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844

INDUSTRIAL AND ENGINEERING CHEMISTRY

Vol. 22. No. 8

Ethylene Oxide and Ethylene Dichloride


Two New Fumigants'
J. M. RUSS,Jr.
CARBIDE
AND CARBON
CHEMICALS
CORPORATION,
30 EAST4

2 ST.,
~ NEW
~ YORK,N. Y.

Fumigation is of great economic benefit. ManufacH E increasing importreated. The forced circulaturers, fruit packers, grain handlers, and warehousetance of fumigation as
tion of air over the surface of
men have been able to eliminate great losses caused by
the liquid aids greatly in the
a means of insect coninsect damage. Furthermore, expensive refrigeration
vaporization of the fumigant.
trol has created a demand for
processes may be supplanted by fumigation, a cheaper
fumigants which can be easily
I n addition to being a good
and more effective means of preventing insect damage
and safely handled without
fumigant, the ethylene dito stored goods.
injury to the materials exchloride mixture has other
Although only recently made available, the use of
posed, a n d w h i c h c a n b e
uses. It is an excellent solthe ethylene dichloride-carbon tetrachloride, ethylene
applied under varying convent for oils and fats and,
oxide, and Carboxide is already established in many
ditions. Many compounds
b ei n g non-inflammable, i s
industries. These materials offer a choice of fumihave insecticidal properties
used as a s p o t - r e m o v i n g
gants which are adaptable to fumigation under widely
but are limited in their use
compound. It makes, therevarying conditions. Separate rooms, apartments, and
as fumigants because of some
fore, an excellent combination
storerooms can be fumigated without vacating other
undesirable characteristics,
fumigant and cleaning soluparts of the same building or inconvenience to other
such as slow vaporization,
tion. Furriers find i t partenants. In like manner expensive shutdowns in
instability, corrosive action,
ticularly suitable for fumifactory operations can be avoided. Foodstuffs can be
odor, retentivity by various
gating and c l e a n i n g f u r s .
fumigated without fear of injury or serious contaminamaterials, difficulty of hanThe mixture is also used in
tion. Finally, fumigation is made easy in many
dling, great inflammability,
the form of emulsions as a
applications which would otherwise be difficult.
or extreme toxicity to man.
contact insecticide.
By the proper choice of processes and fumigants
W h i l e t h e e t h y l e n e diI n the course of an extenmuch of the damage and discomfort caused by insects
chloride-carbon tetrachloride
sive investigation of the possican be eliminated.
m i x t u r e is a very useful
ble use of a large number of
fumigant and solvent, it is
comDounds. the Bureaus of
Entomology and Chemistry and Soils discovered that ethylene not adapted to universal fumigation as is the case with ethyldichloride and ethylene oxide are highly toxic to insects ene oxide.
and have characteristics which make them desirable fumiEthylene Oxide
gants. Both compounds are relatively non-toxic to man.
Ethylene oxide is a colorless, mobile liquid, which boils
Ethylene Dichloride
a t 10.5' C. and is therefore a gas a t ordinary temperatures.
Ethylene dichloride is a colorless liquid of ethereal odor, It has a specific gravity of 0.887 a t 7"/4" C., a molecular
which boils at 83.7" C. It has a specific gravity of 1.27 a t weight of 44.031, and a freezing point of -140" C. The
2Oo/2O0 C. and weighs 10.4 pounds per gallon. It is an ex- liquid is soluble in water and organic solvents. It has a
cellent solvent for oils and fats, but is insoluble in water. faint but distinct ether-like odor, which is easily recognized,
The vapors of ethylene dichloride are approximately 3.5 and its vapors are approximately 1.7 times as heavy as air.
times as heavy as air.
The vapors exhibit remarkable penetration into dense maEthylene dichloride will burn, but it is rendered non- terials such as wheat flour.
inflammable by the addition of approximately 25 per cent by
Extensive experiments with various foodstuffs have shown
volume of carbon tetrachloride. This non-inflammable mix- that no residual taste or odor is left with materials that
have been in contact with the vapors of ethylene oxide.
ture is a very useful fumigant.
A dosage of 8 pounds of the ethylene dichloride-carbon Even the flavor of such a sensitive material as tobacco is
tetrachloride mixture per 1000 cubic feet in an air-tight unaffected by fumigation with it.
A dosage of 1 pound ethylene oxide per 1000 cubic feet
vault a t 70" F. will kill, in 24 hours, clothes moths, carpet
beetles, rice weevils, Indian meal moths, flour beetles, saw- of air in an air-tight vault a t 70" F. will, in 20 hours, kill
toothed grain beetles, and bedbugs. However, for com- clothes moths, carpet beetles, rice weevils, Indian meal
mercial fumigation a dosage of 14 pounds of the mixture moths, saw-toothed grain beetles, red-legged ham beetles,
flour beetles, cockroaches, tobacco beetles, and bedbugs.
per 1000 cubic feet is recommended.
Successful fumigation with the ethylene dichloride mixture For commercial fumigation, however, a dosage of 2 pounds
depends to a large extent upon the method of application. per 1000 cubic feet is recommended. Although the conBecause of its relatively slow rate of vaporization, the liquid centrated vapors of ethylene oxide are inflammable, concensurface exposed should be large. This can be accomplished trations lethal to insects can be used with safety, since the
by placing the mixture in shallow pans and allowing it to lower limit of inflammability is 3 per cent by volume or 3.67
evaporate or in certain cases, provided the walls or floor are pounds per 1000 cubic feet.
Mixtures in air of ethylene oxide and carbon dioxide in
unfinished, the fumigant may be sprayed on the walls or
floor of the fumigation chamber. I n other instances the the ratio of 1 part of ethylene oxide to 7.5 parts or more
liquid may be sprayed or poured upon the material being of carbon dioxide by weight are non-inflammable. Furthermore, ethylene oxide and carbon dioxide have practically
Presented before the Division of Agricul1 Received May 21, 1930.
the same vapor density and do not tend to separate or stratify.
tural and Food Chemistry a t the 79th Meeting of the American Chemical
Therefore, to eliminate possible dangers arising from an overSociety, Atlanta, Ga., April 7 to 11, 1930.

