their mixtur es. 5
If, in additi on to hydro carbon v-apors, other gases (air, H , CO
, etc.) are
2
presen t in the vapor phase, it is recom mende d that an effective pressu 2
re, equal to
the produ ct of the total pressu re multip lied by the square root of the
mole fractio n
of the entire hydro carbon portio n of the vapor, or 7r-VV;;;, be used
in determ ining
the fugacities of the indivi dual hydroc arbons . Fragm entary data
have indioa ted
that this effective pressu re gives better results than either the total
pressure, 7r,
or partia l hydro carbon pressure, 7r'YHC, for determ ining indivi dual
fugacities. Then,
after the fugacities or fugaci ty functio ns have been read from the
charts , the total
pressure is again used as a basis for all equilibl:ium calcul ations
. The following
examp le illustr ates the applic ation of the fugaci ty functi on charts
when other
gases are presen t in the vapor phase:
Examp le 1. Determ ine the pressu re and composition of the
liquid phase in
equilib rium with a vapor of the following composition at gOF:
1st Trial
Component
Vapor.
Mole Fract.
1l'
0.040
.220
.280
.175
.160
.125
1.000
CH 4
C2H6
C3Hs
C 4H 1O
= 25 atm
1I"e = 21.5 atm

F, atm
Air
H2
2nd Trial
*
*
180
38.0
13.5
4.9
0.039
.115
.296
.637
1.087
Interpo lation
11" = 20 I1tm
1I"e = 17.2 atm
F, atm
11"
*
*
180
36.0
12.7
4.4
0.031
.097
.252
.[;68
0.948
= 21.8 atm
x
0.034
.104
.269
.593
1.000
In this example, the fugacity functions of air and H2 are conside

red to be infinite.
where 7r = total equilib rium pressu re

7re = 7rVO.740 = effective pressu re used to determ ine fugaci ty functio
ns
F = 7rfp/!1I" = fugaci ty functi on for pure hydroc arbons
x
~
= 7rY/ F
Relati ve Volati lity

Since relativ e volati lity is quite useful in fractio nation problems,
curves for
the relativ e volatil ities of light unsatu rates and isoparaffins to the
corresponding
norma l paraffins are given on pages 64 to 66. The curves for the
C 4 unsatu rates
IS
Benedict, Webb and Rubin, J. Chem. Phys. 8, 334 (1940); 10, 7474
(1942).
48
inay also be used in conjunction with the normal butane fugacity chart to predict
fugacity functions for these compounds.
Except for butadiene and the normal butenes, these relative volatility curves
were derived from the Kellogg fugacity correlation. Composition was indirectly
taken into account to some extent since the fugacities for each pair of compounds
were read at the same liquid and vapor molal average boiling points as well as
at the same temperatures and pressures.
In general, the relative volatility charts may be considered to have a somewhat greater range of applicability than the simple fugacity charts. They may be
used up to 25 atm, irrespective of the composition of the liquid and vapor phases
of the mixture; beyond this pressure their application is limited to systems in
which there is a difference of at least 75F between the molal average boiling
points of the two phases, but under no circumstancel? should the curves be extrapolated. While all of the curves may be considered to be accurate within 25% for
the relative volatility minus one (0; - 1), deviations from the solid curves rarely
exceed 15% for this difference.
Chemical Structure and Liquid Activity Coefficients
When components in a hydrocarbon mixture are quite dissimilar chemically,
the liquid phase may deviate appreciably from an ideal solution. This effect of
chemical structure is not taken into account in any of the fugacity correlations
heretofore considered. It has been mentioned that in correlations of the Kellogg
type, fugacity is a function of the liquid and vapor compositions, but only with
respect to components of similar chemical structure.
To correct for chemical dissimilarity in solutions of light hydrocarbons in
absorber oils, liquid activity coefficients are given for these light hydrocarbons on
page 67. Within the range of the data these activity coefficients were practically
independent of temperature (100F and 220F) and pressure (500 psia and 1000
psia) .
GENERAL REFERENCES
Brown, Souders and Smith, Ind. Eng. Chem. 24, 513 (1932).
Dean and Tooke, Ind. Eng. Chem. 38, 389 (1946).
Hadden, Chem. Eng. Progress 44, 37 (1948).
Kay, Chem. Revs. 29, 501 (1941).
Lewis, Ind. Eng. Chem. 28, 257 (1936).
Lewis and Kay, Oil and Gas J. 32, 40 (1934).
.
Lewis and Randall, "Thermodynamics," pp. 190-198, McGraw-Hill Book Co. (1923).
Nelson and Bonnell, Ind. Eng. Chem. 36, 204 (1943).
Sage and Lacey, Ind. Eng. Chem. 30, 1296 (1938).
..
~-t-toj-or
~T:~
FUGACITY FUNCTION
1m
OF METHANE
_. t
-l- .
200
r
v.
'I i
. ':.;=
~:-:.:F-~:-~-
-;':~i:
-.
J:-
10
-::-
. -~
100
90
I::f.;=+
80
70
60
50
40
30
20
: :.-;;!
~:.,~
=~~~
-'- :.=;-
j. p-L~-t.: :~- .
~/J::.1~_-,2? ~E=
-
.j...
=:=.
10
9
8
7
5
,
..::~
-300
-200
-100
49
100
200
300
&I
.
..
F~~~CITY FUN~TI~N
OF ETHYLENE
r
+-
..
I-- ~
1 00
90
80
70
60
50
40
30
20
_I~
8
7
6
5
4
-200
-100
50
100
200
300
-~=
--- --
---
=
=
=
=
=
-
FUGACITY FUNCTION
OF ETHANE
--
00
--
--
--
- - --
--
- ~t a -
--
I 00
-- -
90
---
80
70
60
--
50
40
30
20
/
-
--
- -rl=Fl
10
-'
- -
8
7
6
5
4
-zoo
-100
51
100
zoo
300
1.0
0.9
0.8
0.7
0.6
--200
-100
.=a=::-
/M
0.5
-c
FUGACITY FUNCTION
OF PROPYLENE
0.4
0.3
0.2
I~
/1
AI
If I
II
0.1
I 00
90
80
70
60
...
50
40
30
20
I-
-,
I I
IJ
iii
II
10
9
8
7
6
5
4
3
-100
100
52
200
300
400
-200
1.0
0.9
0.8
0.7
0.6
-100
,
0:;
FUGACITY FUNCTION.
OF PROPANE
::
0.5
- . -.
0.4
-+-+-l
0.3
0.2
..
0.1
I 00
90
80
70
60
50
40
30
20
11
-(
If
V
I
iW
II
'.
7
6
l.
-+-
-l-
10
"'T
i,""'"
I
-ir-
!..ll
-j(jO
__.x.
~
If
.-L~
c.:.'_ _,-
100
53
I
I
200
300
400
__
:T"-~
,- FUGACITY FUNCTIO:lI
"OF ISOBUTANE
::
,
0.2
"1J;:,f-;t--l+++H Ifl+I-I-/HI-H+-I--+
,
'I
ElIOO
~l--
=3...J .
~l='-
90
80
70
60
,-
50
40
___ t:::t:::t:=t=J:
30
20
I.-
t;o
r+- -H-lH+I--t+H+t++-H+-H+-l-H-++++H+H-I-+-1-++I-I4-IA+:I4-jll--W-+-I-l--!-l-l--+-W-!-W~-I--l
1
I
~:-:.!-
3:,-'=i-- -i-:-(=F"
-...t.~ ~-- .~~.l
'7
--
""--
It
=-
-~Ig
..;
--t.-
8
7
6
5
4
3
-I- -
1/111
1/
-tOO
tOO
54
200
300
400
100
-!!III
i-tll- f:.Tfl ~aii--~f~

"':::-l_
~---.-.
--r=..t=
:.
-~
8+
-,
I-
-f-
FUGACITY FUNCTION [~I--
r:
i=-I
OF BUTANE
- ffP-i' -:-.:~. '- Ii

~~ H-".IEI:- ~=8::=
_,.-,_-r-F
--=+:~-
--'-+-
'--4-=1=
0.2
1111
--.
100
90
80
70
60
j:-t-;'
:'--;
-I--l.-r~
.. -f~- 3f~
,.J~ 51~
=t--+=!'I !_-l ~~:
- ..:
->-.-
t-
50
,~
f---
...::;C :-I.,
40
i7
30
.-
20
1/
j
=.
-.
-,..
---:::-:~-_.
~r_ ~_r=-- ~ ~ -~_
1=I
j:::f
...
, .-1'\)
10
9
8
7
6
-f-
5
..
. ..
~E:::
r-
:;=. :7t;- ~
3
I
I
H--i--H-+-t-l---H-++-+-+-+-IH-+++-t--HH-++-+-+--HH- 'I - - LIl-lH--H..j-+-HH--H-++-HH--H-++-H-+-H-++-H-+-~--H-j

I
-100
100
55
200
300
400
-100
100
0.9
0.6
0.7
0.6
0.5
~.
FUGACITY FUNCTION
OF ISOPENTANE
~
:
0.4
0.3
0.2
t I I
40
30
20
I
I
4
3
IjjjT-;1-ttttjjjttt::t:t:tttttlltJzt~~:tt:t1tttt:!i!~~~~:t;;'tr~t'ttt:r~;r~11!!!t:!=1
100
200
56
300
400
500
1
H-++++ -H-++-- H-t-f-+- t--H
't+t-i-:+t+'
., -"1f-f-+I H--H-+ t-H-t-f- +-H-+t +t-H-t- f-+-H-+ t+t-Hf- f-t-I-t-t --H-H- Hf-f-t
--:
50
40
...
.
17'
I~
:T 1
17'
20
If
11
It
30
,
.+-H-H-H-H-i+H-H-H-H-H-H-H-H-H-+++++
. I
+++++-hI"'H-T+-H'-H'<H-++++Tt-++++--
H~t-H
!/
II
,"
I -
::E-
,-:=
o-
_~c:~~'%
.)e;d _.
:-r' '. ';:
~ ~~
~~.
.~' ~--
/~ :-='/--::- r:t=-1='
E'
r-+-'
'~.:i=d-. ~ ,.-.
.,;-
:~~ 10
9
8
7
6
, 1=
4
H-
-:!=.::l~::r!.::
.e.;-::!::C
-+- ~~.~!-:. -.
--
:::c.J'
1""- -
1-1-
100
200
57
300
400
500
100
....
0.9
0.8
200
.
::E;'?:::f ~i=ft.
.~ E
-I/~~
I....:_!c~
E'-=H'
0.7
0.6
.CE1.
FF'
.::t::;::
,::
:t
0.5
FUGACITY FUNCTION
OF HEXANE
~/~ ...
0.4
= ......
:~ :4'; i'c
::::
=
....
t-
0.3
,--'
0.2
I
I
c..,
..
. -:- ......
-
~IOO
~90
'. .
80
70
60
~-."'_
~t--
"-
..=l=E ~--::-"'::: . . . . ~'-, _., ....
-=..-_"-
--4-
'-!-
''-
"""T
50
-!--,I
o
40
-"'-r--
._
30
20
Ii
I I
.I
-
:t:-.t=:
_ :-~ .;:~ . ::..:
.:
;:::;:-~. ::H:~;:-: . =r-r :-E~.U~

-r:: . -0-'1:';=1....".[
.:~t""e::l=:
:t=t:: ...c.. r=::::t:::::t=t:
=r-
.I~
'-i-:;:-_
"
~~
=j---:-'
7
6
5
4
3
,
t:b::
...
!
I I
1/-
,
I
100
200
58
300
400
500
200
300
O.9~
0.8
0.7
;::.
0.6
~
~
0.5
I=l=I
FUGACITY
FUNCTION
OF HEPTANE
=
-
0.4
~.
-->-,-
0.3
-'f
-8
0.2
ClhHH-+-++++-++-H-Il--JI+-H--H--I-HH-+-++-
'T
II
0.09
0.08
'
0.07
0.06
0.05
0.04
100
I.O~
0.03
20
0.02
!/
..
1I
200
100
59
300
400
500
100
200
300
0.8
0.7
0.6
0.5
0.4
0.3
FUGACITY FUNCTION
0.2
OF OCTANE
1~
:
0.08
0.07
0.06
0.05
0.04
0.03
30
0.02
20
++++H-Ht-H-+-++ I-f--H-H-+'++++++-++I-I-f--H-+--J----I--++++++-hj.j-I-I-hjoq~
-+--I--t-+-t-+++-+-+-+4 '
-t'i-"'Fff J.
-1:. t=
.-'-=
I.
+ie,'}l
t=: =Lfi
f-L - F.'r
.f-
::-~
&
...
I-~
~
- f:::j:. - -'
,-, .
+-t-
- ~~rj'
~ -l-I' -
II
100
200
GO
II
300
400
500
FUGACITY FUNCTION
OF HYDROGEN
p
::;
THE FUGACITY FUNCTION OF HYDROGEN. IT"fplfll'' IS BASED ON A

PARAFFIN SOLVENT HAVING A MOLECULAR WEIG HT OF 114 (OCTANE).
~ FOR OTHER SOLVENTS MULTIPLY THIS FUGACITY FUNCTION BY THE
..... CORRECnON FACTORS, A, FOR MOLECULAR WEIGHT, AND
FOR
CHARACTERIZATION FACTOR OF THE SOLVENT~
e.
tHw
THIS CHART DOES NOT APPLY AT TEMPERATURES GREATER THAN

0.95 TIMES THE PSEUDO-CRITICAL TEMPERATURE* (OR) OF THE
LIQUID PHASE.
T pc: XH (60) + X HC (T HC )
I I I
o
.
--
_..
- __-_-0
. I
-r
==._.
~.
2000
--
K:l
50
100
150
200
250
300
3
1.0
0.9
0.8
0.7
0.6
40
61
....
60
80
100
120
140
IGO
.2
.3
.4
.5
.6
.8
.1
10
11
12
13
1 ~.O
.9
.8
.8
.7
.6
.6
..
.5
T-
=
A
fLr
II-
f p IP
"':~-:.
=-
~~
.5
VS PIPe FOR LIQUID PHASE
flT/IT VS IT/Pc FOR VAPOR PHASE
.S
i'
FUGACITY OF HYDROCARBON VAPORS
lJ
.2
-,
,6.. -;fu. ~ tl:f

.1...,;....+..........."
It
.1
+.-!
LEWIS AND KAY. OIL AND GAS J. 32. NO. 45, 40 (MARCH 29, 1934)
RE~ERENCE:
.1
.2
.~
.5
.6
.7
62
.8
.9
1.0
J.2
1.3
1.4
',4
4
I. 0
1.6
1.8
2.0
2.2
l.4
2.6
2.8
3.0
32
3.4
3.6
3.8
FUGACITY OF HYDROCARBON VAPORS

.9
..
.9
.8
.7
.7
.7
.6
.6
.6
.5
.5
.4
.2
ot.4
1.6
1.8
2.0
2.2
2.4
2.6
2.8
63
3.0
3.2
3.4
16
18
4.0
<-
RELATIVE VOLATILITY
OF LIGHT HYDROCARBONS
2.00
1.80
1.70
.-++-
.~
1.60
ETHYLENE (ETHANE
1.50
1.40
-::1:; .
-_l
::l"-
~+
1.30
1.20
1.10
:r
1.00
-100
100
200
300
400
:h
1.40
1,30
PROPYLENE/PROPANE
Ir.
1.20
1,10
1.00
-100
100
200
4C0
RELATIVE VOLATILITY
;OF LIGHT HYDROCARBONS
1.30
I J
ISOSUTENE/SUTANE
FOR BUTENE l/BUTANE
MULTIPLY BY 0,980
1,20
ct'
I-
1I0
1.00
100
200
300
400
TRANS-SUTENE-2/SUTANE
.90
1+=
1...
J..~
100
200
300
400
CIS - BUT ENE- 2/SUTANE
1.00
.90
.eo
100
200
300
400
1.3-SUTADIENE/SUTANE
tOO
LIO
tOO
.90
100
200
300
65
400
."
, :'-' -!:-i1-
RELATIVE VOLATILITY
+
,.
80
1111
I.IO.
o
66
~
~O
1111
400
~~
~~'I:
=
FUGACITY CORRECTION FACTOR
LIGHT HYDROCARBONS IN ABSORBER OILS
_ t- .
2.5
2.0
- ~ L
:9..
MULTIPLY FUGACITY FUNCTIONS

(OR VAPOR PRESSURES) OF LIGHT
HYDROCARBONS BY CORRECTION
FACTOR WHICH IS INDEPENDENT
OF TEMPERATURE AND PRESSURE
1.5
*CHARACTERIZATION FACTOR OF THE LIQUID

PHASE IS A WEIGHT FRACTION AVERAGE OF
THE CHARACTERIZATION FACTORS OF THE
ABSORBER OIL a DISSOLVED HYDROCARBONS.
REFERENCE: COMMUNICATION
FROM lHE M.W. KELLOGG CO .. NEW YORK. N.Y.
,-..
10
"
12
67
13
Section 6
CRITICAL PROPERTIES
Analogous to PUl'C substanccs, thc true critical point of a milltUl'c is a uni'lUC
point on thc phase cnvelope where thc dcnsitJy and composition of the vapor
phase arc identical with those of the liquid phase. Sincc the compositions of the
two phascs arc the samc, fractionation of a mixturc is impossible at the critical
point. Conscqucntly, the dcgrec of approach to thc critical point of a mixtuTe sometimes serves as a rough guide to thc fcasibility of separating thc components by
fractionation.
For PUl'C hydrocarbons, it has been found that a number of physical propcrties
may bc correlated by reduced tcmperature, TIT e, and reduccd prcssure, PIPe.
Various data have shown conclusively that none of these correlations apply to
mixtures if the truc critical temperature and pressure of the mixture are uscd to
determine the "edueed conditions. This difficulty has bccn overcomc by thc introduction by Kayl of thc concept of pseudo-critical tcmpcrature and pressure. By
using thc pseudo-critical tempcrature and pressure to predict the reduccd conditiuns, Kay found that compressibility data on pure hydrocarbons could be applied
to mixtures. Although Kay determined the pseudo-critical point by averaging the
critical properties directly for known mixtures and from the averagc molecular
weight for pctrolcum fractions, it has been found that much bcttcr results can be
obtained by using the average boiling point method proposed by Smith and
Watson. 2
As Smith and Watson pointed out, the true and pseudo-critical points must
approach each other as thc boiling rangc of a fraction approaches zero and must
coincidc for purc compounds. These conditions arc fulfilled by the charts in this
section applying to petroleum fractions. Smith and Watson's relation between
t11C true and pseudo-critical pressurcs on page 74 has been checkcd by the true
critical data of Kay on ethane-hcptanc 3 and cthane-butane systems. These data
confirm Smith and Watson's eurvc well into thc region of their recommended
extrapolation.
GENERAL REFERENCES
Doss, "Phyaical Properties of the Principal Hydrocarbons," 4th Edition, The Texas Co.,
Nel\' York, N.Y. (1943).
Internationnl Critical Tables, Vol. III.
Roess, J. Insl. Pelr. Tech. 22, 665 (1936).
'l{ay, Ind. Eng. Chem. 20, 1014 (1936).
2 Smith and Watson, Ind. Enu. Chern. 29,1408 (1937) .
Kay, hId. Eng. Chern. 3D, 459 (1938) .
Kay, Ind. Eng. Chern. 32, 353 (1940).
68
800
._ m Il
~JI '
900
1000
1200
'I
illii
"
600
..
I
i
500
ti, rYlj I'~!

-
In 1m
r:.
iI!lt-f :-!,
.-. T'
r ",
ljl'
,
100
f!
"
"
, I "
:r
'J
r; I ' J
, I,
I
11
,,
;.
j ,
j'
,j i
rnu:
Ill~
mm
,,'
I
I
it
I.11
"
, ,
I 1
'i
!WJ
I"
.1.:
. I
j'"
1-1' I . . ' t
1t
.
It
,I
.,
I'
!II
!l
I
!
f
J!
IIIl
..
I,
, I
200
Iii
'lil!1
I ' Hli' ,: !
HI' , I
300
,j"
'II!, IllliQ,HHlii!!:
400
500
69
600
.1
I II i"
::'
J!
r
I
! II
I II
j
f, I t ,! i' ill dlj!1! liid!! tl!
: .. :-1"'
.
I,
~.1. ;~:
I r,I! tl
HI ':: IJ I 'I. ,I',
i'l:1 II i'
!I
'l f ~ ,..
~:;
." rr"l
,
ill
,'f
''I
'1
'
~.,.., :-1';
;,
!
,
1.
' .. I " ,
. . , ! ' 1.I
1111["1
It!; I
fH.
t
"
. i jiPi
'
:.
f 1 ,,'
! ' r_1 :. L 1!
,I
'. I
,!
t:tll. . t: fl lill
Ijl ill lit!, . iu,1 liP
1f
:
t . Iil" !. ,'I"t. :1::
11
,.
1tI
I
,
IIU11
inl
Iim1
mrr
"
,.
I I
r, (1
,
tlftfi,
, ,
.
i- t1 '.
<i1
:i'
IIWJ
r ~; 111'
mitIHI
I
I~
Hm1
11m!
70
j~
lOOl
iMj
l1m1
800
900
11
1000
II
CRITICA L TEMPERATURE
OF PURE HYDROCARBONS
1100
I~
ffim
I!PI :
I
III li1
700
Jfi1,
.'II
1'0 1
tub
800
-220 -200 -190
80
-160 -140
.,
60
440
CRITICAL TEMPERATURE
40
OF LIGHT HYDROCARBONS
q,
PURE
420
COMPOUNDS AND MIXTURES
20 -
-.
.f!:[
,-
400
'l*
... ' .-
t"
i ,
390
...L
-20
360
-40
340
-60
320
-80
300
100
290
-120
260
240
j.
220
[
,
.. I
1r
I ..
In
I
"
I"
I i:
_I
I J I
200
THE BASE CURVE REPRESENTS CRiTICAL

TEMPERATURE VS. BOILING POINT fOR PURE
HYOROCARBONS ANO PSEUOO-CRIT'CAL TEhIPERATURE vs. MOLAL AVERAGE BOILING POINT
FOR MIXTURES.
THE GRAVITY CURVES REPRESENT TRIJE
I ,
CRITICAL TEMPERATURE YS. WEIGHT AVERAGE
190
160
BOILING POINT FOR MIXTURES. fOR ALL HYDRO-
CARBONS THE PARAFFIN GRAVITY OF THE

SAWE BOILING POINT 5H:XJLO BE USED IN
I
I
140
COMPUTING THE GRAVITY OF THE MIXTURE.
.,
I .,
:_iill
-140
t;
If
I~
,I
120
.fiT
1h .
..
100
,
I
j -,
80
-120 -100
-80
-60
-40
-20
70
20
40
60
80
100
120
140
!mI
CRITICAL PRESSURE
OF NORMAL PARAFFINS
20
'~
60
40
80
100
120
i50
Ii
40
40
30
THE PSEUDO-CRITICAL PRESSURE Of

LIGHT HYDROCARBON MIXTURES HAVING
AN AVERAGE MOLECULAR WT. LESS THAN
BO CAN BE DETERMINED FROM THIS CURVE.
--.-:
20
.-:-
..
20
I
15
10
140
t+:
Iii L
r-
i~- ~i
160
180
200
220
71
240
260
280
900
800
1300
t ....
"
.....,....,
1000
..=r::
':Ct 8<i5-2' -:-'

_.-
-1
.... ,
",.
>:.
~".
'- "-J :....

