I

WILLIAM W. WINSHIP
The Thermal Syndicate, Ltd., New York, N. Y.

Vitreous s i l i c a has been used and specified

by many workers in the field of organic
(chlorination) and inorganic (chloridizing)
reactions with chlorine.
Indifference to severe temperature conditions, to chlorine even in its nascent condition, and to chlorinated organic compounds
and most metallic chlorides, together with
noncatalytic properties and, in the trans-

HEMICAL reactions utilizing chlorine and its compounds on the production scale entail somewhat unusual
problems, often involving considerations of photochemistry and catalysis in addition to the more frequent factors of temperature and chemical resistance.
In many of these operations metals and alloys lack the required resistance to wet chlorine and hydrochloric acid a t high
temperatures, and most ceramics are deficient with respect
to homogeneity, purity, or resistance to thermal shock.
Phosgene is a useful source of chlorine for both chlorina
tion and chloridizing reactions and has been found especially
efficient in the latter field. The chloridizing of mineral
materials in admixture with carbon probably involves the
reversible reaction CO
Clg = COCL. The reducing action of carbon monoxide liberated during the decomposition
may serve a useful purpose in such chloridizing technique

since the maximum was reached a t the temperature where the

latter dissociated.
Von Ktigelgen and Seward (48) stated that when silica is
mixed with carbon, a 2-hour treatment at 900" C. chlorinates
only 1 per cent of the silica present. The surface resistance
of fused silica apparatus under similar circumstances will
greatly exceed the resistance to chemical attack of finely
powdered material; furthermore, reaction on powdered
materials may be due to the presence of impurities.
Nascent chlorine as liberated during the decomposition of
phosgene is the most reactive form of this element. The
complete indifference of silica to chlorine is strikingly demonstrated in the following table by Chauvenet reproduced by
Dyson (18) which shows the reaction temperatures of carbonyl chloride with various metallic oxides and indicates the
resulting anhydrous chlorides:

~~~~~~~~~~~~~

ob"

~~~~~~~~~

parent variety, high transmission of actinic

light, provide a chemical engineering material valuable for reactor construction and
for equipment required in hydrogen chloride, hydrochloric acid, and chloride recovery. An extension of the use of fused
silica and quartz glass on an industrial scale
is suggested along lines of application which
have already proved their value.

Silica

Oxide
Tungstio
Vanadio
Iron
Tantalic
Titanio
Ziroonia
Tin
A 1umi n a
Magnesia,
Zinc
Beryllia

Judged by the criteria of chemical, thermal, catalytic, and

optical requirements, vitreous silica combines the desired
properties in an unusual degree. The transparent variety
(quartz glass) and the translucent and opaque grades (fused
silica) are identical in homogeneity and chemical properties
and similar in thermal, catalytic, and most other physical
characteristics.
The clear variety is unusually transparent to ultraviolet
light (a characteristic lacking in the translucent and opaque
grades), transmitting down to about 2000 A. It is also
highly transparent in the visible and infrared ranges.
CHEMICALRESISTANCE.In chlorination and chloridizing
practice, chlorine and its compounds generally have no effect
on vitreous silica up to its useful temperature limit (1000llOOo C.). Some alkali metal chlorides are an exception;
for example, Maier (60) reported that fused lithium chloride
is rather active in dissolving silica.
Fink and de Marchi (28) investigated the effect of certain
chloridizing reactions on fused silica at about 900' C. and
found i t apparently due to the presence of sulfur compounds,

Temp.,
O C.

Chloride

Oxide
Manganese
Uranium
Barium
Nickel
Chromium
Cerium
Yttria
Lanthanum
Thoria
Silioa

Tzmp.,
C.
Chloride
460
MnClr
450
UC14
600
BaCln
560
NiClr
600
CrClr
600
CeCL
600
YC4
600
LsCL
650
ThCh

Nore-

aotion

....

