4616 4620.output

* GB785023 (A)
Description: GB785023 (A) ? 1957-10-23
Improvements in or relating to methods of detecting loose impurities in
transparent containers
Description of GB785023 (A)
COMPLETE SPECIFICATION
Improvements in or relating to methods of Detecting Loose
Impurities! in Transparent Containers
We, THE GENERAL ELECTRIC COMPANY
LIMITED, of Magnet House, Kingsway, London W.C.2, a British Company,
do hereby de
clare the invention, for which we pray that a
Patent may be granted to us, and the method by which it is to be
performed, to be particularly described in and by the following
statement:
This invention relates to methods of detecting loose impurities in
transparent containers such as glass bottles when these containers are
filled with liquid such as milk. An object of the present invention is
the provision of an improved method of detecting the presence of
broken glass or other loose foreign matter or impurities in a filled
glass milk bottle.
according to the present invention, a method of detecting loose
impurities or foreign matter in a filled transparent container such as
a glass bottle comprises illuminating the container from below so that
the bottom of the container is illuminated, rotating the container
about its vertical axis to set any loose foreign matter in motion, and
rapidly stopping the rotation of the container, any loose foreign mat-
ter in the bottom of the container being arranged to be detected Iby
photo-electric means responsive to the change in reflected light from
a part of the bottom of the container anto which part the foreign
matter travels as it spirals inwards after the rotation of the
container is stopped.
Apparatus for ,detecting loose impurities or foreign matter in a
filled transparent container such as a glass bottle, may comprise

means to rotate la container at high speed about its vertical axis,
means to illuminate the bottom of the container, photo--electric means
arranged to view the bottom of the container and to be responsive to
reflected light, and a slide inserted between the bottom of the
container and the photoelectric means, said slide being entirely
opaque to light except for a narrow spiral slit lying substantially
within an image of the bottom of the container arranged to be produced
upon the slide by an optical system placed between the slide and the
container, the
direction of said spiral slit being opposite to the direction of the
spiral trajectory executed by the image of a loose impurity after
abrupt stoppage of the motion of the container.
An apparatus in accordance with the pre
sent invention will now be described by way
of example with reference to the single figure of the accompanying
drawing, which shows a
diagrammatic perspective view partly in section of the main elements
of the apparatus as
used for the detection of broken glass or other loose foreign matter
in a filled glass bottle of milk.
Referring to the drawing, the apparatus
comprises a lightproof box 1 having in its top an aperture 2 over
which the bottle 3 is
arranged to be placed with its axis vertical so that the bottom of the
bottle can be illumi
nated by one or more lamps 4 set inside the box 1 towards the top
thereof and screened from the remainder of the box. The bottle 3 is
arranged to be rotated about its vertical axis at high speed and a
chuck (not shown) for gripping the bottle and rotating it may be
disposed above the bottle on its axis. Situated directly beneath 'the
aperture 2 in the top of the box 1 and below the screening means of
the lamp or lamps, is an optical system comprising a lens 5, bellows 6
and a slide 7 in that order, the plane of the lens 5, and the plane of
the slide 7 being parallel to the top of the box 1 and the bottom of
the bottle 3, and the slide 7 being entirely opaque to light with the
exception of a narrow spiral slit 8, 'the spiral ,extending from the
centre of the image of the bottom of the 'bottle, formed iby the lens
5 on the slide 7, to a short distance beyond the outside of the image.
The spiral
slit 8 is arranged to execute at least one revolution in the area
covered by the image, in a direction opposite to the spiral executed
by the image of a loose impurity after stoppage of the motion of the
bottle. Situated below
the slide 7 on the axis of the bottle 3 and the

axis of the spiral slit 8 in the slide, is a photo
electric multiplier 9 responsive to light re
elected from the bottom of the bottle.
The photo-.electric multiplier 9 is associated
with an electric control circuit (not shown) arranged to reject or
pass m-ttk bottles de
pending upon whether they contain or do not contain foreign matter and
suitable voltage
amplifying means will be associated with the photo-electric
multiplier.
In operation of the apparatus described
above a bottle 3 is .placed above the aperture
in the top of the Ibox 1 and rotated at high
speed. The milk in the bottle also rotates after
the lapse of a short period and any foreign matter which is in the
bottle is thrown to the
outer periphery of the bottom of the bottle 3 as the milk rotates. The
bottle 3 is then stop
ped rapidly and the milk will continue to rotate on its own for some
seconds, gradually coming to rest During the slowing down of the milk,
any particle of loose matter such as
10 in the bottom of the bottle will spiral inwardly towards the centre
at a rate dependent
upon the mass of the particle, a light particle travelling an almost
circular path while a heavy particle travels much more directly
towards the centre, in a path which may be practically radial. It will
Ibe understood that both extremes of path will intersect an oppo
sitely-directed spiral.
Immediately upon the rotation of the bottle
3 being stopped, the photo-electric system including the multiplier 9
is set in operation so that as any foreign matter 10 spirals inwardly,
its image 11 on the slide 7 will pass over that area embraced by the
spiral slit 8 and will cause a change in the reflected light received
by the photo-electric system including the multiplier 9. This change
is adapted to cause
such operation of the system that the bottle is rejected. If no
foreign matter is present in the bottle, then the photo-electric
system does
not reject a bottle.
One advantage of using the spinning method
to cause relative movement between the foreign
matter and the wall of a bottle is that if the
dirt is initially floating on the top of the milk
the spinning aids gravity to make the impurities sink.

