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I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY

320

TABLE
XXXIV.

STABILITY A S D CORROSION O F CALCIUM PERIIANGANATE SOLUTIONS AT

Control
- E2
El
Piessure, atm.
0 day
1 day.
5 days
10 days
19 days
21 days
56 days
h.InOa-, %
Original
Final
Change
Vol. of tube, ml.
Weight, grams
Initial
Final
Change
a

1.0
1.0
1.0
1.0
1.0
1.0

...

1.0
0.9
1.0
1.0
1.0
0.9
1.0

51.9
52.1
10.2
12.5

51.9
53.5
+1.6
10.5

ITD1010
-Al--^-'

A I , 2S'/aH
-___31

BZ

1.0
0.9
0.9
0.9
0.9
0.9

1.0
1.0
0.9
1.0
1.0
1.0

1.0
1.0
1.0
1.0
1.0
1.0
1.0

51.9
51.1
-0.8
9.43

5f.9
01.3
-0.6
8.87

A2

...

1.0
1.0
0.9
0.9

0.9
1.0
1.0

61.9
51.3
-0.6
9.02

.51,9
51.2
-0.7

2.7508
2.7511
+ 0 , 0003

2,7783
2.7763
+0.0008

8.93

...

1.0579
1,0579
0.0000

1.0575
1,0574
-0.0001

SS Type 304
-~--C1
c2
1.0
1.0
0.9
0.9
1.0
1.0

...

51.9
51.0
-0.9
8.48

Bakelite"
D1
D2

2.8946
2.8948

+0.0002

1.0

0.9
1.0
1.0
1.0

1.0

1.0

1.0
1.0

1.0

1.0
1.0

...

51.9
51.7
-0.2
12.69

2.9235
4.9235
0.0000

50 C.

1.0

1.0
1.0
1.0
1.0
1.0
1.0
1.0

Vol. 38, No. 3

51.9
51.7

51.9
51.8
-0.1
12.77

-c.2

12.55
4.596G
4.5970
4-0.0004

4 . G255
4.6259

-to.0004

Steel test piec:es coated according to CWB, Specification 196-131-207.

TABLExxxv. TESTO F

\rARIOUS ;\IArERIALS I N 5 1 f L . O F
CONCEKTRATED CALCIUM PER\lANGANATE SOLT7TIOS AT ROoX

Koroseal and polyethylene are suitable


for gaskets and
similar applications.
Phosphates are thc
best stabilizers of those
tested. There appears
to be a maximum
concentration above
which a stabilizer
ceases to function.
Concentrated peroxide is insensitive to
shock.
Concentrated calcium
permanganate
solutions are stable a t
temperature up to at
least 50" C. Ordinary
steel containers may be
used for its storage
and shipment.

TEMPERATURE
IN COVERED
TESTTUBE
Wt.
Initial,
grams
0.2376

after 7 Daysa
_ _ Wt,
_ _ _after
_ ~ - 28 Daysa
Final, Change, Initial, Final, Change,
mg.
grams
grams
grams
mg.
0,2375
-0.1
0,2091 0,2093
+0.2

Garlock 7790
Saran tubing
Clear
0.5264 0.5265
+O.l
0.4954 0.4957
Dark
0.6333 0.6331
-0.2
0 , 6 0 2 7 0,6028
Koroseal 117
0.9546 0.9538
-0.8
0.8250 0.8748
2s Alb
0.9486 0,9487
4-0.1
0.9523 0 , 9 5 2 6
+0.2
1.4229 1.4233
SS 446O
1.4152 1.4154
a Test pieces were approximately 0.2 X 0.7 X 2.9 cm.
b Aluminum was given Becco treatment.
C Stainless steel was pickled i n 10% HzSOa a t 80'
C.

4-0.3
+O.l

-0.2
+0.3
+0.4

LlTERATURE CITED

(I) Gilbert, H. N., and Reichert, J. S. (to Du Pont Co.), U. S.