,
..
ct=
.. -
...
1100 ;.~r:$
...
:$. t
,-
"
...
800
'1'=:
,-
700
.
.::r; ":-1.ir
800
,-
.... ..
--
.~
100
200
300
400
500
72
600
700
800
100
200
400
WO
500
100
7('.
PSEUDO- CRITI CAL PRESSURE

OF PETROLEUM FRACTIONS
100
600
500
400
II
300
300
250
200
2 00
-- ~~
tqJ~. .-
IIIII11
t-..l
,.
100
IMmiI
800
900
'.
ahr,f-h----
-- Ffttl
--
1000
73
,
I00
TRUE CRITICAL PRESSURE

OF HYDROCARBON MIXTURES
..
1.18
!l.0
1.20
4.0
1.2.4
1.2.2.
1.2.6
4.0
3.0
2.5
2.5
DETERMINED BY MULTIPLYING ITS PSEUDO-CRITICAL
2.0
PRESSURE BY THE RATIO OF TRUE TO PSEUDO, CRITICAL PRESSURE, PTC/Ppc. THIS RATIO IS
GIVEH BY THE CURVE AS A FUNCTIOH OF THE RATIO
OF TRUE TO PSEUDO CRITICAL TEMPERATURE. TTCl1l'l;.l
""1l1i"
t:J+l
'.5 H-t-t+t-H-t++t-H-t+'
mI.5
~
REFERENCE:
1.02
2.0
SMITH AND WATSON.
1.08
1.04
74
IND.
ENG.
CHEM,
29.
140B (1937)
Section 7
THERMAL PROPERTIES
Specific Heat
Since hydrocarbon vapors deviate considerably from a perfect gas, except at
low pressures, their specific heats arc a function of pressure as well as tempera-
ture. However, vapor specific heats at higher pressures have limited application as
enthalpy correlations may be more readily used for thermal calculations. For this
reason, the specific heat chart~ for gases and vapors (pages 88 to 91) arc given
only for low pressuros (0-1 atm) where deviations from a perfect gas are so
small that specific heat may be considered to be a function of temperature alone.
The specific heat of a mixture of two or more gases at low pressures may be
calculated from either their weight fraclions multiplied by their specific

their mole fractions by their molal heat capacities (MC.).
heat~
or
Two charts are given for the specific heat of. petroleum vapors, one on page 90
for crude fractions and another on page 91 of more general application to both
pure hydrocarbons and petroleum fractions.' The chart for crude fractions is a
modification of the Bahlke and Kay eorrelation 2 and the other the same type as
a chart developed by Fallon and Watson. 3 Both ehart~ are believed to be somewhat morc accurate than the previous correlations and arc also representative
of additional data.
The change in enUlalpy of hydrocarbon vapors with pressure at constant
temperature may be calculated from the chart on page 92. While the ordinate
refers to the difference in enthalpy from the vapor at infinite dilution, this may be
construed as any low pressure (0-1 atm). This chart was used to compute the
enthalpy of hydroearbon 4 and petroleum vapors at elevated pressures in the
development of the enthalpy charts. Since the change in enthalpy at constant
1 These correlations {or petroleum fmctions nrc not quite consistent with the additive
rule for mixtures. Since these curves apply directly to mixtures, the additive rule would hold
only if the specific heals eit,1).cr were independent. of the liquid specific gravity or \'aricd
lillcnrly with its reciprocal (directly with API). With neither of these conditions fulfilled, the
petroleum vapor correlations have a fundamental inconsistency but the resulting errors are
imperceptible as far as the data are concerned.
2 Bahlke and Kay, Ind. Eng. Chem. 21, 042 (1929).
3 Fallon and Watson, Nat. Petroleum News, 'l'echnical Section, R-372 (1944).
4. For the light hydrocarbons below hexane, there was a slight trend with molecular weight
in the change of enthalpy with pressure at constant. temperature. This was taken into account
by the use of other unpublished correlations by Gilliland (sce reference on the chart OD
page 92) for these low-boiling hydrocarbons.
0
75
tottlGl"N"
A.L.)
CO?l A \1i'1B.::1 \. .)
PABLO M01.'"l'A
76
temperature can be read directly from the latter charts, this generalized chart has
little direct application but is included as one of the fundamental correlations.
The chart for the specific heat of hyd!"Ocarbon liquids was developed" directly
from liquid specific heat data on pure hydrocarbons and petroleum fractions.
Since liquid specific heats were not used in the development of the enthalpy charts,
this chart is independent of and not necessarily consistent with the latter correlations." For the sake of consistency, thc enthalpy charts usually will be used in
preferencc to this spccific heat chart but, at the samc time, it is desirable to include
an independent correlation of such a fundamental thermal property.
Latent Heat of Vaporization
The latent heat of vaporization of any compound is the din'erence in enthalpy
between its saturated vapor and its saturated liquid at constant temperature and
may be expressed either as a function of temperature or as a function of vapor
pressure. The latent heats of low-boiling hydrocarbons and, also, higher-boiling
normal paraffins of even boiling point arc plotted again t vapor pressure on pages
94 to 97. While the use of temperature instead of vapor pressure as the correlating
variable would have advantages, it would also result in the curves crossing each
other, thus making the plots difficult to reae!.
The latent heat charts were derived by using a direct proportionality between
the molal heats of vaporization of any two hydrocarbons at the same reduced
pressures.' For the lower boiling hydrocarbons, the latent heat data were smoothed
out and extrapolated by the use of a reference compound (ethane, butane, or
hexane). Where no data were available, as in the case of a few of the light hydrocarbons and all of the higher-boiling normal paraffins, the latent heats were calculated directly from this reduced pressure relationship. The slope or proportionality constant was predicted from the normal boiling point of the hydrocarbon.
The latent heat of vaporization of other hydrocarbons may be calculated
from the normal paraffin cun'es by the usc of this same relation. That is, the
unknown compound will have the same molal heat of vaporization as a paraffin
of the same normal boiling point at the same reduced pressure. In the case of
petroleulll fractions, the mean average boiling point is used for the normal boiling
point and the reduced pres ure i computed f!"Om the pseudo-critical pressure of
the mixture. The "vapor pressure" of thc fraction corresponds to that of a pure
A modificatIOn ot a correlatIOn oy Tne M. W. Kellogg Co., New York, N.Y.
The enthalpy eharls were derived from: (J) the vapor specific heaL eo",elnlions (0-1
aIm); (2) lhe generalized chart for change of enthalpy with pressure; and (3) the latent heat
relations. Inasmuch as the inaccuracies of all three correlations accumulate in Lhe jjqu;:!
enthalpics 01' specific heals, the agreement wit.h the liquid specific heat chart may be ~nnsidcrcd
quite good as average deviations between the two are around 3% wlt.h a maxImum of
about 6%.
7 Maxwell, Ind. Eng. Chem. 24, 502 (1932).
THERMAL PROPERTIES
77
hydrocarbon of the same normal boiling point at tbe temperature of the fraction
and ""ver relers to the bubble point, dew pofnt, or operating pressure 01 the system.
Since the difference in enthalpy between the liquid and the saturated vapor of
a pctroleum fraction always involves change of enthalpy of the vapor at constant
temperature in addition to latent heat, except at low pressures, the enthalpy correlations are much more convenient to use than these individual therm,.l properties.
Thc following examples illustrate the usc of the latent heat charts:
Example 1. Compute the latent heat of benzene at 1 atm.
The boiling point of benzene is 176.2F and its critical pressure is 47.9 atm.
The molceular weight of a normal paraffin boiling at 176.2F is 91.5 and its critical
pressure 28.3 atm. The vapor pressure of the normal paraffin corresponding to a
reduccd pressure of 1/47.9 ( - 0.0209) is 0.0209 X 28,3 - 0.59 atm.
The molal heat of vaporization of the normal paraffin at 0.59 atm is 91." X
(146 BTU/lb) - 13,360 BTU/mole.
The latent heat of benzene at 1 atm is then equal to 13,360 BTU/malo or
171 BTU/lb. The Bureau 01 Standards Circular C461 gives 169.3 BTU/Ii> '.s the
latent heat of vaporization of benzene at 1 atm.
Example 2. Determine the latent heat of vaporization of the following ga9
oil at 500F.
10% Distillatioll
10% @ 430F
50% @ 540F
70% @ 605F
90% @ 680F
Gravity
35API
Vol. Av. B.P. = 547F; Slope = 2.9F/%

Mean Av. B.P. = 547 - 9 = 538F
Molec. wt.
= 211
Vapor pressure (538F normal B.P.) = 0.63 atm. at 500F
Pseudo-critical pressure = 266 psia co 18.1 atm
I'l'lolee. wt. of normal paraffin (538F normal B.P.) = 222
Critical pressure of normal paraffin = 15.0 atm
Vapor pressure of normal paraffin = (l5.0/18.1)0.63 = 0.52 !!.tm
Latent heat of normal paraffin = 104 BTU/lb
Latent heat of vaporization of the gll3 oil!!.t 500F
=
22Z X 104 = 108 B1'Ulib

214
78
Enthalpy of Light Hydrocarbons

The enthal py 8 or heat content of low-boiling paraffins, olefins, and aromatics
is given by the chart.s on pages 98 to 113. These charts can be applied to mixtures
of light hydrocarbons on the basis of the following assumptions:
1. The entha!pies of individual components of a mixture are additive in

the !iquid phase, that is, the mola! heat content of the mixtttre equals the sum
of the products of the mo!al heat contents of the components by their mo!e
fractions.
2. The entha!pies of individua! components are additive in the vapor phase
at !ow pressures (0-1 atm).
3. The change in enthalpy of the vapor with pressure at constant temperature is the same for a mixture as for a sing!e compound having the same mo!ecular
weight as the mixture.
The first assumption is substantially true for hydrocarbon mixtures (especially for homologous series) at temperatures below the critical regions of all
components. At temperatures near to or above the critical temperatures of any of
the components, the liquid mixture is no longer an ideal solution of its components
and there is some deviation from the rule of additive heat contents. However, since
these deviations arc not too serious, and since no other simple method has been
developed for determining the heat content of a liquid mixture, the rule of additive
enthalpies should be used for all hydrocarbon mixtures irrespective of the critical
temperatures and chemical composition of the components.
The second assumption is strictly true only for vapor mixtures at infinite dilution (0 atm) but is a very close approximation for pressures up to 1 atm.
The third assumption is empirical but has been shown indirectly to give quite
accurate rcsults for mixtures of homologous series and petroleum fractions. Also,
the usc of the average molecular weight to determine the change of enthalpy with
pressure is the simplest average which can be used.
Above thc critical temperature a dashed line is shown for the heat content of
the gas in solution. This line was based on the assumption that thc gas in solution
at any temperature would have the same partial density and enthalpy as the pure
compound at a pressure corresponding to an extrapolation of its vapor pressure
curve above the critical point. Obviously, this is only a rough approximation since
both a vapor prcssure curve and an ideal liquid solution arc meaningless in this
regIOn.
E:rample 3. Determine the difference in enthalpy bctween the liquid at

100F and the vapor at iiOOF and 20 atm for a mixture having the following
composition:
8
Based on on entholpy of zero for the saturated liquid
01,
-200"F.
THERMAL PROPERTIES
Component
Mole Fraclioll
C,H.
CsH.
C,H lO
C,H,
CsH.
0.100
.500
.100
.050
.250
1.000
79
The enthalpy of the mixture as a liquid at 100F and as a vapor at 500F and
0-1 atm is computed from the individual components as tabulated below:
Com-
Mole
poncnt
Fract.
CzH s
0.100
.500
.\00
.050
.250
CaH s
C 4 H 1O
C2H 4
C3 H,
Enthalpy of Liquid
lOOF
l\lolcr, Wt.
Enthalpy of Vapor
5OQF and 0-1 elm
Lb/Mole
of Mixture
BTU 1~lole
BTU lIb
3.0
22.0
5.8
1.4
10.5
42.7
of Mixture
239
171
159
223
169
li y (500F, 0-1 atm) - li L
BTU lIb
720
3760
920
310
1770
7480
BTU ll\lolc
of J\'lixture
553
530
525
506
508
1660
11660
3040
710
5330
22400
= 22,400 - 7480 = 14,920 BTU/mole
The change of enthalpy of the vapor at 500F betwecn 0-1 atm. and 20 atm.
is computed by interpolating between C,H. and CsH.:
C,H.:
1f,,(500F, 20 atm) - li y (500F, 0-1 atm) = 30(546 - 553) = -210 BTU/mole
CsH.:
H y (5OOF, 20 atm) - li y (500F, 0-1 atm)
44(522 - 530)
-350 BTU/mole
Mixture:
li y (500F, 20 atm) - li y (500F, 0-1 atm) = -210
=
- 30
+ 42.7
H _ 30 {-350 -
(-21O)J
-340 BTU/mole
Therefore,
li y (500F, 20 atm) - liL(100F) = -340
or
14,580
42.7
= 849
+ 14,920 =
14,580 BTU/mole
BTU/Ib
The foregoing procedure can hc simplificd, with a loss of accuracy which does
not usually exceed 5%, by interpolating on a basis of molecular wcight and total
so
olefin content between the initial and final states:
CaH s:
H v (500F, 20 atm) - Ih(IOOF) = 44(522 - 171) = 15,440 BTU/mole
C ZH 4 :
H v (500F, 20 atm) - Ih(lOOF) = 28(500 - 223) = 7750 BTU/mole
CaHe:
H v (500F, 20 atm) - HL(lOOF) = 42(500 - 169) = 13,900 BTU/mole
Since the average molecular weight of the paraffin portion of the mixture is 44, the
propane values can be used directly, making interpolation unnecessary.
The average molecular weight of the olefin portion is 39.7; hence the enthalpy
difference between the initial and final states will be:
7750
+ 3:;7 _- 2~8 (13,900 -
7750) = 12,880 BTU/mole
Interpolating between the paraffin and olefin portions,

Hv(500F, 20 atm) - HL(lOOF)
or
X 15,440 + 0.30 X 12,880

= 14,670 BTU/mole
= 0.70
14,670
42.7 = 344 BTU/lb vs, 342 BTU /lb by the longer method.
Enthalpy of Petroleum Fractions

The enthalpyO of petroleum fractions is given by the charts on pages 114 to
127 for both paraffinic stocks, having a characterization factor of 12.0, and nonparaffinic stocks, having a characterization factor of 11.0 over a mean average boiling point range from 200F to 800F. Theoretically, these charts
represent pure hydrocarbons of the designated characterization factor and boiling
point, but they may be applied to petroleum fractions if the following assumption
is made in addition to the three previous ones pertaining to light hydrocarbon
mixtures:
4. 'The avemge difference between the enthalpy of the vapor at low preSSU1'es
(0-1 atm) and the enthalpy of the liquid, at constant temperature, is the same f01'
a rni.'l:ture of chemically similar hyd1'Ocarbons as for a single compound of the
sct'1ne molecular weight (or mean avemge boiling point).
\\'hile this assumption is empirical, it is accurate \\'ithin a few percent excrpt
in the region of the pseudo-critical temprrature \\'here the enthalpy of the liquid
is subject to variation depending upon the true criticaltemperatUl'e of the mixtUl'e.
Since the dashed line starting at the pseudo-critical point applies only to a pure
compound in solution above its critical point, another dashed line was arbitrarily
drawn for mixtUl'es, joining the satUl'aled liquid line below the pseudo-critical
9 Based on all enthalpy of zero for the saturated liquid at 00 F .
THERMAL PROPERTIES
I
81
point with the pure compound line about 50F above the pseudo-critical tempera_ ture. This is more representative of a mixture and should be used in preference
to the pure compound line.
These charts may be interpolated and extrapolated linearly with both
characterization factor and mean average boiling point. Occasionally, in inter
polating between two adjacent boiling point chart~ the pressure and temperature
of the vapor will be such that they fall inside of the "dome" of the higher boiling
point chart.. Since it is impossible to use the charts in this region, it is recommended that the two adjacent lower boiling point char'" be extrapolated upward.
Following are two examples illustrating the use of these charts:
Exan,ple 4. Determine the ditTcrence in enthalpy between the liquid at 500F
and the vapor at 775F and 25 psig for the following refined oil fraetion:
Grauity
40 0 API
Crude Assay DistillatiOlt

I.RP. 300F
50%
440F
F.B.I'. 580F
Vol. Av. RP. = 440F
'11 .
81 ope 0 f t}Ie dIstl
atlOn eurve
580 - 300
100
2.8 0 F/%
Mean Av. B.P. = 440 - 6 = 434F

Characterization Factor = 11.65
hI' = Enthalpy of the vapor at 775F and 2.7 atm (25 psig)
h L = Enthalpy of the liquid at 500F
Mean
Ch.
Cb.
Cb.
Au. B.P. -400F

Factor = 12:
h" - hL = 567 - 286 = 281 BTU/lb
Factor ~ II:
h v :- h L = 538 - 263 ~ 275 BTU/lb
Faetor = 11.65: hI' - h L = 275 + 0.65(281 - 275) = 279 BTU/lb
Mean
Ch.
Ch.
Ch.
Au. B.P. -500F

Faetor = 12:
hI' - h L = 556 - 273 = 283 BTU/lb
Factor = II:
hI' - h L ~ 534 - 255 ~ 279 BTU/lb
Faetor = 11.65: hI' - hi = 279 + 0.65(283 - 279) ~ 282 BTU/lb
Mean Au. B.P. - 434F

Cb. Factor = 11.65: hI' - hL = 279
+ 1.'.. (282
- 279) =.280 BTU/lb
If the char'" for 300F and 400F Mean Av. B.P.'s had been extrapolated, the
result would have been essentially the same, 281 BTU/lb.
Example 5. Determine the difference in enthalpy between the liquid at 425F

and the vapor at 925'F and 350 psig for the following gas oil:
82

10%
10%
50%
70%
90%
VoI. Av. B.P. = 455
Distillation
@ 455F
@ 560F
@ 620F
@ 695F
Gravity
15.5API
+ 2 X 560 + 695 = 5670F

4
.
SI ope 0 f di Bt I'II ation
curve
- 455
= 620 69
= 2.8F/%
5 = 562F
Mean Av. B.P. = 567 Characterization Factor = 10.48
h v = Enthalpy of the vapor at 925F and 24.8 atm (350 psig)

h L = Enthalpy of the liquid at 425F
Av. B.P.-400F
Factor = 12:
hv - h L = 662 Factor = 11:
h v - h L = 622 Factor = 10.48: h v - h L = 406 Mean Av. B.P.-500F
Ch. Factor = 12:
hv - hL = 642 Ch. Factor = 11:
h v - lt L = 606 Ch. Factor = 10.48: hv - h L = 398 Mean Av. B.P.-562F
Ch. Factor = 10.48: ltv - h L = 388 Mean
Ch.
Ch.
Ch.
233 = 429 BTU/lb

216 = 406 BTU/lb
0.52(429 - 406) = 394 BTU/lb
224 = 418 BTU/lb
208 = 398 BTU/Ib
0.52(418 - 398) = 388 BTU/lb
M(394 - 388) = 385 BTU/Ih
MollieI' Diagrams
The MollieI' diagrams for the individual light hydrocarbons are of essentially
the same type as the familiar one for steam. To minimize confusion and to make
the charts as easily usable as possible, lines of constant volume are omitted and
lines of constant temperature replace lines of constant superheat in the superheated vapor region. These charts will be used principally for adiabatic compressions and expansions.
In applying the MollieI' diagrams to hydrocarbon mixtures, the mixture
should be treated as a single compound of the average molecular weight. An
empirical study of the diagrams indicates that successive charts of the same
series (paraffin or olefin) may be interpolated (or extrapolated) by assuming a
linear relation exists between melecular weight and (1) isentropic change of
molal enthalpy with pressure and (2) the product of the square root of the
molecular weight and the isentropic ehange of temperature with pressure.
If both paraffins and olefins are present in the mixture, the charts of each
THERMAL PROPERTIES
83
series are interpolated (or extrapolated) to the average molecular weight of t.he
total mixture. These values corresponding, respectively, to a 100% paraffin mixture
and a 100% olefin mixture are used for linear interpolation to the actual olefin
content of !lie mixture.
The following example illustrates the application of the MollieI' diagrams to a
hydrocarbon mixture:
Exmnple 6. Determine the work of compression 1 0 and final temperature when
the following mixture is compressed adiabatically from atmospheric pressure and

60F to 50 psig:
Average
Molee. WI.
M ok Fraction
Component
CH, . ....... .
C,H, ........
C2 H ....... .
C3 H.
C3 H s ..... - ..
C,H s
C.H, 0
C.H, .......
0.050
.100
.150
.100
.200
.100
.200
.100
-1000
0.8
2.8
4.5
4.2
8.8
5.6
11.6
7.2
-45.5
Values corresponding to adiabatic compression from 1 aIm and 60F to 4.4

atm were read from the individual charls and arc tabulated below:
BTU/lb
Compound
C,B,
C~HIO
C2H..
C3H e
0.763
.680
.935
.780
By interpolation,
lif{ =
6fl
M(h, - h,)
I,
S
h,
112
301.5
295
300.5
303
338
321
363.5
3!2
'F
1M
135
1610
1510
1760
16iO
221
164
1600 BTU/mole and litVM
61VM
BTU/mole
625
570
850
675
620 for a saturated hydro-
carbon mixture of 45.5 malec. wt.
By extrapolation, li.H ~ 1610 BTU/mole and li/V,lf

hydrocarbon mixture of 45.5 molec. wI.
632 for an unsaturated
By interpolation, li.H ~ 1603 BTU/mole and litVM
6z.t for a hydrocarbon
mixture of 45.5 malec. wt. containing 30% unsaturates.

10 Change in enthalpy which includes the difference between the work of expulsion and
work of admission.
84
:. The theoretical work of compression is 35.2 BTU/lb and the final tempera.ture
is 152F.
If other gases (H 2 , O2 , H 2 0, etc.) are present in a mixture, it is recommended
that effective IJressures equal to 7rVYlfC be used to determine the total work of
compression and final temperature of the hydrocarbon portion of the mixture.
The inert g&ses usually may be assumed to be ideal and the w'ork of comprestlion
and final temperature for this portion of the mixture calculated by the adiabatic
compression formulas for perfect gases. The work of compression for the mixture
is then evaluated by combining the change of heat content for the hydrocarbon
portion with that for the inert gases on the basis of their mole fractions. In determining the final temperature of the mixture, it is assumed that the ch.ange in
enthalpy of each portion from its final temperature to that of the mixture is
equal and opposite in sign to the other. This method is illustrated by the following
example:
Example 7. Determine the work of compression and final temperature when
the following mixture is compressed adiabatically from 25 psig and 01" to 150 psig:
Hydrocarbon Portion
Average Molec.
Wt.
Mole Fraction
Component
Average Molec.
Wt.
1.0
1.6
4.5
11.0
0.500
.100
H,
CH,
C,H.
C,H.
Mole Fraction
.ISO
.250
1.000
0.200
.300
.500
1.000
18.1
3.2
9.0
22.0
34.2
The effective pressuras to be used for the hydrocarbon portion of the mixture
are:
7rei
7r.2
25
+ 14.7
14.7
150
vO.500 = 1.91 atm
+ 14.7 vO.500
-=
14.7
7.91 atm
Values read from the ethane and propane charts are tabulated below:
BTU/lb
Compound
C,H.
CaR.
0.837
0.686
t,
h,
h,
294
278
340
307
6.H
OF
M(h, - hi)
MvM
121
92
1385
1280
663
610
THERMAL PROPERTIES
85
By interpolation, UTi = l35~ BTU/mole and t:.tVM = 6-1.7 for a saturated hydrocarbon mixture of 3-1.2 molee. wt. The corresponding final temperature for
the hydrocarbon portion of the mixture is 111F.
For the H 2 portion of the mixture, the work of compression and final
tcm.pera~
ture arc calculated as follows:
MCp
UTi
2.016 X 3.46
6.96;
-.
6.97
99
6.97 - I.
1.40
~I R1'[("2)K~' - IJ
J( -
"1
[(1647)1.40-' I J
I. 40
X 1.99 X 460
__
.
1.40
1.40 - I
39.7
= 3200(1.502 - I) = 1610 BTU/mole
=
I.fO -1
7'2 = (164.7)1:<0 X 460

39.7
691R <> 231F
For the mixture, the work of compression = 0.500 X 1354

= 1482 BTU/mole <> 8f! BTU/Ib
+ 0.500
X 1610
The final temperature of the mixture is assumed to be the temperature I, at
which
0.500[Ji Jre (t, 7.91 atm) - Jilfc(l1lF, 7.91 atm)J
~
0.500[Ji Il (23IF) - flll(t)] = 0.500 X 6.97(231 - t)
Since it is necessary to use enthalpy for evaluating UTi lie, t will be determined
by trial and error.
Assume t = 140F.
Interpolating between the charts on pages 99 and 100,
0.500 X 34.2[312 - 328J = 0.500 X 6.971231 - 140]
240 "" 317
Assume t = 148F.
0.500 X 34.2[346 - 328J = 0.500 X 6.971231 - 148]
:l08 "" 290
By interpolation, the final temperature is I/.7F.
While the foregoing procedure permits the ~follicr diagrams to be used for
mixtures of hydrocarbons and inert gases, the method of combining the cnthalpics
and the temperatures of the two portions of the mixture is theoretically incorrect.
In this procedure it is assumed that if two gases, ha,-ing different thermal propcries, arc compressed individually from the same initial temperature and pressure
86
to the same final pressure and then mixed, the resulting thermodynamic properties
of the mixture will be the same as if the gases were mixed initially and then compressed. This assumption is not quite correct and will always lead to small positive
errors in the work of compression and temperature rise. The errors usually will
not exceed a couple of percent with a maximum of about 50/0 if the average
molecular weight of thc hydrocarbons is not greater than 50 and the compression
ratio is not greater than 5: 1.
As an alternative to this method, the equations for an ideal gas may be
applied to the entire mixture, provided the gas law correction facwr for the hydrocarbons, P-YC, is not less than 0.05. In arriving at an average molal specific heat
at constant pressure for the mixture, the molal specific heats of the individual
components at 0-1 atm should be used irrespective of the initial and final pressures
of the compression. The following equations apply to this alternative method:
= (y HCIlIlC + Yalla + Ybllb + ... )

(MCP)m = YlIc(MC p )llc + y.(MCp). + Yb(MCph
Il ..
K =
AU
Tz
where
Il
+ ...
(MC p ).,
(MCp) .. - 1.99
= K K-
1l.,R1"
[(7I'z)K;:
1
71'1
= (::) \-1 T 1
= correction factor for deviation from the ideal gas law at initial conditions
Y = mole fraction of any component

MC p = molal specific heat at constant pressure (0-1 atm) and at the average
temperature
MC p
K=MCv
d' b t' compression = work of
AH = change in enthalpy during an a la a IC
compression
. 0
7", Pz = initial and final temperatures m R
71' = initial and final pressures
71'1'UC = subscript referring to the ~otal hydrocarbons
= subscripts referring to mdlvldual mert gases
a, bJ et c.
Example 7 will be recalculated by the alternative method:
For the hydrocarbon portion:

= 1.91 = 0.041; 1l1IC
460
.
T r = -575 = 0.80e, <fer 472
.
MCp(70 0 F) = 34.2 X 0.410 = 14.0
= 0.966
THERMAL PROPERTIES
87
For the hydrogen:

I' =
1.000;
MOp = 6.97
For the mixture:

I'm
MOp
K
= 0.500 X 0.966 = 0.500 X 1.000 = 0.983
+ 0.500 X 6.97 =
0.500 X 14.0
10.5
_
10.5 - 1.99 - 1.230
10.5
1 235
[( 6 ) . 235
6H = 9:235 X 0.983 X 1.99 X 460
1 \7 1.235
39
1]
4740[1.311 - 1] = 1470 BTU/mole as compared with 1482 BTU/mole

previously calculated.
T, = 1.311 X 460 = 603R "" 143F as compared with 147F by the first
method.
IC desired, this alternative method may also be applied to hydrocarbon mixtures
if I' at tbe initial conditions is ?!at less than 0.95.
GENERAL REFERENCES
Communication from The M. 'V. }{ellogg CO' l New York, N.Y.
Gary, Rubin and Ward, 11ld. E1lg. Chem. 25, 178 (1933).
Gilliland l Unpublished data, Mass. Inst. Tech.
Keenan and Keys. "Thermodynamic Properties of Steam1 " John \Viley &; SODS (1936).
Misc. Publicatio1l of Bur. Standards, No. 97 (1929).
Nat. Bm. Statuiards Circular C461 (1947).
Sage, Webster a-od Lacey, Ind. E1lg. ahem. 29, 1309 (1937).
Weir and Eaton, Ind. E1lg. Chem. 24, 211 (1932).
'i
400
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fiffi'[ili'
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SPECIFIC HEAT OF
MISCELLANEOUS GASES
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--'
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NAT. BUR, STDS, CIRCULAR C461 (1947)

KEENAN AND KEYES. 'THEfNODYNAMIC PROPERTIES OF STEAM' JOHN WILEY AND SONS ~O.46
( 1936)
800
1000
1200
1.2
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. . . . .9
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89
+f~-l.J..Ht+Ji
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SPECIFIC HEAT OF
PETROLEUM VAPORS
CRUDE FRACTIONS AND FOR OTHER

PETROLEUM FRACTIONS THE FOLLOWING
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CRUDE FRACTIONS. 0-1 ATMOSPHERES
.9B
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I,
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lit
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4
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3
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t:-:' ~ :;E
::T:_ Pi
<
400
..
<
!:tt .
..
"
gg
300
='
..
..
...;,
"
, Cl
~
"
- '.
""
-$
200
::t::
'~
100
.-,
100
200
126
300
400
500,
500
600
700
900
800
127
1000
1100
IZOO
oCD
'"
'"
'"
<D
<t
'"
.,.o<t.
o<D
8
'"
'"
.,.
'"<t
o
~
<D
'"
.,.o
'"
'"'"
.....
o
,.
'. -
"
-t
lHin . t
. I
l.:
:- j~ '::.
, . '0 OJ'
. :r". Cia
L;.: :p
I,I -! _,_
..
.,'
.,
"_ .........
~
g
<D
lI')
lI')
<D
<t
'"
lI')
o
o
lI')
.,o
CD
.,o
.,o<t
<D
128
.,'"o
o
CD
III
<D
III
<t
III
'"
III
.7
360 .......... , :l:tll