As will be appreciated from the above de
ascription, the apparatus differentiates between
loose foreign matter inside the bottle and dirt
or embossing on the outside of the bottle since
at the critical time of viewing, the bottle itself
is stationary, the only movement being in the
milk itself.
What we claim is: -
1. A method of detecting loose impurities
or foreign matter in a filled transparent con
tainer such as a glass bottle which comprises
illuminating the container from below so rhat
the 'bottom of the container is illuminated, ro
tating the container about its vertical axis to
set any loose foreign matter in motion, and rapidly stopping .the
rotation of the container,
any loose foreign matter in the bottom of the container being arranged
to be detected by photo-electric means responsive tot he change
in reflected light from a part of the bottom of ,the container into
which part the foreign matter ,travels as it spirals inwards after the
rotation of the container is stopped.
2. Apparatus for detecting loose impurities or foreign matter in a
filled transparent container such as a glass bottle, comprising means
to rotate the container at high speed about its vertical axis, means
to illuminate the bottom
of the container, photo-electric means arranged to view the bottom of
the container and to he
responsive to reflected light, and a slide inserted between the bottom
of the container
and the photo-electric means, said slide being entirely opaque to
light except for ,a narrow spiral slit lying substantially within an
image of the bottom of the container arranged to be
produced upon the slide by an optical system placed between the slide
and the container, the
direction of said spiral slit being opposite to the direction of the
spiral trajectory executed by the image of a loose impurity after
abrupt stoppage of the motion of the container.
3. A method for detecting loose impurities or foreign matter in a
filled glass bottle, or
apparatus for carrying out the method, substantially as hereinbefore
described with refer
ence to the accompanying drawing.
PROVISIONAL SPECIFICATION
Improvements in or relating to methods of Detecting Loose

Impurities in Transparent Containers
We, THE GENERAL ELECTRIC COMPANY
LIMITED, of Magnet House, Kingway, London
W.C.2, a British company, do hereby declare this invention to be
described in the following statement:
This invention relates to methods of detecting loose impurities in
transparent containers such as glass bottles when these containers are
filled with liquid such as milk. An object of the present invention is
the provision of an improved method of detecting the presence of
broken glass or other loose foreign matter or impurities in a filled
glass milk bottle.
According to the present invention, a
* GB785024 (A)
Description: GB785024 (A) ? 1957-10-23
Composition for eliminating minor element deficiencies in plant growing
media
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The EPO does not accept any responsibility for the accuracy of data
and information originating from other authorities than the EPO; in
particular, the EPO does not guarantee that they are complete,
up-to-date or fit for specific purposes.
Composition for Elisz atillg Minor Element Defidencies in
Plant Growing Media
We, THE Dow CHEMICAL COMPANY, a
Corporation of the State of Delaware, United
States of America, of Midland, State of
Michigan, United States of America, do hereby declare the invention,
for which we pray that a patent may be granted to us and the method by

which it is to be performed, to be particularly described in and by
the following statement:
This invention relates to the supplying of trace metals to plant
growing media and it has particular relation to compositions including
metal salts of trivalent metal chelates of alkylenediamine acetic
acids which are water insoluble and capable of releasing their
chelated metal through association and/or through exchange with other
more strongly bound metals.
It is an object of this invention to provide compositions including
the metal salts of the trivalent metal chelates of alkylenediamine
polyacetic acids which are useful as agricultural aids in overcoming
metal deficiencies, i.e. iron chlorosis, both in soils and in plants
themselves.
Another object of this invention is to provide compositions including
carriers which are not metabolized by bacteria.
Still another object of this invention is the provision of water
insoluble organic metal carriers.
Still another object of this invention is the provision of metal salts
of trivalent metal chelates of alkylenediamine polyacetic acids which
control the activity of the metal ion and which can exchange their
chelated metal for other more strongly bound metals.
Another object of the invention is to provide metal salts of trivalent
metal chelates which have wide utility in the art as metal carriers
and which are not metabolized by bacteria.
The compounds with which the present invention is concerned have one
of the general formul :
<img class="EMIRef" id="026700791-00010001" />
where M is a trivalent metal atom other than cobaltic (Co), preferably
a ferric, chromic, manganic, or aluminium atom; R is -CWCOO- or
-CW.CH2O-; Y is an aikylene or cyclo-alkylene radical which places 2-3
carbon atoms between the indicated nitrogens, preferably ethylene,
propylene, trimethylene, isobutylene or cyclohexylene; B is a divalent
metal atom which forms a chelate of lower stability with the chelating
agent than does the metal M and is preferably a calcium, cadmium,
lead, zinc, magnesium, manganous, cupric, ferrous, nickelous, barium,
strontium of cobaltous atom; and x represents the charge on the anion
and is
-4. The method of correcting metal deficiencies in plant growing media
is to apply the compounds or compositions which include the compounds
in a carrier to an area around the plant.
The structure of the metal chelates is dependent to some extent upon
the pH and upon the metal M. In the case of trivalent iron, for
example, all four substituents on the nitrogen atoms are attached to
the central metal. When R represents -CH2CH2OH an alcohol ate link is

