1116 T H E J O U R N A L OF I N D U S T R I A L A N D ENGINEERING C H E M I S T R Y
12
SUMMARY
I-A convenient and rapid method was devised for
comparing t h e film-forming properties of possible
anti-dimmers. By this niethod one observer made
56 tests in I j minutes,
11-Organic sulfates as a class are not effective;
the presence of t h e sulfonic acid group does not guar-
antee effectiveness; t h e position of sulfonic acid groups
is of little importance; sodium benzene trisulfonate
is less effective t h a n t h e di- or monosulfonate; naph-
thalene ring sulfonates are no better t h a n benzene
ring sulfonates; t h e amino and hydroxyl groups are
of no material value.
111-High molecular weight is not a vital factor as
shown by poor results with Twitchell’s benzene stearo-
sulfonic acid and similar compounds. Since moisture
should condense in films, rather t h a n in drops, for good
visibility, t h e best anti-dimmers should lower t h e sur-
face tension of water greatly. They must be soluble,
but not too soluble or they have no staying powers:
They should also be deliquescent enough t o prevent
drying out.
IV-Alkali soaps of unsaturated f a t t y acids are
much superior in film-forming power t o soaps of sat-
urated f a t t y acids.
V-Soaps in general are improved b y t h e addition
of a few per cent of glycerol, I O t o I j per cent sodium
hydroxide and a few per cent of rnarine oil. Water
glass in small amount serves well as a binder.
ORIGINAL PAPERS
PHTHALIC ANHYDRIDE. 11-THE MELTING POINT OF
PURE PHTHALIC ANHYDRIDE. THE SYSTEM:
PHTHALIC ANHYDRIDE-PHTHALIC ACID
By K. P. MONROE
Reccived September 13, 1919
An interesting consequence of t h e recent develop-
ment by Gibbs and co-workers’ of a catalytic process
for air oxidation of naphthalene t o phthalic anhydride
has been t h a t t h e consistent melting point ( 1 3 1 ~ )
of t h e purified product2 exceeds by three degrees t h a t
previously recorded in t h e literature.3 Both practical
1 See first article of this series, “Phthalic Anhydride, I,” by H. D.
Gibbs, THISJOURNAL, 11 (1919), 1031.
* Phthalic anhydride derived from both laboratory and factory opera-
tion of the air oxidation process was tested in the usual capillary tube
manner by various workers. In each case the crude product was purified
by re-sublimation; the mateiial was chemically pure so far as could be
detected by titration.
a Reilstein, Handbuch d . org. Chem., 2 (1794) (3rd Ed.), gives 1.78’.
with references t o the following:
Laurent, Liebig’s Ann. d . Chem., 19 (1836); 38, gives 105’, presumably
an the Reamur scale (131’ C . ) . Phthalic anhydride was prepared from
phthalic acid by one sublimation a t atmospheric pressure.
Lossen, I b i d , 144 (1867), 76, gives 128’. Phthalic anhydride was
prepared from phthalic acid by sublimation a t atmospheric pressure. This
melting point was verified by testing phthalic anhydride from phthalic
acid ,prepared by various methods, which are not enumerated.
Anschiitz, Ber., 10 (1877), 326, gives 127’. Phthalic acid was de-
hydrated by acetyl chloride, which was removed by absolute alcohol;
crystals of phthalic anhydride were pressed between filter paper.
Lachowicz, Ibid., 17 (1884), 1283, gives 128O. Phthalyl chloride was
warmed with lead nitrate; phthalic anhydride was recrystallized from
benzene.
Stohmann, J. pvakt. Chem., 40 (1889), 139, gives 128’. Phthalic
anhydride prepared by distillation of commercial phthalic acid was re-
crystallized from benzene-ligroin mixture.
Vol. 11, No.
100 parts sodium salt of 65 per cent sulfonated rape oil, 35
per cent water
Sulfonated 20 parts sodium hydroxide
Rape Oil 2 5 parts water glass syrup
3 parts glycerol
3 parts marine oil
. Dried to form a solid stick when compressed
15 parts sodium hydroxide
3 parts water glass syrup
__
3 -Darts alvcerol
I 3 parts marine oil
[ Dried t o form a solid stick when compressed
OBERLINCOLLPIGE
OBERLIN,OHIO
-7
and theoretical considerations led t o t h e present in-
vestigation, with t h e object of establishing t h e melt-
ing point of pure phthalic anhydride and also of ob-
serving t h e melting points of known mixtures of phthalic
anhydride with phthalic acid, t h e impurity most
likely t o be found in t h e technical anhydride as well
as in t h e samples examined by t h e earlier observers.