While investigating the thermal decomposition of phosgene,

Ingelson (86) found that glass was attacked by the chlorine
set free; therefore, vitreous silica had to be used as a container
for the gas.
THERMAL
RESISTANCE.Vitreous silica apparatus can be
used continuously without loss of strength a t temperatures
up to its crystallization point, 1000-1100' C. The upper
limit is favored by the absence of strongly reducing gases,
while the lower limit may be depressed by certain substances
(for example, sodium tungstate, vanadic acid, or sodium and
potassium chlorides) which tend to accelerate this so-called
devitrification.
On the other hand, in a favorable chemical environment
143

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

144

vitreous silica equipment will withstand operating temperatures up to 1400" C. if it is not allowed to fall below the
low-temperature transition point a t 300" C.

Vol. 33, No. 2

OPTICALCHARACTERISTICS.
I n appearance similar to a
high-quality colorless glass, quartz glass analyzing (like all
vitreous silica products of high quality) about 99.8 per cent
SiOz possesses high optical transmission up to its crystallization point, from the long infrared range through the short
ultraviolet. It is therefore particularly useful where actinic
light is employed to accelerate reactions or to supply visibility under temperature conditions impossible with glass.
On account of its high electrical resistance a t elevated temperatures, vitreous silica offers special advantages for insulating current leads, arcs, and other elements in processes
utilizing electrical forces in the conversion of hydrocarbon
compounds by chlorination. The low expansion of vitreous
silica, which is much less than that of metals or alloys,
demands special care when assembling silica apparatus with
other chemical plant details.

Lacy (46) showed a chlorinator comprising cylindrical iron

shells with cylindrical silica linings, the spaces between being
filled with finely ground flint (Figure 1). Ground fused silica
might be substituted for the flint to give the low expansion
characteristic of fused silica equipment.
Groll and Hearne (29) mentioned four methods of accelerating hydrocarbon chlorination reactions: radiation by actinic
light, presence of a catalyst, induction by simultaneous
chlorine addition, and heat. The reacting gases may be preheated before mixing, or the mixed gas may be passed through
a heated tube.
Egloff said that actinic light, heat, and catalysts have
been extensively used to accelerate the chlorination of the
paraffin hydrocarbons (19) but posed a question as to the actual wave lengths of Iight which are effective. He calls attention to the zero catalytic effect of fused silica in these reactions.

SILICACHLORINATOR
ASSEMBLY
FIGURE
1. FUSED
The thermal conductivity of vitreous silica (0.0035 calorie/
second/cm./sq. cm./" C. for the transparent grade and
0.0025 for the nontransparent) is excellent and, in general,
increases with rising temperature. But the thermal property
of outstanding technical importance is its exceptionally low
expansion and contraction with temperature change, which
ensures immunity to thermal shock in a degree possessed by
no other ceramic material.
Not only is the linear coefficient of 0.00000054 per " C.
smaller than that of any other manufactured product, but it
is practically constant and gives a straight-line curve up to
about 1100" C. Vitreous silica can accordingly be employed
over this entire temperature range without thermal strains
due to critical temperature zones.
CATALYTIC
CHARACTERISTICS.Vitreous silica is chemically
inert and homogeneous and lacks the property of a practical
adsorbent owing to its low retentivity (56). While various
porous forms of silica have been recommended as catalysts
in Chlorination processes, especially when preheated to high
temperatures (48), the value of vitreous silica in such operations is rather as a catalyst carrier, because of its catalytic,
chemical, and thermal inertness. The essentially noncatalytic character of vitreous silica apparatus, combined with its
resistance to chemical attack, is of the highest importance in
safeguarding against secondary reactions involved in organic
chemical operations generally.

FIGURE2. FUSEDSILICAS-BENDREACTION
SYSTEY
FOR
COUNTERCURRENT
LIQUID-PHASE
CHLORINATIONS

Chlorination reactions are often highly exothermic (5'4)

and require reactors capable of resisting sudden cooling;
or the chlorinating vessels may have to be heated in order
t o bring about the reaction (19, 46). Vitreous silica reaction vessels may be air- or water-cooled, or may be heated
externally by fuel gases; and tubular reactors may be wound
with resistance wire for electrical heating in continuous flow