.. ~ : 1
!~:
~ ~ ;.
;;:.. , ;.
1.0
1.1
1;'0' ;1';.11'
~;;t,I''':Y
"':'1": T ......
:..: ., . ~"1:
~Z.b~. "j'
': . z
1.3
12
If
usn :)
'/
I,.
.-
)--r--/
IJ
14
!
i' 1.1' t 11
t.,....,...
.. ,I J;~.:.)r.::-:':':':':jr.
15
;n 360
r,.:.:l]
u:: ).';~Jl;~
340
320
..
.... ., .
~_.~
_.Iil.n;
..
- ... ...
'"
~:'::~'. 1
,1' ... , , .
~."..,
300
..
...... , __,
'J/
,_H, /"
..
. ..
......... -
..
280
.., ,.. _, ... .,-,' " ... ,----11 260
::1.":'J~:lnl
-.
;;;
<C
: ....
240
230
'
'---....... .... 220
210
200
190
180
170
~+"
ill.
.6
.7
.8
.9
1.0
1.1
1.2
1.3
1.4
160
1.5
II
10
-,
12
_ _~1Lf'l
_
440
MOLLIER DIAGRAM
FOR ETHYLENE
420
400 IlfIf1TH1-
440
420
400
1
380
t-; -
360
340
130
.62
.64
.66
.68
.70
.72
.74
.76
.78
.80
.82
.84
.86
_ _11
290
I
280 HffiH+/lI~~*l'
340
.14
.16
78
.80
520
~oo
480
460
.,
,I
, !i
" .
,x.
,.84
.86
134
"
JI
.88
1:
,
,,
c
" ,
.,
, ,
-,
l. '
"
.92
, .( r
I Ii
'I
I'
"
.94
,I
.96
.64
.66
.68
.70
.72
.74
76
.78
.80
.82
.84
560
.86
88
560
540
540
520
520
440
440
~._.400
400
380
360
380
li!triffiiRflHl
350
340
340
330
llEllE31 330
320
310
310
300
300
290 _ _
290
280
28C
.62
.64
.66
.66
.70
.72
.74
.76
135
.78
.80
.82
.84
.66
.68
.90
Section 8
DENSITY
Low-Boiling Hydrocarbons
The specific gravity of the saturated liquid, from low temperatures to the
critical point, is given on pages 140 to 142 for a number of low-boiling hydrocarbons. A hydrocarbon mixture is assumed to be an ideal solution, and its specific
gravity can be calculated by adding the products of the specific gravities of individual components times their volume fractions. This assumption is essentially
true for members of a homologous series and is a good approximation for mixtures
composed of hydrocarbons l'om different series as long as no component is in the
region of it-s critical temperature.
Thermal Expansion of Liquid Petroleum Fractions
The thermal expansions of liquid petroleum fractions at pressures up to 1500
psig were derived from the thermal expansion and compressibility corrclations of
Watson, Nelson and Murphy.! As in the case of many physical propcrties of
petroleum fractions, thermal expansion is more sensitive to averagc boiling point
than it is to gravity, although both independent variables arc necessary to correlate the data properly. Up to 1.25 multiples of the volume at 60F and 1 atm, it
was found that gravity could be neglected and that the thenpal cxpansion could
be represented by the molal average boiling point alone. Above this expansion of
1.25 volumes, gravity is introduced into the correlation in the form of characteri7,ation factor. For each average boiling point two lines are shown, one corresponding
to a characterization factor of 12.0 and the other to 11.0. Interpolation and extrapolation may be made on the basis of characterization factor or, if preferred,
gravity, which is also given for each curve.
P-V-T Relations of Hydrocarbon Vapors
A series of charts on pages 148 to 153 give I' ~ PV IRT, the correction factor
to be applied to the ideal gas law for hydrocarbon and petroleum vapors. The
correction factor is plotted as a function of reduced temperature, TIT" and
reduced pressure, PIP" where 7' and P arc the temperature and pressure of the
vapor and T c and Pro its critical temperature and pressure. A explained in the
scction on Critical Properties, the pseudo-critical, not the true critical, tempcraturc and pressure should always be used for hydrocarbon mixtures. This method
of using the pseudo-critical properties of the entire hydrocarbon mixture is not
only more accurate but more readily used than the application of either Amagat's
Law or Dalton' Law to the individual components.
10;/ and Cas Jonma/35, 85 (1936).
136
DE"SITY
137
Since there is c\'idcncc of ::omc lr('nel in p- with incr('a~c in molecular \\"eight

for T,. ;> J .00, there are thrC'c Ect~ of charts for the rq:rinn where T,. i~ {.!;I'cntcr than
1.0, c-o\"('rinf.!: din'erent r:ln~c~ of ll1ol<.'('u]:lr ""('i,,rla. Bt'!o\\" 1',- = 1.0, Ihe data arc
jn~llmcjcnllo take into account n similar trend, so a ~illglc chart 2 covers the entire
molecular \\'eight range.
if olher gases (1-1,,0,,1-1,0, clc.) arc present in a mixlUl'e 01 hydrocarbon
Yapors, an cfTccti\'c Jlrc~surc equal tn 7rV?!IIC E"hould be used to obtain the rceluted
pressure of the h~'drocarbon portion. Likcwi:::e, if it.
ncc(':;:sary to lake int.o
account ~as Jaw dc\'iations for any of the oth,,1' gn::=c<:, p. should be determined for
carh of thc[o;(' g-ascs at an cO'celi\"(, Jln'.~:'llrc C''ll,lal to the total pressure multiplied
by the square root of its muIr frnction. The molal \'oIUine is then calculated by
Amilgnr~ Law,
111'
V'" = - (y
+ y,,,, + y,,,, + ... )
is
11'
"C""C
\\-here I'm is the molal \'0Iu1l1e 01 the mixture, lhe subscript He relers lo lhe lolal
hydrocarbon fraction, and the subscripts 0, b, et.c., rcfer to other gases. l.:'sua.Jly
P-a/ jJ.ln etc., mar be taken as l.OO \\;ith ycry little error, sincc most of these gases
approximate a perfect ~as at thc efl"ecti\'c pressures encountered. In the absence of
other data, the hydrocarbon charls may be u,ed lor these gases.
VAl..UES
OF
GAS
Pressure
Lhlsq in. abs

Lb/sq It abs
ALm
Alm
Atm
;\1 m or Ilg
Lb sq rl abs
Cli It Ih-mole
Cu It/I h-mole
Cu It/lh-mole
Liters, g-Illolc
Cu III I h-mole
Liters ~-molc
Cu It I"-mole
CONST..... ~T--R
Temp.
'n
10.73
1545
0.7302
0.08205
OR
'H
OK
0J{
OK
OK
GENERAL REFERENCES
l1e:l.ttie, IIar/lork :lIlrJ Poffenberger, J. Chem. Phys. 3, 93 (1935).
Beattie, Ka.\' and I\:aminsky, J. Am. Chem. Soc. 59, lii~9 (I93i).
l1entlie, Rim:lnl and ~u, J. Am. Chem. SQr. 61, 2li (103D).
Tnlcl'n:llional Criticnl Tnhl('f:, Vol. lIT.
Kay, /11'/. "ng. Chem. 28, IOI~ (1030); 30, 1,,0 (J03S); 32, 3,;8 (l9~O).
J(cl~o:lnd FC'I!olinl!;. J. Am. Chem. Sn 62/ 3132 (19-10).
L(>\\'i~, Inl/. Htl(l. ('hem. 28, 2.37 (I!l36).
S.a~c :md L'l(,cy, Ind. Hllg. Choll. 30, (l7:~ (ID3R).
Sal-!C'. Srh:t;lr"ma :,"d Lacey. hid. En9. ('Iu'm. 26. 121S (1!l~-I).
S:l~C, \\'C"h<.;tC'1' :inti Larcy. I nIl. [.,'lIq. r1l,.,.". 29, G;j.". II~S (193i).
Smith, I3c:\ttic~nd K3~. J. Am. Chl"-'. Soc. 59,1:')1;)7 (lfl:li).
c
,.
;!
COpC'. Lewis and Wcber, Ind. P;,IO. Chem. 23, 88i (931).
1.31~
62.3G
2781
10
20
40
30
..-0++ '1,
I:NV :r1~
",
60
50
..
3'
mt
~.
8.8
SPECIFIC GRAVITY AND POUNDS

PER GALLON VG API GRAVITY
8.6
~ r..=:n:
~
'.I.... _
.API' 141.!5
131.5
SP:GR.
1=;
...
141.5
API + 131.!5
SF! GR.'
7.8
..
.-: --'-f.:..v::r
~
.98
:=: ._ ..
"".
.96
.....
+I'
7.6
.-
-:.'
= ~
. u.;
.t:tl _ -...-
.94
7.4.
.,
+~
-.;
...
~7.2
.92
,.,..... -
.90
7.0
"'" rl'>."T ,,:
,,= ".
.88gs
.89
-.......-...
~-
.- rti:: ....
.=.=
::::t:
6.8
..~.
:r
j
.84
.3
,.
.82
.so
...
6.2
...... __ ._:
~I'_
.=:
~
.78
,..
-t
'ra
6.0
,",...-
...
5.8
_ .::t.:::
.......,.
,.
1- __,
" ..-
j:j,-
_ r
...-
.74
::>::::..
.,
..- ..
._-'
.72
.70
10
40
30
138
50
60
70
70
80
90
100
110
120
130
140
80
90
100
110
120
130
140
139
150
160
170
180
190
200
210
III
CD,
nIl n'1 '1+
11
irr1
litl
::r
'f
Eli;
m'
<t
,r
,H
i.
;'1'
IT, '
i,
....
~1
~:
II;
II
oj
,-
t-o-
_I
...
;:1.
""I- r
. _ 01 . _ .
h!~ '::'; 'ill, t'_: t
tJiR,.:. ,'J , ~ .
it '++1 'l=!, i1'1-1, , :11," n:...
+;.11 !r;:
:1
...
,fr; :1:i:
~.
r'"!
..
Sf
;j:j.H
Ilti
-:
,"
;-t
. 1:
1,
t~..
, I
,i .
'"
- - ..:i~"
I;n:
f
:r
"
l-'o.i
.1b
'S1' ..!
,0
,0
,'"
"T"
..
",
i= -
i,~
~.
I!:.
'8
'""
........
.....:;..: -0
140
-...
200
100
600
500
700
....
OO!
SPECIFIC
LIQUID
GRAVITY
~f9
'ig
AROMATICS
OF
IN EQUILI8RIUM WITH ITS VAPOR
,mh"m!'~!k~il'~':ll::"i'~i~l
ttl
.'1111'
,.~'..
. . ..
,
1'4
--
USE
...
XYLE NE
CURVE
t
t
.
,
FOR
OF ETHYL8ENZENE
.8
m-
SPECIFIC GRAVIT.Y
-+
.
-
.'
7
~
if,:~
'I
ill! ,.
'
"
I~ , ,
.7
f
:
r
,6
. -,
R!
.5
"
:..
.3 .. ~
l-
1
I')()
JV
142
.8
100
200
300
400
500
600
700
800
900
1000
1.7 _ _
THERMAL
EXPA:N:S~,~o:N~~~1I1I1I1I1I1
1.6
1.5
1.4
:;:
co
1.3
_1.2
1.1
100
200
300
400
soo
600
700
800
900
1.7
100
200
300
400
500
600
700
800
900
1000
THERMAL EXPANSION
1.6
1.6
OF L10UID PETROLEUM FRACTIONS

250 LBS.I SO. IN. G.
j-l-l.
1.5
1.5
'"'t:::nlo
1.4
....
:t
1.3
,,--
I"-I"i ~
1.4
=:: t:tt;j t.lith:: .-
;~I.,..;4",
'~1=1:1;-tt~t~
.h";::
...I,,"'..
1.3
1.2. tT+-
1.2
..".,
PARAFFINIC; CHARACT. FACTOR, 12.0

---NON-PARAFFINIC "
"
11.0
(8ELOW AN EXPANSION OF 1.25, THE SOLID LINE
REPRESENTS AN AVERAGE OF ALL STOCKS.)
o:r.l"
. . .1
1.1
1.1
;..Il-.4.
100
200
300
400
500
600
700
800
900
1.0
1000
__ _
300
200
300
1.6
...",
~
1.2
1.1
100
400
500
600
700
800
900
1.0
1000
i-rJ:,
1.6
!l=W~
r~:l:
t
1.5 Eb_
Lo:"j,
/tit Ii
':3:rf1
'<
,,"
l!Q'1h:Hl4tlq
i~
"'--'It+!H
I'r-~"'",
..
_ :H-"-
lr..:.:
,;
l.:t:Jut
.,
t:...
.. dttt!
_I
Irl-J
1~
tt=
.i1E
.
:;t:l
....i
"""=',
';11' ,,~~~ !Ll
"
.~.
rlrl'"i It-! I Yi
:.4
'V.-t
, +.: ,i
Vi
"
"
,~;
H-It I f . 41...... '1' !.-t1,......
H:
_I:'
-.. ,~
.~;..I
~/,
,~
100
..,...t-:
lfir.
PARAFFINIC; CHARACT.
NON-PARAFFINIC"
,..f-i
ilWW
;tHi1-;,
.-.
300
FACTOR = 12 .0
..
II .0
.2
(BELOW AN EXPANSION OF 1.25, THE SOUD III ~E

REPRESENTS AN AVERAGE OF All STOCKS. I
..
200
!ffiI,
'~
~i
iii
!.3
~-tttt:r.
1.4
_li.1,l
,lTIf~
till
~l;nilqi.
+- it/-:
......
Jl.U:'_~
"~
11.,:t
"r:.
,:r:
.'
".
:::r.
,
1m
~'
P-
fl
t' IIlJr.
r-:- :'" ~I,/r
t,:'
~fi-i ::l11:t!
:=("1
~f:.J.I;:~
- -.
'~
~.
;.+--dL-' ~ t:'~
..
~. :~A:'
...."
,..~1 ;'<.111'_
rl
w. . . +-
.." I
'"'t
1.6
:.5
~.
.~.
i i-
0+
1.1
~:..
M.i
.:
t:'t
l~ ',:!.'--
I=
t:ti,,;
:=rr '!:If'' '.--!Jatj;t j:\{lR ,ilE liiJlOi.IG' J?C \-}, .+
im
r,."."
1.7
~
:q::.'
t::tt ~
li iT"
,m'ft:: tit,
,'; ,. l1:J.fi~ ,-)(' ':J.;;-::;:;
i!?- 2'~,J l,'_
:n:r.,!1=:'1
-~,:n:: ~ ......i1 :-:-::-=
t+ T.!1t ...;:t :u E;:r
~~l~
. IW
-,
! p.;:l
1;
H:.ti;.ll~i-Cl?11
~:;t.l.f!]J+7~'" -W.j l,.~ :r;J:; . j .....
$!:Ii Ji-,
~'-'j ~:
F ~ p.~'
"'J::J:
C'!:!' lpo,,-j
1m
1000
;:.~b
mIT!' /:;:j.tlr.!'ll
l!
';il
-.-tot
'~T'"
1000 lBS.lSO.IN. G.
'":1":
'.-.,
.T
r:
THERMAL EXPANSION
OF LIQUID PETROLEUM FRACTIONS
900
BOO
..
h~
+rt.
....
700
600
-n_-,::1=li:S1m..-tt:.':r;::::;
;:rt:fE-tt..,
t:'
500
.:j::;'+"w~~;U:l~
!:tt::l 1r
14
400
300
200
100
1.7
400
500
600
.I
i ....
.,
700
a
800
900
.0
1000
<:>0
-0
Q
:il
g
CD
r-
oCD
'"
8<t
8N
o
o
lIIIIo
q
147
...
CD
..
rr
w
m
w
~
V>
~.
-'
.w
"o
u
...
ffii ,.,.:ill 1:1:,

.
148
'.
.2
.6
.8
1.0
1.2
1.4
1.6
1.8
2.0
2.2
2.4
2.6
2.8
3.0
3.2
3.4
3.6
3.8
1.1
.9
.8
:;:
<a
.5
: j;I;JF~J;
.1.4
1.6
1.8
3.0
3.2
3.4
3.6
;.J'lU+:"RJ.4
3.8
4.0
d!
-H"
~
.Wlj':-"H~'
t'....~- ""1b1fJ1n
"' ,'c:t!" :Vf!.iJ i~ffi,
1;Jlh.:.;f
1#
,;.u
m::T'
~ "'"
ttl:
"
~:
~ j
!:iJ,'
-i
""~
~2
,-,: <t
....... >
::: u..
o
J;1:
i:..::
+~
en
z
o-
:.". ~
I,
.:11r
~ :t:
,.
~:'"
.I"
,.. p
"ll"~'
." ,x:.., ..
:.; Ll ,l:.tt!
'.'
..... ! . . .
+
.....
-
I-;L
'd
,~'~:H.;
i1
......
',,-~
I .....
;JIO
I" .. :-
~ J":
.,.
".
f'j
':/I/:: --',
N-.
' - ' :: I .';;.
'-I-
;f"".:";'.J"-;. . ,
"
:j.;;
17
..
J ..
...
~,
.~
.
,~
~h 1~;''';:,'
"
::t11nittt
j.I
",liE
M
.,
~t.;
..; 'UP.'
...._..
p~
[j:lJ~
l'
_. ;~~l
... J
i:.
rttH-!
,~
at: ..
r//I/'!<' All-!'
,'
':/: ''r LY'; ,.. +1f1 t
'V" " ' 'jj'
Z~ :~;- t;~: !1: Hi
b;j1~ r
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:
, ,
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'
"rlli';; '.1: ';:/1 ;01. 41' ~l~

.:1
:ilit.lliJJ~ e,: H'-1 "I ~ ~ Ii!: ,: II :,I I
':I1:j.l.!!:..IL:;;V"
t:t~::"t~:tt:;':lttl .. -,
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;! !~!: ~d'
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tJ
T; liH,.1
In l'iHllitt-l
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,
i.i.~ll
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...
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rl.-.
'l:
.:..l....
iii.
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-~ 1:"
Uil ~!; ~1:rth:_
.;~l r:p+H-~tr
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it
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t
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,lim
:
-- :i~.;tli:"
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~ t..:J~ I-:r~.
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:ttl ~h
' _ ."It
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:j
....+'
wr
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:r:tt.. ,
,~_
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qnn
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ltU:'"
~,~.,
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::1:
'~,., -:r-,:i1~
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i~
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: '1+
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tF
'.1;
",' 4''Il:. r II:"'~"

:ttl"C<' ' T
t :d'
.. H
"._ ;,. ....,'
"H:,..;.r-::
....... I
:~
> ~.,~
, '=
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. :.:.= .:::c +;-:: :.- -::; E
.7
.6
2.8
3.0
3.2
3.4
3.8
4.0
4.2
151
4.4
4.6
4.8
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5.4
5.6
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152
1.6
1.8
2.0
2.2
2.4
2.6
2.8
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2.8
3.0
3.2
3.4
3.6
3.8
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4.2
153
4.4
4.6
4.8
5.0
5.2
5.4
Ii.
P-V-T
1.0 1I! IIII!II!!! '1111111111111111111111111 j Ii IllllllllllllfffFfFFfl313"B3iFFl"EfffEfIII i 1111111 i 11111 III II I1111 1I111 11111 1111I III 1a:a:tlllllll l ! IIIII1111111I1 i I: Ii: II i:1111111 Sitll: II1II1 !11111 II! I !I! II! 11.0
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.8
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.6
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All
III
.1
m
o
...
.1
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em
.3
.2
.3
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Mi
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;m
.1
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1,0
Seclion 9
VISCOSITY
Absolute Viscosity
]n the metric system the unit of viscosity is the poise which is equivalent to
force of I dyne pcr sq cm shcaring a liquid at the ratc of I cm pcr sec per cm.
By reduclion to minimum dimensionality, the poise becomes I g/(cm) (sec). The
corrcsponding English unit is I Ibl (ft) (sec), or (pouodal) (sec) I (ft) 2, which is
equal t.o 14.88 poises.
Howcvcr, the unit of viscosity most commonly used is the centipoisc (0.01
poise), which happens t.o be the viscosity of water at almost cxactly 68F. Thereforc, the absolute viscosity of any fluid in centipoises may bc considered to be
oumerically equal to its viscosity relativc to water at 68F.
Kinematic Viscosity
Since thc density of thc liquid involved in the measurement of viscosity by the
standard industrial viscometers, it is necessary to introduce kinematic viscosity,
which is the absolutc viscosity of a fluid divided by its density at the temperature
under consideration. The metric units of kinematic viscosity corresponding to
poises and centipoises arc stokes and ccntistokes, of which the latter is more commonly used. The kinematic viscosity of water is I centistoke at just about 68F.
Industrial Viscometers
The industrial viscometers which are widely used throughout the petroleum
industry in this country are the Saybolt Thermo for rcfined oils, the Saybolt
Universal fur lubricating and gas oils, and the Saybolt Furol for crude residua and
heavy fucl oils. The Redwood Standard and Engler viscomctcrs arc used mostly
abroad. Curves for the conversion of these standard viscometer measurements
to kinematic viscosity arc gi\'cn on pages 158 to 160.
Except for the EnglCl' instrument, these conversions arc slightly affected by
the tcmperature at which the viscosity is mcasured, but this effect has been
neglcctcd in thc prescnt convcrsion charts, While Saybolt Universal viscosity may
'>e measured at anyone of several temperatures, lOOF, 130F, or 2lOoF, the
maximum variation between the temperature extremes in the conversion to
kinematic "is('o~ily is only 3% and, above kinematic viscosities of 5 crntislokes,
it is Icss than 270. The va,'iation between the extremes of the Redwood Standard
instrument (70F to 200F) is appreciable at low viscosities but does not exceed
3% above 10 centistokes. Saybo!t Thermo viscosity is normally measured at room
155
156
temperature and Say bolt Furol at 122F so that it is usually unnecessary to

consider conversions at any other temperatures for thcsc instruments.
Change of Viscosity with Temperature
Viscosity-temperature curvcs arc given for pure hydrocllrbons and crude
fractions on pages 161 to 165. In the absence of other data, these curves may be
used to approximate viscosity-temperature relations for othcr hydrocarbons and
petroleum fractions if the viscosity is known at only one temperature. However,
if the viscosity is known at two or more temperatures, the charts on pages 166
and 167 should be used for linear interpolation and extrapolation.
Viscosity Index
Viscosity index is a generally accepted criterion for evaluating lubricating oils
with respect to change of viscosity with temperature. The vi cosity index of any
oil may be read directly from the charts on pages 168 to 172 if its viscositics at
100F and 210F arc known. If these particular viscosities are not available, but
viscosities are known for two other temperatures, the viscosity-temperature charts
on pages 166 and 167 may be used to find the values at 100F and 210F.
Viscosity Blending
To predict the viscosity of a blend of two or more fractions at any given
temperature, the blending index for each fraction is determincd from its viscosity
at this temperature, using the chart on page 173. The blending indexes of the
individual fractions are additive by volume fraction and the resulting sum may be
converted to the viscosity of the mixture by referring to the blending chart again.
If the viscosity of one or more of the components is not available at the desired
temperature, it must be converted.to this temperaturc, since blending indexes arc
additive only at constant temperature.
The viscosity of a blend of two stocks may also be obtained graphically by
using the viscosity-temperature charts. A straight line eonnccting the viscosity of
the lcss viscous stock on the 01" abscissa and the more viscous stock on the 100F
abscissa reprcsents the locus of the viscosity of all blends of these stocks. The
ordinate corresponding to the percentage of the more viscous stock-whcreby the
temperaturcs between 01" and 100F are considcred per~entages-represents the
viscosity of the blend. While thc blending indcx chart was derived from the
ordinate scales of the viscosity-temperature charts, the two methods will differ
slightly since thc tcmperature divisions vary between 01" and 100F.
Viscosity of Gases
While pressure has very little effect on the viscosity of liquids except near
the critical temperature, its effect on gases may be considerable, especially above
the critical pressure. The change in viscosity of a gas or vapor with p1'essurc
VISCOSITY
157
may be predicted from the chart on page 177. By the use of reduced temperature
and pressure, this chart provides a generalized correlation of the ratio of \'iscosity
at any temperature and pressure to the viscosity at the same temperature and
atmospheric pressure.
The viscosity of a mixture of two or more gases at atmospheric pressure may
be computed by the following formula:
m -
N,Z,v'M; + N 2 Z2VM; + ... + NnZ.VM:

-'---'------==----=-'-="'--''------'-----~==_----''
N,VM; + N 2VM; + ... + N.-vM n
where Z... = the viscosity of the mixture

N" N 2 , etc. = the mole fractions or moles of individual components
Z" Z2, etc. = the viscosities of the individual components
M M 2 , etc. = the molecular weights of the iudividual components
"
The chart for change in viscosity with pressure may be applied to mixtures by
using the pseudo-critical properties of the mixture to determine reduccd tempera-
ture and pressure.