August, 1930

I N D U S T R I A L A N D ENGINEERING CHEMISTRY

dose of ethylene oxide, it is advisable to use carbon dioxide


with ethylene oxide for fumigation.
Carbon dioxide has also proved to be of material aid in
killing insects. Cotton and Young (5) determined that the
presence of carbon dioxide increases the insecticidal action
of ethylene oxide by causing an acceleration of the respiratory
actions of insects. A dosage of 1 pound ethylene oxide and
7.5 pounds carbon dioxide per 1000 cubic feet is approximately equivalent to a dosage of 2 pounds ethylene oxide
alone.
Cotton (6)has shown that carbon dioxide causes a decrease
in the adsorption of fumigants by various materials. This
effect is especially apparent in vacuum fumigation, where
the adsorption of fumigants is usually great. For example,
in the fumigation of raw peanuts a dosage of 3.5 pounds
ethylene oxide and 28 pounds carbon dioxide per 1000 cubic
feet will give the same result as 7 pounds ethylene oxide
used alone.
Carbon dioxide is non-injurious to materials met with in
fumigation. It is available as a liquid in cylinders under
pressure and can also be obtained as a solid in the form of
carbon dioxide snow or blocks of the compressed snow. Solid
carbon dioxide is volatile and therefore must be used within
a certain limit of time. The solid is of special benefit in
certain instances, such as in the fumigation of grain and
when it is desired to lower the temperatures of a material
being fumigated.
It has been found possible to mix liquid ethylene oxide
and liquid carbon dioxide without reaction between the
components. This mixture is stable and can be stored indefinitely in cylinders without deterioration of its insecticidal
properties. It eliminates the necessity of handling two separate materials. This mixture is being marketed under the
trade-mark Carboxide.
Carboxide cylinders are equipped with eductor tubes for
easy and rapid withdrawal of the fumigant. The mixture
issues from the cylinder as a liquid which is atomized to a
fine mist. Vaporization of the mist requires only a few
minutes, thereby making available the maximum concentration of fumigant in a very short time.
The availability of Carboxide in various-sized cylinders
eliminates the necessity of measuring apparatus and makes
the application of the fumigant extremely simple. When
a number of cylinders are required they may be distributed
throughout the space to be fumigated and the fumigant
released from the cylinders in the order of their location with
respect to the exit, the cylinder farthest from the exit being
released first. When spaces are to be fumigated, it is usually
desirable to introduce the fumigant through piping, using
either small heavy-walled copper tubing or iron pipe. Under
certain conditions, in vacuum fumigation, it may be preferable to vaporize the fumigant by passing it through a copper
coil immersed in hot water.
Vault Fumigation