Patents 2,001,509 (1935) and 2,091,178 (1937).
(2) Maas, O., and co-workers, J. Am. Chem. SOC.,42, 2548-74
(1920) ; 44, 2472-80 (1922); 46, 200-308, 2693-2700 (1924);
51, 674-87 (1929).
(3) Reichert, J. S., Chem. Eng. News, 21, 480 (1943).
(4) Reichert, J. S.(to Du Pont Co.), U. S. Patent 2,008,726 (1935).
(5) Spring, W., 2 . anorg. Ch,em., 8,424-33 (1895).
RELEASED
b y authority of the Chief, Chemical Warfare Service.

Vapor Pressure-Temperature
Nomographs
SAMUEL B. LIPPINCOTT AND MARGARET M. LYMAN
Esso Laboratories, Standard Oil Development Company, Elizabeth, N . J .
Nomographs are presented that give vapor pressure-temperature relations for compounds boiling from -50" to
550' C. If any two of the three related quantities, vapor
pressure, temperature, and normal boiling point, are
known, the third can be found by a single setting of a
straight edge.

THE

need often arises in the laboratory and plant for a rapid


method of calculating vapor pressure-temperature relations.
A number of nomographs for this purpose have appeared in the
literature, but for the most part each nomograph represents only
a single class of compounds, and each compound is represented
by a given point. The nomographs presented here can be used
for all pure liquids boiling between -50' and 560" C. The slide
rule for vapor pressure described by Miles ( 2 ) can be applied to a
similar range of compounds. The nornographs have the advantage that they do not have to be cut out and mounted before use.
Miles gives a complete bibliography of the subject.
The nomographs presented here are based upon a method for
the correction of boiling points to standard pressure by Hass and
Xewton (1). They used a modification of the integrated form of
the Clausius-Clapeyron equation:
4

At =

(273.1

+ t)(2.8808 - log p )

+ + 0.15

(2.8808

- log p )

where At =

C. to be added to obseTed boiling point

t = observed boiling points, C.


2.8808 - log p = log of observed pressure subtracted

from log of 760


d. = quantity proportional to entropy of vaporization of 760 mm.

Thc solution of this equation is rather laborious and time consuming. First a value for must be determined. For this purpose all compounds are divided arbitrarily into eight groups and
listed (Tables I and 11). Substances not included in the tabula,tion may be classified by grouping them with compounds which
they resemble closely in physical and structural properties.
When the compound has been classified, the value of + can be
estimated from a graph in which is plotted against boiling point
for each of the eight groups. If the normal boiling point is the
unknown, a t least two calculations must be made. The first gives
an approximate boiling point; the latter, in turn, is used to obtain a value of + from which to make the more accurate calculxtion.
The nornographs (Figures 1 and 2) solve the equation by a
single setting of a straight edge. The eight curves through the
center of each nomograph represent. the eight groups. The scale
along these Eurves gives the normal or standard boiling point a t
760 mm. Thc scale a t the right gives the observed boiling point,
and the logarithmic scale a t the left gives the observed pressure.

INDUSTRIAL AND ENGINEERING CHEMISTRY

March, 1946

321

Group

760

-1
-31

100

90

-I 0 4

00

70

60

r"
2
E

zl5
.
4

'Oi

G
Copyright, 1946,

by S.B.Lipp;nco+t

Figure 1.

Vapor Pressure-Temperature Nomograph for Low-Boiling Compounds

INDUSTRIAL AND ENGINEERING CHEMISTRY

322

Vol. 38, No. 3

Group

LI

E
20

fL

,704

15

3
21

-1

2.5

2
1.5,

i Copyright, 1943, by

S.E.Lippinsott

Figure 2.