probably formed which imparts increased stability to the compounds
over the stability of the compounds wherein
R represents -CH2-COO- and imparts to these compounds utility as
agricultural aids in calcareous soils.
Minor element deficiencies of one type or
another are known to be universal in existence
and to greatly influence the economics iof an
area by affecting the growth of vegetation and
foodstuffs and of livestock. The elimination
of minor nutritional deficiencies can, to some
extent, be accomplished by the application
of inorganic salts of the deficient metals.
The problem of supplying sufficient
amounts of metal ions to trees and plants is an important one
particularly in those areas in which deficiencies of certain metals
exist in the soil and in cases wherein the plants are unable to
acquire metals already present in the soil, as in iron chlorosis.
Of the several mineral nutritional deficiencies which exist, iron
deficiency is one of the most widespread and is most difficult of all
nutritional difficulties to correct.
Iron chlorosis is found to occur in almost every major fruit growing
area in the world and is generally associated with alkaline and high
lime soil reaction. Excesses of certain materials such as phosphate
and the heavy metals, copper, zinc and manganese also appear to induce
iron chlorosis. The liberal use of copper, phosphate and possibly
manganese in citrus fertilizers appears to be related to recent
increases in iron chlorosis.
In the citrus growing areas of Florida, for example, iron chlorosis is
widespread and occurs in both acid and calcareous soils. It is the
most extensive and serious nutritional problem in acid soils in which
most of the citrus is grown. Such deficiencies result in a loss of
fruit production and a gradual withering of the tree.
At present, such metal deficiencies are treated with a soluble
inorganic salt of the deficient metal, said salt being applied to the
soil as such or admixed with fertilizer or some inert material, by
spraying or by injection.
In the case of iron chlorosis, application of sulfur, lime sodium
heametaphosphate, sodium tripolyphosphate and tetrasodium
pyrophosphate have been tried with little or no success.
Our new approach to the problem of mineral deficiencies involves the
addition of a metal chelate of the deficient element to the soil or
plant and is the first successful means of overcoming iron chlorosis.
The compounds of this invention possess a high metal content and
possess the important feature of beng able to exchange the chelated

metal with a metal which has the property of becoming more strongly
chelated.
These compounds, therefore, function in a manner somewhat lilre that
of the ion exchange resins now commercially available as is
illustrated by the following equation:
Such an exchange is possible when the
equilibrium constant of the chelate involving
My is greater than that of the chelate involving M1.
The present invention involves the discovery of a new class or organic
compounds that possess properties eminently suitable for use as
agricultural aids. The coordinated metal M is released in small but
definite quantities and any action resulting in a removal of the metal
M will cause a further dissociation of the metal chelate in accordance
with the Law of Mass Action as illustrated in the equation:
M+^(Ke)3+3 < oM+s + Kex
An important feature of the compounds of the invention is their
ability under proper conditions to exchange the central metal atom for
another metal atom which is more strongly coordinated. The chelated
manganese atom of calcium manganic ethylenediamine tetraacetate for
example, is readily replaced by the ferric atom merely by bringing the
calcium manganic salt into contact with an iron salt such as ferric
phosphate or ferric sulphate, in the presence of moisture or water.
When an insoluble iron salt is used, the exchange is readily observed
to occur since the original water medium becomes an orange-brown color
characteristic of the calcium salt of ferric ethylene diamine
tetraacetate.
This property permits the compounds of this invention to function in a
manner somewhat like that of the ion exchange resins now commercially
available. (Y ethylenediamine tetraacetic acid anion)
M+ + (M,+3Y) - > 3oM1+3 + (M2Y)X+3
Such an exchange is possible when the equilibrium constant of the
chelate involving M2 is greater than that of the chelate involving Ml.
Measurements of the equilibrium constants of several chelate compounds
of ethylene diamine tetraacetic acid have shown the order of
increasing stability to be: - Ba+ < Sr+2 < M+2 < Ga < Mn+Z Fe+2 < L' <
;Co+2 < Zn+ < Cd+2 < Pb+ < Ni+' < Cu+ < Al+' < Fe+3
Any metal in the series will displace any metal occurring below it in
the series. This order of stability will hold for the metal salts of
the metal chelates.
Hence, elimination of iron chlorosis in areas where the iron is
present in a non-assimilable form, can be accomplished by adding, for
example, the 'calcium calcium chelate to the soil. By an exchange
mechanism, the iron is bound up by the chelate and calcium is released

to the soil. The resulting calcium salt of the iron chelate of
ethylene diamine tetraacetate is then slowly dissolved by the water in
the soil putting the formerly non-available iron in a readily
assimilable form.
When the metal salts of the trivalent metal chelates of this invention
come into contact with water the following reactions occur: (Y
represents 'the ethylene diamine tetraacetate anion)
The coordinated metal M is released in small but definite quantities
and any action resulting in a removal of the metal M will cause a
further dissociation of Ithe metal chelate in accordance with the Law
of Mass
Action.
As a result, a small but definite concentration of the chelated metal
M is available in a form that can be assimilated by the plant.
These compounds are, moreover, biologically and chemically inert and
possess the important feature that, because of their low solubility,
they are not easily washed or leached out of the soil las are
inorganic salts which are used to treat the metal deficiencies. The
compounds possess another advantage in that because of the relative
stability of the metal chelate, the chelated metal ions do not exhibit
their normal reactions in the presence of precipitating agents.
The compounds may, in addition to their direct application to the
soil, be combined with compost, cattle fodder, fertilizers or some
inert ingredient such as sand (attapulgus clays and vermiculite) to
insure uniform distribution in the proportions suitable for
application to the soil under treatment. This procedure offers Ithe
advantage of a single treatment whereby the necessary elements are
added to the soil.
Because of their ability to hold two metal atoms, which are different,
these compounds possess the novel feature of being able to supply
soils, which are deficient in two different metals, with the deficient
metals in a single application. Thus, zinc and iron deficiencies can
be treated by a single application.
of the zinc salt of the iron chelate of ethylenediamine tetraacetate.
Another method of application consists in the uo-precipitation of the
metal salts on or with resinous materials such as acrylonitrile resins
particularly the polyacrylonitrile soil conditioners. In such cases,
the metal carrier is readily available to release its metal to the
soil and/or to exchange with a metal which forms a stronger chelate;
for example, iron will displace 'calcium.
When the metal salts of the metal chelates of this invention come into
contact with water, the following reactions occur. For the sake of
demonstration, the calcium iron salt