The efficiency of fumigation depends largely upon temperature, concentration of fumigant, time of exposure, and nature
of the material treated. The most favorable and economical conditions prevail where the temperature is above 70 F.
and the effective concentration of fumigant can be maintained for the time required to give effective results on the
particular material being treated. These conditions can
be best maintained in vaults or rooms which are specially
equipped for fumigation.
When speed is essential vacuum vaults can be used. When
speed is not important and space is available, atmospheric
vaults are satisfactory for most materials. Some materials,
however, because of their dense nature, are best fumigated
under vacuum.

845

I n vacuum fumigation greater dosages of fumigant are


required to give good results in the short period of exposure.
The dosage of fumigant will depend upon the material treated
and the available time of exposure. For example, in the
fumigation of dried raisins, a dosage of 20 pounds of Carboxide per 1000 cubic feet will give a complete kill in
hour, while 10 pounds of Carboxide require ll/z hours. For
the treatment of dried beans a dosage of 20 pounds Carboxide
per 1000 cubic feet will give a complete kill in l/Z hour while
10 pounds require 1 hour for the same result.
I n atmospheric vaults the forced circulation of warm
air aids greatly in the penetration of the fumigant into dense
materials. Heating of the air can be accomplished by means
of units heated by steam, hot water, or completely enclosed
electric elements. Circulation of the air in the vault may
be accomplished by a fan connected by means of a shaft
through the wall or ceiling to a motor outside the vault.
It is preferable to place the heating and circulating apparatus
near the roof of the vault to conserve space.
The dosages of fumigant and time of exposure in atmospheric vaults depend upon the material treated. For example, dried fruits in bags can be fumigated successfully
with 10 pounds Carboxide per 1000 cubic feet in 12 hours,
while flour in bags requires 20 pounds for 16 to 24 hours.
Carboxide can be used for the fumigation of all materials
in vacuum or atmospheric vaults. It is particularly well
suited for vacuum fumigation owing to the beneficial effect
of the carbon dioxide in decreasing adsorption of the ethylene
oxide by the material treated.
No data are available on the use of the ethylene dichloride
mixture in vacuum fumigation. Doubtless the dosages of
fumigant required would be so great that complete removal
of the vapors from the fumigated material would be difficult.
The ethylene dichloride mixture can be used in atmospheric vaults for the fumigation of many materials such as
furs, clothing, furniture, bedding, rugs, and certain foodstuffs, including grain.
For ready reference a table of dosages and time of exposure
for various materials when using Carboxide and the ethylene
dichloride mixture in an air-tight vault a t 70 F. is given
below. The dosages are based on the space in an empty
vault with no allowance for the space-taken up by the material being treated.
Dosage a n d T i m e of Exposure Using Carboxide a n d E t h y l e n e
Dichloride Mixture
ETHYLENE
DICHLORIDE-CARBON
TETRACHLORIDE
MIXTURE

CARBOXIDE
MATERIAL

Atmomhere

Vacuum

Dried fruits
Cereals in cartons
Brans, rice, corn, I
and other grain
in bags
Flour i n 1 0 0 pound bags
Tobacco in bales
Candy in cartons
N u t meats
Almonds and peanuts in shells
Clothing f u r s,
furnitdre, a n d
rugs