GENERAL REFERENCES
ASTM Standard Viscosity-Temperature Chart. for Liquid Petroleum Products (D341-39),

Charts C and D.
Deale, "The Science of Petroleum," Vol. II, 1080, Oxrord University Press, New York,
N.Y. (1938).
Comings and Egly, h,d. Eng. Che11l. 32, 714 (1940).
Davis, Lapeyrouse and Dean, Oil Gas J. 30, No. 46, 92 (1932).
Dean and Davis, Chem & Met. Eng. 36, 618 (1929).
Edwards and Bonilla, !rId. Eng. Chem. 36, 1038 (1944).
Etherington, Sc. D. Thesis, Mass. Inst. Tech. (1948).
Evans, J. Insl. Pelroleum Tech. 24, 321 (1938).
Forlch and Wilson, Ind. Eng. Chen!. 16, 789 (1924).
Ine nnd Dean, Ind. Eng. Chon. 16, 905 (1924).
Lipkin, Duvi!'on and }(urtz, Ind. Eng. Chern. 34. 976 (1912).
Nat. Bur. Standards Circular CI,61 (1947).
llnd Lacey, Ind. Bng. Chtm. 30, 829 (193 ).
~llge, Yale and I.,cey, l1ul. Bng. Chem. 31, 223 (1939).
~age
Watson, Wiell and i\furphy, Ind. EnO. Chem. 28, 605 (1936).
1000
10
20
60
80 100
300 400
600 800 1000
800
800
CONVERSION
600
500
TO
600
500
KINEMATIC VISCOSITY
400
400
300
200
100
60 -
50
40
-F_'':':
20
2000
10 _
1000
800
"
600
500
.. 400
k'.,:: ~#l
:::
....
I::: :~. i
l~! :il~
J.".i , .
,h '
i1
~;
!lIT"
I
400
!Hl~
600 800 1000
15!3
2000
4000
I'
300
100
10000
f,i
8000
200
-i.Jk.ti
600 800 1000
1000
.q
-=tot
800
600
6000
=11111
500
400
300
200
1000 -
100
::: cf
80
60
50
40
30
200
20
10
10
8
8.
6
:r;
3
>
t!
"
10
159
20
30
40
60
80 100
FROM SAYBOLT THERMO VISCOSITY
,.
4
SAYBOLT THERMO VISCOSITY
-lOX (SAYBOLT THERMO TIME)
100
200
600
300
160
700
VISCOSITY OF NORMAL PARAFFINS
.1
-100
.I
100
200
161
300
400
1
1.8
...,..
_. -_.. ,-_r:r::
1.6
I
-:
+-
VISCOSITY OF AROMATICS
:=T._.
1.4
-=1=
.,
H
r -i' -r+--r-'.
.-;...... -;- -
++-
..
0.2
I
I
50
..,...
.-i---
::!..
- I'-L
I-f
12
-- .
150
162
,.
- lJiIllI
100
-j
I
L..j _
200
250
300
- -ri
40
KEY
,5:
10
-i:!...:?!=
r.l-
'i_: :;.'-=:'-~:. . ;<ic --=.t:-~
~~ ~ti ~~~ ~~ .~ .~
4' ; :1.si?=a"
6.0 ~i=LGl,{:
-.M cFI..i.~:',r ;L,- l'!'=!o\2, ::EJ=L-"
I-W::-;:;\ :jeil- _til
1-. \1 .,='1: -~l-+" =
T:~ ,---+-+ - .-~-t-t \.tr--l=
80_.
t
7.0 _0 __ e\'=~ ;~:il'ii ft
lc
I
2
3
4
5
6
7
8
9
10
26,8' API
33.2' API
35.0API
36.~API
38,2'API
39.2API
43.~ API
46.0' API
48,7'API
51.soAPI
~ ~:..~:::~ ~~~=;~;:~
13
62.9API
rt:'
"-+i-L
-i-tREFERENCE:
0.1
212 - 257F.
NOTE- 801LING POINTS OBTAINED IN A

HEMPEL COLUMN.
_'
RESIDUUM
527-572F. AT 40"...
482-527F. AT 40M",
437"462" AT 40"".
392-437'F AT 40"M.
UP TO 39rF.AT 40""482 - 527F.
437 -482F.
392 -437F.
347-392F.
LANE AND DEAN. IND. ENG. CHEM. 16. 905 (1924)
1+
'i', .
100
200
!r~r~I'
300
163
400
500
600
700
-;~
80
70
60
...
=.=t=<="
VISCOSITY OF
MID CONTINENT OILS
50
40
30.~
KEY
I
2
3
4
5
6
20
7
8
9
10
II
12
13
~
..
.. =~---
l4~ 0 API
~3. API
o
RESIDUUM
CYLINDER STOCK
23.l API HEAVY MOTOR OIL
(lO5 SPGR) ROAO orL
24.2API RED OIL
o
26.l API LIGHT MOTOR O~.
27.1 API LIGHT PARAFFIN OIL
32.8~PI
WHITE OIL
28.8API
3D.OoAPI
35.2API
35.6API
40.4API
I~
LIGHT PARAFFIN OIL

PRESSED DiSTILLATE
CRUDE otL
MINERAL SEAL
KEROSENE
GASOLINE
15
GASOLINE
do'
L
-,.,<i=-
09,_I,~
...
_~c_o
_ .
5". . . =
.=
0.4
..
0.3
_-
0-2
REFERENCE,
FORTCH AND WILSON.

I
100
200
400
300
164
IND .. ENG. OlEM.

II
II
II
500
II
16. 789 (1924).

I
600
II
II
7'00
wo
90
80
70
60
~~...:-
_ _T";.
- VISCOSITY OF CALIFORNIA
CRUDE FRACTIONS
50
40
30
20
KEY
I
2
3
4
5
10
7
8
8
7
9
10
II
12
6
5
4
18.7 'API
20.3 'API
22.8 'API
25.0 'API
27.3 -API
30.4 'API
33.0 'API
38.2 'API
41.5 -API
44.3 'API
49.5 'API
54.5 'API
527-572'F. AT
482 - 527'F. AT
437- 482'F. AT
392-437'F. AT
UP TO 392'F. AT
482-527'F.
437-482'F.
392 -437'F.
347- 392'F.
302- 347'F.
257-302'F.
212 -257'F.
40 MM.
40 MM.
40 MM.
40 MM.
40 MM.
NOTE- BOILING POINTS OBTAINED

IN A HEMPEL COLUMN
REFERENCE:
0.1
100
LANE AND DEAN. IND. ENG, CHEM. 16. 905 (1924)
200
300
400
165
500
600
700
500
600
700
00
-:fl 10eo
VISCOSITY - TEMPERATURE CHART

HYDROCARBONS AND PETROLEUM FRACTIONS
KINEMATIC VISCOSITY. LOW RANGE
6.0
5.0
4.0
30 I I I I I I I I I I I I I I I II I I I II III II1II II i III1II1 \1IIII11 i 111I1 11111 11I11 11111 11111 II!! 111111111111111111111111111 II I 11 III ITTTRRTlI I I I I I I I I i I m 3.0
20 I I I ! I I I I I I ! I ! ! I I I I I I II II ! ! I ! ! I ! I I I ! I I " i I II ! III " III !!III 1!1111111 ! I I !I !!! !111111 111 !111 1!III!! I! !I!III !II I I I I I I ! ! I I I I ! ! I
!
!!
! I I ! I I ! Ii! ! ! 12.0
1.501 I I ! ! I I I I ! ! I ! I I I I I I I I ! I I II I: II;! I : I ; ; I : 111!!11 ; 111111111: il! 1111111111: 111111111 illil I: illllIillliil iIi II I UElJ:Jl1IU Li LOll Llu i 1,50
1.00
0.90
0.80
0.70~~
0.70
0.60~
'060
I .
():
j:;:
o.sOt~
J"
!!
.0.50
Zi
s;2i
0.40
!!!
!
~
0.40
0.30 I I I I I I I I I I I I i I I I I I I I II I I I II I I I i I : 1111 i II ; 1111 !l111 i 1111 ;11111111111111111111111111111111111111111 i 111111 i II I I I i I I I I 1I I i I I I I I i I I I I I I I I I I I 10.30

R~FERENCES:
A.S. tM. STANDARD VISCOSITY - TEMPERATURE CHARTS 0341-39

NAT. BUR. STD5. CIRCULAR C 461 (1947)
WATSON, WIEN AND MURPHY, IND. ENG. tHEM. 28,605(1936)
0.20
'"
"'MM I ,
:bx,,1 I I I I I J,M
!
N
~
JsMO.20
......... 199
10,000,000
'i'
200N
I,.
1~9.
, 2~q"" ~
400
450
..
500
600
700
800
VISCOSITY - TEMPERATURE CHART
1,000,000
500,000
200.000
100,000
50,000
20,000
10,000
5,000
HYDROCARBONS AND PETROLEUM FRACTIONS

KINEMATIC VISCOSITY, HIGH RANGE
10C\OOO
50,000
20.000
10,000
5,000
2,000
2,000
1,000 (/)
1,000
500 ~
~4
-...
0>
500
'""'h-
kb!
, W'2ffi E' bt!-bikffi.::tt!"ttJ:tl'!ifl
L141l114lWJtUifflfiltlitfilll!ifl J II J I !J btl ! I I I ! I I
! !
Ifu:'1200
w
<.)
I
>-
50~
(/)
:>
<.)
201::~ I 1I I I II I I 1111111111 ! I: III! ! III! : I IIIIIIIIIII!! 11111' 11111 11111 11111 11111 III:! III I! 1111"IIIIIIIIIIIII!:1 ! ! I I I II I I I I I II! I I 1II I ! !
::;;
w
IJIIEJ 20
i:
10
10
8.0
8.0
60
5.0
6.0
5.0
, ,
4.0
4.0
,
3.01 1I 1I 11I I I I I I I I I I I I I I I I II 1111I11 , 111111111 , " IIIIIIIIIIII! 11111111111111111
, ,
'
REFERENCES:
WATSON. WIEN AND MURPHY, IND. ENG. CHEM. 28,605 (193G)
, TEMPERATUflE.~ ..F. ,
2.0
A.S. TM. STANDARD VI$CO$ITY- TEMPERATURE CHARTS 034139

NAT. BUR, STOS. CIRCULAR C 461 f'947)
3.0
,
34
33
VISCOSITY INDEX ALIGNMENT CHART

2.0 TO 50 CENTISTOKES AT 210F.
32
140
31
130
30
29
120
28
I"~
27
26
25
110
100
-"S
24
23
22
21
20
19
18
90
u:
)(
...
<t
>-
'"
...
...'"
0
.-
16
15
<:>
<:>
l/l
!Q
l/l
C\J
70
>
2:
17
t:
l/l
W
80
f2
60
;g
$
0
50
14
13
40
12
II
30
10
9
20
10
6
5
168
~50
440
140
430 -
40 TO 60 SAY80LT SECONDS AT 210"F.
420
130
410
400
120
390
380
60
370
58
360
5;>
350
56
340
s.,
330
300
5,3
"'
290
280
'"0z
270
260
250
100
55
320
310
110
59
5f!
><
;;
>>iii
'">-
230
'"
70
..J
!!!
>
'">-
80
8w
240
90
60
<l
220 -
50
210
200
40
190
180
170
30
160
150
20
140
130
120
10
110
100
0
90
1G9
1650
1600
VISCOSITY INDEX
1550
140
ALIGNMENT CHART
50 TO 120 SAY80LT SECONDS AT 210F.

130
1500
1450
120
1400
1350
110
1300
1250
100
1200
1150
1100
1050
90
u:
!<.'
~
C\i
0
0
1000
Vl
0
900
<>
,,'"'"
800
750
Vl
m
><t
Vl
>-
in
0
<>
tJ:;
UI
....
(j'
80
f--
850
....
f-<t
950 -
70
<fl
'"
:>
60
cJ
50
700
650
40
600
550
30
500
450
20
400
350
10
300
250
200
150 1.
170
3800
VISCOSITY
3700
INDEX ALIGNMENT CHART
80 TO 200 SAY80LT SECONDS AT 210"F.
3600
130
3500
3400t
120
::1
110
3000+t
100
2800:1-
90
3100 -
1900+
2700t
2600 i
u:
"0
24COt
,
'"z
0
"""
>!:::
2300+
2200t
2100
f
T
2000
0'"
":;'"
'"
:;
70
60
al
><l
50
'"
1900
80
""
:;;
2500!
40
1800
1700
1600 I
T
1500+
,
30
1400+
20
1300+
t
+
10
1000:1-
1200+
1100+
900t
800 1
171
7800 T
7600
1400
100 TO 350 SAYBOLT SECONDS AT 210F.
130
7200
120
1000
6800
6600
6400
6200
6000
5800
5600
5400
5200
u;
~
<f)
5000
<.)
4800
4600
4400
<Il
16>-
..
<f)
4200
4000
3800
3600
3400
3200
20
3000
2800
10
2600
2400
2200
2000
1800
172
0.2
0.3
0,4 0.5
2.0
35
30
80
25
60
20
40
15
10
10
20
200
300 400 500
2000
5000
10000
.030
.030
.028
.028
.026
.026
.024
.024
.022
.022
.020
.020
.018
.018
.016
.016
.014
.014
;,
.012
;+
.012
.010
.010
.008
.008
.006
.006
.004
.004
.002
.002
200
400
600
174
100
80
~IIII-!!IIII
20
10
.BEALE.
THE SCIENCE OF PETROLEUM. VOL. 11. P.
. OXFORD UNIVERSITY
PRESS (1938)
0.1
100
200
300
175
400
500
200
mtmm
400
600
800
1200
1000
.040
.040
ABSOLUTE VISCOSITY OF
.038
..038
.0.36
.034
.034.
.032
.030
.032
.030
.026
.026
.026
.024
024
.022
.020
.020
.018
"
.018
.016
.014
.0/4
.012
012
,
.010
.,
.008
.006
l' fr ~ f
i
r t
200
600
TEMPERATURE -
176
800
0
iJ. .
1000
.009
1+
;:j~ ~
1200
.006
.3
.2
.4
.5
.6
.7
.8
.9
1.0
3.0
4.0
10
10
9.0
8.0
9.0
~~. ,~,E~E~,,~~~~,~,~~,IN.~~.,.6:~"~, ,~~,;~~,~~~",r' " " "'~
8.0
7.0
7.0
6.0
6.0
I :: i
!
I i
I
i
i i I II II
I
VISCOSITY OF GASES AT HIGH PRESSURES
4.0
4.0
3.0
3.0
2.0
2.0
..,
-.J
1.5
H;tt+tttf+
1.5
H
,
,
"
11'i],11
1.0 T 11
.2
1.0
.3
.4
.5
.6
.7
.8
.9
1.0
1.5
2.0
3.0
4.0
5.0
6.0
7.0
80 9.0 10
Section 10
COMBUSTION
Liquid Fuels
The heats of combustion of fuel oils and petroleum fractions are expressed as
a funcLion of gravity by the chart on page 180. Both the high and low heating
values have becn correcLed for the average impurities other than water which
are usually prcsent in oils of various gravities. These average impurities, tabulated
on the chart, are fairly represcntative, although there may be appreciablc deviations for a given stock. In general, the heating valucs of average fuel oils arc
within 1'i& of the curves.
The heat available from the combustion at 60F of liquid fuels is given on
pagcs 186 to 188 for fuel oils of 5, 10 and 15API. Because of the small variation betwecn these charts, interpolation is unnecessary and the available heat at
any tempcrature and percent excess air may be read from the chart which most
nearly corresponds to the gravity of the fuel oil. If the impurities are known to
be appreciably difTerent from the average values tabulated on page 180, the
available heat may be corrected in direct proportion to the bydrocarbon portion of
the fuel with sulfur considercd as inert material.
Gaseous Fuels
Heats of combustion of paraffin and olefin gases arc given as a function of
molecular weight by the chart on page 181. The paraffin curves on this chart were
used as a basis for deriving the charts on pages 184 and 185 for the heat available
from the combustion at 60F of dry refinery gases having high heating values
of 1000 and 1600 BTU/S.C.F. Allo\\ance was made for average impurities of
2.570 H 2 S and 2.5% inerts (equal parts CO 2 and air) by volume. As in the case of
liquid fuels, the chart more nearly corresponding to the high heating value of the
fuel gas may be used without interpolation with very little error. However, in correcting for variation in impurities, the available heat must be adj usted in proportion
to the weight pmcenlage of the hydrocarbon portion of the fuel gas. In making
an adjustment for thc H 2 S content of thc gas, its volume percent may be distributed equally between the inerts and hydrocarbon portion as a good approximation. The following table gives relevant information for refinery fuel gases of
9.verage impurities:
\78
COMI3 S
no"
Nominal HHV, BTU/S.C.F.-, .. _.....
1000
1200
Wt. Percent Impurillc~ ... ~.
10.1
8.3
~p
0.60
0.73
16.5
1037
20.4
1248
G, of Fucl Gas ('-or - 1.0'-.
M.W. of H)'drocarbon Poruon.

Actual HHV of He Purthm-U rU/ti.C.F. '
I
Calcubtcu by the perfcct gas hw at GOoF and
179
1400
7.1
0.86
24.3
1458
1600
6.2
a.utl
28.2
1609
1SOO
2000
5.4
4.00
1.2b
1.12
32.1
1879
36.1
2090
atm.
Properties of Flue Gas

The CO 2 content of flue gas and the lI'eight ratio of flue gas to fuel are
given both for liquid and gaseous fuels as a function of excess air on pages 189
<1nd 190. Since the effect of percent excess of air is almost imperceptible on the
viscosity and thermal cunduetiyity uf flue gas, it has been ncglected entirely and
each of these properties is expressed as a function of temperature alone.
;e
. ,.it
tit~~'
Jif-
- i.!
...
'H-
HEAT OF COMBUSTION OF FUEL OILS

AND PETROLEUM FRACTIONS
,~
..
,f
~":4
_(,,!It. ::::
:;t;:t!1
".
IMPURITIES IN AVERAGE FUELS . "

"A.P.I. I % S
%INERTSI'M~Y,m'tV
20000
RESIDUAL FUEL OILS AND CRUDES

o
2.95
1.15
4.10
5
2.35
100
3.35
10
I. 80
.95
2.75
15
I. 35
.85
2.20
20
1.00
.75
1.75
CRUDE OILS
25
.70
.70
1.40
30
.40
.65
1.10
35
.30
.60
.90
19500
... -+---
.~
,., .
~.
.,
.. 1;...
......:...1-_
.~
..
:=+--~E-f,
~t
19000
..
fD
18500
[I
+
il
~.
:~11
+.
18000
~, '.
,.,
I::;
.....
~X -tE':-::~
:-T.r~."""
\1
.,
17500
4-
THESE VALUES REPRESENT AN AVERAGE

OF CRACKED AND VIRGIN FUEL OIL DATA
UP TO 20"API,AND THE CORRELATION
ALLOWS FOR AVERAGE SULFUR AND INERTS
(EXCLUDING WATER) FOUND IN AVERAGE
FUELS. ABOVE 40"API THE CORRECTION
FOR IMPURITIES IS NEGLIGIBLE AND THE
CURVES REPRESENT PURE PETROLEUM
LIQUIDS.
17000
10
20
30
180
40
50
60
19
4600
4409
4200
4000
001.
341
3200
2800
2600
2400
2200
2000
1800
1200
1000
10
181
900
ENTHALPY OF
FLUE GAS COMPONENTS
,
~.
0-1 ATM.
B"
~.
Ii
-<-.!.
;'If!- ~ ~ _:.:. -:
t t
800
700
600
+
500
200
400
600
1000
800
182
1200
1400
2200
2000
1800
1600
1400 .
1000
600
400
200 .
1600
1800
2000
2200
183
2400
2600
2800
3000
HEAT AVAILABLE FROM THE

COMBUSTION OF REFINERY GAS
1000 B.T.U.I CF (60 F)
3000
r. :..
j"
2000
1000
. ,:}:-
zoo
400
600
800
1000
1200
1400
1600
184
1800
2000 2200
.~
~.
2400 2600
2800 3000
14
400
600
800
1000
1200
1400
1600 1800
186
2000 2200 2400
2600 2800 3000
,. ,
k
"
,;
t
~
.~
THE COMBUSTION OF
50 API FUEL OIL

15000
~=
..
12000
9000
,-
8000
I
7000
. -r-r--
6000
~~
l.';.
.,_ ~.,... ~: .....
.m:-. .::z::::
5000 ; . . ,
t:[
l-
4000
.
Ii'!
"
3000
.,
"'tt"
1-
.,..,
-+-
.,...
.....
.,~
;
~
-trt!
r- ..:
.,tl~
,
.;in
,;
2000
1000
200
400
600
800
1000
1200
1400
1600 1800 2000 2200 2400
186
2600 2800 3000
17000
9000
.,
,~
=-
9000
,-
7000
~.
---
6000
4000
3000 _ _
200
400
600
800
1000
1200 1400
1600
J87
1800
2000 2200 2400 2600 2800
3000
1000
200
400
600
800
1000
1200
1400
1600
188
16
15
14
111
13~
12~
"
101111
:
'"
9
8
7
rJiJf 'I I TI'li:r
5~~q;;$~;;:!fl!;:m;=;;'I;jj~
4
3 _ _
20
40
60
80
100
120
140
160
180
200
220
240
260
280
300
320
340
360
380
400
8<t
ill
II
"'"
o
o
<D
.Im
'"
o
MlW
'"
o
~
,,
, -
.j:
.'
t
. ti
j
....
t"
.,
'7:
1li
,.
~.
!.
<l
'M1Ii
..
r>
(/)
(/)
(/)
I i t~
J:
0-
a:
"
r;
W
0-
p~
<t
"
~I
.J
II
<D
:~
'1
,~.. 81
it
~ ,. ,u; ,
W
n!: ""0 I-wz :. ilL
~;
N
N
to
:I41
" T
::> 0
IIi!
1
1- 1
w w
r:,
't
a:
a:.
II
,
,-
.8
/ffil.
I.
I'
.I
I
...o
, ".
I
!
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1
I :
~~
mf:
, il!S
o<t
I i
,
i
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190
,
o
N
1fIt\;,1
!
o
--_._--
191
<t
~
(!)
IJJ
::J
..J
LL.
LL.
>-
!::
~
::J
0
Z
0
0
..J
<t
D::
IJJ
:I:
I-
o
o
"
...q
CD
192
Section 11
FLOW OF FLUIDS
Friction Factor
The friction factor for turbulent flow of all fluids (liquids and vapors) is
expressed as a function of a modified Reynolds number (DUS/Z) by the chart on
page 198 for both commercial pipes and smooth tubes. In the unstable flow region
between values of DUS/Z of 0.135 and 0.390 (or approximately 1000 and 3000
in consistent units for DUp/p.) the turbulent flow curves have been extended to
the stable streamline flow region. These extrapolated curves for turbulent flow
give maximum values of the friction factor in the unstable region and are
representative of the flow usually found in commercial pipes. For streamline flow
the pressure drop may be computed directly from either of the formulas given on
the chart, since the friction factor is incorporated in these formulas.
Pressure Drop in Commercial Pipes
To facilitate the determination of pressure drop for liquids in commercial
pipe" the charts on pages 199 to 201 were derived from the friction factor curve
and the formula for turbulent flow. The following example illustrates the application of these charts:
Exampte I. Determine the pressure drop for 21,800 gnl/hr of gasoline f1owin~
through 800 ft of standard 6-in. pipe. The kinematic viscosity of the gasoline is
0.60 cs and its specific gravity is 0.750 at 100F, which is the average temperature
of the gasoline in the pipe.
21,800
Q/D = 6.065 = 3600 gal/hr/m.

By following the dotted lines on the chart on page 200 as indicated for
~ 3600 gal/hr/in. to a kinematic viscosity of 0.60 cs, then over to the inside
pipe diameter of 6.065 in., the value of AP/S ~ .38Ib/sq in. per 100 ft.
Q/D
The pressure drop for 800 ft of pipe will be:
t:.P
0.38 X 0.750 X
~:
2.3 Ib/sq in.
Equivalent Lengths of Fittings

Data on the frictional resistance of fittings are usually correlated by the
equation Ah ~ Ku 2 /2g,where K is a constant for each type of fitting. However,
193
194
in problems of fluid flow it is more conycnicnt to express thesc resistanccs as

equivalent lengths of straight pipe for use in thc gcneral friction factor equation.
Since the latter is a function of Reynolds numbcr "'hile J( i" an independcnt
constant, it is nccessary to corrcct the equivalent lengths for variation in Reynolds
number in inverse proportion to the friction factor. In the table on page 202 the
equivalent lengths correspond to a Reynolds number of 10 and, for appreciably
different values of the latter, should be multiplied by the correction factor on
page 203.
Example (Liquid Flow). Kerosene at lOOF is being pumpcd at a ratc of
18,000 gal/hI' (gal/hr at 60F) through 500 ft of standard steel 4 in. pipe in
which there are eight standard elbows, one tee (side out) and two gate valves.
Calculate the pressure drop through this line using the friction factor curve for the
1I0w through the pipe and the "K" factors for the fittings; check the result using
the pressure drop charts and equivalent lengths for the fittings. The kerosene has
an absolute viscosity of 1.5 cp at lOOF, a specific gravity of 0.825 at 60F, and a
volumc cxpansion ratio of 1.025 at lOOF relative to 60F.
Q = 18,000 X 1.025 = 18,500 glll/hr at lOOF

U - 0.00680 X 18,500 - 78 f
(.1.026)2
-.
t sec
,..
0.825
SpeCific GravIty at lOOF = - - = 0.805
1.025
4.026 X 7.8 X 0.805
1.5
DUS
----z=
ti
168;
0.0052
P (. ) _ 0.323 X 0.0052 X 0.805(7.8)2 X 500 _ 0 lbl .

pipe 4.026
- 1.2
sq Ill.
.
fi
tiP (lttlllgS)
(8 X 0.45
+ 1 X 0.90 + 2 X 0.19)
(7.8)2 X 0.805
148.2
Ib/'
4.88 X (7.8)2 X 0.805
= 1.6
sq Ill.
148.2
= .
Total pressure drop = 10.2
+ 1.6
= 11.8 lblsq in.
Check
Uncorrected equiv. length of fittings = 8 X 6.6