CaFe(OH)K will be used.
As a consequence of the above equilibria, a small but definite
concentration of Ithe chelate and chelated metal is available in a
form that can be assimilated by the plant These compounds are,
moreover, biologically and chemically inert. The compounds of this
invention possess the added and highly important feature that, because
of their low solubility, they are not easily washed or leached out of
the soil as are inorganic salts which are used to treat trace metal
deficiencies. A second great advantage, the failure of the chelated
metal ions to exhibit their normal reactions in the presence of
precipitating agents, arises from the stability of the metal chelates.
These two features combine to produce a medium which continues to
function as a supplier of trace minerals over an extended period even
in areas of heavy rainfall.
The metal metal chelates of this invention are, under closely
controlled conditions such as exist in hot-houses, aids in preventing
the occurrence of metal deficiencies. Because of their low solubility
these compounds are not readily leached from the soil even in regions
of heavy rainfall. The compounds may be added to the soil with the
assurance !that their beneficial effects will prevail and continue to
operate for an extended period of time.
The preferred method of application, which has been found to give
satisfactory results, consists in applying the equivalent of 10 grams
to 300 grams of chelated metal in a circle of 8 to 10 feet around the
tree. Best results have been obtained by the application of 10 to 50
grams of chelated metal per tree. This is especially true of the
calcium salts of the iron chelate in treating iron chlorosis in citrus
trees on acid soils. Calcareous soils generally require the addition
of a substantially greater quantity of chelated metal because of the
effect of the higher pH of the soil of the equilibria involved.
Satisfactory results have been obtained in calcareous soils by using
the metal salts of the iron chelates of N-(2-hydroxyethyl)-N, N1)
N1-alkylenediamine trice tic acids which are more stable at higher pB
values than are the metal salts of the iron chelates of
alkylenediamine tetraacetic acids and do not precipitate the iron as
ferric hydroxide.
The application of the metal salts of metal chelates eliminate the
nutrient mineral deficiencies within 4 to 8 weeks following
application; the effects lasting at lelast one year. In many instances
new flushes of gmvSth and even flowering have been observed to follow
the application of these mineral bearing compounds to the soil around
chiorotic trees. As a consequence, applications should preferably be
made in the spring or in - late January or

February.
In the treatment of iron chlorosis in citrus trees with the calcium
salts of the iron chelates of 'this invention, an increase in iron
uptake has beenfound to take place. The reason for this is as yet
unknown but it is probable that the chelated iron, which is held in a
non-precipitable form, is exchanged with cations in the roots. The net
result is that the iron is held in a form readily assimilable by the
plant roots.
Excessive amounts of the metal metal salts are to be avoided since
overdoses may produce harmful resltlts.
For the purposes of this invention, the pure metal salts are not
necessary. The inorganic alkali metal salts present do not interfere
in the operation of the products as agricultural aids.
In the following examples specific methods illustrating the subject
matter of The invention are described.
EXAMPLE 1.
Ten ounces of the calcium salt of ferric ethylenediamine tetraacetate
(40.3 grams of chelated iron) were thoroughly mixed with 5 pounds of
sand. The resulting mixture was spread evenly in an 8 foot circle
around a mature, severely chiorotic orange tree located on soil having
a pH of 4.5, and the treated area thoroughly irrigated. Within a few
weeks this tree (A) showed considerable amelioratiolr over a similarly
chiorotic but untreated tree, (B) used as control. Tree A continued to
show improvement, the characteristic etiolation being completely
eliminated over a 12 week period. Control tree B in tbe meantime
continued its downward tren:l, -defoliation and finally dieback
occurred.
EXAMPLE 2.
A mature orange tree, suffering from an iron deficiency and growing on
a calcareous soil having a pH of 8.5 was treated by- applying a solid
carrier !containing 31 Ibs. of the calcium salt - of the iron chelate
of N- (2hydroxyethyl)-N, Nl, Nl-ethylenedlamine triacetic acid
(containing 225.7 grams of chelated iron) in an 8 to 10 foot circle
around the - tree. Complete greening of the chlorotic leaves occurred
within 8 weeks and new leaves coming out in the spring were green and
appeared about 2 weeks earlier than those on untreated tree. New
flushes of growth were also observed on the area covered with the
calcium iron salt.
EXAMPLE 3.
The application of a solid carrier containing two pounds of the
calcium salt of the iron chelate of N-(2-hydroxyethyl)-N, Nl, N'-
ethylenediamine triacetic acid (129 grams of chelated iron) to a
moderately chlorotic mature orange tree standing on acid sail (pH 4.8)
produced results similar to those reported under Example 2.