February, 1941

operations, temperature gradients being maintained by varying the winding on the same tubular vessel.
Chlorination processes may require that the chlorine gas
be preheated and mixed with the hydrocarbon vapor, and that
the mixed vapors be passed through a heated zone where
their temperature is gradually increased (21). Fused silica
tubes with separate windings of resistance wire offer obvious
advantages for such operations, and vitreous silica equipment will also provide for collecting and absorbing the
separated hydrogen chloride.
Wiezevich and Vesterdal (71) suggested the use of glass
vessels in the absence of iron to obtain the best yields in
chlorinating various petroleum products. Obviously the use
of fused silica would permit the employment of larger individual units, under more severe temperature conditions.
I n countercurrent chlorinations of organic liquids, vitreous
silica packed towers may be water-cooled to remove reaction
heat. A more efficient type of apparatus for such operations
is the flattened S-bend absorber (Figure 2).
Organic chlorinations may utilize the direct action of chlorine gas, or use hydrogen chloride or phosgene as the chlorinating agent. Groggins and Newton noted that vapor-phase
reactions, especially those employing light as an accelerant,
require equipment very different from that used for liquidphase chlorinations (28) and mentioned fused silica as a suitable material of construction for the former.
Wet hydrochloric acid gas has always presented a difficult
engineering problem in developing vapor-phase chlorination
processes. Roka (61) pointed out that silica vessels enable
the chlorination of methane to be
effected a t high temperatures with
moist reaction gases. Moisture was
also claimed by Lacy to be advantageous in manufacturing methyl
chloride (@), and he mentions the
use of vitreous silica equipment.
Vapor-phase reactions calling for
accurate temperature control in continuous operations may well be conducted in vitreous silica tubeswound
with electrical resistance wire for
direct heating. A f l i n g of ground
fused silica between tubing of the
same material and metal enclosing
cylinders offers possibilities of an
assembly for high-pressure hightemperature endothermic reactions.
Carter and Coxe (12) mentioned
the use of tubular chlorinators,
which may be made of fused silica
and maintained a t 400-650' C. by
any suitable means, for producing
chloro derivatives of methane. I n
the production of chlorinated hydrocarbon derivatives, Jackson,
Wainwright, and Hailes (37) speciFIGURE
3. VITREOUS
fied an electrically heated silica
IMSILICA
ELECTRIC
tube through which the reacting
MERSION HEATER
vapors pass a t 700" C. Heated
vitreous silica reaction vessels were
also suggested by Lacy for manufacturing organic halogen
products (46),including ethyl chloride (44).
The reaction of hydrocarbon gases with chlorine may be
promoted by passing the hot mixed gases through porous
plates of sintered fused silica (16). Such plates have recently
been offered for commercial use. Vitreous silica electric immersion heaters (Figure 3) are particularly convenient for internally heating chlorination equipment in either gas- or
liquid-phase reactions.