Although numerous titrations of re-sublimed phthalic
anhydride derived from t h e air oxidation process
indicated a high degree of purity, i t was first deter-
mined t o adopt a still more rigorous purification. This
material’ was warmed in a vacuum oven for 5 hrs.
a t g o o , fused carefully in a casserole and decanted
into a mortar. For t h e purpose of decomposing possi-
ble traces of phthalic acid and separating any non-
volatile impurities, t h e pulverized anhydride was
twice re-sublimed in vacuo in t h e presence of phos-
phorus pentoxide. The apparatus designed for this
sublimation is illustrated in Fig. I . A glass tube, A ,
sealed a t one end and widened t o thrice its diameter
a t t h e other was fitted co-axially inside a longer tube,
B, also sealed a t one end, with a ground glass joint.
Through a phosphorus pentoxide bulb, C, t h e system
was evacuated t o a pressure of approximately four
millimeters by a vacuum pump. On warming B,
phthalic anhydride contained in t h e lower portion
vaporized a n d after filtering through a tight plug
of glass wool was condensed on t h e lower portion of
A, which was cooled by a n air stream.
1 Thi; crystallized in long, colorless glistening needles.
Dec., 1919 T H E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y
Results of a large number of sublimations indicated
t h a t t h e only detectable impurities were occasional
minute traces of t a r filtered out by t h e glass wool,
and a trace of nonvolatile residue. Titration and
combustion' established t h e chemical purity of t h e
final sublimate. N o difference between t h e first
and second vacuum sublimate could be detected
either b y analysis or b y melting point test in t h e ac-
curate manner t o be described later.
FIG.1-VACWWM SUBLIMATION APPARATUS
It will be noted, however, t h a t t h e method of total2
titration leaves much t o be desired as a test for the
presence of minute amounts of phthalic acid in t h e
anhydride, for t h e difference between t h e molecular
weight of phthalic anhydride (148.07) and t h a t of the
acid (166.09) is so slight ( 1 8 . 0 2 ) t h a t with usual analy-
tical accuracy this method cannot detect with cer-
tainty less t h a n approximately I per cent of acid.
d number of attempts at digerential titration of acid
in t h e presence of anhydride, in which mixtures were
dissolved in nonaqueous solvents and titrated with
N / I O NaOH, indicated t h a t t h e anhydride is rapidly
hydrated in t h e presence of excess alkali. The fol-
lowing method was finally devised by E. Q. Adams,3
of this laboratory, and is a remarkably sensitive test
for traces of phthalic acid in t h e anhydride:
A half gram sample of t h e anhydride is dissolved
10.5320 g . and 0.5956 g. sublimate required 7.206 and 8.042 mllli-
moles "OH. Calculated weights anhydride: 0.5333 g. and 0.5952 g.
0.3233 g. sub1imat.e gave on combustion 0.6765 g. COz and 0.0905 g.
1 1 2 0 . Per cent C = 64.8, per cent H = 3.1. Calculated. Per cent
C = 64.9, per cent H = 2.7.
2 This method involves the addition of excess N / 5 NaOH t o weighed
samples of the anhydride in glass stoppered flasks, which are warmed on
the steam bath for an hour. T h e excess alkali is then titrated by A7/S
HCI.
a Dr. Adams is continuing t h e investigation of this and other methods
for differential titration of phthalic acid in the presence of the anhydride.
1117
in 5 0 cc. of acetone, a few drops of a solution of brom-
phenol blue1 are added, and t h e acetone solution is
titrated with M / I O solution of normal potassium
phthalate in 80 per cent alcohol. If phthalic acid is
present the end-point of t h e titration is reached when
sufficient normal phthalate solution has been added
just t o produce t h e acid phthalate, and further addi-
tion of normal phthalate solution causes a color change
t o indigo blue. The original color in t h e acetone
solution is pale yellow, while t h e tint a t t h e end-point
is greenish blue. Unfortunately, t h e end-point is
not sharp, since i t is difficult t o reproduce t h e exact
shade of green. Nevertheless, this is a very sensitive
test for t h e absence of traces of phthalic acid in t h e
anhydride. When t h e second sublimate was tested
in this manner, a single drop (0.03 cc.) of normal
phthalate solution caused a color change t o indigo-
blue, showing t h a t t h e end-point must have been ex-
ceeded, and t h a t this sample of anhydride must have
contained less t h a n 0.1 per cent acid.