EXAMPLE 4.
Four pounds of the zinc salt of the iron chelate of
N-(2Thydroxyethyl)-N, N1, N - ethylenediamine triacetic acid (258.0
grams of chelated iron) were mixed with ten pounds of atticulite and
evenly distributed on a 50 x 25 foot plot of yellowing celery
characterized by a green pattern of the leaves. The pH of the soil was
8.0 and containing sufficient iron which was, however, unavailable
to the plants because of the prevailing pH.
Within four weeks the chlorotic condition had completely disappeared.
The preparation of compositions carrying the heavy metal chelates in a
carrier which includes an alkaline earth metal compound, for example,
agricultural lime or agricultural limestone, is very rapidly carried
out in a manner which avoids the necessity of isolating the chelate
salt per se. Thus, the heavy metal chelate of iron, for example, may
be formed in its acid form and while it is still in solution it is
reacted with agricultural lime or limestone to form the calcium salt
of the iron chelate. Operating in this manner, a concentrated solution
of iron chelate of ethylene diamine tetraacetic acid is prepared and
reacted with the agricultural lime, or limestone. The composition thus
obtained comprises excess lime containing the calcium iron chelate in
admixture therewith. The amount of excess lime may be varied as
desired. Where the solution of the iron chelate is not concentrated,
it may be necessary to dry the product somewhat to render it capable
of being handled. Where, for example, the sodium salt of rhe chelate
is used the prepare the calcium salt in this fashion it may be desired
to wash the sodium carbonate or sodium hydroxide out of the lime or
limestone composition, because the alkali metals in ionic form
generally are not desirable constituents of soil. Thus, where the
sodium salt is used the mixture of the lime or limestone with the
solution of chellate may be washed with water to wash out the soluble
ingredients, which would be sodium hydroxide or sodium carbonate, and
leave behind the calcium salt for admixture with the agricultural lime
or limestone.
The compounds of this invention are all stable non-hygroscopic
powders. The metal salts of the trivalent metal chelates of ethylene
diamine tetraacetic acid are water insoluble products which readily
separate in almost quantitative yields, whereas those of
hydroxyethyl)-N,N1,N1 ethylenediamine triacetic acid are soluble in
water and are obtained by evaporation of the water. The color of the
salt is dependent on the metals present in the molecule. The following
table lists some of the metal salts of trivalent metal chelates
together with their colors: - (Y= ethylenediamine tetraacetate anion,
and X = N- (2-hydtoxyethyl) - ethylenedianline - N,NI,N'- triacetate
anion)

TABLE I
Compound Color
Ca Fe Y Tan
Mn Fe X Orange-brow
Mn Fe Y Orange-brown
Ca Cr Y Violet
Ca Al Y White
Zn Al Y White
The compounds of this invention can be prepared according to any of
several modifications, for example, by reacting the proper acid metal
chelate, such as calcium dihydrogen ethylenediamine tetraacetate, with
a 1:1 molar ratio of the appropriate metal salt, such as aluminum
sulfate in an aqueous medium.
A method of preparation we have employed consists in reacting a metal
chelate, such as zinc diftydrogen ethylenediamine tetraacetate, with
the salt of a metal, for example, aluminum sulfate, lying higher in
the stability series listed above, whereby a displacement reaction
occurs resulting in formation of thc metal salt of the chelate having
a higher equilibrium constant.
When the pure metal salts of the compounds of this invention are
desired, they are conve niently obtained by employing the carbonates
or hydroxides of the metals desired in the metal salts.
- However, for the purposes of this invention, the pure metal salts
are not necessary and the sulfates, chloddes and any other readily
available salts may be employed as well as any of the allQali metal
salts of the alkylenediamine polyacetic acids. The inorganic alkali
metal salts produced do not interfere in the operation of the products
as agricultural aids.
If desired, however, they can easily be removed by washing vwlth
water.
In the following examples specific methods illustrating the subject
matter of the invention are described.
EXAMPLE A
Calcium Salt of Aluminum Ethylenediamine
Tetraacetate
One-half mole of aluminum sulfate was gradually added to a well
stirred solution of one mole of calcium disodium ethylenediamine
tetraacetate in 1500 milliliters of water at 85"
C. and the whole stirred and heated for an additional 2 hours. The
white slurry which formed was then cooled to room temperature,
filtered, washed with water until a negative sulfate test was
obtained, and then dried. A nearly quantitative yield of the calcium
salt of aluminum ethylenediamine tetuacetate is obtained. Analysis
showed 7.10% aluminum to be present

EXAMPLE B
Calcium Salt of Ferric Ethylenediamine
Tetraacetate (Pure)
One mole of ferrous sulfate hepltahydnate and one mole of calcium
disodium ethylenediamine tetraacetate were reacted together as in
Example A. About two-thirds of the water was removed by evaporation,
the orangebrown slurry cooled, filtered, washed with water to remove
sodium sulfate and dried at 80" C. The product, an orange-brown
powder, contained 14.2% ircn. The iron is, present in the ferric form
because of the rapid oxidation of the initially formed ferrous chelate
by oxygen under the reaction conditions employed.
EXAMPLE C
Calcium Salt of Ferric Ethylenediamine
Tetraacetate
One-half mole (189 grams) of ferric sulfate and one mole of calcium
diso dium ethylenediamino !tetraacetate were reacted together as in
Example A. The suspension was heated at 80" -85 C. for one hour and
then evaporated to dryness. The resulting buff colored solid contained
9.9% iron.
EXAMPLE D
Calcium Salt of Aluminum Ethylenediamine
Tetraacetate
One-half mole of freshly prepared aluminum hydroxide was added ito a
slurry of one-half mole ethylenediamine tetraacetic acid in one liter
of water at 80"--85" G. The slurry was thoroughly stirred for one-half
hour and then one-half mole of calcium. carbonate was gradually added.
When evolution of carbon dioxide ceased, the suspension was cooled,
filtered and dried. Analysis showed the resulting white powder ItO
contain 11.0% calcium.
EXAMPLE E
Calcium Salt of Ferric N-(2-hydroxyethyl)
N,N1,N1-ethylenediamine Tricacetate
One mole (278.Q grams) of ferrous sulfate heptahydrate and one mole of
calcium, sodium N-(2-hydroxyethyl)-N,N1,N1-ethylene diamine triacetate
were reacted together as in Example
B. About Itwo-thirds of the water was removed by evaporation, the
orange-brown slurry cooled, filtered, washed with water to remove
sodium sulfate and dried at 80 C. The product, an orange-brown powder
contained 13.9% iron. The iron is present in the ferric form because
of the rapid oxidation of the.
initial ferrous chelate by oxygen under the reaction conditions
employed.
EXAMPLE F.
Zinc Salt of Ferric N-(24iydroxyethyl)-N,N1,