Lbs./l000

Lbs./1000

10

12-16

20

20
20
16
20

16-24
16-24
16
12-16

20

1
2
I1/z

10

12-16

20
20

30

30

16

22

24

14

24

28
24
Notrecommended
Not recommended
Not recommended
Not recommended
14

24

Grain Fumigation

Insect control in grain is of particular importance because


of the investment involved and the potential damage which
can be caused by insect activity. Insects destroy grain and,
in so doing, bring about a rise in the temperature of the
grain which eventually results in fermentation; this, being
a progressive action, will finally end in actual carbonization

846

INDUSTRIAL AND ENGINEERING CHEMISTRY

of the grain. Even slight damage due to insect infestation


or fermentation affects the market value of grain.
Fumigation is the most economical method of insect control in grain. It is effective in killing all forms of insect
life and, in contrast with mechanical and heat-t,reating
methods, does not involve great power costs and loss of grain.
By the proper choice of fumigants this process can be carried
out without any deleterious effect on the grain.
Aside from temperature, the most important factors
intluencing the effectiveness of a good grain fumigant are
diffusion and distribution of the fumigant. Tests have
shown that diffusion of gases in grain is very slow because
of the dense nature of the material. Other experiments
have shown that diffusion is hindered by adsorption and
absorption of the fumigant by the grain. Therefore, for
effective fumigation provisions must be made for proper
distribution of the fumigant in the grain to insure proper
diffusion. The most effective method of distribution thus
far developed involves the mixing of the fumigant with the
grain as it enters a bin.
When a liquid fumigant is used in deep bins, the loss due
to evaporation in falling to the lower depths necessitates
the use of quantities in excess of the theoretical amounts.
The amount of fumigant lost depends upon several factors,
such as temperatures, height of fall, and the rate of displacement of air in the bin by grain. It is therefore difficult to
calculate the quantities of liquid fumjgant needed for effective treatment under these varying conditions.
The ideal grain fumigant is one which offers a minimum
of hazard and can be buried in the grain before vaporizing.
These conditions are met by a mixture composed of ethylene
oxide absorbed in solid carbon dioxide. In the ratio of 1
part by weight of ethylene oxide to 8 parts of finely pulverized solid carbon dioxide, a semi-solid mass is formed which
can be gradually introduced into the grain stream entering
a bin. Volatilization of the ethylene oxide does not occur
to any appreciable extent until all solid carbon dioxide has
passed into the gaseous state, by which time the mixture
is well imbedded in the grain. The mixture is of such nature
that comparatively little solid carbon dioxide is vaporized
in the fall to the lower depths of deep bins. Variations in
temperature, height of fall, and rate of air displacement do
not materially affect the quantities of mixture required.
The application of the mixture can be made without disagreeable effects on the operator.
The application of the mixture involves preparation in
small batches and introduction into the bin a t intervals
timed with the rate of grain flow. The mixture is prepared
by placing a weighed quantity of crushed solid carbon dioxide
in a container and adding to it the proper quantity of ethylene
oxide. The solid carbon dioxide absorbs the liquid ethylene
oxide and a slushy product is obtained. The mixture should
be introduced into the bin by shaking or scooping from the
container, or by means of a machine feeder. At no time
should the mixture be directly handled, even with gloves,
because it is extremely cold and the cold liquid is absorbed
by leather and fabrics. The size of the batches is determined
by the size of the bin and the rate a t which it is filled. It
should be assumed that proper diffusion will not take place
through a column of more than 2 feet. Each batch should
be gradually introduced, rather than dumped in all at once.
The mixture of ethylene oxide and solid carbon dioxide
kills the insects and at the same time cools the grain. The
cooling effect is important because it either halts or decreases
fermentation. The extent to which the grain is cooled depends upon the quantity of the mixture used. A combination of the cooling effect and the chemical action of the
mixture may be responsible for the sweetening of musty
grain, which has been observed in several instances.