To determine t h e melting point of t h e second subli-
mate, approximately 15 g. were placed in a wide test
tube, which was closed by a stopper in which were
inserted a Reichsanstalt "Centigrade-Normal" short
stem thermometer2 and a glass guide t u b e for t h e
platinum stirring rod. The test tube was placed in
a snugly fitting stoppered glass air-bath3 clamped
vertically in a liter sulfuric acid bath, which was
stirred b y a turbine. After fusion t h e temperature
was lowered slowly t o t h e point of incipient crystalliza-
tion while t h e melt was stirred constantly b y a me-
chanical device. The equilibrium temperature of
crystals and liquid was 1 3 0 . 8 4 O . ~ A melting point
identical within experimental error was obtained under
similar conditions for t h e original anhydride which was
t h e source of t h e carefully purified material, confirm-
ing t h e previous conclusion t h a t no more t h a n traces
of impurities were contained in this.5
I n an effort t o search out sources of discrepancy
between t h e values previously recorded in t h e litera-
ture and t h e melting point of pure phthalic anhydride,
which seemed now definitely established, samples of
Kahlbaum's "Phthalsaure Anhydrid"6 were ex-
amined in t h e usual capillary tube manner. I t was,
indeed, observed t h a t t h e material began t o sinter
a t 128-12g0, t h a t a liquid meniscus appeared near
1 3 1 O , b u t t h a t t h e solid phase did not completely
disappear until 178". On examining a larger quantity
in the manner described for t h e pure anhydride a
well defined freezing point was observed a t 15g.8", but
1 This is the abbreviated name for tetrabromphenolsulfonaphthalein.
2 This was graduated t o fifths of degrees, and recently calibrated by the
Bureau of Standards.
8 For description see Phthalic Anhydride, 111, the accompanying third
article of this series (p. 1119).
4 Under these conditions no correction is necessary, for the exposed
stem was but 15", and the portion of thermometer not submerged in the
melt was surrounded by air and vapor in the inner tube a t a temperature
differing but slightly from t h a t of the melt.
6 Through the courtesy of Prof, G. A. Hulett the writer obtained a
sample of phthalic anhydride prepared by sublimation from pure phthalic
acid which was dehydrated in vacuo a t 115'. This anhydride melted a t
131' when tested in the capillary tube.
6 Presumably obtained by sdblimation from phthalic acid derived by
one of the "wet" oxidation methods, which was the universal method of
preparation before development of the air oxidation process.
I118 T H E JOURNAL OF I N D U S T R I A L A N D ENGINEERING CHEMISTRY Vol. 11, No. 12

after this lag t h e temperature fell steadily with con- TABLEI-FREEZING POINTS OF MIXTURESOF PHTHALIC ANHYDRIDE
AND
PHTHALICACID
tinual separation of crystals t o 129.6”,where t h e ap- WEIGHT MOL.
PER CENT PER CENT FREEZING
pearance of a distinctly different solid phase was ob- ACID ACID POINT
served and the thermometer halted until solidifica- Solid Phase: Anhydride
0.0 0.0 130.84
tion was complete. Since the impurity most likely 0.29 0.26 130.7
0.98 0.87 130.4
in phthalic anhydride prepared by sublimation from 1.44 1.30 130.1
Eutectic
phthalic acid is t h e acid itself, i t seemed probable 1.96 (interpolated) 1.75 (interpolated) 129.74
t h a t the Hahlbaum material contained a considerable Solid Phase: Acid
2.02 1.81 130.0
admixture of phthalic acid, and t h a t 1 2 9 . 6 ’ would 2.44 2.18 131.9
lie near t h e eutectic temperat cid and anhydride. 2.70 2.41 133.2
3.02 2.70 136.3
Analyses1 confirmed t h e conclusion, and 3.47
3.91
3.10
3.50
137.2
139.7
subsequent determination of t h e eutectic temperature, 4.27 3.83 141.1
4.80 4.30 143.8
using pure materials, gave t h e value 129.74’. 5.57 5.00 146.4
To obtain additional evidence upon the melting
hydride. It may be pointed o u t t h a t t h e capillary
point of pure phthalic anhydride, the Kahlbaum
tube method is a sensitive criterion for presence of
product was twice re-sublimed in the vacuum apparatus.
acid in t h e anhydride if the temperature a t which solid
T h e second sublimate was observed t o have a constant
acid completely disappears is noted, for in t h e capillary
freezing point a t 1 3 0 . & ~ . ~
tube solid acid usually survives much above the true
Since the behavior of Kahlbaum’s “Phthalsaure melting point of t h e mixture.