N1-ethylenediamiae Triacetate
One mole of ferrous sulfate heptahydrate and one mole of zinc sodium
N-(2-hydroxyethyJ) - N,N1,N1 - ethylenediamine triacetate were reacted
together as in Example A and; worked up as in Example E. The
yellowbrown powder contained 12.8pro iron.
EXAMPLE G
Manganous Salt of Ferric N-(2-hydroxyethyl)
N,Nl,N'-ethylenediamine Triacetate
Same procedure as in Example F but using manganous N-(2 -
hydroxyethyl) - N,N1,N1- ethylenediamine triacetate in place of the
zinc chelate. The product, a yellow-brown solid contained 8.8% iron.
What we claim is: -
1. A composition for application to plant growing media for the
elimination and control of trace element deficiencies in the said
medi!a which comprises a carrier and a metal salt of a metal chelate
having one of the general formulae:
wherein M is a trivalent metal atom other than cobaltic (Go), R is
either -CH.COO or --CH,CH,O, Y is an alkylene or cycloalxylene radical
which places 23 carbon atoms between the indicated nitrogens; B is a
divalent metal atom which forms a chelate of lower stability with the
chelating agent than does the metal M; and x represents the charge on
the anion and is -4.
2. A composition as ,claimed in claim 1, wherein Y is an ethylene,
propylene or trimethylene radical and M is a ferric, chromic, manganic
or aluminium atom.
3. A composition in accordance with claim 1 or 2, in which the carrier
is sand.
is a fertilizing material.
is lime
is limestone.
7. A composition in accordance with claim 1 Or 2, in which the metal
salt is the calcium salt of ferric ethylenediamine tetraacetate.
8. The method of forming a composition useful for application to plant
growing media for the elimination and control of trace element
deficiencies in the media, which comprises forming a suspension in a
carrier of a compound of the general formula I or the general formula
II of claim 1, by reacting the corresponding trivalent metal chelate
with a basic divalent compound of the corresponding divalent metal.
9. The method in accordance with claim 8, in which the divalent metal
is calcium.

compound is agricultural lime and the metal in the chelate is iron.
compound is agricultural limestone and the metal in the chelate is
iron.
12. Compounds corresponding to the general formulae I or II of claim
1, wherein M is la trivalent metal atom other than cobaltic (Co), R is
-CH2COO- or -CwwO'-, B is a divalent metal atom which forms a weaker
chelate with the chelating ag
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* GB785025 (A)
Description: GB785025 (A) ? 1957-10-23
Manufacture and use of complex iron salts
PATENT SPECIFICATION
785,025 i k Date of Application and filing Complete Specification:
April 20, 1954.
No 11405154.
Application made in Switzerland on April 20, 1953.

Complete Specification Published: Oct 23, 1957.
Index at acceptance:-Classes 2 ( 3), C 212 (A 1: G 1 A: K); 81 ( 1), E
1 C( 5 D: 13); and 111, B 3 (C 1: C 4:
F 1).
International Classification:-A 611 C 05 c, d, f CO 7 f.
Manufacture and Use of Complex Iron Salts We, CIBA LIMITED, a body
corporate organised according to the laws of Switzerland, of Basle,
Switzerland, do hereby declare the invention, for which we pray that a
patent may be granted to us, and the method by which it is to be
performed, to be particularly described in and by the following
statement: -
This invention relates to the manufacture and use of complex iron
salts of nitrilotriacetic acid Various salts of trivalent iron with
nitrilo-triacetic acid are already known.
In volume 249 ( 1942) of the "Zeitschrift fiur anorganische Chemice"
is described on pages 301-303, the manufacture of two iron salts.
By heating a solution of ferric ammonium sulphate with nitro-triacetic
acid there is obtained a salt which is very sparingly soluble in water
and contains one mol of nitrilo-triacetic acid bound to one atom of
iron This salt is referred to as being noncomplex By reacting a
freshly prepared suspension of ferric hydroxide with free
nitrilotriacetic acid there is formed an iron salt which is also
sparingly soluble in water, and contains a ratio of iron to acid
amounting to 2:3 In an article in the Helvetica Chemica Acta, Vol 31,
page 333 ( 1948) is described in connection with methods of analysis
the formation of complexes between ferric salts and nitrilo-triacetic
acid It is stated that when solutions of equimolecular quantities of a
ferric salt and the dipotassium salt of nitrilo-triacetic acid are
brought together an acid solution is produced which requires one or
two equivalents of alkali for neutralisation.
The resulting complex ions are referred to as monohydroxo and
dihydroxo derivatives of the following formulae lX Fe OHl and lX Fe
(OH)2 l in which X represent /V -153 v Coo el coo lPrice 3 PM 1 4 ' 6
d The present invention is based on the observation that the complex
ferric compounds of nitrilo-triacetic acid referred to above are
stable not only in aqueous solution, 45 but are also obtainable in
solid form and easily dissolve in water Accordingly, this invention
provides a process for the manufacture of solid water-soluble complex
ferric compounds of nitrilo-triacetic acid, in which 50 one atom of
iron is present per molecule of acid and which contain 0, 1 or 2 of
alkali metal or ammonium ions per ion of nitrilotriacetic acid-iron
complex, wherein a ferric salt is reacted with an alkali metal or 55
ammonium salt of nitrilo-triacetic acid in equimolecular proportions