145

I n certain chlorination processes, notably the manufacture

of rubber hydrochloride (65), pure dry hydrogen chloride
rather than chlorine is used as the halogenating agent. Saturated hydrocarbons (42)may be chlorinated by reaction with
hydrochloric acid and oxygen a t temperatures up to 650" C.
Hydrogen chloride is also the reacting agent, with oxygen,
in producing chlorobenzene from benzene (67); and in some
modifications of the Friedel and Crafts reaction (go), aluminum chloride, reacting with hydrocarbons, yields hydrogen chloride which takes part in further
reactions. The presence of the
latter also appears to be essential
to the reaction of certain hydrocarbons with aluminum chloride.
Hydrogen chloride hydrolysis
may be applied to organic compounds and hydrogen chloride as
a hydrolyzer, and as a by-product
of hydrolysis may present a considerable engineering problem
(2%). With larger sizes of vitreous
silica equipment now available i t
should be possible to extend the
use of this material on the plant
scale.
Hydrogen chloride for the production of lower alkyl chlorides
must be of extreme purity, and
special precautions are necessary
to obtain the gas as free as possible from admixture with chlorine
and other permanent gases. A
patent describes the production of
such gas and its use with a suitFIGURE4.
FUSED
able catalytic agent (39). One
SILICABURNERFOR
COMBUSTION OF
of the most important requireCHLORINE
IN HYDROments in chlorinating rubber is
GEN
a supply of anhydrous hydrogen
chloride, which may be dried over
sulfuric acid or anhydrous calcium chloride (63). About 5
per cent of hydrogen chloride contained in the spent acid is
usually recoverable.
Large volumes of hydrogen chloride gas are evolved in industrial Friedel and Crafts reactions, and the corrosion problem is always present (41). I n rubber chlorination, boiling
vessels must be employed (69) to remove hydrogen chloride
and free chlorine. Egloff (20) stated: "In many of the reactions of pure hydrocarbons in the presence of aluminum chloride, hydrogen chloride is a highly important component of the
system. It may be added to the reaction or may be present
as a result of hydrolysis of the aluminum chloride by water,
or may arise as a product of the hydrocarbon reaction."
Hydrocarbon halides in the presence of steam and catalysts
may decompose to give hydrochloric acid and water vapors
(48). Hydrochloric acid may be formed in the thermal
purification of chlorinated hydrocarbons containing similar
compounds, in the presence of suitable dehydrogenation
catalysts (8). Methane will produce hydrogen chloride (IO)
by a highly endothermic reaction with sodium chloride, and
calcium, lithium, and potassium chlorides can be used similarly. A tubular reactor with excess of water vapor should be
employed a t 700-800" C. (64) in the synthesis of hydrochloric
acid by reaction of methane, water vapor, and chlorine.
Conditions of economy as well as sound engineering practice
require that the loss of chlorine as hydrogen chloride from
hydrocarbon halogenations be kept to the minimum, and hydrochloric recovery systems are standard features of most halogenation processes. Hydrogen chloride liberated in hydro-

INDUSTRIAL AND ENGINEERING CHEMISTRY

146

carbon halogenations might profitably be decomposed and

the chlorine recirculated for further use. Patents (49,
66) cover methods for effecting this recovery. Here the conditions of corrosion are severe, and proper choice of equipment material is essential.

4i'

SILICA ROTATING
FURNACD
FOR ANEIYDROUS
FIGURE
5. FUSED
METALLICCHLORIDE
PRODUCTION

High-quality hydrochloric acid of 20" BB. strength suitable

for marketing is usually obtainable from the chlorination of
hydrocarbons. In some chlorination processes the liberated
hydrogen chloride may be recirculated with the gaseous mixture through the reaction chamber (66); where hydrogen
chloride is the original reacting agent, this is especially practicable (67). A patent issued to Ayres (2) illustrates a typical
vitreous silica absorption system used in recovering hydrogen
chloride from chlorinated solvent manufacture.
Water is particularly suitable as an absorbent for recovering hydrogen chloride from chlorination processes, not only on
account of the high solubility of hydrogen chloride in it, but
because of its substantial immiscibility with most halogenated
organic products (22). Its high heat capacity and latent heat
make it an effective cooling agent when used in small quantities to avoid excessive dilution of the hydrochloric acid
formed.
Methods have been devised for preventing the formation
of organic films on the absorbent ( I ) , and for rectifying the
liquid mixture of chlorinated products and hydrochloric
acid to produce anhydrous hydrogen chloride (16). Fused
silica condensers arranged on the reflux principle enable
water cooling to be employed a t temperatures impossible
with glass or stoneware equipment.
Hydrochloric acid separated in chlorination processes is
often obtained free from arsenic and sulfur compounds (9)
and may be anhydrous (63). In gas-phase reactions, washing
with water is often sufficient to separate the hydrogen chloride
from residual organic gases (44). Hydrogen chloride produced
in liquid-phase reactions may be scrubbed with the make-up
hydrocarbon compound entering the process before absorption
in water (14).
Baxter suggested the separation of by-product hydrogen
chloride from admixed organic vapors by scrubbing in a tower
containing boiling water, the heat of reaction maintaining
the scrubbing solution a t about 110" C. (6). He claimed that
20 per cent hydrochloric acid can be so obtained. Thomas
(68) described the separation of hydrochloric acid from the
chlorination of pentane and its absorption in a countercurrent
fused-silica system, giving hydrochloric acid of 20" BB.
strength for sale.
In the production of hydrogen chloride for chlorination and
chloridizing processes, the combination of chlorine and hydrogen by combustion gives gas of high purity and high
strength. With gas supplies adjusted in proper ratio and adequate cooling, a plant of this type will operate continuously
with the minimum of supervision.