Vol. 22, No. 8

While perfect kills and an appreciable lowering of the


temperatures have resulted, in completely enclosed bins,
from a dosage of 2 pounds ethylene oxide and 14 pounds
solid carbon dioxide per 1000 bushels of grain it is advisable
to use an overdose rather than an underdose. It is t h e r e
fore recommended that the dosage, in completely enclosed
bins, should be 2.5 to 3 pounds ethylene oxide and 20 to 30
pounds solid carbon dioxide per 1000 bushels of grain. The
heavier dosages should be used in bins of large diameter.
Large-scale experiments in the fumigation of grain with
the ethylene oxide-solid carbon dioxide mixture have been
conducted in various localities under representative conditions. Bins varying in height from 25 to 100 feet and capacities from 2500 to 140,000 bushels of grain have been
successfully and easily fumigated. The results have been
more than satisfactory as 100 per cent kills of all grain insects have been obtained.
When it is not practical to use the ethylene oxide-solid
carbon dioxide mixture in the fumigation of small bins and
freight cars, the ethylene dichloride-carbon tetrachloride
mixture will give results comparable with those obtained
with any liquid fumigant. A dosage of ll/z to 2 gallons of
the mixture per 1000 bushels of grain will give good results
in tight bins. The mixture can be applied by pouring on
the grain stream entering a bin or on top of the grain in a
freight car.
Fumigation of grain in freight cars is at best uncertain
because of the loose construction of the average car. It
is very seldom that a perfect kill of all insects is obtained
in freight cars; however, this type of fumigation is often
justified because enough insects can be killed to prevent
serious damage to the grain.
The time of exposure in grain fumigation will depend
upon whether the grain is to be moved immediately or stored.
I n such tests as have been conducted with ethylene oxidesolid carbon dioxide mixture and the ethylene dichloridecarbon tetrachloride mixture the time of exposure has varied
between 24 hours and 3 weeks.
House and Apartment Fumigation
Houses and apartments have been successfully fumigated
with Carboxide and the ethylene dichloride-carbon tetrachloride mixture. Separate rooms and apartments can be
fumigated without vacating other apartments in the same
building. For this purpose Carboxide is superior to the
ethylene dichloride mixture.
I n tight spaces where the temperature can be maintained
above 70" F., a dosage of 1 pound ethylene oxide and 7.5
pounds carbon dioxide, or 10 pounds Carboxide, per 1000
cubic feet for 10 to 16 hours will kill bedbugs, roaches, carpet
beetles, silverfish, clothes moths, and mice. I n spaces which
are not tight it is necessary to increase the dosage and time
of exposure.
While ethylene oxide and Carboxide and the ethylene
dichloride mixture are not dangerously toxic to humans,
overexposure to the concentrated vapors will cause severe
nausea. For house, apartment, or any type of fumigation
where the operator is liable to overexposure, it is advisable
to wear a mask which will absorb organic vapors.
Fumigation of Storerooms
Storerooms in candy factories, hospitals, restaurants,
storage warehouses, navy depots, and grocery stores have
been fumigated successfully with ethylene oxide and carbon
dioxide. Insects in packages of cereals, dried fruits, and
flour can be killed when the proper conditions are observed.
Overstuffed furniture has been successfully rid of live clothes
moths and carpet beetles when fumigated in separate storage compartments.

August, 1930

I X D U S T R I A L AND ENGINEERING CHEJ4ISTRY

Carboxide is well suited to the fumigation of storerooms


because of the variety of materials usually present and the
ease of application. The method of application is similar to
that used in vault fumigation. The dosage should be based
on that material present which requires the greatest quantity
of fumigant.
Fumigation in Refrigerator Cars

It is sometimes necessary to fumigate in refrigerator cars.


This is especially true in the dried-fruit industry, where
sufficient vault capacity is not always available. This type
of fumigation may not always be effective because of the
loose construction of some cars. Carboxide is excellent for
fumigation in refrigerator cars provided they we properly
sealed.
Before fumigation the cars should be sealed as effectively
as possible. The drain pipes from the ice compartments
are fitted with liquid seal caps, but these caps are generally
clogged with dirt or else are subject to being jarred from
position by moving of the car. The most effective method
of sealing the drain pipes is to provide wooden plugs which