Anhydrid” confirmed t h e previous conclusion t h a t
presence of phthalic acid is a factor which must be
cons’idered in observations upon anhydride prepared
by sublimation from t h e acid, mixtures of t h e pure
anhydride with very pure phthalic acidg were weighed
into t h e t e s t ’ t u b e and t h e freezing points were de-
te.rmined as for t h e pure a n h ~ d r i d e . ~
unfortunately t h e limitations of this method were
such t h a t only a very restricted region of this system
could be explored, for, as will be observed from t h e
steep slope of the right-hand curve in Fig. 2, the tem-
peratures necessary t o fusion soon became so high t h a t
satisfactory Checks cobld not be obtained. Only those
experiments in which close duplicate freezing points
could be obtained are noted in the graph a n d table.
Although i t was not feasible t o seed t h e melt, very
great care was taken t o lower the temperature ex-
ceedingly slowly5 in t h e neighborhood of t h e freezing
point while t h e walls of t h e tube were continually
scratched by t h e platinum stirring rod, operated by
a mechanical device. 0 2 4 ’ Percent
I n t h e light of these d a t a i t is obvious t h a t any 0 2.24 4.46 6.68 Weiqhf per cent
mixture of pure phthalic anhydride with the pure acid Per cent Acid
will, when tested in t h e capillary tube, begin t o sinter FIG.
2-PREEZING-POINT CURVES FOR S Y S T E M PHTHALIC ACID-PHTHALIC
ANHYDRIDE
a t t h e eutectic temperature (12g.74’), which may
obviously be depressed by other impurities in the an-
It is of interest t o note the bearing of t h e results
10.6165 g. and 0.4423 g. Kahlbaum’s “Phthalsaure Anhydrid” re- in Table I upon t h e melting point of pure phthalic
quired 8.202 and 5.902 millimoles NaOH. calculated weights anhydride:
0.6089 g. and 0.4368 g. Calculated per cent phthalic acid: 10.0 and 10.3. acid, for on account of t h e readiness with which this
0.2891 g. Kahlbaum’s “Phthalsaiire Anhydrid” gave on combustion decomposes near its melting point into the anhydride
0.6729 g. COz and 0.0729 g. Hz0. Per cent C = 63.7, per cent H = 2.8.
Calculated for mixture containing 10 per cent phthalic acid: per cent
and water, the melting point may be approximated only
C = 64.1, per cent H = 2.8 roughly b y direct measurement.’ Direct extrapola-
* 0.5126 g. and 0.6465 g. sublimate required 6.936 and 8.748 milli- tion of t h e right-hand curve in Fig. 2 is not feasible,
moles NaOH. Calculated weights anhydride: 0.5134 g. and 0.6475 g.
a This was prepared by boiling the pure anhydride with distilled water, 1 T h e early impression t h a t phthalic acid melted a t 184’ (Lossen,
subsequent recrystallization from hot water, and thorough drying at room Loc. c&), near which its water vapor tension reaches atmospheric pressure
temperature i n bacwo over phosphorus pentoxide. and the acid decomposes rapidly to a mixture containing anhydride, was
0.7694 g. phthalic acid so prepared required 9.268 millimoles NaOH. first corrected by Ador, A n n . , 163 (1872), 230, who states t h a t pulverized
Calculated weight acid: 0.7697 g. phthalic acid melts a t 203”, while whole crystals melt a t 213O.
4 For discussion of the applicability of this method t o mixtures of I n an attempt t o verify Ador’s results a quantity of very pure phthalic
substances which sublime readily at the melting point see Phthalic An- acid was sealed in an evacuated glass tube, which was attached to a ther-
hydride, 111, the accompanying third article of this series. No ap- mometer and immersed in a paraffin bath which was vigorously turbined.
preciable sublimation was observed during the composition range given. On heating t h e bath very slowly, in order t o prevent thermal lag, the ma-
* This procedure was especially necessary in determining the freezing terial in the tube was observed t o melt a t 199-200°. This must, however,
points on the right-hand curve in Fig. 2, for since each mixture contained be regarded as merely a rough minimum value, for a t this temperature t h e
a relatively minute mol. fraction of acid, separation of this as solid phase water vapor tension exceeds one atmosphere and the melt must contaix
caused a rapid change in composition of the melt. very appreciable amounts of dissolved anhydride and water.