Vol, 33, No. 2

Figure 4 shows a standard fused silica burner employed for

the combustion of chlorine in hydrogen, an excess of the latter
gas flowing through the outer tube. A vertical combustion
chamber and cooling equipment of the same material are
followed by absorbers if liquid hydrochloric acid is required.
~~~~~~~~~~~~~~~~

gf raor[ynEliu:)

JpqPlreraricPera

Apparatus for chloridizing must ordinarily withstand temperatures considerably higher than those encountered in organic chlorinations; the production of aluminum chloride,
for example, necessitates resistance to chlorine a t 1000" C.
(41), that of beryllium chloride involves a temperature of
800" C. (72), while zinc chloride can be formed from its elements a t 600-700" C. (60).
Selective separation of metal chlorides by heating ores and
similar materials in the presence of chlorine has been carried
out a t 1100" C. in separating chromium, nickel, and iron
values (SI),a t 1050" for separating niobium and tantalum
(64), a t 900" in the case of chromite (87), a t 900" for obtaining aluminum chloride from clay or bauxite (@), a t 700-900"
for separating iron and nickel (SO), and a t 400" for lead
vanadates (6). Such processes may be made continuous, employing fused silica apparatus.
It may be advantageous in
chloridizing operations to introduce the chlorine through a small
fused silica tube directly into the
boat containing the charge in a
larger tube of vitreous silica ( 3 ) .
Electrically heated vitreous silica
retorts are suitable for preparing
beryllium chloride from beryl and
carbon in a stream of carbon tetrachloride and chlorine a t 800" C.
(7B). Phosgene undergoes extensive decomposition a t temperatures above 300' (18) and is also
decomposed in radiation of wave
length 2750-3050 b. On the
other hand, it may be formed by
the photochemical union of its
elements (36).
In producing anhydrous aluminum chloride from either aluminum oxide or metallic aluminum
and chlorine gas, the apparatus
must be capable of withstanding
chlorine a t 1000" C. Intimate
contact of the reacting materials
is required for efficient results (41).
FIGURE6. VITREIn preparing aluminum chloride, it
OUS SILICARDACshould be kept in mind that molten
TION CHAMBER
AND
CONDENSER FOR
aluminum readily attacks vitCONTINUOUSCornreous silica equipment. The latTIRCURREINT CHLOter has, however, been successRIDIZATION
fully used for purifying aluminum
chloride bv admixture with aluminum powder and resubliming (68).
Carl (11) described in detail an electrically heated fused
silica rotary furnace for making anhydrous aluminum chloride, and Wohlers (73) applied similar equipment to the
production of anhydrous metallic chlorides in general (Figure
5 ) . Baughman (6) used a rotating fused silica cylinder, 13
inches (33 cm.) in diameter, 60 inches (152 cm.) long, heated
by an electrical resistance coil, in the chloride volatilization
of Black Butte ores and in separating the mixed oxides by
volatilization. Baskerville (3) recommended vitreous silica
tubing for chloridizing thorium oxide mixed with carbon.

CHLaRINATidN

Fused silica equipment is very suitable for u88 as condensers or mbliming chamber8 in chloridizing operatiom
where sudden cooling under severe cbemical conditions is required. Such condenser chambers, like the chloridizenr, may
be provided with eeveral independent electrical windings
for murate temperature control (60).
Maier (61) specised a vitrabu. silica reaction chamber
and condenser for the continuous countercurrent chloridisation of ores. As Figme 6 shows, the temperature conditions
here are unusually wvere, the pteheating and chlorination
mes being maintained a t about 900' C. by electrioal resiatom while water cooling is employed a t the lower end of both