847

can be inserted in the pipes for the duration of the treatment. Care must be taken, however, to remove the plugs
after fumigation or else the compartments will eventually
be flooded.
The required quantities of fumigant can be introduced
through the ice ports of a refrigerator car. Carboxide cylinders are of such sizes that one cylinder can be used for each
car. The contents of a cylinder may be emptied into the
ice compartment through a hose connected to the cylinder
on the outside, or else the cylinder may be placed bodily
in the compartment. The dosage for dried fruits should be
16 pounds of Carboxide per 1000 cubic feet for an exposure
of 10 to 12 hours at 70 F.
Literature Cited
(1) Back, Cotton, and Ellington, J . Econ. EnlotnoL., 23, S o . 1 (1930).
(2) Cotton, Ihid., 23, S o . 1 (1930).
(3) Cotton and Roark, I b i d . , 20, 636 (1927).
( 4 ) Cotton and Roark, IND.Exc. CHEM.,20, 80: (1928).
( 3 Cotton and Young, Proc. Enfomol. Soc. Washington, 31, 97 (1929)
(6) Hoyt, ISD. ENO.c.HElf., 20, 460 (1928).
(7) Jones and Kennedy, Ibid., 22, 146 (1930).

Effect of Priming-Coat Reduction and Special


Primers upon Paint Service on
Different Woods
F. L. Browne
FOREST
PRODUCTS
LABORATORY,
X m ~ s o x -Wrs
,

Past efforts of chemists to make better house paints


have been seriously hampered by the fact t h a t paint
varies widely in its performance on different kinds of
wood. Changes in paint composition t h a t otherwise
would be advantageous have often proved impracticable
because they accentuate the discrepancy in behavior on
different woods. Disagreement about the best formula
for the white base of house paint is largely due to this
situation.
From empirical exposure tests it appears t h a t t h e
variable behavior of paint on different softwoods is due
primarily to lack of specific adhesion between aged coatings and wood substance. Instead of wearing down from
the surface, the coatings break up and fall off, starting

over the summerwood. The present paper reports empirical tests of certain modifications of painting practice
t h a t have been supposed to improve durability of coatings
over summerwood. The results indicate t h a t past recommendations have usually been based upon inadequate
theory rather than upon sound experience. In the authors opinion the problem of adhesion is a fundamental
one that must be solved before substantial improvement
in the serviceableness of house paints on wood can be
achieved. With permanent adhesion between coatings
and wood, variable paint behavior between woods and
uncertain service on repainting would be eliminated,
leaving the paint chemist free to build wear-resistant
coatings on a firm foundation.

. . . . . . . .......

N 1924 the Forest Products Laboratory started an ex-

tensive series of exposure tests of painted wood, the


object of which was to compare the behavior of coatings of typical house paints on wood surfaces of different
kinds under normal conditions of exterior exposure ( 1 ) .
Many technologists have been of the opinion (15,16) that
such comparisons between woods are fair only if the primer
is mixed with linseed oil and thinner-that
is, reducedin proportions determined by the characteristics of the wood.
The theory underlying this opinion is that some woods require a larger proportion of thinner in the priming coat
than others in order to obtain maximum durability of the
coating. Inquiry, however, revealed the fact that, although
reasonable agreement exists among technologists about good
practice in reducing white-lead paste paint or lead and zinc
Received April 4, 1930. Presented before the Division of Paint and
Varnish Chemistry a t the 79th Meeting of the American Chemical Society,
Atlanta, Ga., April 7 to 11, 1930.
1

prepared paint for new exterior woodwork in general, there


is no agreement either about the woods that require modification of this general practice or what that modification should
be for specific woods. It mas therefore decided to begin
the 1924 tests with the same reduction of the primer, which
this paper will call the standard reduction, for all woods
and then to start a second series of tests in 1925, using the
woods on which less satisfactory paint service was expected,
to see whether the durability of the coatings would be affected
by changing the standard reduction of the primer or by
using some of the special priming paints that have been suggested for such woods. Results of the 1924 tests are being
published elsewhere (4, 5 ) . This paper presents the outcome of the 1925 tests.
Woods Selected
The woods for the 1926 tests were selected partly on the
basis of observations after the first year of exposure of the