Correction factor
(D~
16.8)
+ 13.2 + 2 X 2.8
1.1
Corrected equiv. lcngth of fittings = 1.1 X 71.6 = 79 ft
= 71.6 ft
FLOW OF FLUIDS
Total equiv. length
500
579 ft
18,500
.1.026 = 4600;
D=
tJ,:
+ 79 =
195
S=
1.5
0.805 = 1.9
2.5 lb/tiq in./lOO ft
Total pressure drop = 2.5 X 0.805 X
~~~
11.7lb/sq in.
Example (Vapor Flow). Propane vapor at 90F and an upstream pressure

of 20 psig is flowing through 800 ft of 6 in. standard steel pipe at a rate of 25,000
Ib/hr. Determine the pressure drop through this line assuming the ideal gas law
applies to propane under these conditions. At 90F the viscosity of propane vapor
is 0.0095 cpo
Thc following cquation for isothermal flow of ideal gases and vapors can be
derivcd by applying Bernoulli's theorcm to a diffcrential length of pipe and integrating thc rcsulting cquation between the limits, 0 and L:
gI?T(P,' - 1'2 2)
2MP,2 [/L
-
2m
I' J
+ In-'
P
2
where U 1 = upstream velocity in ft/sec

PI = upstream pre ure in )b/sq ft abs
P 2 = downstream pressure in Ib/sq ft abs
T = absolute temperatme-OF + 460
L = Icngth of pipe in ft
m = hydraulic radius in ft = d/4 for pipes
I = friction factor
9 = gravitatioual constant = 32.2 ft/sec/sec
R = ideal gas law constant = 1545
M = molecular weight
By substitution flnd rearrangement the abovc equation can be converted to a
modified form of the equation for liquids, or
tJ,P = P - P =
I
PI
+ In P24/P.
+ 1'2 [0.323 (If,
D
I
21'\
S U
1
'J
where PI, P 2 = upstream and downstream pressures in Ib/sq in. abs
S I = speci'fi c gravity
. 0f
l
vapor
re '
atlve
D = pipe diameter in inches
I,0
M1' I
water = 000
. 150 T
196
Trial and error must be used in the solution of the above equation since P 2 is
unknown. The friction factor, I, is independent of the variation of pressure since
the mass velocity term, US, in the Reynolds number remains constant, U varying
inversely and S directly with the pressure.
D = 6.065 in.
S = 0.00150 X 44 X (20
90 + 460
Density
= 0.00416
X 62.4
+ 14.7)
= 0.00416
= 0.259 Ib/cu ft
U 25,000 X 144 X 4
_ 134 ft/sec
, - 0.259 X 3600 X..- (6.065)2 DU,S,
6.065 X 134 X 0.00416

0.0095
= 355; f = 0.0031
For the first trial assume P 2

Ii P =
= P,
0.323 X 0.0031 X 800 X 0.00416(134)2

6.065
9.
9 lb/
sq tn.
For the second trial assume P 2 = 24 Ib sq in.

liP = 2 X 34.7 [0.323 X (0.0031 X 800
6.065
34.7 + 24
=
1.18[0.323 X-(0.409
+ 0.015)
+ 0.37) X 0.00416 X
(134)2]
24
X 74.5J
12.1 lb/sq in.
A third trial would give a liP of 11?,4 lb/sq in.

In this example neither the initial velocity nor a contraction loss from a
larger vcssel into the line was taken into account. If thc propane vapor wcrc flowing from a drum into the 6 in. line, it would be necessary to calculate an initial
pressure drop as follows assuming isothermal flow:
RT In P /P
01
M
= U,2
0.5U,2
2g+2g
The first term on the right-hand side is the velocity head, and the second term
is the actual contraction loss due to friction.
If the available head in the drum, Po, is 34.7 psia, PI is determined by trial
and error and for the first trial U, is assumed to be 134 ft/sec.
In Po/P,
1.5M
2
2RTg U,
-6
1.2 X 10
U,
In PO/PI = 1.2 X 10-6(134)" = 0.0216

PO/PI = 1.022
PI = 34.0 psia
FLOW OF FLUIDS
197
Since the differential is so small, 0.7 lb/sq in., a second trial is unnecessary.
If this loss had been considered at the beginning of the example, the latter would
then have been based on an upstream pressure of 34.0 instead of 34.7 psia.
GENERAL REFERENCES
Beij, J. Research Nat. Bur Standards 21, 1 (1938).
Chilton and Colburn, Ind. Eng. Chern. 26, 1183 (1934).
Crane Company, "Flow 01 Fluids Through Valves, Fittings, and Pipe" (1942).
Drew and Genereaux, Trans. Am. Inst. Chern. Eng. 32, 17 (1936).
Foster, Trans. Am. Soc. Mech. Engrs. 42, 647 (1920).
Gourley, Proc. Inst. Civil Eng., p. 297 (1910, Part 2).
Karl' and Schultz, J. Am. Soc. Naval Engrs. 52, 239 (1940).
Schader and Vanderlip, Cornell Univ. Eng. Exp. Sla. Bull. No. 130 (1935).
Walker, Lewis, McAdams and Gilliland, "Principles 01 Chemical Engineering," pp. 71,
87-89, McGraw-Hill Book Co., New York, N.Y. (1937).
0-+,
t1lt:r
... tt
:M1
'11'
!".
. ,
t,t
'l'
nt' I~"rr
Tl
,
T-
.,
'"II'
I:
H
lU!-
FRICTION FACTOR
FOR FLUID FLOW
t r I H+ 1+
I
ffi1'i3ii ~ :e:: j~;; .f:: : " i l l . Uij H Ii1I ni 'Iii HL
....
, ... ",. , ' . "
[""j
IliI '"
.I
:::.
,-"~, :.:: .':' -+ I I I' I'
~J' I
"'I,tt''
I.fflJ. .:'II'1r- ."
.. .....
+, +.'1
'j!~ EIII11.:ll'f:t11+
::t:
rt::lJ'Tltl!.
!Wi If1
r : f"
IP =I+ -IH-H
R~
1
r FffllHll +h Ih,j rtiH
"
1',-
"1ffilIrlJ ~ ~f,=
'
'-
~,rfl;';;r,:~~
.:;::;.+:: -,' .~ . I~
t
~i
nn
1m'
1
, 0'" -...
-.
I.
,ft
1il
I.
:;:':'-'1:s}~~ij.L:::
"" +~;: 'I"
rm'
,I
I
..q.;
11
rt,
Th l'
-'
I'"
1-
-f
-,
.1-
"-=,:"W.l.l':'-'
t"1-:
1 1'1,
r-..,
t-t+t Hf-l llt-t+
~t
++r-i-
I.
U
,005~
rl
. , 4,
:-U..
:rr
r-tr
.3
~
~
J;
#t
1
.,l
~'
'1"
010
+I--t~;r :j
Ii
H!
t-
.6
1.0
'j j31'
illJ E
003
REFERENCE,
2.0
3.0 4.0
,006
004
I -
'R+f
.008
005
.,' Il'
..,
....
.4
,1'1 _.
''11'J
"~'i-llll~ tHHiJI !i,'' ! T

iii :twrp :! Hi; II '
.. j.
iJl ,-', I mr fH-' t;ttf-i:: .., I
h, ;::1:1:1: ml 'jn
.2
II
liT'
.J
.004
~iil'
+1++ Ittii HW+++

+, I-"~
rilmW It:t ii~! 111 :s.j 1: ;j:::l ;!lr i~Hm! ~i~~
"!lill!
. '; n" --r 1!=Rf"" ! i i ': :l~
; ~
~f4
1 ...,.....,~_
.006
SDS
Z ~ ABSPLUTE VISCOSITY IN CENTIPQISES

S ~ SPECIFIC GRAVITY RELATIVE TO WATER
L ~ LENGTH OF PIPE IN FEET
Q~ QUANTITY OF FLUID IN GAL.lHR.
W' WEIGHT OF FLUID IN LBS.lHR.
U ~. 006BO Q /0 2
~.000816 W/SD 2
f!l-UI,
I .,.,
ttT
, ; .;_i 1,,Ii
::1
05
WHERE
Ll.P ~ PRESSURE DROP IN LBS.lSQ.IN.
0' PIPE DIAMETER IN INCHES
t
eM
'1.495 X IO'5fSQ2L
D4
U ' LINEAR VELOCITY IN FT.lSEC.
I'm" 'jj'm
I
.. "n.
N,-H 'I""r
t-,
n
t'
+-t.(.
-0-
~2.15 X IO'7r W2 L
1 ' . 'it. 4"H-"" H'II:
jj'
.. -.;~:.
rf
:.:,,'
",. "
~'-Il.:r:::
. ~
. .::.
XIO'6ZQL
;W:
-~. ~iJ:1i;i: l~T:n:_iJft-fm:1?
.c ..;..' . ,,~t'
"'I',-,mt~n
I,.,,,c~l'
".'.;.
J
I I,b
-I-
++
.I
'~I
Ll.P'.323f SU 2L
"[5Z
~ ~~ Ui1 ~::; ~ ~ ~ ~'l~lllii~ :,': illi"

l\$f.!ji; oL4'ii ,'i:; j~:, ".' lj
'+!.i 11'.' t; iE: !I r r: ii Iii;
.006
.002
'
Ll.p, 6.68 X 10'4 ZUL

~4.55
'"
.010
.-,
,'ll"t-t,h
",,1+
hr
003
,
'I
'
TURBULENT FLOW
STREAMLINE FLOW
,til~,
'il
'
l'
+,
"+t.
-..
PRESSURE DROP
It"
l I t
Ti
~
~ J~'~lll~I~~ ~~~I~
~FrFi 1+U {l+! lfin .n I j HWi

11111'"
Iq,~'il" l'ii:'1
I -m-1. ,11: .1.:h . ,n
:"1'
~ IN CIRCULAR PIPES
'I
,1~'1:l: T 1 j ., ,,~
~"I+ 1
~h
. 11
i'
fHllh;; " 1 - .
rnnffi.,
+ i
l_
'*H'i
~-1,
DREW AND GENEREA~,)('
6.0 8.0 10
20
1111=lllllwmlm~~il,002
Cli,Wo1:
'fil~S", PM .JNST.
40
60
80 100
EN~,
32,
200
000 400
17 (19361
600 eoo
-C>P'PRESSURE DROP IN LBS./SQ.IN./IOOFT.

D' ACTUAL INSIDE DIAMETER IN INCHES
Q' QUANTITY OF FLUID IN GAL.lHR.
Z' ABSOLUTE VISCOSITY IN CENTIPOISES
S' SPECIFIC GRAVITY
Z/& KINEMATiC VISCOSITY IN CENTISTOKES
li~rPRESSURE
,:n
I .J
I J I I
h-i-rll i dli II ill 11.11. i Ii ITTn1l11t11
DROP IN COMMERCIAL PIPES
rr- I .
HI
TURBULENT FLOW
~n~:
+~
"X:I~,::.
II-Icl=q.,
. ;'~"'::ttt1:..r.
~z
STREAMLINE FLOW
""""54
Tl
+0:
"ir
~-r-----"-'+
",-
T'"
.1
"
~.
,... -.If 1 -1-+ 1-..
-r7trt' '1---/' ,
;'1
-.r.
I'
.- , - -
-!-, ........
'- -'-
r.
I.
.-
'W'rl"<'
.J
...
, .r
'-"''''''71,:-
'-rJo" ....-
-'
"r.'tT,
. -~~r'"
r: ~
~
"I"f-
"
,4_
l"
t,t:'!:
r~'
''''
."
j.'r:-'"
:~
..
~::-..:--:
fl-
1 H
~~I
100
200
-iT ti~
..
XiI E;il5 -'i....
.. . .
-r -
"
;\'1
.6
.8 1.0
2.0
f
, I
.3.4
II
500
--
.....,.
,..7-';t..Y;.
I-'f:" F ~L:D~-~f-. ' - , ,

~_
~~''''*''
i 1:"
- .,. '.,til R-t:J
m:
'I': ..~-'1i: :::1 ,
'~I"
I,
L.
-~~~'~';;1l
:~-c:-:.:.~
_.-~
~....
"I
lr
---/,",
''-'
"':~=-g.
...,.T-
_~_
CO'
II
50
'1+;
~'-~,"
m-r.
.H-
rI
IYf
I"
~.
OJ
IIII
~
...
r:.:: -.
, .; tm:
,-_.
J,
......
l- ~.
'"
,.
liE#hf:7.Ht:-
'-l.
co
co
t,v.t=L
3.0 4.0
6.0 8.010
20
' t':!.+,
,
30
~.
40
60 80100
.:I.P= PRESSURE DROP IN LBS./SQ.IN./IOO FT.

0= ACTUAL INSIDE DIAMETER' IN INCHES
Q: QUANTITY OF FLUID IN.GAL/HR.
Z: ABSOLUTE VISCOSITY IN CENTIPOISES

S' SPECIFIC GRAVITY
ZIS- KINEMATIC VISCOSITY IN CENTISTOKES
..
"
,,"
.,
PRESSURE DROP IN COMMERCIAL PIPES

TURBULENT FLOW
STREAMLINE FLOW
.:I.P'4.55 X 10-4 ZQ
04
TOr
~I,
...,
8
11
~dIt
~l"
..
rm
\.
~
1000
2000
5000
.2
.3
T?
.6
",
.8
1.0
4.0
6.0 8.0 10
60 80100
5'.. ; ....
~:.'
./lop, PRESSURE DROP IN LBS.lSQ.IN.lIODFT.

0' ACTUAL INSIDE DIAMETER IN INCHES Q'QUANTITY OF FLUID IN GAL.lHR.
'.
Z 'ABSOLUTE VISCOSITY IN CENTiPOISES
S'SPECIFIC GRAVITY
Z!S'KINEMATIC VISCOSITY IN CENTiSTOKES
.' +:- ......-r.
~I~ .... t--r---t-t-~I T.-'
",~,-,
PRESSURE DROP IN COMMERCIAL PIPES

TURBULENT FLOW
~I'
_ ... J
Ii
r_l""iJ
.,...1"'"
STREAMLINE FLOW
AP'4.55X 10-4ZQ
04
TTj'l'n.
'-"ft,
.Y~,
~,
J
I
~
~=-Y~ ~;:;,~~A.J,.;I
"En"'"
1i1!;i..
0
a'"
~
TJTf"I:t1fwm
I
I
,
'~".A~
,n
t;
=-
i
"='
:=
''''.1ffl
5000
10000
50000
.2
.3
.4
.6
.8
1.0
8.010
40
60 00 100
EQUIVALENT LENGTHS OF FITTINGS

Pipe size -
Equivalent Lengths' - Feet
Incbes
Elbows
Vah'es
1.D.
Tees
Dends
Nominal
Inside
Diam.
0.0.
Standard
Extra
Strong
Globe! Galc
-- -.WKt 10
Stanrlard
Long
00'
Sweep RID = 6
----
45
= 1.5
Close
Return
= 1
Side
Out
End
Out
Run of
Standard
.25
.21
.75
.no
1.3
.30
0.4
07
o.n
1.1
03
0.6
0.7
1.0
0.3
0.5
0.6
0.8
1.0
1.7
2.3
3.9
1.2
2.0
2.7
3.4
1.7
3.0
3.9
5.0
0.4
0.7
0.9
1.1
2.6
3.4
5.0
6.6
1.8
2.3
3..4
4.4
1.5
1.9
2.8
3.7
1.2
1.6
2.4
3.1
4.4
5.7
8.4
11.1
5.3
6.8
10.1
13.2
7.7
9.8
14.6
19.1
1.8
2.3
3.4
4.4
29.
38.
48.
.45
.30
0.3
0.4
0.6
0.7
4.0
6.8
n.o
II .5
0.6
1.0
1.3
1.7
17.6
23.
34.
44.
0.540
0.810
1.050
1.315
0.364
0.622
0.821
1.04n
0.302
0.516
0.742
0.n57
1)1
2
3
4
1 !l00
2 375
3.500
4.500
1.610
2.067
3.068
4.026
1.500
1. 93!)
2.!l00
3.826
59.
75.
ll2.
147.
1.1
1.4
2.1
2.8
6
8
10
12
6 62.5
8 625
10.75
12.75
6.065
7.981
10.020
12.000
5.761
7.625
9.750
II. 750
220.
290.
360.
440.
4.2
5.5
7.0
8.3
66.
S7.
llO.
131.
10.0
13.1
16.5
19.7
6.6
8.7
11.0
13.1
5.5
7.3
9.1
10.9
4.7
6.1
7.7
9.2
16.6
22.
27.
33.
1!l.9
26.
33.
40.
14
14.00
16.00
18.00
20.00
13.25
15.25
17.18
19.18
480.
560.
630.
700.
9.2
10.6
11.9
13.3
145.
167.
188.
210.
22.
25.
28.
32.
14.5
16.7
18.S
21.
12.0
13.n
15.6
17.5
10.2
11.7
13.2
11.7
3(; .
42.
47.
53.
44.
50.
63.
56.
82.
91.
)1
""o
""
13.3
23.
30.
38.
Angle
16
lS
20
The equivalent lengths tabulated correspond to a value of

on the opposi te page.
XC;,
S
KC;'S
pP=-X- =-2q
2.31
148.2
: For swing che('k valve, usc ~~
or globe
D~S
valve equivalent lengths.
J)[''i
63.
57.
72.
6.6
8.7
11.0
13.1
14.5
16.7
18.8
21.
10. For other values of - Z:"" , apply correction factor from the chart
CD
~'I
..
:. t 1I-
.1. I
--l
It
l-
Ia::u.
0u.
O
. t"T -
1. ~
i~
-'_.
l~'
r~!-t
T':
It-t - T t l ' '
;::
,i~; :~jl:
r"--' "-r
"... ..
..,
l.m='O,::I,'",: I':; 0": '.1'
.-...,.- ,... -. .. r-~
....... '4tc '"
~
::r -:!;-! 4tt~ ::!.
~.
I.
Lten
::I:
Zl-
O~
.
,
1""";
+,
,+ ..
+"I! .,
jIll
: .: :-4 ~
ill! iJ.l '
O...J
I-W
O...J
a:: Ia::Z
OW
1"
It)
~.
,
ri=-
..I
ili!
'u
...j.
;'
..
'(,
It 'iI'
!!Ii i .. ii; i
'II'
1 jI!
"I
'I
l1
"
hit
r:-, "
'1
l,'
::>
LLl
-t.; j
C)
tt
! ;
::j
J I,
en
+1
"'
II. ~
Ii
' It- "
ti
:f
H'! I
"
;f
.,;
H'l I
.,
.f,
'h
.,'
litf
I,
1 i,
I
.;:
1I~
iii!
,h
II
'~
ir!,
:]11 '
n
4
I 'J H
i I" !.
j".t
."
ljo.
It)
},
,-,
'1' I
,
if!
'!..:
ii~
,tH
j.j
'"
'"
0
r<'i
203
'"
FRICTION LOSS DUE TO SUDDEN

CONTRACTION AND ENLARGEMENT
TURBULENT FLOW IN PIPES
LOSS DUE TO CONTRACTION
LOSS DUE TO ENLARGEMENT
(U2)2
Fe' K64:3
(U,-U2)2
64.3
A2'
F
K
U,
Ue.
DOWNSTREAM AREA
FRICTION LOSS, FT. OF LIOUID
FACTOR FROM CHART
UPSTREAM LINEAR VELOCITY - FT. / SEC.
DOWNSTREAM LINEAR VELOCITY FT. / SEC.
lip PRESSURE DROP DUE TO FRICTION
LBS./SO.IN.
LOSS S SPECIFIC GRAVITY OF FLUID AT
TEMPERATURE UNOER CONSIDERATION
.4
.3.
.~
.2
.~-
:: :.T'/.
,.
-'- .
. WALKER. LEWIS. MC ADAMS ~D GILLILA~D. 'PRINCIPLES or CHEMICAL ENGINEERING.

PP.
8789.
MC
GRAWHILL
BOOK CO. (1937)
u.
r.
. ..
l-!r..
0
y..l~:'
:t '-I:
.1
.2
.3
.4
.5
.6
.7
204
.8
.9
1.0
_7
2.
DISCHARGE CHARACTERISTICS OF
RECTANGULAR AND CIRCULAR WEIRS
3400
6000
1
'
3200
"
3000
2400
2200
.2000
1800
1600
1400
1200
1000
800
600
400
200
7 0
205
.01
04
.02
.3
.45.6
.6
.03
.02
610..04
REFERENCE,
COLBURN.
IND.
ENG.
CHEM.
26.
.03
1183 (1934)
.01
01
PRESSURE DROP
ACROSS TUBE BANKS
.006
.005
Ii .....L.,. N""('- ')2'(~)
. 004
liP' 3B90
GM
Os
.008
006
005
f'
.003
"")' FOR TUBE ANO SHELL HEAT
MULTIPLY 4P BY A BUNDLE
FOLLOWS;
0.'0 FOR SQUARE-TUBES
0.40 FOR SQUARE - TUBES
EXCHANGERS
FACTOR AS
.002
IN LINES
AT 48
GM IS EVALUATED AT CENTER ROW OF TUBES
.01
..001
.006
.006
.004
.003
__
"
.002
'
.001
.001
.0006
.0006
.0005
.0004
.0003
.0002
10
006
liP
:: PRESSURE
0006
0005
,DROP ~ LB./SO. IN.
N 'NUMBER OF ROWS OF TUBES
S
GM
Do
GRAVITY OF FLUID RfLATIVE TO WATER t
0004
,MAXIMUM MASS VELOCITY' LB'/SEC./SQ. FT.

(THROUGH MINIMUM FREE CROSS-SECT. AREAl,
.0003
:: SPECIFIC
1.
:: OUTSIDE TUBE DIAMETER INCHES

1~
::; MINIMUM CLEARANCE BETWEEN TUBES-INCHES;
Os
f' 'FRiCTION FACTOR FUNCTION
ZF -; FILM VIS'COSllY - CENTlP<XSE$
20
30 40 5060 60 100
0002
200
300 400
206
600 6001000
Section 12
FLOW OF HEAT
18
Heat Transfer
The film transfer cocfficient for liquids flowing inside tubes (page 211) is
based on the Sieder and Tatc corrclation l which is generally acceptcd as the
most rcliable for this type of hcat transfcr.
Thc chart on pagc 212 for the outside film coefficien~ for flow across tube
bundlcs was derived from a corrclation by Chilton and Colburn 2 with thc consistent units in the dimcnsionless terms replaccd by more common units. Comparison of limited data with this correlation has indicated that the film coefficient
should be multiplied by the "bundle factors" given on the chart when GM is taken
as the mass velocity at the center row of tubes. Kon-uniformity of flow and
by-passing bctween the tube bundle and shell appear to bc the principal reasons
for this diffcrence.
Thermal Conductivity of Petroleum Liquids
)8
)6
)5
)4
)3
)2
Attempts to correlate thermal conductivity of petroleum liquids as a function

of gravity in addition to temperaturc havc resulted in contradictol'y trends with
API gravity.3.4 In view of this inconsistency and since Smith 5 has shown that,
at 86F, a single value represents the reliable data belter than either trend with
gravity, the relabon for the thermal conductivity of petroleum fractions on page
213 is shown as a function of temperature alone. This chart may also be used for
pure hydrocarbons, although the data on low-boiling aromatics arc about 1070
higher than the curve.
Thermal Conductivity of Hydrocarbon Gases
As most data on the thermal eondueti"ity of hydrocarbon gases were obtained
at room temperature, it is was necessary to find some means of extrapolation to
higher temperatures. This was done by using two different methods: (1) assumption that the Prandtl number is a constant independent of temperature and
(2) employment of Sutherland's equation. As the results of the two methods
became more divergent with increasing temperature, it was a question of selecting
either one or the other or using an average of the two. An average was chosen
I Sieder and Tate, l1ul. Eng. Chem. 28, 1429 (1936).
2 Chiltonllnd Colburn, Ind. Eng. Chem. 26, 1183 (l934).
3 MUic. Publication 01 Bur. Sta>l(lards, No. 97, 24 (l929).
4 Kaye and Higgins, Proc. Royal Soc. 117, 459 (1928).
5 Smith, Trans. Am. Soc. Mech. Engrs. 68, 719 (l936).
207
208
since, while it was felt that the Prandtl number was probably more relia~le, the
Sutherland equation gave lower and consequently more conservative values. In
view of the uncertainties of these extrapolations any refinement beyond the use
of a straight line was unwarranted. Consequently, the chart on page 215 gives the
thermal conductivity of hydrocarbon vapors as a linear function of temperature
for various molecular weights.
Logarithmic Mean Temperature Difference
In the transfer of heat between two fluids, the log mean temperature difference
applies to flow that is either entirely countercurrent or entirely concurrent. nder
conditions where there is a combination of these two types of flow, such as a heat
exchanger with more tube passes than shell passes, Nagle 6 has shown that a
correction factor should be applied to the log mean temperature difference. This
correction factor is given herein by either one of two types of charts, the first
on page 218 and the second on pages 219 to 221. The chart on page 218 may be
more convenient to use when the factors R and A do not approach unity. If these
factors arc near to unity, it is necessary to use the other charts. The following
example illustrates the application of these charts:
Example 1. Determine the correct temperature difference and the number of
shell passes required in the heat transfer between two fluids having the following
inlet and outlet temperatures:
Shell side: T I (inlet)

Tube side: t l (inlet)
R = TI
=
=
-
t2 -
m =
t2
TI
400F;
275F;
T 2 (outlet)
t 2 (outlet)
=
=
300F
320F
T 2 = 100 = 2.22
t1
45
tl
45
= - = 0.36
tl
125
From the chart on page 219, it is seen that one shell pass is insufficient since
F is close to O. With two shell pa scs F ~ 0.90, and this arrangement would appear
to be satisfactory.7 The corrected log mean temperature difference is:
0.90(L.M.T.D.) = 0.90 X 47.3 = 42.6F
The solution of this sample is also illustrated on the chart on page 218.
6 Nagle, Ind. Elly. Chern. 25, 604 (1933).
While other faclors may enter into the number of shell passes selected for a given
design, allY arrangement which results in a correction factor of less than 0.80 should be rejected.
7
HEAT LOSS BY RADIATION
3.8
3.6
3.4
3.2
3.0
COEFFICIENT
EMISSIVITY
Of
MATERIAL
IRON OR STEEL
BRIGHT
OXIDIZED
HIGHLY OXIDIZED
COPPER
POLISHED
OXIDIZED
BRASS
BRIGHT
DULL
.20-.35
.60~70
.90-.95
.10
.70
.07-.10
.25
ZINC
BRIGHT
.10
DULL
.20
ALUMINUM PAINT
.50
NON-METALLIC SURFACES
BRICK,WOCO,CLOTH
PAINT .95
2.6
1.8
THE VALUES OBTAINED FROM THESE
CURVES ARE FOR IDEAL BLACK BODIES
AND FOR OTHER MATERIALS MUST BE
1.6
EMISSIVITY.
1.4
1.2
1.0
.8
100
200
300
400
209
500
600
HEAT LOSS TO THE ATMOSPHERE

BY NATURAL CONVECTION
,1
. I ..
1
1 ,
.T
t
I
" , 1
.,
1.6
1.5
1.5
l4
1.31iiJ
1.4
E
!
-.
..
lt
~~tl,
'
:,If. ~
"f".
,-:"":J:>
--., in !~J:r
.. , ,
-,
,, I ,
~t
I
.5
At"
.4
.3
.2
,
.tt
_J
t _.-
:F _
~
!f
.- ~l
:1
, t,
1:
.. _
-::
'"
Ilmlli
:~i
., 'IT"
Ii
;-rr.- ....
.i';":+
Ttl-
r::i+ tH .
!'~ ~
Hi
.r~t
-:..
(n1:i ~i
:1. ,.
200
itt
'I'
.;.
'!
~J::J-'
:Hi
1i
...
"
'
_PP.
100
" >I: ,Itij

""'!'.
VALUES FROM THE CHART ARE TO

BE MULTIPLIED BY THE FOllOWING
SHAPE FACTORS:
1.3
VERTICAL PIPES
1.3
HORIZONTAL PIPES
1.3
VERT ICAl PLATES
HORIZONTAL PLATES
FACING UPWARDS
2.0
FACING DOWNWARDS
1.2
M4.
1'1:.'
.._'1, '-1,
ri' 1,'
-f 1-- ._.~ ~i~ ."., 9
~il ltt. :{-E
ipi ~
t
.-
_ %'f~~fl.il 1m lit
i ~i Ilr, ~
u.3:1
I'''''':''.t
t
I ' - ...
t'
llIIJ;J
'+
1.0
':*., ::It:
:!~i
i1T!
t
I"
'-'1
1 ,
1.1
in
. I
rtt ::tl::'
H+
,t.
-.
!tt.,
T1
, '.';!'
."
-t.
Wlei,
-~.~
HEILMNI.'TRANS,
.1
~::
..
. t"
l
l'r. fl: ;'rittl
.. (, 1-" ~"..Jl' ~f
.7,
,
~
,,
1.2
1.0
.6
,f!
I
,..
.8
,-
., .1
1.1
1.3
- .
1.2
. I,
400
210
500
4
3
soc. MECH. ENG. 51, 287 (1929)

240241. MIC.GmR~~W~'~H~ILiLIIlO~onKdCjOi'tt(~'rn9~42~)~11
300
600
2000 30004000 6000
, ,
!
I!
..
r
,
I' i
ItB'F
+J ' '
f1:,
;J'
II
f'+H+H
HEATING AND COOLING
...
,11
I t
111lJjtl"
Ii
l,
d 11'1:1)
- .--1:1
:II!
1,I I
l-
'poo
800
-I
Ii! II,"; I! ]
1'1 ,Ii!
I,! II,Ii-
_.
rm
_',
I I ;
III
1.
,.
SpOO
eu5,ooo
'I"
'
4,000
I'
,I
II
Iii -
: 'I '
r , ii llil
I,
40000 GOOOO
,1
20000
1,
'1.1 II "'I. 11 r H
IOPOO
8000
,10000
--
,', ..,
1~r1":
-t~1~~':t~ 1"im!m::lmJ'i:!~jl-f1:;Ifm~-:HI4~Hg-::I;lr!m,jI~;1l#iR'~: :ljli-i'-~8!1-~mt'+'H-,mf-~H-hH~l-:l~1I'f+~;W"''!~~:I,i!j~,~:! ~,~'~'~i:~;i~~!;Hi~:I;t-mffi~liTtm~lllffi -
:- ::1 H::!:ii 1 ~j I Iii

. "r~.. 'II-++J1+HJH+-\-H-j+i+l-r!-+-HtH-l-H-H-8If.lll+I+++I+H+f-'--H+!A:, '1I',"P!
r
100
I-t+t"
,t" lli;l
' I
80 ,.,
"
60
j)-
50
40
Ii'!
I'
","
1+"
.\+
_: ~
IIW
'I .iJ.rlI(i, j.rH
i,' il?
II,
*I!iii
t.
...-r' .,.
l.J..
',/1
""Ii'
t
\'
h = K (CKZ)
014
3(ZZW)
tiI_
(OZG)
, . . . ,:\_
"WI!' 'oJ "lll
1111
0
300
I'
I:t
_j_
I-t lU fit1 "':,.i.f' 'I, Jl.

I I, L' :.J'
:;)0 1+ I I II!!
.. -r- II , :I I-i
i,
, 'I::
,. , .
U:- ITfW1 ,;; ,!:;.-H-;

I~ n- ,::. ~"",n
30
, I< . " " ... 'i"
+'1: :;
0-
.:
SPECiFIC HEAT OF FLUID AT AV, FLUID TEMP.-BT.U./LB.I,
~ <::. i _::, :::: l:~: 0;:: ~ I+~ .

t Z =ABSOLUTE VISCOSITY-CENTIP()SES AT AV. TEMP. OF FLUID
20 ll'f:.:.;.; 4;:, ;, i: iii I::: ; II:
r .Til! 'ZW'ABSOLUTE VISCOSITY-CENTIPOlSES AT AV. TUBE WALL TEMP.
, iil"/ "~'I'ili!iril'I:Il;!'! II!: ".iUI HI! .l'i1I:!'I!1f:l:-:,:I::;:I:'.;.III:I':"-O:::J.,.rmillUCllI=II:liI:Jlilll::l-T
l+H:tt'ti'rtJ-I'
':
,I "I.! .;. REFERENCe:
S I EDER AND TATE, I NO, ENG, CHEM, 28, 1429 (1936)
/0
ilJI, iili
2
[ I!;j Iii: 1111111

3
5 6
fiiUH1il~!Jl~il!H]liWltnrilllfH-'-lmrllllllif.lrrm
10
20
30
211
40 50 60 80 100
200
100
80
60
50
40
G,MASS VELOCITY -LB,/SEC /SO.FT.
C'
200
I' 0' INSIDE TUBE DIAMETER INCHES
600
500
400
f ; 'rlt" h = FILM COEFFICIENT - a.l.U. /HR ./SQ. FT./ F.

I :)-r:-/" K' THERMAL CONDUCTIVITY - B.T.U.!HR/SO. FT.!(OF PER FT.l
:. ~
, ' , L :HEATED TUBE LENGTH fEET
. II"
j.:
-t-
04'
iIll .
--
-Ttl!
Fcl!-i'IIi+!-1:.'-P'-;.'f,lfH1!j-'
300400
30
20
GOO 800 1000
10

10
60
80 100
200
300 400
600 8001000
2000
4000 6000
8000
1000011
8000
6000
~~# t~.:H:H. :~ ~;;1 l:-=l:
~
I'
5000 CH 1LTON AND COLBURN. IND. ENG. CHEM. 26. 1183 (L934) ...,i::rn:;- LiC
4000
.,: -j- ....
t::l -':" -r- .. , ---,..--<--
-r
6000
5000
::t"
lEEEIEEm]4000
HEAT TRANSFER TO
FLUIDS OUTSIDE TUBES
3ooo~mWi
3000
=-crlffil2000
1000
800
600
500
"'0= OUTSIDE FILM COEFFICIENT O:r.U./HR.lSQ.FTjOF
400
K :: THERMAL CONDUCTIVITY OF FLUID atU'/SQ.FT.!HR./(OF PER FT.)
300
C ::;
00=
OUTSIDE TUBE DIAMETER - INCHES

SPECIFIC HEAT OF FLUID - 8.T.U.lLB./F
Zr::; FILM
200
#jffitl1ltm 300
VISCOSITY - CENTIPlEES
.200
{THROUGH MINIMUM FREE CROSS-SECTIONAL A~EAl

- +J-'-
111,00
80
60
50
-. -i
40
MULTIPLY he BY A NeUNDLE FACTOR" AS
30
FOLLOWS:
o.~o fOR SQUARE PITCH - TUBES IN LINE
0.55 FOR SQUARE PITCH - TUBES AT 45
10
.01
.02
.03 .04
.06 .08 .1
.2
.3
212
.4 .5.6
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5 6
20
8 10
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o
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~-88
8 8
-""
'"
\00
200
300
Xl
500
600
700
800
900
1000