Vapor Pressure-Temperature Nomograph for High-Boiling <:ompoiirid.s

3
354

INDUSTRIAL AND ENGINEERING CHEMISTRY

March, 1946

TABLE

TABLEI
COMPOUND
Acetaldehyde
Acetic acid
Acetic anhydride
Acetone
ticetophenone
Amines
Ammonia
n-Amy+ alcohol
Anthracene
Anthraquinone
Benzaldehyde
Benzoic acid
Bensonitrile
Benzo henone
Bensyy alcohol
Butylethylene
Butyric acid
Camphor
Carbon disulfide
Carbon suboxide
Carbon sulfoselenide
Chloroanilines
Chlorinated derivatives
Cresols
,
Cyanogen
Cyanogen chloride.
Dibenzyl ketone
Dimethylamine
Dimethyl oxalate
Dimethylsilicane
Esters
Ethyl alcohol
Ethers
Ethvlamine

GROUP B.P.,

3
4
6
3
4
3
5
8
1
1
2
7
2
2
5
1
7
2
1
2
2

COMPOUND
Heptanoic acid
Hydrocarbons
Hydrogen cyanide
Hydrogen fluoride
Isoamyl alcohol
Isobutyl alcohol
Isobutyric acid
Isocaproic acid
Mercuric chloride
Mercurous 'chloride
Methyl alcohol
Methylamine
Methyl benzoate
Methyl ether
Methyl ethyl ether
Methyl ethyl ketone
Methyl formate
Methyl salicylate
Naphthols
Nitrobenzene
Nitromethane
Nitrosyl ohloride
Nitrotoluenes
Nitrotoluidinea
Phenanthrene
Phenol
Phosgene
Phthalic anhydride
Propionio acid
n-Propyl alcohol

20.2
118.1
140.0
56.5
203

....

-33.3
138
341
380
179.5
249
190.7
306
205
64.1
164
204
46.3
7
84.5

.. .. .. ..

3,

....

4
4
3
2
4
4
2
3
8
2
4
7
3
3

-20.6
13.8
330.5
7.4
163.3
-20.1

....
78.6
....

GROUP B.P.,

c&ino;le

Sulfur dioside
Sulfur monochloride
Tetranitromethane
Trichloroethylene
Valeric acid
Water

16.6
197.2
10.7
100.7
189

4,

* Same group

C.

....

as though halogen were hydrogen,

4 straight edge connecting an observed pressure with the corresponding temperature indicates the normal boiling point on the
center scale by its intersection with the curve representing the
gwup to which the compound belongs. If any two of the three
related quantities (vapor pressure, temperature, and normal
boiling point) are known, the third can be found by a single setting of the straight edge.
Typical compounds are listed in alphabetical order in Table I
and divided into the eight groups in Table 11. If a compound is
not listed in Table I, i t can be placed in a group containing similar
substances by referring to Table 11. For example, amines in
general are classified in group 3, but dimethylamine and ethylamine are in group 4, and methylamine is in group 5. If ethylmethylamine were under consideration, it would be placed in
group 4. Dibutylamine would be placed in group 3. Hydrocarbons] in general, are in group 2, but there are exceptions, anthracene, phenanthrene, and butylethylene being listed in group 1.
The use of the nomograph can be illustrated best by an example. Bis-8-chloroethyl ether distills at 59' at 10 mm. What is
the normal boiling point, and at what temperature will it distill
when the pressure is 25 mm.? Chloroethyl ether is not listed in
Table I, but halogen derivatives are stated to be in the same group
as though the halogen were hydrogen, and therefore it belongs
in group 2 with ethers. The straight edge is placed so that i t
connects 10 111111. on the pressure scale with 59' on the temperature scale, and the point of intersection with the group 2 curve
TABLE111. COMPARISONOF CALCULATED
AND LITERATURE
6
VALUESFOR VAPORPRESSURE-TEMPERATURE
DATA
No. of
Compounds
Acids, carboxylic
Alcohols
Amines
Tbtpr.

Halogenated compohnds
Hydrocarbons, aromatic
Hydrocarbons, aliphatic
Phenols
Miscellaneous
Total

7
6
9
12
8

7
19
6
10
84

No. of
Points

56
77
60

70
86
86
315
64
87
890

3i3

Deviation, C.
Av. Abs.
Max.

1.4
0.9
0.7
0.9
0.4
0.6
0.8
1 .o
0.8

0 9

7.0
3.0
8.0
3.5
3.0
3.0
3.0
6.0
4.2
8.0

7
2
3
2
8
8
6
7
3
8
7
6
3
3
3
2
4
2'
3
3
3
4
2
2
1
5

2
2
5
8
2
2
4
1
3
1
7
6

C.