in aqueous solution, the resulting acid is at least partially
neutralised by the addition of an alkali metal or ammonium base and
the aqueous solution 60 is evaporated to dryness, or wherein a ferrous
salt of nitrilo-triacetic acid is oxidised in aqueous solution to the
ferric salt, the resulting acid is at least partially neutralised by
the addition of an alkali metal or ammonium 65 base, and the aqueous
solution is evaporated to dryness.
As ferric salts for the present process there may be used any desired
water-soluble salts of trivalent iron, for example, ferric 70 ammonium
sulphate or ferric chloride.
Among the ferrous salts, which may be used for making the ferrous
salts of nitrilo-triacetic acid, here is advantageously used ferrous
sulphate owing to the ease with which it can 75 be obtained The alkali
metal or ammonium salts of nitrilo-triacetic acid may contain one, two
or three equivalents of alkali per mol of acid There are
advantageously used potassium salts Instead of using the preformed 80
salts, it will be understood that they may be formed in the reaction
solution by reacting free nitrilo-triacetic acid with a corresponding
quantity of an alkali metal hydroxide or carbonate or ammonia In order
to neutralise 85 the acid resulting from the formation of the iron
salt there may also be used an alkali r:.
> 2 785,025 metal hydroxide or carbonate or ammonia.
The quantity to be added depends on whether it is desired to impart to
the final product a neutral, weakly alkaline or weakly acid reaction
For the method in which oxidation is carried out there may be used any
oxidising agent which is capable of converting ferrous salts into
ferric salts Advantageously hydrogen peroxide is used The evaporation
of the reaction solution in order to produce a dry product is
advantageously carried out under reduced pressure.
The products so obtained are mixtures of complex ferric salts with
other water-soluble salts They are easily soluble in water The complex
ferric salts have different constitutions depending on the degree of
neutralisation In the light of the information contained in the
article in the Helvetica Chemica Acta referred to above it is probable
that the products are substantially salts having the following
constitutions, when a potassium salt is used for neutralisation:
and o vC% Coo OK+ N _, _CO When the neutralisation is incomplete a
part of the iron salt is in the form of acid, and such salts are to be
given the following constitution in analogy with the salts.
H+ It has also been found that the watersoluble complex ferric salts
of nitrilo-triacetic acid of the invention are valuable agents for
protecting plants They can be used for the treatment of diseases
caused by a deficiency of iron, because the complex salts are easily
taken up by plants and are not adsorbed to any substantial extent by

the constituents of the soil.
Accordingly, the invention also provides preparations for protecting
plants, which consist of or contain wvater-soluble solid complex
ferric compounds of nitrilo-triacetic acid, which contain one mol of
acid and one mol of iron and 0,1 or 2 alkali metal or ammonium ions
per ion of nitrilo-triacetic acid-iron complex The complex salts may
be used as such.
Advantageously, however, they are mixed with an inert solid carrier,
such as kaolin or talc, or with a solid fertiliser, and are used by
scattering the mixture below the plants to be treated It is of
advantage to prepare aqueous solutions by dissolving the solid complex
compound in water and to use the solutions for watering the plants
Also in the case of solutions prepared by dissolving the solid complex
ferric salts in water there may be added a fertiliser and/or a
pest-combating substance and/or a weed killer.
The following Examples illustrate the invention, the parts being by
weight unless otherwise stated, and the relationship of parts by
weight to parts by volume being the same as that of the kilogram to
the litre:
EXAMPLE 1.
To a suspension of 22 2 parts of nitrilotriacetic acid of 90 per cent
strength in 150 parts by volume of water there are first introduced,
while stirring, 27 8 parts of crystalline ferrous sulphate and then 20
parts of calcined potassium carbonate There is obtained a solution
which is still acid (p H value about 4), in which there are slowly
introduced, while stirring, 7 1 parts of hydrogen peroxide of 28 per
cent strength diluted with 15 parts by volume of water The temperature
rises to 30-35 C and the solution becomes dark in colour After
stirring the mixture for one hour at room temperature hydrogen
peroxide can no longer be detected and a test portion of the solution
remains clear after the addition of sodium carbonate.
The whole is then rendered weakly alkaline by -the addition of 6 parts
of calcined potassium carbonate, and the solution is evaporated to
dryness in vacuo There are obtained parts of a brown powder which is
very easily soluble in water, and solutions of which form no
precipitate with sodium carbonate at ordinary temperature Instead of
potassium carbonate there may be used for the neutralisation an equal
quantity of aqueous ammonia solution.
EXAMPLE 2.
13.8 parts of potassium carbonate are added 95 to a suspension of 21 2
parts of nitrilo-triacetic acid of 90 per cent strength in 150 parts
by volume of water 16 2 parts of pulverised anhydrous ferric chloride
are scattered, while stirring, into the resulting 100 solution of the
dipotassium salt of nitrilotriacetic acid, and then the whole is