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"
_,::-r
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i
oj
:tl
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.39
-"'f
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.33
,t
THERMAL CONDUCTIVITY
OF LIQUID WATER
.34 -
d
I
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.1.
..
,35
1
l
,~
,3 I
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.'30
t
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.28
,
I.
.27
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'I
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.26
,
o
.,
,
.25
BEALE. 'THE SCIENCE OF PETROLEU M' VOL. II. P, 1261, OXFORD UNIVERSITY
PRESS ( 1938)
.... HH
,
100
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300
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216
LOGARITHMIC MEAN TEMPERATURE DIFFERENCE

100
100
90
90
80
80
80
70
70
70
60
60
60
55
55
50
50
... 45
5 40
45
55
w
50
!i
w
::i
45
40
w
~
35
90
40
35
..
35
w 30
<l
30
~
a:
,:"
30
100
<3
Q.
25
20
I.'
25
25
20
20
15
15
10
10
10
...zw
~
:IE
J:
t:
a:
...
'"
15
..J
M.T.D.:
.0.TI- ATz
LOG
.o.T,
E ATZ
WHEN Ll.T, AND Ll.Tz ARE NOT WITHIN THE CHART RANGE,
THESE VALUES MAY BE MULTIPLIED BY A FACTOR, AS 0.5,
2,10, OR 100. ETC.
FOR EXAMPLE:
GIVEN Ll. T, (ACTUAL): 200, AND Ll.TZ (ACTUAL): 20.
USE 0.5 AS FACTOR, AND Ll.T,' , '00, AND .Ll.TZ: 10.
FROM THE CHART, M.T. D." 39.5
OR M.T.D. (ACTUAL): 0'.5 X 39.5' 79.
REFERENCE:
217
POWER PLANT ENG. 35. 937 (1931)
.02
...
04
.06 .08 J
r
'1" I
LOG
MEAN TEMPERATURE
DIFFERENCE
CORRECTION
,,,
.2
,'"
.3 4 S .6 .7.8.9'
iJ+;:rorh; l,m
5 6 7 ~~.IO
-_....,r,
:;:C:I
20
IIIIIII
'-~~1
FACTOR
,H
:~
t.:>
~
""
:1
T
EXAMPLE:
.t
T2'300 T,'400
" '275 '2' 320 .
A' 300-275
400-320
, 0.312
TI :: TEMPERATURE AT WHICH HOT FLUID ENTERS

T2 ' TEMPERATURE AT WHICH HOT FLUID LEAVES
t l TEMPERATURE AT WHICH COLO FLUID ENTERS

'la II TEMPERATURE AT WHICH COLD FLUID LEAVES
F
II
CORRECTION FACTOR BY WHICH

MULTIPLIED
L~.T.O.
jf!
I
.01
.02
.04
D6 .08 .1
.3
.4
.6
45678910
29
IS
10.0
9.0
I SHELL PASS
ao
2,4,6 ETC. TU8E PASSES
2 SHEL L PASSES
7.0
6.0
5.0
4.0 3.0,
"
i
2.0 -
1.0'11
0.9~
0.8.
0.7t'lJI:Mm
0.61;1;
0.5
0.411
0.3
0.1
0.2
0.3
0.4 OS 0.6
0.8
1.0
219
02
0.3
0.4
OS 0.6
0.8
1.0
3 SHELL PASSES
4 SHELL PASSES
4.011"
3.0 ".
0.2 "
0.2
0.3
0.4
05 0.6
0.8
1.0
220
0.2
0.3
0.4
05 0.6
os
LO
I~.~ m~mw'''''""~~~~:HE~L~L:=;P~A;SS~E~S~~
8.0 :
7.0
III~
10,20,30 ETC. TUBE PASSES
6 SHELL PASSES
12,24,36 ETC. TUBE PASSES
JmllM
6.0111
5.0
4.0 lttlHtl+ltt
3.01fm~m
2.0 ~FfHtttl*
119331
"
0.1
02
03
0.4
Q5 0.6
08
1.0
221
0.2
0.3
04
0.5 06
0.8
1.0
Section 13
EQUILIBRIUM FLASH VAPORIZATION

The vapor-liquid equilibrium relations for hydrocarbon mixtures of known
analysis can be determined by trial and error from the equilibrium relations of
the individual components and a material balance. For any component, i(i = 1,
2 .. , n) ,
(1)
Yi = Kixi
and
Xi = xiL
+ y;(100
- L)
(2)
where Yi = mole fraction of i in the equilibrium vapor

Xi = mole fraction of i in the equilibrium liquid
Ki = equilibrium constant of i
Xi = total moles of i per 100 moles of total mixture
L = moles of equilibrium liquid per 100 moles of total mixture
Substituting Kixi for Yi in equation (2) and rearranging
Xi
Xi
= -L-+--'--K-i ("--l'""""OO---L-)
(3)
At equilibrium, the sum of the mole fractions in the liquid phase, x, + X2 +

... + x., must equal 1.00. While two variables, Land K" appear in the right-hand
mcmber of equation (3), there are actually three variables involved sinec K, is a
function of both pressure and temperature. To predict the equilibrium conditions,
any two of these variables must be known and successive values oj the third
assumed until the sum of the x's equals 1.00. Usually, temperature and pressure
are the two variables specified, and then the trial and error involves L.
Flash Vaporization of Petroleum Fractions
Although the foregoing method applies to complex petroleum fractions as
well as to hydrocarbon mixtures of a comparatively few known components, it has
little practical significance for petroleum fractions because of the laborious calculations ...required even when component analyses are available, which is
rarely the case. As a result, empirical correlations have been developed for predicting equilibrium flash vaporization curves from distillation data on crudes and
petroleum fractions. The flash vaporization curve is a plot of temperature against
liquid volume percent vaporized, the total vapor being in equilibrium with the
unvaporized liquid at constant pressure.
222

/
223
A number of empirical correlations for determining the atmospheric flash

vaporization curve have appeared in the literature, but only a relatively simple
correlation would seem to be justified in view of the discrepancies between the data
of various investigators. The present correllition is of the same general type as
those of Piroomov and Beiswenger l and Nelson z and applies to both petroleum
fractions and whole crudes. For petroleum fractions, either the 100/0 (ASTM)
distillation of the fraction itself or the portion of the crude assay (True Boiling
Point) distillation corresponding to the fraction may be used for predicting the
flash curve. For whole crudes, the crude assay distillation should always be used
in preference to the 100/0 distillation. The latter should never be used if the
distillation curve flattens out below the 70'1'0 point in the neighborhood of 700F
since this is indicative of cracking.
In extrapolating the atmospheric flash curves to higher or lower pressures it
is suggested that the parallel method proposed by Piroomov and Beiswenger be
used up to pressures of 15 psig for whole crudes and wide cuts, and up to pressures
of 50 psig if the slope of the flash reference line of the fraction is not greater than
2F/ro. By this method the atmospheric flash curve is shifted parallel to itself by a temperature interval equal to the extrapolation of the 40'1'0 point 3
on the flash reference line (FRL) as a pure compound on a vapor pressure
chart.
This parallel method is unsatisfactory for higher pressures, since it is known
that the flash curve becomes more horizontal with increasing pressure until its
slope is zero at the true critical pressure. Beyond the pressure limits recommended
in the preceding paragraph for parallel extrapolation, it is suggested that a variation of the method of Watson and Nelson' be used, since no very elaborate method
appears to be justified by the data. The 40'1'0 point on the FRL is extrapolated on
a vapor pressure chart to a temperature 150F above the critical temperature of
the normal paraffin having the same boiling point as the 40'1'0 point. This extrapolated tempera:tur~ and corresponding vapor pressure is then used as a focal
point through which straight lines are drawn on a redilinear vapor pressure chart
(page 42) from the atmospheric flash temperatures for various percents vaporized. The flash curve at any pressure is determined from the temperatures at
which the given pressure ordinate intersects these constant percent off (or quality)
lines. These linear extrapolations do not apply if the true critical point of the
fraction is approached since the copstant percent off lines become curved and
converge to the true critical temperature and pressure.
Piroomov and Beiswenger, Proc. API 10, No.2, Section II, 52 (1929).
Nelson, "Petroleum Refinery Engineering," pp. 242-243, McGraw-Hill Book Co., New
York, N.Y. (1941).
3 This i3 a slight modification of the Piroomov and Beiswenger method as they use the
point of intersection between the flash and distillation curves for extrapolation.
Watson and Nelson, Ind. Eng. Chern. 26, 880 (1933).
1
224
Reduced Crudes
Perhaps the most direct method of predicting the atmospheric flash curve of
a reduced crude (or .any reduced stock) which at the same time is reasonably
accurate is the following:
(1) Construct an atmospheric flash curve for the original crudc.
(2) Determine the number of moles of both original crude and reduced crude
per given volume of original crude.
(3) At the dew point (lOOro vaporized) of the original crude, assume that the
reduced crude vapors are at their dew point at a partial pressure equal to
their mole fraction in the total vapors (moles of reduced crude/moles of
original crude) multiplied by 1 atm.
(4) Extrapolate the 40% point on that portion of the flash curve corresponding to
the yield of reduced crude from the partial pressure computed by (3) to 1 atm.
(5) If the reduced crude has been stripped of light ends, its atmospheric flash
curve is drawn through the extrapolated point parallel to the flash curve of
the original crude between the abscissas corresponding to the yield of
reduced crude.
(6) If the reduced crude has not been stripped of light ends, a smooth curve is
drawn from the split point on the flash curve of the original crude to the 20%
point on the flash curve constructed by (5) to approximate the front end of
the flash curve of the reduced crude. Establishment of the 20ro point as the
point above which unstripped light ends cease to affect the reduced crude
flash curve is, of course, entirely arbitrary but, at the same time, fairly
representative.
While the method outlined above is empirical to a large extent, it does have
some theoretical justification. If all but one drop of reduced crude were flashed,
this last drop of liquid would be in equilibrium with the reduced crude vapors
at 1 atm. It is then assumed that if 100% original crude were flashed at 1 atm, the
last drop of liquid would have the same composition as the last drop of
reduced crude, and the latter vapors would be at a partial pressure corresponding to their mole fraction multiplied by one atmosphere. The basis for
this assumption is that the temperature difference between the boiling range of
the last drop and 'that of the vapors romoved in reducing the crude is usually so
great that these vapors can be considered the equivalent of steam or gas in so far
as the equilibrium relations of the last drop is concerned. Making the flash curves
of reduced crudes parallel to the flash curves of their original crudes was originally
suggested by Piroomov and Beiswenger and appears to be fully justified by
their data.
Example 1. Determine the atmospheric flash vaporization curves of an East
Texas crude and its 35% bottoms (both stripped and unstripped) from the following data taken from an assay workup of t.he crude:

Assay (T.B.P.) Distillation
I.B.P., of
122
5%
177
10%
262
20%
350
30%
443
40%
538
50%
636
60%
752
70%
(905)
80%
Gravity
API
37.4
47.7
20.9
Crude
Overhead (0-65%)
Bottoms (65-100%)
Slope of DRL* =
225
Lbs/Gal
6.98
6.57
7.73
752 - 177
60
= 9.6F/%
DisLillaLion reference line-through 10% and 70% points.
50% Point (DRL) = 177
+ (50 -
10)9.6 = 561F
The slope and 50% point of the flash reference line are determined from the
chart on page 228:
Slope (FRL) = 6.4F/%;
50% Point (FRL) = 561 - 40 = 521F
The atmospheric flash curve is derived from its reference line by lIsing the
relation on page 229.
Percent
Vaporized
5
10
20
30
40
50
60
70
80
Assay Distillation (OF)

Curve
DRL
t>t'
Ratio
of (t>t')'s
122
177
262
350
443
538
636
752
(905) -
129
177
273
369
465
561
656
752
848.
-7
0.40
.36
.34
.34
.34
.33
-11
-19
-22
-23
-20
.33
+57
Flash Vaporization (F)

t>t'
FRL
Curve
-3
233
265
329
393
457
521
585
649
713
230
265
325
387
450
513
578
649
.732
-4
-6
-7
-8
-7
-
+19
The flash reference line and the atmospheric flash curve of the original crude
are-shown on Figure 1. Proceeding from (1), the flash curve of the original crude,
the atmospheric flash curves of the stripped and unstripped reduced crudes are
derived by the method outlined in the text:
(2) Vol. Av. B.P. of whole crude
262
+ 538
+ 905 = 568F
3
226

Mean Av. B.P. of whole crude = 568 - 70 = 498F (Section 2)
Molec. wt. of whole crude = 197 (Section 3)
Vol. Av. B.P. of 65% overhead =
Slope of DRL (65% overhead) =
203
+ 373
+
3
558
= 378F
495 - 139
60
= 5.9F/%
Mean Av. B.P. = 378 - 38 = 340F

Molec. wt. of 65% overhead = 139
(3)
(4)
(5)
(6)
Per 100 Gal

of Crude
Moles of crude = (6.98 X 100)/197 =
3.55
Moles of overhead = (6.57 X 65)/139 =
3.07
Moles of reduced crude
0.48
Partial pressure of reduced crude at the dew point of the original crude
0.48
= X 1 = 0.135 atm.
3.55
The 40% point on the reduced crucle flash curve corresponds to 65 + 0.40
X 35 = 79% or 722F on the flash curve of the original crude.
By extrapolation from 0.135 atm. to 1 atm., the 40% point on the
atmospheric flash curve of the reduced crude is 900?F.
The atmospheric flash curve of the stripped reduced crude is drawn through
the extrapolated point parallel to the 65-100% portion of the flash curve
of the original crude. This reduced crude flash curve may be converted
to percent on reduced crude by proportioning the 65-100% yield on
original crude to 0-100% on reduced crude. Both curves are shown in
Figure l.
The front end of the atmospheric flash curve on the unstripped reduced
crude is constructed by drawing a smooth curve from the 65% point on the
flash curve of the odginal crude to the 20% point on the flash curve of the
stripped reduced crude as shown in Figure 1. This curve is also given on
the basis of 0-100% reduced crude.
GENERAL REFERENCES
Edmister and Pollock, Chem. E7l{J. Progress 44, 905 (1948).
Katz and Brown, Ind. E7l{J. Chern. 26, 1373 (1933).
Packie, Trans. Am. Inst. Chern. Engrs. 37, 51 (1941).
227
1100
1000
900
800
700
600
!lOO
400
300
200
10
20
30
40
50
FIGURE
60
1
70
80
90
100
PREDICTION OF FLASH REFERENCE LINE

FROM DISTILLATION REFERENCE LINES
--JfJ1
.r
.. ~.
. FLASH AND DISTILLATION REFERENCE

LINES (FRL AND DRLl ARE STRAIGHT
LI NES THROUGH THE 10% AND 70%
, POINTS. THE TEMPERATURES AT THE
I
-
i li
If
50% POINTS REFER TO THESE

REFERENCE LINES.
10
II
,,'
m
I
.
12
.~ I~
40
~
~
E
: ... RE~G~l~it!fI:~:':I~-'~ 1
.... ;~~
2
60
i ~If
U4
!'iii R,f;f,Et EN' ~...
!; - .
10
II
12
11- -
40
20
..
II
BI
O
-20
-40
-60
-40
228
tlI
,
,
,
tmI,
: t
1.
..
Mm
c
too
1.00
.80
lm!l
100
I..
PREDICTION OF FLASH CURVE

FROM ITS REFERENCE LINE
1'-'-
fmII
mIl
tmn
II
11UlI
_ 11$ CRUDE
, .
.60
ASSAY (T.B.P.) DIS TlLLATION
'gmj
,20
11m!
-,,",p .. I:J
t"
10
1.00
20
30
II
40
50
11m
60
70
90
100
lmJU
.JI#J:
"* lIV IS THE DEPARTURE
n5
.60 f:fk,'ll
OF THE ACTUAL
FLASH AND D1STI LLATION CURVES FROM
THEIR RESPECTIVE REFERENCE LINES.
WHILE THE INDIVIDUAL (lIl')'S MAY BE
EITHER PLUS OR MINUS, THE RATIO IS
ALWAYS POSITIVE.
~
, ' '.
..
~l'mIJ
Iflill
.20
80
lEE
'
10% (A.s:tM.) DISTILLATION
.80
!l0
II
10
30
w_
40
60
ro
229
90
100
.1
Section 14
FRACTIONATING TOWERS
In order to simplify the work involved in making stepwise calculations for
the rectification of binary and multieomponent systems, Gilliland' has presented
an empirical correlation between theoretical steps and reflux ratio. To use the
Gilliland correlation to predict the number of theoretical plates for a given reflux
ratio, the minimum number of steps at total reflex and the minimum reflux ratio
are required.
Minimum Number of Theoretical Steps
When a separation is specified with respect to only two components of a multicomponent mixture, the lower boiling of these two components is designated the
light key component and the higher boiling the heavy key component, and the
minimum number of steps can be calculated by the well-known Fenske equation 2
as follows: a
log
8 Af=
(XXLKlV
LKD) (X HKlV)
XHKD
log aLK
[aLK]SM =
or
(XXLKlV
LK D) (X HKlV)
XHKV
(1)
(1 a)
After equation (1) is solved for 8M , the latter may be substituted in this
equation along with the distribution of either key component to prcdict 4 the distribution of the other components, or
(X
,.D) X HKlV) = 8 M log aL

XX
log ( -
(2)
LK
log (X lilY) (X LKD) = 8 M log (a )
XlID
XLKlV
all
(3)
!-IV
11 K D
Likewise,
In any of the above equations, moles per 100 moles of feed may be replaced
by total mo)es, or volume or weight units since in any of these conversions the
multiplying factors cancel out.
Gilliland, Ind. Eng. Chern. 32, 1220 (1940).
Fenske, Ind. Eng. Chern. 24, 482 (1932).
A table o( nomenclnture is given on page 243.
This equation may be used (or any pair o( component8.
2
S
230
2H1
When the dcgree of separation is specified for more than two components,
equation (1) must be applied to all critical combinations of these components and
the maximum SJ/ determincd for the most difficult case. If the separation is specificd with respect to the total quantity of two or more components, as in the
case of Examplc 1, trial and eITor is required for thc solution of SjJ.
It should be pointed out that the concentrations calculated by equations
(2) and (3) actually apply only to the separation at total rcflux and, with the
exception of the two key components, there will be some variation of thc degrec
of separation with the reflux ratio. As the rcflux ratio decreases, there is some
improvement in separation betwecn light and heavy componcnts boiling outside
the range of the kcy components and some deterioration in the separation of components boiling intermediate bctween the kcy components. However, in so far as
the present procedure is concerned, the distillate and bottoms compositions for
other reflux ratios are assumed to be thc Same as those calculated for total reflux.
Minimum Reflux Ratio
Gilliland 5 has proposed several diffcrent formulas for predicting minimum reflux
ratio and all have the disadvantage of being composcd of a number of complex
terms in addition to requiring trial and error for solution. Although all these
equations appeal' to give satisfactory rcsults, the tcrms are so complcx that it is
difficult to bc ccrtain that therc arc no numerical crrors in thcir application.
In order to apply the Gilliland method with greater facility, the following
equation was developcd for predicting the minimum rcflux ratio of a multicomponent system:
(O/Dhf
+ 1=
(aLKTf.FC +
('(LK - 1
1) (XLKD
ILK
XIIKD)
(4)
(O/D)M can be calculated for two arbitrary states of feed vaporization:
1. "Liquid" feed, cOITesponding to vaporization of the feeu equivalcnt to the
fraction of the feed lighter than the light key component. For the components
lighter than the light key, h = ZL/aL and for the light key and heavier components, ILK = ZLK, and III = Zfl.6
Gilliland, Ind. Eng. ehe",. 32, HOI (1940).
] components, intermediate between the two key components, are present, they are
considered ei her light or heavy componen'" depending upon which key their volatility more
nearly approaches. In the case of "liquid" feed, I L = Zl. and I II = ZH for these intermediate components; in the case of "vapor" feed, I L = ZL/aL and I II = ZuaH/aLK.
5
232
2. "Vapor" feed, corresponding to vaporization of the feed equivalent to the

fraction of the fecd consisting of the hcavy key component and lighter. For the
components lighter than the heavy key, If_ = ZL/CtL and ILK = ZLK/aLK and
for the components heavier than the heavy key, 1/1 = ZI/.6
After the minimum reflux ratios have been calculated for "liquid" and "vapor"
feeds, the minimum rcflux ratio for the actual vaporization of the feed can be calculated by direct interpolation or extrapolation. However, extrapolation beyond
50% of the difference between "liquid" and "vapor" feed may lead to serious
deviations.
The first term of the right-hand side of equation (4) is the same as for binary
mixtures, and the equation reduces to the cquivalcnt of a binary mixture whon
all light components other than the light key have infinite volatility and all heavy
component other than the heavy key have zero volatility. Under these circumstances the equation is exact when hK is taken as the ratio of the two components
in the liquid phase of the feed. That is, if the feed is introduced as a liquid at its
bubble point, hK = ZLK, which is the ratio of the two components in the feed;
if the feed is introduced as a vapor at its dewpoint, hK = Z',K/OtLK, which is the
ratio of the two components in the cquilibrium liquid. For intermediate stages
of vaporization hK can be calculated from the flash vaporization formula, although direct intcrpolation of the minimum reflux ratio on the basis of percentage
vaporization between thc sat urated liquid and saturated vapor feeds gives values
only slightly in error on the conservative side.
In the case of multicomponent mixturcs, equation (4) is semi-empirical since
it was necessary to make simplifying approximations in its derivation. Furthermore, the exact values of the various 1's cannot be calculated directly from the
composition and state of vaporization of the feed, since the liquid on the feed
platc is not identical to the liquid phase of the fecd as in the case of a binary
mixture. As a result, it was necessary to define the 1's empirically for two states
of fced vaporization, arbitrarily choscn to simulate a binary mixture of the two
key components, and then intcrpolatc or extrapolatc to the minimum reflux ratio
corresponding to the actual vaporization of the fced.
Equation (4j has been checked for a number of multicomponent systems on
which the minimum reflux ratio was determined by stepwise trial and error calculations. Generally, unusual systems were chosen with respect to composition and
relative volatility in order to reveal the maximum deviations ever likely to be
encountercd in practice. The agrecment was quite satisfactory as the average
deviation was less than -+-5% and the maximum about lOra. The latter occurred at
the limit of extrapolation relative to the arbitrary feed states.
233
Also, the minimum reflux ratio was calculated for these same systems by the
Colburn method 7 with about the same degree of accuracy. It should be pointed
out that the latter gave better results than equation (4) when the relative volatilities and compositions were not so abnormal as the systems selected. However,
under these circumstances both methods were quite accurate as the deviations
seldom exceeded a few percent, and the present equation has a distinct advantage