mwtion chamher and condenser. The d u e n t gsses may contain hydrochloric acid and water vapor.
Richsrdson (SO) claimed that s h u n assist% materially in
chloridizing metals or metallic compounds, and recommended
a tubular silica furnaoe maintained a t !3GtMooOo C. for prcduaing anhydrous chlorides. In chloridbing operations a
mixture of gwous hydrogen chloride and steam (70)wae
recommendedfor treatingoxide o m aontsining smallamounta
of nickel and large amounta of iron, and a mixture of hydrogen
chloride gas and chlorine may be employed (17) in refining
mixtures of the platinum group metals. Chlorides may also
be formed by renetion between the oxide and a mixture of
hydrogen chloride gas, hydrogen, and steam; a rotmy siliaa
tube furnaca is conveniently employed (86).
Carrying chloridixing resctions further, metallic chlorides
treated with hydrogen and steam at a high temperature are
in aome c a w converted into the corresponding oxides and
hydrogen chloride (86). Hydrogen chloride is also a frequent
by-product of inorganic chloridiaing processes (69) and may
besepsratedfromthemixedgasesandrecoveredforre-use(70).
Phosgene (26)rescta readily with most metallic oxides to
giw the chloride of the metal and carbon dioxide. Resistancewire-wound fused silica tubes are a convenient form of reactor. Bsskerville (4) e m p h w i d the simplicity of the prcoedure-merely heating the pulverised material in a silica
tube in a stream of &aseous phmgene. Hulett (33)employed
this reaction for purifying inorganic m a t e d contsining iron,
including silica ssnd intended for optical glass manufacture.
Metallic anhides treated with phosgene give the ohloride of
the metal and carbon oxysulfide (36). By hydrolpi8 p h w
gene yields hydrogen chloride and carbon dioxide.
The preparation of very pure metallic chlorides often involves ae a 6nal step the fusion or dehydration of the d t in
a current of hydrogen chloride, the material being contained
in a vitreous &ca boat inside a heated tube of the same matarial (60).

Photoehemioal A p p l i ~ a t i o ~
Actinic light has long been employed to promote chlorination processes. It ha! been claimed that under the influence
of ultraviolet light a molecular rearrangement d t a during
the ohlorination of hydrocarbons, very liMe hydrogen dorids being liberated (67). Payne and Montgomery (66)
demiba a procam involving the expoeure of gaseous hydrooarbons to ultraviolet light after treatment with chlorine in
amtact with a catalyst formed by the chlorination of a liquid
hydmcarbon. In chlorinating rubber, ultraviolet rays may
be used in preparing the rubber solution in order to increasa
ita cancenhtion, to p m o t a halogemtion, and to s t a b
the finished product (13, 84). Ultraviolet rays are also
olsimed to he valuable in promoting the reaction of chlorinatedhydroosrbons with sulfur dioxide and chlorine for tho
production of organic h a I o g e n 4 o n i c acid chlorides (38).
The exact reqnirementa in this field are not definitely
known, and it has been suggested that various parta of the
ultraviolet range below 3132 A. may have specifio action re-

,147

sulting in ditrerent products from the same raw materiala

(86). Where light of extremely short wave length is required,
the low-pressure mercury vapor lamp in quarts (operating
mostly in the 2536 A. region) may der advantagen in same
c~se8on account of ita low temperature. On the other hand,
the heat contributed by the high-pressure quartz mewuryvapor lamp may in some instance be advantageous in promoting an endothermic reaction (68).
While glass equipment is photOchemicaUy suitable for
chlorinations employing tho longer rays of the ultraviolet
spectrum,fused quarts is necessary as an apparatus material
whem the full actinic power of quarts mercury-vapor l a m p is