 T B E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C E E M I S T R Y 11’19
Dec., 1919

but if one plots on a large scale t h e reciprocals of t h e near the upper end and SO extended t h a t when t h e
absolute freezing points against t h e logarithms of t h e air-bath was clamped vertically in a liter sulfuric acid
mol. fractions of phthalic acid a straight line results, bath t h e test tube was entirely below t h e acid level.
from which t h e melting point of pure phthalic acid is
indicated t o be 2 0 8 O * 2’. This linear relation is
predicted on t h e assumption t h a t t h e freezing-point
curve conforms t o t h e law deduced for ideal systems,
for it follows from Equation I in the-accompanying
third article of this series t h a t

T
I _--_-
- I
To
log10 x
C
when
c = 0.4343 L R
and T = freezing point of t h e mixture, To = freezing
point of pure phthalic acid, x = mol. fraction of
phthalic acid in t h e mixture, L = molecular heat of
fusion of phthalic acid, and R = t h e gas constant.
SU Y MA R Y
The melting point of pure phthalic anhydride has
been determined ,to be 130.84’, and t h e freezing
curves for t h e system: phthalic anhydride-phthalic
acid have been established within t h e limits of compo-
sition for which t h e experimental method is applicable.
By graphical extrapolation t h e melting point of pure
phthalic acid is indicated t o be 2 0 8 ’ * 2 ” .
COLORLABORATORY
U. 5. BUREAUO F CHEMISVRY
WASHINGTON, D. C .
--
PHTHALIC ANHYDRIDE. 111-THE SYSTEM: NAPH-
THALENE-PHTHALIC ANHYDRIDE
B y K. P. MONROE
Received September 13, 1919
Investigation of t h e freezing-point curves of this
system was undertaken in order t o assist the solution
of certain problems arising in fractional sublimation
of t h e mixture of naphthalene and phthalic anhydride
which is t h e crude product of t h e air oxidation process
developed b y Gibbs and co-w0rkers.l Apart from
their practical value, t h e results are of interest in t h a t --
they offer striking conformation t o t h e familiar thermo-
dynamic law which determines t h e freezing-point FIG.1
curves of ideal systems, while the following experi- Since t h e air-bath was also stoppered, with b u t a
mental method which has been devised would seem narrow opening t o t h e atmosphere through a glassI
particularly well adapted t o t h e investigation of similar guide tube, practically no sublimation was observed
systems of substances which sublime readily a t t h e throughout t h e entire range of mixtures examined;
melting point: for t h e test tube was thus surrounded by air a t a tem-
Mixtures of pure naphthalene2 and phthalic anhy- perature differing b u t slightly from t h a t of the melt,
dride3 were weighed into a wide test tube. After and there was practically no convection current through
closing t h e tube by a stopper in which were inserted the two guide tubes.l
a “TYCOS” short stem thermometer4 and a glass guide
After fusing t o a clear, homogeneous liquid, t h e
tube for t h e platinum stirring rod, the whole was
temperature was permitted t o fall slowly t o t h e point
lowered into a cylindrical glass air-bath which fitted
of incipient crystallization while the melt was stirred
snugly t h e length of the test tube, b u t was widened
constantly by a mechanical device. The freezing
1 THIS
JOURNAL,
11 (1919), 1031.
point was determined in the usual manner from t h e
* The BUredU of Standards’ purest naphthalene was used. Compare
the observed melting point, 80.05’, with 80.09’, the value obtained by time-temperature curve. Although it was not feasible
Washbnrn and Read, PYOC. Nnt. Acad. Sci., 1 (1915), 191. t o seed the melt, care was taken t o lower t h e tempera-
a The fused phthalic anhydride described in the accompanying second
article of this series, Phthalic Anhydride, 11, was used. ture exceedingly slowly in the neighborhood of the
This was graduated t o tenths of degrees, and calibrated by com- 1 The vapor required t o saturate the free space was negligible, for the
parison with a Reichsanstalt “Centigrade-Normal” thermometer. mixtures averaged 20 g. in weight and the free space was less than 60 cc.