in that it is explicit and does not require trial and error.
Both methods are quite sensitive to the selection of key components, and
the selection of the wrong key components can lead to a much greater error than
is inherent in either method. If the desired separation is between adjacent components, there is usually no doubt about selecting these as the key components.
However, if there are additional specifications relative to other components, it
may be necessary to try two or more combinations of key components to make
sure that the minimum reflux ratio is sufficient to fulfill all specified conditions.
Correlation of Theoretical Steps with Reflux Ratio
As mentioned at the beginning of this section, Gilliland correlated the results
of a large humber of stepwise calculations on various binary and multicomponent
mixtures by plotting
[S-SM) I[ S + 1] ~</> (S) against [(OlD) - (OID))f)/[ OlD + 1)-F (OlD)
and found that all points could be represented by a single curve irrespective of the
type or degree of separation. These points, along with about half again as many
additional points, were replotted, and the best curve through them was essentially
the same as Gilliland's original correlation.
In arriving at the coordinates for the additional points the minimum reflux
ratio was calculated by equation (4); therefore these points are a criterion of the
present method as well as the curve itself. In no case did the deviations exceed
either 3 theoretical steps or 15%, and the average deviation was less than 1
theoretical step and also less than +50/0. To take care of the maximum deviation
it is recommended that in any design the number of theoretical steps predicted
~ from the correlation on page 244 be increased by either 3 theoretical steps or
100/0, whichever is greater.
Plate Efficiency
Because of the large number of factors which undoubtedly influence the
plate efficiency of a fractionating tower, any fundamental formula accounting
for even the most important variables must necessarily be quite involved. For this
reason, a simple empirical correlation of the limited data on hydrocarbon mixtures
seemed to be the most promising method of predicting plate efficiency.
7
Colburn, Trans. Am. Inst. ehem. Engrs. 37, 805 (1941).
234
Gunness 8 correlated the results of several tests on petroleum mixtures on the

basTs of vapor pressure of the liquid. As he points out, this is a method of indirectly
correlating plate efficiency with liquid viscosity since viscosity of pure hydrocarbons and narrow boiling fractions is an approximate function of vapor pressure
over a fai,rly wide range of vapor pressures.
In view of the consistent results obtained by Gunness, pla.te efficiency was
plotted directly against fluidity (reciprocal viscosity) for a number of tests on
commercial towers including those upon which Gunness based his curve. The curve
on page 245 represents this correlation. While the overall plate efficiency exceeds
10070 at fluidities greater than 9 Cp-1, this is not inconsistent as the flow of the
liquid across the plates results in concentration gradients which may achieve a
greater degree of fractionation than predicted by stepwise calculations in which
the liquid is assumed to leave the plate in equilibrium with the composite vapor.
Lewis 9 has shown theoretically that different combinations of liquid and vapor
concentration gradients across the plate may give overall plate efficiencies as
high as 200--300'10 when based on stepwise calculations.
There is no reason to believe that this correlation applies to mixtures other
than hydrocarbons, and with the exception of alcohol-water mixtures there are
too little data available to afford a comparison. Although there is considerable
variation in the alcohol-water data, there is some indication that plate efficiencies
are somewhat greater than for hydrocarbons of the same viscosity.
Location of the Feed Plate
As a simple approximation for locating the feed plate, it may be assumed that
the proportion of actual plates above the feed will be the same as that required to
effect the same separation between the key components at total reflux. That is, the
number of theoretical steps at total reflux is calculated for the concentration
change in the key components between the feed and distillate compositions. It is
then assumed that the ratio of this to the total number of theoretical steps at an
infinite reflux ratio is the same as the ratio of actual plates above the feed is to
the total number of plates. Application of this method is illustrated by Example 1.
In some cases where there are oritical components other than the two key
components, it may. be necessary to check the total reflux steps above and below
the feed on the basis of these components, since the optimum location of the
feed plate will be different with each pair of components. Usually the separation
of components other than the key components is so complete that only the latter
need be considered.
8
9
Gunness, Sc.D. Thesis, Mass. Inst. Tech. (1936).

Lewis, Ind. Eng. Chern. 28, 399 (1936).
235
Packed Towers
The charts on pages 246 to 248 giving the H.E.T.P., capacity and pressure
drop in packed towers are self-explanatory. Since practically all of the H.E.T.P.
data were on towers less than 12 in. in diameter, caution should be used in the
design of larger towers. One of the greatest sources of inefficiency in a packed tower
is poor liquid distribution. If good distribution can be achieved by efficient distributors, the extrapolations may be used for larger towers with reasonable
assurance.
Example 1. At an operating pressure of 100 psig determine the number of
plates and reflux ratio required to separate the mixture given below so that the
bottoms contain at least 90ro of the butenes-2 present in the feed and at the
same time have an isobutene content not greater than 5%:
Component
i-C,H lo
i-C,H s
C,H s-1
C.H IO
t-C,H s-2
c-C,H s-2
Feed
(Mole %)
40.0
20.0
15.0
5.0
10.0
10.0
100.0
(1) Dewpoint of Distillate and Bubble Point of Bottoms
In order to calculate the average volatilities, the dewpoint of the distillate

and bubble point of the bottoms must be found by trial and error using assumed
compositions. These are tabulated below.
Moles Per 100 Moles of Feed

Component
i-C.H LO
i-C.H,
C.H...1
C.H,o
t-C.H,2
.,.C.H...2
Mole Fraction
Feeti
Distillate
Bottoms
Distillate
Bottoms
40.0
20.0
15.0
5.0
10.0
10.0
100.0
39.3
18.7
13.0
1.0
1.5
0.5
74.0
0.7
1.3
2.0
4.0
8.5
9.5
26.0
0.530
.253
.176
.014
0.027
.050
.077
.154
.327
.365
1.000
.OW
.007
1.000
As a first trial, assume the dewpoint of the distillate is 14tlF at 7.8 atm (114.7
psia) .
236
First Trial
Component
YD
':"C,H IO
i-C,H,
C,H,-I
C,H,o
t-C,H...2
c-C,H ...2
a'D
Pt
:i;
HOF
140F
"yiP
1.29
1.155
1.13
1.00
0.97
0.91
8.4
7.5
7.35
6.5
6.3
5.9
0.493
.263
.187
.017
.025
.009
0.994
0.530
.253
.176
.014
.020
.007
1.000
Relative volatilities to C 4H 10 or (0")'8 aTC used as a matter of convenience; then, the

(a'.,.)'s are converted to (a)'s, the relative volatilities to t-C,H,-2, which will be seleetcd as
the heavy key component.
t Computed from the fugacity function of butane multiplied by the relative volatilities.
Since the sum of the x's is 0.994 instead of 1.000, the assumed temperature
should be lowered slightly, but the difference would be so small (less than lF)
that the change in the (a'Jl) 's would be imperceptible. Consequently, 140F will
be used as the dewpoint of the distillate.
The bubble point of the bottoms is assumed to be 165F at 8.0 atm 10 for the
first trial.
Second Trial
First Trial
Component
i-C,H,o
i-C,H,
C,H ... I
C,H,o
t-C,H ...2
c-C,H,-2
XIV
0.027
.050
.077
.154
.327
.365
1.000
a' w
165F
pt
165F
Pxl..
1.26
1.14
1.115
1.00
0.97
0.915
10.7
9.7
9.5
8.5
8.25
7.8
0.036
.061
.091
.164
.337
.356
1.045
a'w
160F
160F
1.265
1.145
1.12
1.00
0.97
0.915
10.25
9.3
9.1
8.1
7.85
7.4
0.035
.058
.088
.156
.321
.338
0.996
Pt
Relative volatilities to C~HIO or {')'8 are used ns a mnttcr of convenience; then, the
(a'av)'S are converted to (aU\')'s, the relative volatilities to t-C IH:;-2, which will be selected as
the heavy key component.

t Computed from the fugacity funet:on of hutane multiplied by the relative volatilities.
The bubble point of the bottoms wiil be taken as 160F. The relativ~
volatilities are averaged and converted to t-C~ H s -2 as the heavy key in the following table:
\0
After allowing 3 Ib/sq in. as the approximate pressure drop through the tower.
aD
aw
aA
Component
140F
7.8 at.m
160F
8.0 atm
150F
7.9 atm
i-C,H ID
i-C,H.
C,H.-l
C,H ID
t-C,H8-2
c-C,Hg-2
1.29
1.155
1.13
1.00
0.97
0.91
1.265
1.145
1.12
1.00
0.97
0.915
1.275
1.15
1.125
1.00
0.97
0.91
237
a a.
(a' Da'wa'.A.)~!l
1.275
1.15
1.125
1.00
0.97
0.91
aa.
1.315
1.185
1.16
1.03
1.00
0.94
(2) Minimum Theoretical Steps (Total Reflu:t)

The minimum number of theoretical steps by which the desired separation can
be accomplished is calculated as follows:
Let
t = moles of t-C 4 H s-2 in the distillate per 100 moles of feed

10 - t = moles of t-C 4 H s-2 in the bottoms per 100 moles of feed
Since 90% of the butenes-2 must be.retained in the bottoms, the cis-butcne-2
content of the distillate and bottoms will be:
(2 - t) moles in the distillate per 100 moles of feed
(8 + t) moles in the bottoms per 100 moles of feed
and
Using the previously assumed values of 18.7 moles of isobutene in the distillate and 1.3 moles in the bottoms, the following equations must be satisfied:
C1~;) CO t- t)
18.7) (~)
( 1.3
2- t
= (1.185)8 M
=
(1.185)8
0.94
A trial and error solution of these equations shows that they are satisfied by
SM = 25.5 and t = 1.62.
The distribution of the other components can be calculated from SM and the
distribution of t-C 4 H s -2.
i-C 4 H IO : Let u = moles of i-C 4 H IO in bottoms
(
40 u
1') (8.38) = (1.315)25.5 = 1075

1.62
= 0.19 moles of i-C4 H IO in the bottoms

C 4H s-1: Let v = moles of C4 H s-1 in the bottoms
(
15 v
v) (838)
1.62
(1.16)25.5
44
v = 1.58 moles of C 4 H s-2 in the bottoms
238
C.H IO : Let w = moles of C.H IO in the bottoms

(
5W
W)(8.38) = (1.03)25.5 = 2.12

1.62
= 3.55 moles of C.H 10 in the bottoms
The percentage of i-C.Hs in the bottoms will be:

(0.19
+ 1.3 + 1.58 ~33.55 + 8.38 + 9.62) 100 = 5.3%
In order to meet a maximum of 5.0ro i-C 4 H s specified for the bottoms, it is

necessary to reduce the 1.3 moles to 1.22 moles in the bottoms. This would require
an increase in SM to 25.8 which would modify the distribution of the other components. However, the latter change is so slight that it can be neglected. The
composition of the overhead and bottoms will then be:
Mole Fraction
Moles Per 100 Moles of Feed

Component
iC,H,o
iC,H,
C,H..1
C,H IO
/C,H,-2
.,.C,H..2
Fecd
Distillate
Bottoms
Distillate
Bottoms
40.0
20.0
15.0
5.0
10.0
10.0
39.81
18.78
13.42
1.45
1.62
0.38
75.46
0.19
1.22
1.58
3.55
8.38
9.62
24.54
0.528
.249
.178
.019
.021
.005
1.000
0.008
.050
.064
.145
.342
.391
1.000
(3) Minimum Reflux Ratio

Since the critical separation is between isobutene and the butenes-2, the
former is naturally selected as the light key component and trans-butene-2, since
it is more volatile than the cis-butene-2, as the heavy key component. Butene-l is
considered a light intermediate component because of the proximity of its relative
volatility to that of isobutcne; normal butane is considered a heavy intermediate
component since its relative volatility is nearer to the heavy key than the light
key. The following tabulation gives the necessary information for calculating the
minimum reflux ratios for the two arbitrary states of feed vaporization:
Mole Fraction
Component
':-C,H,o
i-C,H,
C,H ..1
C,H IO
t-C,H,.2
.,.C,H..2
Type
L
LK
L
H
HK
H
"'BV
Feed
Distillate
Bottoms
0.400
.200
.150
.050
.100
.100
1.000
0.528
.249
.178
.019
.021
.005
1.000
0.008
.050
.064
.145
.342
.391
1.000
1.315
1.185
1.16
1.03
1.00
0.94
HLiquid tl
lIVapor"
Feed
Feed
3.04
2.00
1.50
4.00
3.04
1.69
1.29
3.48
2.00
2.00
239
"Liquid" jeed-40% vaporized

(O/D)
+1 =
M
1.185 X 2.00 + 1.0 (0.249 _

1.185 _ 1.0
2.00
+ 01. 31 5 (0.528 .315
1.03
(O/Dhf
1)
.
02
3.04 X 0.021)
(0.249
+ 1.16 (0.178 0.16
0.94
+ 1.185 - 1.03 4.00 - 0.019 + 1.185 - 0.94

= 1.88 + 1.94 + 1.07 + 0.29 + 0.46 - 1 = 4.64
1.50 X 0.021)
(0.249
)
2.00 - 0.005
"Vapor" jeed-90% vaporized

(O/D) M
+1 =
1.185 X 1.69 + 1.0 (0.249

- - - 0.021 )
1.69
1.185 - 1.0
1.16 (
+ 1.94 + 0.16
0.178 1.03
+ 1.185 (O/D)M
1.03
1.29 X 0.021)
(0.249
)
3.48 - 0.019
= 2.06 + 1.94 + 1.10 + 0.35 + 0.46
- 1
+ 0.46
= 4.91
Assume that the feed is sufficiently preheated to vaporize a percentage

equivalent to the distillate or 75.4670. By interpolation, the minimum reflux ratio
corresponding to this feed vaporization is:
(O/D)M
75.46 - 40)
= 4.64 + ( 90 _ 40
(4.91 - 4.64) = 4.83
(4) Theoretical Steps vs. Reflux Ratio
Using the values determined in preceding sections for minimum theoretical

steps,. 25.8, and for minimum reflux ratio, 4.83, the number of theoretical steps
for various reflux ratios can be predicted from the correlation on page 244:
OlD
F(OID)
4.83
5.25
5.75
6.50
7.50
0.067
.136
.223
.314
</>(8)
0.570
.502
.430
.366
Theoretical Platea-
61.3
52.7
46.0
41.3
25.8
60.3
51.7
45.0
40.3
24.8
- The reboiler i. considered the equivalent of one theoretical step. With a partial instead
of a total condenser, a second theoretical step also could have been deducted.
240
(5) Number of Actual Fractionating Plates
To predict the number of actual plates it is necessary to determine the average

viscosity of the liquid on the plates. Since the temperature difference between the
top and bottom of the tower is so small, the average viscosity may be taken as
the viscosity at the average temperature. For this purpose the viscosity of butane
at 150F will be used.
Viscosity of C.H IO @ 150F = 0.216 cs "" 0.216 X 0.523 = 0.113 cp
Fluidity = 1/0.113 = 8.9 Cp-l j Plate efficiency = 99%
Using a plate efficiency of 99% the number of actual plates is computed for
various reflux ratios:
OlD
4.83
5.25
5.75
6.50
7.50
.,
Theoretical Steps
Actual Plates
.,
.,
.,
61.3
52.7
46.0
41.3
25.8
60.3
51.7
45.0
40.3
24.8
60.9
52.2
45.5
40.7
25.0
The number of actual plates is plotted against reflux ratio in Figure 1.

A reflux ratio of 6.50 to 1, or 1.35 times the minimum, is selected. The number
of actual plates corresponding to this reflux ratio is 45.5 so that a 50-plate tower
would be required.
(6) Location of the Feed Plate
The number of plates above the feed is based on the proportion of theoretical
steps at total reflux which would be required to effect the change in concentration
of the key components between the feed and distillate. This proportion is applied
to the actual number of plates (including the reboiler) to determine the number
above the feed plate.
In order to take into account any appreciable difference in relative volatility
above and below the feed, the relative volatility used for calculating the steps at
total reflux between feed and distillate is the geometric mean of aD and a" or,
an
=(
1.15)~i
1.155
0.97 X 0.97
1.19
The number of total reflux steps which would be required between the feed
and distillate is calculated by the following equation:
l8.78) (~)
( 20
1.62
1.19n
= 5.79'
'
n = 10.1
FRACTIO ATING TOWERS
241
50
40
30
6
FIGUllE
Number of actual plates above the feed would then be:

10.1 (50
25.8
+ 1)
20
The vaporization of the feed can be taken into account by adding the fraction
vaporized to n since 10010 vaporization would be equivalent to a theoretical step
at total reflux. This would change the proportion of plates above the feed as
follows:
(
10.1 +
I
0.75) (
00"
+)
1 = 21.4 pates
above the feed
20.8
Feed lines would probably be installed above the 2'!th, the 28th and 32nd
plates from tile bottom of the tower.
242

GENERAL REFERENCES
Atkins and Franklin, Refiner Natural Gasoline Mfgr. (Jan. 1936).

Brown, Sanders, Nyland and Hesler, Ind. Eng. Chem. 27, 383 (1935).
Brown and Souders, Oil and Gas J. 31, 34 (1932).
Chilton llnd Colburn, Trans. Am. Inst. Chern. Engrs. 26, 178 (1931).
Elgin and Weiss, Ind. Eng. Chem. 31, 435 (1939).
Fenske, Lawroski llnd Tongberg, Ind. Eng. Chern. 30, 227 (1938).
Fenske, Unpublished data, Pennsylvania State College.
Gilliland, Ind. Eng. Chent. 32, 918, 1101, 1220 (1940).
Gunness, Ind. Eng. Chern. 29, 1092 (1937).
Lewis and Wilde, Trans. Am. Inst. Chern. Engrs. 21, 99 (1928).
Perry, "Chemical Engineers' Handbook," pp. 829-832, McGraw-Hill Book Co., New York,
N.Y. (1941).
Sherwood, Shipley and Holloway, Ind. Eng. Chem. 30, 765 (1938).
White, Tram. Am. Imt. Chem. Engrs. 31, 390 (1935).
243
.vomenclature
X
x
moles of any component in distillate or bottoms per 100 moles of feed

mole fraction of any component in liquid
y
mole fraction of any component in vapor
D
moles of distillate per 100 moles of feed
o
moles of reflux per 100 moles of feed
OlD
reflux ratio
(OIDhl minimum reflux ratio corresponding to S = 00
S
number of steps from still to distillate
8,1/
minimum number of steps corresponding to OlD = 00
P
number of theoretical plates; with a partial reboiler and partial condenser, P = S - 2, and with a partial reboiler and total condenser,
P=S-l
ZH
aD
alV
LK
HK
L
H
D
W
n
m
ratio of mole fraction of any light component to heavy key component

in the feed
ratio of mole fraction of light key component to any heavy component
in feed
relative volatility of any component to heavy key at the dew point of
the distillate
relative volatility of any component at the bubble point of the bottoms
relative volatility of any component at the arithmetic average temperature of the dew point of the distillate and the bubble point of the
bottoms
mean relative volatility of any component, (aD' alV . a.4)fi
used as a subscript to refer to the light key component
used as a subscript to refer to the heavy key component
used as a subscript to refer to any light component
used as a subscript to refer to any heavy component
used as a subscript to refer to the distillate
used as a subscript to refer to the bottoms
used as a subscript to refer to the plates above the feed
used as a subscript to refer to the plates below the feed
1IIIriCORRELATION OF THEORETICAL
STEPS WITH REFLUX RATIO
MULTICOMPONENT AND BINARY MIXTURES
.9
.8
.6
.5
.4
.3
.2
.1
244
OVERALL PLATE EFFICIENCY vs.

FLUIDITY OF LIQUID ON PLATES
120
1.11111
120
110
100
100
90
90
80
80
70
ONLY DATA 00 HYDROCARBON MIXTURES WERE

USED IN THIS CffiRELATION, AND THERE WERE
INSUFFICIENT DATA ON OTHER TYPES TO JUSTIFY A MORE GENERAL USE. HOWEVER, THERE
WERE SOME EVIDENCE THAT THE CURVE IS A
LITTLE CONSERVATIVE FOR ALCOHOL - WATER
60
40_
50
70
60
50
MIXTURES.
40
30
20
: :
ll!IIflE:IJffi
10
_ _ _ _ _ '0
2
245
10
II
12
13
14
45678910
20
.:_.
30
:t';
HEIGHT EQUIVALENT
TO A THEORETICAL PLATE
4a!f11i1
2
(I) WHILE THIS CORRELATION WAS DE'
VELOPED fROM DATA ON RASHIG

RINGS AND 8ERL SADDLES, IT PR08ABLY APPLIES TO OTHER SIMILAR
TYPES OF HOLLOW PACKING.
(2) VALUES OF H.E.lP. FROM THIS CHART
CORRESPOND TO THE MAXIMUM TOWER
CAPACITIES GIVEN BY THE CHART ON
THE OPPOSITE PAGE. FOR THE VALUES
OF HE.T.P. AT CAPACITIES BETWEEN 80%
AND 100% OF THE MAXIMUM, DIVIDE
H.E.T.P. FROM CURVES BY THE FRACTION
OF ULTIMATE CAPACITY (.80-1.00) AT
WHICH THE TOWER WILL OPERATE.
mIR~12ioll~3IoI14~oll~ 60
246
7'08090 I
* USE VALUES OF S/F 3 FROM CUR\IE
~-d
FOR RASCHIG RINGS. BERL SADDLES

W PACKING UP 10
2 INOiES IN SIZE. FOR SIZES GREATER'THAN 2 INCHES, USE INDIVIDUAL
.2
.,.,,
~li
VALUES OF SAND F.
.1
lilt! 1)
r r 1111
'r-
.08
jj
.06
.05
.04
e:l3
.f+
"t~
I 1 I
ltllllltltrTl1111
;~':+fTo"",
1000
800
,I';r.j
.....'11:;::;:1-0-
~~i:-:'l:::.Jx
""'-:1=
I"4T'
r.... ' ....
tI
600
500
400
300
'J="~J';+:
-j:,l
r,
rt~'-I--t"""'
'it
L-
..
"llOUIO-
m.
"
80 - reNSlTY OF VAPOR - LeS/CU FT.

8L fl
L1QUIO"
..
Uo-SUPERFICIAL VAPOR VELOCITY AT INITIAL FLOODING-FT/SEC.
S*-SURFACE AREA OF PACKING- SO. FT./CU.FT. TOWER VOLUME

F*-F'RACTION OF FREE VOLUME IN PACKING
.002,
OF LIQUID - CENTIPOISES
-GRAVITY CONSTANT-32.2 FT./SEC~
...
SHERWOOu
_......
~MlrLEY
..mI;,;:; I ;'i-;t:;:-..J:,
AND HOLLOWAY. IND . ENG. DiEM. 30. 765 (1930)
~
rF!:tJ~ lii r:'~
., !
/+l!;I"'
."
001
.01
.OZ
.03.04
.06 .08 .fO
.2
.3
I'
.,
.4.5.6.7.8.910
"'.
'n
100
80
60
.M -VISCOSITY
9
" .200
f"'";
SUPERFICIAL MASS vaoCITY OF VAPOR-L8SISEC/SO.FT.
AP/H <KFLA 15 eo 85 uI.85
DL50
.,I(
eo
U
o
FL
K
VISCOSITY OF VAPOR - CENT'POISES

DENSITY OF VAPOR - LBS.lCU. FT.
'VAPOR VELOCITY - FT.lSEC.
< SIZE OF PACKING - INCHES
"LIQUID RATE FACTOR
<1.25 FOR BERL SADDLES
<I. 75 FOR RASCHIG RINGS
<
<
_1lI4.0
o
1.5
1.0
20
248
.0
:0
.0
CONVERSION FACTORS
TEMPERATURE
To Convert
From
To
e
OF
oR
oK
OR
ox:
1.8(OC) + 459.7
of + 459.7
C + 273.2
(OF + 459.7)1.8
R/1.8
OF
1.8(OC)
.
(OF - 32)/1.8
. (OR - 491.7) /1.8
.
oK - 273.2
+ 32
OR - 459.7
1.8("K) - 459.7
LENGTH
To Convert
From
To
Meters
Cm
Inches
Feet
Multiply By
1.000
100.0
2.540
30.48
Centimeters
.
Meters
__
Inches ...............................
Feet.................................
0.0100
1.000
0.0254
0.3048
0.3937
:19.37
1.000
12.00
0.03281
3.281
0.08333
1.000
AREA
To Convert
From
To
Sqem
Sq em .......................
Sqm
.
Sq in
.
Sq ft. .......................
1.000
10,000
6.451
929.0
VOLUME
To Convert
From To Cu in.
Cu ft
US gal
Sq m
Sq in.
Sq ft
M ullilJ/Y by
1.000 X10- 4
O. J550
1.000
1,550
6.451 XIO- 4
1.000
0.09290
144.0
1.076 XI0- 1
10.76
6.944 X10-1
1.000
eu em
Dbl (42's)
Imp
g&~
Liters
l>h,/liply by
Cu in
Cu ft.
US gal
Imp gal. ..
Cu em
Liters
Bbl (42'S).
FORCE
To Convert
From
1.000
1,728
231.0
277.3
0.06102
61.02
9,700
5.787 X 10- 4 4.329 X 10-3 3.607 X10-3 16.39

0.01639
1.000
7.481
6.232
2.832XI0 4 28.32
0.1337
1.000
0.8326
3,785
3.785
0.160.~
1.200
1.000
4,543
4.54a
3.531 XIO-' 2.642 X 10- 4 2.201 XIO- 4 1.000
1.000 X 10-3
0.03531.
0.2642
0.2201
1,000
1.000
5.614
42.00
34.97
1.590XIO' 159.0
To
Poundals
Pounds
1.031 XIO-4
0.1781'
0.02381
0.02857
6.290XIO-&
6.290 X 10- 1
1.000
Dynes
Grams
I a,830
4.448 X 10'
1.000
980.7
14.10
453.6
1.020XltJ"
1.000
Multiply by
Poundals
Pounds
Dynes
Grams
.
.
.
.
1.000
32.17
7.233XltJ'
0.07093
0.03108
1.000
2.248 X10-'
2.205 X 10-3