desired. In d d e equipment tubular reaction ahamhem
of nontransparent f d silica may have inteersuJr fused-in
sections of transparent quarts glass where required for ultraviolet irradiation. Large-ade equipment may be provided
with quarts glass details for internal irradiation and reaction
v d of other materials may be fitted with windows of
quarts glass in suitable packing glands.
The least expensive type of quartz glass apparatus for
carrsing out photochemical chlorinations is an arrangement
of Btrsight quartz tu& through which the gam or liquids
paes while expoeed to the actinic light source. A coil of
quarts glass tubing surrounding the ultraviolet light is more
&cient.
Various forms of quartz glsss equipment have been deviaed
for bringing reacting m a t e d into intimate contact with
the actinic rays in continuous photochemical chlorinations in
the liquid or vapor phase. Typical arrmgement.9 of this kind
are shown in Various patents (7,30,40,47,74).

Literature Cited
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10,1931).
(2)
.. Avrea.
. E. E.. Jr. (to Shamlea 8olvents Co.). IM..1,836,201
(Deo. 8,1931).
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(6) Bsulrhman.. W..
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Barter. J. P. (to Imperial Chemioal Industden, Ltd.). U. 8.
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>an,G. H.,and Zemba, J. W. (to Don

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C.,'Ma.~&rc&?mMioirr39,1139 (July 16, 1LW)
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Fnmch Patent 841.W (May 18,1939).
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(ZO) E&S, Quatav, W h n , E., HUUS. 0.. Van A d 4 P. M..
IW.,
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(Oot. 24, 1916).
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(lueprint) (1W).
(24) Flaresoo, W.. Frenoh Pstsnt 788,632 (Aug. 10,1934).
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1917).
(26) Gibb.. W. E., Rept. Tin and Tungaten
B o d (Brit.),
1922.

INDUSTRIAL A N D ENGINEERING CHEMISTRY

148

(27) Great Western Electroohemiad Co.. Brit. Patent 609.368

(July 14, 1939).
(28) Gro-a,
P. H., "Unit Pmeessas in Or-c
Byntheaia". and d.,
1938.
h l l . E. P.. and H e m e , G.. ID. ENQ.Carnu.. 31,1684-7 (1939).
Hart. C.. U. 8. Patent 2,030,867 (Feb. 18.1936).
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Bolt. L. C.. and Daudt. E. W. (to E. I. du Pont de Nemoun 6.
Co.. ho.).lbid.. 2.091.986 ( b t . 7. 1937).
H i & . G.'A.. U.8.'Pat&t 1;3&,38e web. 16. 1921).
1. G. Farbenindukie, Brit. Patent 283.106 (Dea. 6,1928).
I n g e h , H. J.. J . Chem. 800.. 1927.2244-64.
Jackmu. K.E., J . C h . Education. 10,622-6 (1838).
J a b . K. 8.. Waioaripht. 0 . E.. and Hail-. E. R. (to Imwrid 'chermiod Indun&.
Ltd.).Brit. Psterk 438,Wk (Oot.
?. 1936).
(38) Johnmn, G. W. (to I. 0. FarbenindustriB). IW.. 616,214 (July

z&

1.a3'1.662 ( A U ~21,1917).
.
Elipstein, E.E., C h . Mark&, 25.6936 (1029).
Kmw. %oh, and R 6 b , K. (to Hohverkohlwmr-hdmtrie)
U. 8.Patent 1,664,821 (Jan.3.1928).
Kgelgen, F. von, and & w d , 0 . 0. (to VirSinia Lsb. Co.).
bid., 1.147.83a (J* 27,1916).
Lacy. B. 8.. U.8. Patent 1,242,208 (Oot.9.1917).
L w . B. 8. (to Roesaler & Edsoher Chemical CO.), Ibid..
i.iii,84a (&pt. ag. 1914).
Ibid., 1,263,wW (April 23,1918).
, F.. U. 8. Pateut 1,459,777 (June 26.
1933).
(48)Lloyd,
~~~.
8. J., and Kennedy, A. M., IW., 1,849,844 (March 16,
1932).
(40) Low. F. 8. (& Wedtvaco Chlorine Fmducta Co.), Ibid., 1,746,-2 m h . 11.
8Ml)..
- 1..__,
(4) Maim. C. G., U. 8. Bur. Mined. T d .Paper 360 (1826).
(61) Maier. C. G.. U.8.Patent 2,183,987 (Oot. as. 1938).
(62) Msier, C. G. (to Glad Weatem Eleotroohemioal Ca.), Ibid..
2 . 1 4 a . e ~(J-. a. 1 ~ 9 ) .