221

....

26
19.4
132
108
154.5
207.7
302
383.7
64.7
-6.6
199
-23.6
10.8
79.6
31.5
223

iio:s
101
-5.6

....

&io*

182 .
8.3
284.5
141.1
.97.2
237.3

....
-10.0

138
125.7
87
187
100.0

GROUPI
Anthracene
Anthra uinone
B u t let% lene
Cargon dmlfide
Phenanthrene
Sulfur monochloride
Trichloroethylene
GROUP2
Benzaldehyde
Benzonitrile
Benzo henone
Camptor
Carbon suboxide
Carbon sulfoseleniae
Chlorohydrocarbons
Dibenzyl ketone
Dimethylsilicane
Ethers
Halogenated hydrocs trbons
Hydrocarbons
Hydro en 5uoride
Methy'! ethyl ketone
Methyl salicylate
Nitrotoluenes
Nitrotoluidines
Phosgene
Phthalic anhydride
Sulfides
Quinoline

11
GROUP3 (Cont'd)
Nitrobenzene
Nitromethane
Tetranitromethane
GROUP4
Acetic acid
Aceto henone
CresoE
Cyanogen
Dimethylamine
Dimethyl oxalate
Ethylamine
Glycol diacetate
Methyl formate
Nitrosyl chloride
Sulfur dioxide
GROUP5
AMMOnia
Benzyl alcohol
Methylamine
Phenol
Propionic acid
GROUP6
Acetic anhydride
Isobutyric acid
Water

GROUP7
GROUP3
Acetaldehyde
Acetone
Amines
Chloroanilines
Cyanogen chloride
Esters
Ethylene oxide
Formic acid
Hydrogen cyaqide
Mercuric chloride
Methyl benzoate
Methyl ether
Methyl ethyl ether
Naphthols

Benzoic acid
Butyric acid
Ethylene glycol
Heptanoic acid
Isocaproic acid
Methyl alcohol
Valeric acid

GROUP.^
n-Amyl alcohol
Ethyl alcohol
Isoamyl alcohol
Isobutyl alcohol
Mercurous chloride
n-Propyl alcohol

is the normal boiling point, 178". The straight edge is rotated


about this point to 25 mm. on the pressure scale. The reading on
the temperature scale, 77", is the boiling point a t 25 mm.
I n order t o check the accuracy of the nomographs, seventyfive problems were solved, and the answers checked with those
obtained by mathematical calculations. Sixty-seven of the
answers agreed with the calculated within 1" C. Only one answer
differed from the calculated by more than 2". A further check
was made by determining with the nomographs the temperatures
a t which certain compounds possessed given vapor pressures and
comparing the answers with published data. Some nine hundred
sets of data representing eighty-four compounds were checked.
The average absolute deviation of the nomographic values from
the published values was 0.9' C. The maximum deviation was
8.0" C. These data are given in Table I11 as they apply to various types of compounds. The larger deviations are associated
with the amines, carboxylic acids, and phenols. It is possible
that some of the larger deviations are due to inaccuracies in the
published data. I n fact, in some cases in which the nomographic
and the published values disagreed greatly, a search of more
recent literature revealed values that checked closely with the
nomograph. These results were obtained by using a larger size
nomograph'.
ACKNOWLEDGMENT

The authors are indebted to their colleagues at the Standard


Oil Development Company for suggestions during the formative
period of these nomographs, and t o Mrs. B. M. Vanderbilt for
the lettering of the charts.
LITERATURE CITED

(1) Hasa, H. B., and Newton, R. F.,in Handbook of Chemistry and


Physics, 28th ed., p. 1731, Cleveland, Chemical Rubber Pub.
Co., 1944; Cragoe, in "International Critical Tables", Vol.
111, p. 246, New York, McGraw-Hill Book Co., 1928.
(2) Miles, F. T., IND.ENG.CHEM.,35, 1052 (1943).

_
.

1 The larger size nomographs (approximately 10 X 14 Inches) may be obtained upon request from 9. B. Lippincott, as long a8 the supply lasts.