249
250
DENSITY
To Convert
From
To
Sp gr
Lb/gal.
Lb/eu ft
.
.
.
Sp gr
Lo/gal
Lb/eu ft
1.000
0.1108
0.01602
Multiply by
8.3'17
1.000
0.1337
62.43
7.481
1.000
PRESSURE
To Convert
From
To
Lb/sq in...
Lb/sq ft ...
Atm .......
Kg/sq em ..
In. of Hg ..
Mm of Hg
Ft of H,O
(60F)
Lb/sq in.
Lb/sq ft
1.000
6.944 X10-3
14.70
14.22
0.4912
0.01934
0.4335
144.0
1.000
2,116
2,048
70.73
2.785
62.43
Kg/sq em
AIm
In. of
Hg
Multiply by
0.06804
0.07031
2.036
4.726XIo-' 4.882 XIO-' 0.01414
1.000
1.033
29.92
0.9678
1.000
28.96
0.03342
0.03453
1.000
1.316 XlO- 3 1.360 X10- 3 0.03937
0.02950
0.03048
0.8826
Ftof H,O
(60F)
Mmof
Hg
2.307
0.01602
33.90
32.81
1.133
0.04461
1.000
51.70
0.3592
760.0
735.5
25.40
1.000
22.41
RATE OF FLOW
To Convert
From To
Liters
per sec
Liters/sec 1.000
Gal/min. 0.06308
Gal/hr .. 1.052XI0-3
Cuft/see 28.30
Cuft/min 0.4717
Cu ft/hr. 7.862 X 10- 3
Bbl/hr .. 0.04415
Bbl/day. 1.840XlO- 3
Gal
per min
Gal
per hr
15.85
1.000
0.Ol667
448.9
7.481
0.1246
0.6997
0.02917
951.2
60.00
1.000
2.693 XlO'
448.9
7.481
42.00
1.750
ENERGY. HEAT. AND WORK

To Convert
BTU
To
From
BTU ...........
Gm-eal .........
Ft-lb ...........
Hp-hr..........
Kw-hr .........
1.000
3.968XlO- 3
1.286 X 10-3
2,547
3,415
Cu ft
Cu ft
per sec
per min
Cu ft
perhr
M,diiply by
0.03532
2.110
127.1
2.228XIO- 3 0.1337
8.010
3.713XIO-' 2.228 X 10-3 0.1337
1.000
60.00
3,600
0.01667
1.000
60.00
2.778 X 10-' 0.01667
1.000
1.560 X 10- 3 0.09359
5.615
6.498XlO-' 3.899XIO- 3 0.2340
Bbl
per hr
Bbl
per day
22.66
1.429
0.02382
641.1
10.69
0.1781
1.000
0.04167
543.8
34.30
0.5716
1.538 XIO'
256.5
4.272
24.00
1.000
Gm-cal
Ft-Ib
Hp-hr
Kw-hr
252.0
1.000
0.3241
6.417XIO'
8.605XIO'
Multiply by
777.5
3.086
1.000
1.980 XI0'
2.655XIO'
3.928 X10-'
1.558 X 10-'
5.050 X 10-'
1.000
1.341
2.928 Xio-'
1.162 Xio-'
3.767 Xio-'
0.7457
1.000
CONVERSION FACTORS
251
POWER
To Convert
From
To
BTU/hr ..
Ft-Ib/min
Ft-Ib/sec
Hp......
Kw. . . . ..
Kg-cal/sec
G-cal/sec
Tons of
refrig
BTU
per hr
1.000
0.07715
4.630
2,547
3,415
1.428X10'
14.28
1.2ooX10'
Ft-Ib
Ft-Ib
per min
per sec
12.96
0.2160
1.000
0.01667
60.00
1.000
33,000
550.0
44,250
737.6
1.851 X10 5 3,086
185.1
3.086
1.555X10 5 2,592
Hp
Kw
Multiply by
3.928X1O-' 2.92SX10-'
3.033X1O- 5 2.260X1O-'
1.820X1o-' 1.356X10- 3
1.000
0.7457
1.341
1.000
5.610
4.183
5.610 X10-3 4.183 X 10-3
4.712
3.514
Kg-cal
G-cal
per sec
per sec
6.999X1O- 5
5.402X10-
3.241 X 10-'
0.1782
0.2390
1.000
0.0010
0.8400
Tons of
refrig
0.06999
8.333X1o-'
5.402X1O-' 6.431X1O-'
0.3241
3.858X1O-'
178.2
0.2122
239.0
0.2845
1,000
1.191
1.000
1.191 X1o-"
840.0
1.000
INDEX
Acetylenes, physical constants of, 4
Activity cOF!'f5cien~J 48
for light h)-d:ocubons b absorber oils, 67
Adiabatic comp;'0mion of gases, 82-87
Air, enthalp:i of, 182-183
specific }'ea.t cf, 88
t,hermal conductivity of, 216
viscosity of, 176
Alcohols, physical constants of, 6
Aldehydes, physical constants of, 7
Amagat's l,fr", 136-137
Area, conversion table for, 249
Aromati~s (see al~o individual compounds)
physicai constants of, 5
specific gravity of saturated liquids, 142
vapor pressure of Cs, 38
viscosity of liquid, 162
A,S.T.M. distillation of petrolcum fractions,
11
average boiling points frOID, 15
equilibrium flash vaporir.ation curve
from, 223, 228-229
Avcrage boiling point3 of petrolcum fractions, 10-15
from crude ass"y (T,B.P,) distilhtions,
11
from 10% (or A.S.T.M.) distillations, i5
Benzene, enthalpy of, 112 I
latent heat of vaoorization of, 77
physical constants of, 5
specific gravity of the satnrated liql\id.
Butadiene-1,3, relative volatility of, 65

spccific gmvity of the saturated liquid,
141
v::.por pressure of, 36
Butane, enthalpy of, 101
fugacity function of, 55
latent heat of vaporization of, 94-95
Mollier diagram for, 135
relative volatility of C. hydrocarbons to,
65-66
specific gravity of the saturated liquid,
140
specific heat of vapor, 89
vapor pressure of, 30
viscosity of, 161
Butene-I, enthalpy of, 110
relative volatility of, 65
141
vapor pressurc of, 30
Butene-2, cis- and trans-, enthalpy of, 111
specific gravity of the satur:l.ted liquid,
141
Capacity of packed towers, 247

Carbon dioxide, enthalpy of, 182-183
vapor ?ressure of, 37
specific heat of, 88
viscosity of, Ift2
~b.ermn.l conductivity of, 216
Berl saddles. 246-248
viscosity of, 176
Blending index, viscosity, 156, 173
Cnrbon monoxide, enthalpy of, 182-183
Boiling point, of hydrocarbons, 2-5
of miscellaneous gases, 9
of miscellaneous organic compounds, 6-7
thermal conductivity oi, 216
of petroieum fractiallS, cubic average, 11
viscosity of, 176
menu avern.ge, 10, 1<1-15
Chn.racterization factor, definition, 12
molal average, 10, 14-15
from gravity and boiling point, 16
proper average for correlating physical
of typical crude fractions, 12, 17
data, 10
Columns (see Fractionating towers)
volume average, 10-11
Combustion (see also Flue gas)
weight average, 10, 14-15
heat of, fuel oils, 178, 180
Bubble-cap towers (see also Fractionating
hydrocarbons, 2-5
towers)
miscellaneous gases, 9
overall plate efficiency, 233, 245
miscellaneous organic compounds, 0-7
Butadiene-1,3, physical constants of, 3
253
112
254
INDEX
Combustion, heat of, paraffin and olefin

gases, 178, 181
petroleum fractions, 178, 180
refinery gases, 178-179
heat available from, fuel oils, 186-188
refincry gases, 184-185
Compressibility, of gases (see P-V-T relations)
of liquid petroleum fractions, 136, 143147
Compression, adiabatic, 82-87
Conductivity, thermal (see Thermal conductivity)
Constants, physical (see Physical constants)
Contraction, friction loss in pipes uue to,
204
Convection, heat 10SR by natural. 210
Conversion, of A.1'.I. to specific gravity
and pounds per I';allon, 138-139
of Engler to kinematic viscosi ty, 159
of Redwood seconus to kinematic viscosity, 15X
of Saybolt Furol seconus to kineml\tic
viscosity, 15~-159
of Saybolt Thermo viscosity to kinelIultie viscosity, J 60
of Saybolt Lniversal seconds to kinematic viscosity, 15X
tables [or, area, 2'19
density, 250
energy, heat, anel work, 250
force (weight), 249
lenl\th, 249
power, 251
pressure, 250
rate of flow, 250
temperatlll'e, 249
volume, 249
Critical pressul'C, of hydrocarbons, 2-5, 74
of normal paraffins, 71
pseudo-, of light hydrocarbon mixtllres,
71
of petroleum frael-ions, 73
true, of pet.roleulll fractions, 74
Critical telllpemture, of hydrocarbons. 2-5,
69-70
of light hydrocarbons, 70
of mis('ellaneous organic compounds, 6-7
of petroleum fractions, 72
Crude assay distillation, definition, 1,
average boiling points of petroleum fractions from, 14
equilibrium flash vaporization curve
from, 223-229
Crude fractions, classification of various, 13

typical, characteriz:Ltion factor of, 12, 17
gravity, A.P.I., 1:
molecular weight of, 22-23
viscosity index of lube fractions of, 12
Cubic average boiling of petroleum fractions, 11
Cyclohexane, physical constants of, 5
Cycloparaffins (see also individu:Ll compounds)
Cyclopent:Lne, physical constants of, 5
vapor preSSlll'e of, 39
Dalton's L:Lw, 45, 136
Density (s('e also Specific gravity)
conversion table for, 250
nitieal, hydrocarbons, 2-5
miscell:Lneous oq;anic compounds, 6-7
Dimethylacetylene, physical const:Lnts of, 4
Diolefins (-,ee also individual compounds)
physical constants of, 3-4
specific 1\1'lwity of satumted liquids, 141
Distillation (see A.S.T.M., Crude assay,
lind Tme boiling point distillations)
Efficiency of bubble-cap towers, 233, 245
Emissivity, radiant heat coefficients of, 209
Energy, conversion table for, 250
En~lel', degrees, conversion to kinematic
visco!$ity, 159
Elliargement, friction loss in p;pes due to,
201
Enthalpy of, :IiI', 182-183
benzene, I 12
butane, 101
butene-I, 110
butene-2, cis- and tl'ans-, III
ethane, 99
ethylene, 10~
flue gas components, CO" CO, T, etc.,
182-183
heptane, 104
hexane, 103
hydrocarbon vapors, eh:Lnge with pressure, 92
isobutane, 106
isobutene, 110
isopentane, 107
methane, 98
mixtures of light hydrocarbons, 78
pentane, 102
petroleum fractions, 80-82, 114-127
INDEX
Enthalpy of, propane, 100
propylene, 109
toluene, 113
Entropy (see ;\10Ilier diagrams)
Equilibrium flash vaporization, of known
mixtures, 222
of pctroleum fractions, 222-229
Ethanc, cnthalpy of, 99
MollieI' diagram for, 131
140
vapor pressurc of, 28
Ethers, physical constants of, 7
Ethylacetylcne, physical constants of, 4
Ethylene, cnthalpy of, 108
latcnt hcat of vaporization of, 94-95
Mollicr diagram for, 130
141
vapor prcssure of, 28
Feed pbtc, optimum, fractionating towers,
234
Fenske cquation, mllumum theoretical
steps at total reflux, 230
Fittings, equivalent lengths of, 193-194,
202-203
Flash vaporization, equilibrium, of known
mixtures, 222
.
of petrolcum fractions, 222-229
Flow of fluids, across wcirs, discharge
characteristics, 205
friction factor for, 193, 198
friction loss, contraction and enlargement, 204
pressurc drop across tubc banks, 206
streamlinc, prcssure drop in pipes, 198
turbulent, equivalent Icngths of fittings,
202-203
friction factor for, 193, 198
pressurc drop in pipes, 193, 198-201
Flow of hcat (sec Heat tmnsfer)
Flue gas, components, enthalpy of, 182183
percent CO, in, 189
pounds per pound of fuel, 190
thcrmal conductivity of, 192
viscosity of, 191
Force, convcrsion table for, 249
255
Fractionating towcrs (see also Fractionation)

bubble cap, overall efficiency of, 233, 245
optimum feed plate, 234
packed, capacity of, 247
H.E.T.P., 216
prcssurc drop in, 248
Fractionation, minimum reflux ratio, 231-
233
minimum theoretical steps (Fenske equation), 230-231
theoretical steps and reflux ratio, correlation of, 244
Francis formula for rectangular weirs,
205
Friction factor, for flow of fluids in pipes,
193, 198
Fuel oils, heat available from combustion
of, 186-188
heat of combustion of, 178, 180
Fugacity, of hydrocltJ'bon vapors, 62-63
of light hydrocarbons in absorber oils,
activity cocfficient, 67
function of, butane, 55
ethanc, 51
ethylcnc, 50
heptaue, 59
hexane, 58
hydrogcn, 61
isobutanc, 54
isopcntanc, 56
mcthane, 49
octane, 60
pentane, 57
propane, 53
propylene, 52
Gas(es) (see also Fine gas, Refinery gas,
and individual compounds)
miscellancous, enthalpy of, 182-183
spccific hcat of, 88
thermal conductivity of, 216
viscosi ty of, 176
Gasolines, vapor prcssure of, 44
Glycols, physical constants of, 6-7
Gravity, convcrsion from A.P.I. to specific
gravity and pounds per gallon, 138139
of typical crude fractions, 18
specific (sec Specific gravity)
Heat, available from combustion (see Com.
bustion)
capacity (see Spccific heat)
content (see Enthalpy)
.,
latent (see Latent heat of vap0rlZatlon)
256
INDEX
Heat, loss, by no.tural convcction, 210

by radiation, 209
transfer, to fluids insidc tubes, 211
to fluids outside tubes, 212
Height equivalent to tI theoret,ir.otl phte,
p:teked towers, 24(J
Heptane, enthalpy of, 101
latent hetlt of vaporization of, 94-95
140
viscosity of, 161
Hydroe:lrbon(s) (see also individual compounds an,l Arom"tics, Olefins, etc.)
critic"l temperature of, 69
light, eritic"l temperature of, 70
liquids, specific heat of, 93
vapors, chauge in enthalpy with pressure,
92
fugacity of, 62-63
P-Y-T relations of, 136-137, 148154
specific hcat of, 89, 91
vapor IJre8sure of, 40 -12
Hydrogen, fugacity function of, 61
viscosi ty of, 176
Isobutane, enthoJpy of, 106
140
Isobutene, cnth:llpy of, 110
specific gravity of the satur:lted liquid,
141
Isoparaffins (see also individual compounds)
molecular weight of, 20
Isopenlane, enthalpy of, 107
lat~nt heat of vaporization of, 94-95
pbysical constants of, 2
Isopen~ane,
rel'!'tive volatility of, 66

speCific gravIty of the saturated liquid
140
'
Ketones, physical constants of, 7

Kinematic viscosity, blending index Irom,
173
conversioll to, 15.1-156, 158--160
definition of, 155
temperature charts, 166-167
Latent heat of vtlporization, 76-77
of hydrocarbons, 76-77
of low boiling hydrocarbons, 94-95
of p"raffin hydroc:lrbons, 96-97
of petroleum fractions, 76-77
Length, conversion t"ble fur, 249
Log:lrithmie mean temperature diO'erence,
208, 217
correction fotctors for lllulti-pas.~ exch:lngers, 208, 218-221
Mean average boiling point, of pet,roleum
fractions, 10-11, 14-15
Melting point, of hydroc:lrbons, 2-;;
of inisr.ell,meous gases, 9
of miscelbncous organic compounds,
6-7
Methane, enth:llpy of, 98
latent he:lt of v:lporiz:ltion or, U1-95
MollieI' diagrams for, 128-129
physic:ll constants of, 2
specific gravity of thc satnrated liquid,
140
V:lpor pressure of, 27
Methy1:lcetylene, physical coustllnts of, 4
v:lpor pressure of, 35
Methylcyclopentane, physical cOIl.;tants of,
5
Minimum, reflux ratio, 231.-233
theoretical fmctionating steps, 230-231
Molal avemge boiling point, of petroleum
fractions, 10-11, 14-15
Molecular weight (see also Physical constants)
of p:lraffins, 20
of typical crude fractions, 22-23
Mollicr diagram (s) for, butane, 135
ethane, 131
ethylene, 130
methane, 128-129
INDEX
Momer diallram(s) for, propane, 133-134
propylene, 132, 134
Natural convection, heat loss to atmosphere
by, 210
Nitrogen, enthalpy of, 182-183
thcrmal conductivity of, 216
viscosity of, 176
Octane, enthalpy of, 105
latent hcnt of vaporization of, 94-95
140
specific hcat of vapor, 89
viscosity of, 161
Oil(s) (sec also Crude fractions and Petroleum fractions)
fuel, heat "vailable from combustion of,
186-1 8
hent of combustion of, 180
lube, viscosity index of, 156, 168-172
Olefins (sec also Hydrocarbons and individunl compounds)
critical temperature of, 69
hent of combustion of, 181
specific gravity of, 141
Olefins-acetylenes, physical constants of,
4-5
Optimum fccd point, fractionating towers,
234
'
Organic compounds, miscellaneous, physical constants of, 6-7
Oxygen, enthalpy of, 182-183
physical contitants of, 9
specific hent of, 88
viscosity of, 176
Packed towers (see Fractionating towers,
packed)
Paraffins (sec also Hydrocarbons and individual compouuds)
critical tcmperature of, 69
heat of combustiou of, lSI
molecular weight of, 20
normal, critical pressure of, 71
viscosity of, 16!
specific gravity of, 140
Pentane, enthalpy of, 102
257
Pentane, fugacity function of, 57

latent heat of vaporizntion of, 94-95
phYSICal constants of, 2
specific gravity of the snturated liquid,
140
viscosity of, 161
Petroleum fractions (sce also Crnde fractions and Hydrocarbons)
average boiling points of, 10-11, 14-15
critical temperature of, 72
enthalpy of, 80-82, 11'1-127
equilibrium 11,,"h vaporizntion of, 222-229
hent of combustion of, 178, 180
Intent heat of vaporization of, 76-77
liquid, thermal conductivity of, 213
thermal ~xp:lllsion of, 136, 143-147
pseudo-critical pressure of, 73
pseudo-critical temperntuI'C nf, 72
viscosit.y-temperature charts for, 166-167
Physicnl conRt'lnts of (sec also individual
compounds)
acetylenes, ,1
alcohols, 6
aillehydes, 7
aromatics, 5
cycloparaffins, 5
diolefins, 3-4
ethers, 7
glycols, 6-7
isoparaffins, 2-3
ketones, 7
normal paraflins, 2
olefins, 3
olcfins-ncetylcucs, 4-5
Pipe, steel, dimCllBions of, 202
Plate efficiency of buhble-cap towers, 233,
245
Power, conversion tahle for, 251
Pressure, conversion tahle for, 250
critieat ('Pc Critic,d pres"ul'e)
drop, across tube hanks, 206
due to fittings, 202
for streamline flow in pipes, 198
for turbulent flow in pipes, 198-201
in commercial pipr.s, 193, 199-201
effect of, on enthalpy of hydrocarbon
vapors, 92
on viscosity of gases, 177
vapor (sec "apor.pressure)
Pl'Opadiene, physical constants of, 3
141
Propane, enthalpy of, 100
258
INDEX
Propane, latent heat of vaporization of, 9495

MollieI' diagrams for, 133-134
specific gravity of the saturated liquid, 140
viscosity of, 161
Propylene, enthalpy of, 109
Mollier diagrams for, 132, 134
specific gravity of the satumted liquid,
141
Pseudo-critical pressure, 68
of mixtures of light hydrocarbons, 71
Pseudo-critical tempemture, 68
of mixtures of light hydrocarbons, 70
P-V-T rel:,tions of, hydrocarbon vapors,
136-137, 148-154
mixtures of gases, 137
R, gas constant, numerical values of, 137
Radiation, heat loss by, 209
Raoult's Law, 45
Raschig rings, 246-248
Rate of flow, conversion table for, 250
Rectification (see Fractionation)
Redwood viscosity, conversion to kinematic
viscosity, 158
Refinery gas, heat available from combustion of, 184-185
heat of combustion of, 178-179
Reflux ratio (scc Fractionation)
Reid vapol' pressure, conversion to true
vapor pressure, 4-1
Relative volatility of, C, hydrocarbons,
65-66
ethylene-ethane, 64
isopentane-pentane, 66
propylene-propane, 64
Reynold's number, e01'l'ection for equivalent
lenl-(th of fittings from, 203
friction factor from, inside pipes, 198
across tube banks, 206
heat trnnsfer film coefficient from, inside
tubes, 211
across tube banks, 212
Saybolt, seconds Furol, conversion to kinematic viscosity, 158-159
Saybolt, seconds Universal, conversion to

kinematic viscosity, 158
Thermo viscosity, conversion to kinematic viscosity, 160
Specific gravity, conversion from 0 \ PI
138-139
, .. "
conversion to density, 250
of aromatics, 5, 142
of diolefins, 3-4, 141
of hydrocarbons, miscellaneous gases and
organic compounds, 2-9
of olefins, 3, 141
of paraffins, 2-3, 140
Specific heat of, crude fmction vapors, 90
hydrocarbon liquids, 93
hydrocarbon and petroleum fraction
vapors, 91
light hydrocarbon vapors, 89
Steam, enthalpy of, 182-183
viscosity of, 176
Steel pipe, dimensions of, 202
Streamline flow of fluids, pressure drop in
pipes, 198
Temperature, conversion table for, 249
Theoretical stops, fractionating towers, 230,
233, 244
Thermal conductivity of, flue gas, 192
hydrocarbon gases, 215
liquid petroleum fractions, 213
water, 214
Thermal expansion of liquid petroleum
fractions, 136, 143-147
Tolnene, enthalpy of, 113
specific gravity of the saturated liquid, 142
vnpor pre"sure of, 37
viscosity of, 162
Towers (.,cc Fractionating towers)
Tme boiling point distillation (<ee Crude
assay distillation)
Tube banks, heat tmnsfer film coefficients,
212
pressure drop ncross, 206
Turbulent flow of fluids (see Flow of fluids,
turbulent)
Units, conversion of (see Conversion, tables
for)
Valves, equivalent lengths of, 202
Vapor pressure of, benzene, 37
bu tadiene-I ,3, 36
259
INDEX
Vapor pressure or. butane, 10
butene -I, 30
butene-2, cis- nnd trans-, 30
cyclohexane, 39
cyclopentane, 39
dimethylacetylene, 36
ethane, 28
ethylacetylen~, 36
ethyl benzene, 38
ethylene, 28
gasolines, 44
heptane, 33
hexane, 32
hydrocarbons, 40-42
isobutane, 30
isobutene, 30
isopentane, 31
methane, 27
methylacetylene, 35
methylcyclopentane, 39
octane, 34
pentane, 31
propadicne, 35
propane, 29
propylene, 29
toluene, 37
vinylncetylene, 36
xylene s,38
Vaporizatiun, eqnilibrium flash (see Equilibrium flash vaporization)
latent he:lt of (see Latent heat of vaporizatiun)
Vinylacetylene,
physical
consta nts
of,
vapor pressure or, 36

Viscosity, or aromatics, 162
of California crude fractions, 165
conversion of (see Conversion)
or flue gas, 191
of gases at high pressures, 177
of hydroc arbon vapors, 174-175
of Mid-C ontine nt oils, 164
of miscellaneous gasf's, 176
of normal paraffins, 161
of Pennsy lvania crude fractions, 163
Viscosity blending index, 156, 173
Viscosity index of lube oils, 156, 168-
172
Viscosity-Temperature charts, 166-167

Volume, conversion table for, 249
Water therma l conduc tivity ot, 214
Weight, average boiling point of petroleum
fractions, 10-11, 14-15
conversion table for, 249
Weirs dischal'i~e characteristics of, 205
Work; converSIOn tables for, 250
Xylenes, ]lhysi~al consta nts of, 5
specific grltvlty of the satura ted liquid,
142
viscosity of, 162

Data Book On Hydrocarbons. Application To Process Engineering (Maxwell, J. B.)

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DATA BOOK ON

ROBERT E. KRIEGER PUBLISHING COMPANY

ORIGINAL EDITION 1960

Printed and Published by

STANDARD OIL DEVELOPMENT COMPANY

All rights reserved. No reproduction in any form

PRINTED IN THE UNITED STATES OF AMERICA

Library of Congress Cataloging in Publication Data

Hydrocarbons, 2-Miscellaneous Organic Compounds, 6--MisceIlaneous Gases, 9

Average Boiling Point, 14-Characterization Factor, Hi-Gravity, 18

Paraffins, 20-Petroleum Fractions, 21

Paraffins and Olefins, 27-Diolefins and Acetylenes, 35-Aromatics, 37

Critical Temperature of Pure Hydrocarbons, 69-Critical Temperature

Heat of Combustion of Petroleum Fractions and Hydrocarbon Gases,

Friction Factor for Fluid Flow, 19B-Pressure Drop in Commercial

Heat Loss by Radiation and Natural Convection, 209-Heat Transfer

14. FRACTIONATING TOWERS.. ..

Minimum Reflux Ratio and Theoretical Steps, 23O-Correlation of

"Sclcdcd Values of Propertips of Hydrocarbons," Nal. Bur.

PHYSICAL CONSTANTS OF HYDROCARBONS

303.4 345.2 384 .4 421.3

16.0 -258.9 -296.5

2,2,3-Trimethylbutane (Triptane) ....................

Heat of combustion as a gas-otherwise as a liquid.

Critical temperature-boiling point correlation.

* Mixture of cis- and

PHYSICAL CONSTANTS OF HYDROCARBONS (Cont.)

Butyne-1 (Ethylacetylene) ...

Hexyne-1 (Butylacetylene) ...

Toluene ..... ...............

o-Xylene .... ...............

, Heat of combustion &8 a gas-otherwise &8 a liquid.

Critical temperature-boiling point correlatioil.

Mixture of cis- and trans' isomers.

PHYSICAL CONSTANTS OF ORGANIC COMPOUNDS

600 j600 Lb jgal

6.61 469.6 63.1

6.73 506.7 50.0 .273

148.1 -143.7 0.796

(CH ahCHCH 2OH

CH a(CH 2) aCH 20H

CH aCH 2C(OH) (CHah

GLYCOLS AND GLYCEROL

6.63 464.0 78.7 0.272

Propanetriol-1,2,3 (Glycerol). CH2(OH)CH(OH)CH 2OH

Propyl Ether .............. CH 3(CH 2)20(CH 2)2CH 3

Butyl Ether ............... CH 3(CH 2)30(CH2)3CH 3

Ethanal (Acetaldehyde) ..... CHaCHO

Butanal (Butyraldehyde) .... CH 3CH 2CH2CHO

* Calculated or estimated with a probable accuracy of 2%.

u Heat of combustion as a gas-otherwise as a liquid.

PHYSICAL CONSTANTS OF GASES

Carbon Dioxirle ......

Carbon Monoxirle ....

Ethyl Chloride .......

Hydrogen Chloride ...

Hydrogen Sulfide .....

Methyl Chloride .....

Sulfur Dioxide .......

Many physical properties of pure hydrocarbons can be correlated with specific

True critical temperature

Watson and Nelson, Ind. Eng. Chem. 26, 880 (1933).

CHARACTERISTICS OF PE'l'ROLEUM FRACTIONS