--

vol. 33, NO.

(63) Moffett, E. W., Winkelmann, H. A. and Willisma. F. E. (to

~ a r b o uCOW.).IW.. 2,138,ma (Deo. 6, i9as).

(64)Padrovmi, C.. D e Bartholomasis, E., snd 8inirsmed. C., Ani
X" cam.idem Aim., 41,6143 (1939).
(66)
. . Palmer. W.0 . . and Clark. R. E. D.. ploe. Rar. 800. (London).
..
Al49,'3&
(1984). .
(66) Payne. E. E., and Montgomery, 8. A. [to Standard Oil Co.
(Id.)]. U. 8. Patent 1,463,766 (May I. 192.3).
(67l Prshl. W., and Mathen, W. (to F. Raaohig. Q.m.b.H.), W..
2,Oa6,917 (March 31, 1936).
(68) Ralaton, 0. C.. U. 8. Bur. Mines, T d .Papa 321 (1923).
(69) Raalin Corp., Brit. Patent 489,964 (Aug. 6. 1938).
(60) Riohsrdmn, H. A., Ibid.. 621,976 (June 6. 1940).
631) Rob. K. (to EohverLohI-Indwtriatrie
Akt.&.).
IW..
14, 1921).
U.6.
Patent 1,383,366 (Dee. 14. 1920).
(64) 8oaYt6 Sen&& m6tallur(pque de Eobokeu, Brit. Patent 47.124
(68) Bsunders, H. F., and Butherland. L. T. (to Glyain Corn.).
I1.321pI

(66) 8ooi66 intemationds des industried ohimiques et d6riv&a,8. A.

Holding. h o b Patent 834,124 (Nov. 14, 1938).
(66) &ell, J., and Runkel, C. (to I. Q. Farbenindustrie), U. 8.
Patent 1.880.167 (Nov. 28,1932).
(67) Teichmaoo. C. F.. Klein, H., and Rathemsaher. 0. P.. U. 8.
Patent 2,016,044 (8ept. 17. 1936).
(68) Thomaa.C.A.."Scienoeof Petmleum",Vbl.4.pp.a7862801.Oxford univ. Praaa. 1938.
(69) W-uht,
R.. C h . F&.
1923.121-2.
(70) Wesoott. E. W., U. 8. Patent 2,036,684 CApd 7, 1936).
(71) Wiwevich. P. J., and Vederdel. H. Q., C h . Rea.. 19, 101-17

.- _.

and Yntema, L. F.. Tram. Am. &I&&.

-I
EQUIPMENT
M. A. KNIGHT, J R ~
Maurice A. Knight, h.
Ohio

TRICTLY speaking, chlorination involves the substitution of chlorine atoms for other atoms in molwules of
a substance. In a broader sema it may be conaidered
ea any pmoeas or chemical d o n involving chlorine itself
or one of ita compounds in whioh substitution or addition

of chlorine atoms occura. The aotivity of chlorine with nearly

every metal in the presence of water, the temperatures
reached in some meas, the organic solvent nature of many
of the compounds p r o d , and the frequent praeenoe of
hydrochloric acid rule out all forms of equipment except
ceramicware or g l m .
Definition of Chemical Stoneware
Bow is chemicsl stoneware M e r e n t from pottery, porcelab, clay building tile, or m e r pipe since they are all made
from day?' Brielly, the above forms are essentially aluminum silicates plus minor amounts of other materials. Chins

and poroelain are white, dense, often translucent ceramic

bcdies that are fuUy vitrified and acidpmf. Highly p u m
raw m~terialssre used to en%unr whiteness, and the body is
highly fluxed to obtain maximum denaity. This last oharaoteristio pub definite Dse limitations on true porcelain
articles. Pottery such as flower v ~ s e sand mme d i m a r e
is not alwap v i W and depends on an applied glase for
service. Elementa added for coloring and for manufacturing
eaee would lesoh out in acid Service. Mechanical strength is
comparatively low. Building brick and sewer tile generally
take raw clay from local murcea, and it is formed m d fired
without puriscation to mske a earviceable prcduot. The
premnce of iron permits lower firing temperah snd imparts the familiar red color. The raw clays are too impure
to be used for other ceramic purposes. Chemical stoneware,
in addition to being acidpmof, must meet phyeical requhmenta ea to stmngth, tempersture,'pamsify, snd dimenDona in a variety of &apes which am much larger than