heated for a short time at 809 C After the mixture has been cooled to
room temperature, the finely crystalline precipitate of the acid iron
105 salt is formed Upon introducing 13 8 parts of potassium carbonate
the latter passes into solution accompanied by the production of a
red-brown coloration The p H value of the 785,025 acid, conducted
substantially as described in Example 1 or 2 herein.
Water-soluble solid complex ferric compounds of nitrilo-triacetic
acid, which contain one atom of iron per molecule of the acid and 0, 1
or 2 alkali metal or ammonium ions per ion of nitrilo-acetic acid-iron
complex.
6 Water-soluble solid complex ferric compounds of nitrilo-triacetic
acid, whenever made by the process claimed in any one of claims 1-4.
7 A preparation for the protection of plants which consists of or
contains a watersoluble solid complex ferric compound of
nitrilo-triacetic acid containing one atom of iron per molecule of the
acid and a 0, 1 or 2 alkali metal or ammonium ions per ion of
nitrile-triacetic acid-iron complex.
8 A preparation as claimed in claim 7, which also contains a
fertiliser and/or a pestcombating agent and/or a weed killer.
9 A preparation as claimed in claim 7 or 8, which is obtained by
dissolving the solid complex compound in water.
ABEL & IMRAY, Agents for the Applicants, Quality House, Quality Court,
Chancery Lane, London, W C 2.
solution is 6 5 By evaporating the solution in vacuo there is obtained
a solid salt mixture which is easily soluble in water.
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* GB785026 (A)
Description: GB785026 (A) ? 1957-10-23
Metalliferous mono-azo dyestuffs of the benzene-azo-pyrazolone series

Date of Application and filing Complete Specification: April 20,
No 11406/54.
785,026 1954.
l t ER 2 M Application made in Switzerland on April 21, 1953.
Application made in Switzerland on March 29, 1954.
(Patent of Addition to No 741,602, dated July 18, 1952).
O)O Complete Specification Published: Oct 23, 1957.
Index at acceptance:-Class 2 ( 4), P 1 (A 4 83: F 5), P 8 (A 1 B: B 1:
C 2: C 3: E).
International Classification:-C 09 b.
Metalliferous Mono-Azo Dyestuffs of the Benzene-Azo-Pyrazolone Series
We, CIBA LIMITED, a body corporate organised according to the laws of
Switzerland, of Basle, Switzerland, do hereby declare the inventions
for which we pray that a patent may be granted to us, and the method
by which it is to be performed, to be particularly described in and by
the following statement:-
This invention is an improvement in or a modification of the invention
forming the subject of Specification No 741,602.
That Specification describes a process for the manufacture of
mletalliferous azo,-dyestuffs, wherein one or two monioazo'dyestuffs
which are free from sulphonic acid and carboxylic acid groups and
correspond to the general formula HO OH VC-N-Q R.-N=N-C| S O 1 N W,, N
CH 3 in which R, represents a benzene residue bound to' the azo
linkage in ortho-position relatively to the hydroxyl group, and R 2
represents a benzene residue, and in which at least one of the
residues R, and R contains an aliphatic group, or a halogen atom, or
two moneazoi dyes of which one corresponds to the above formula and
the other is ant ortho:
orth o$-dioxy-monoazo dyestuff of the benzeneazo-naphthalene series
free from: sulphonic acid and carboxyli& acid; groups, is or are
treated with an agent yielding cobalt or chromium in such manner that

the resulting metalliferous dyestuff contains, per molecular
proportion of dyestuff, less than one atomic proportion of cobalt or
chromium.
According to the present invention valuable new metalliferous
azodyestuffs are made by treating one or two monoeazo-dyeswffs which
are free from sulphonic acid and carboxylic lPrice Jiri Sl 4 S 6 d
acid groups and correspond to the general formula ( 1) OH I RI-N =
N-Pz-R, in which R, represents a benzene residue bound to the azo
linkage in orthe-position to the hydroxyl group, Pz represents a
5-pyrazolone residue bound to the azo, linkage in the 4-position, and
R represents an, aromatic bicyclic hydrocarbon residue bound directly
to the 1-position or by the group -CONH to; the 3position of the
pyrazole ring which residue may contain substituents, and in which at
least one of the residues R, and R contains a -SO 2 NH group, with an,
agent yielding chromium or cobalt under conditions such that a
metalliferous azoi dyestuff is formed which contains less than one
atom of cobalt or chromium in complex union per molecule of
monoiazc-dyestuff Especially valuable results are obtained if
monoazedyestuffs are used which are free from sulphonic acid and
carboxylic acid groups and which correspond to the formula ( 2) Ira X
t/ inl which X represents a chlorine atom or hydrogen atom, and R
represents a diphenyl or naphthyl residue.
Among these monoazo-dyes tuffs those of the formula ( 3) #o 1 t 3 are
especially suitable.
The monoazo-dyastuffs corresponding to the above formula and used as
starting materials in the present process can be obtained by coupling
an ortho-oxy-diazocompound of the benzene series which is free from
sulphonic acid and carboxylic acid groups with a pyrazolonc which
contains an aromatic bicyclic hydrocarbon residue bound directly to
the 1-position or by the group -CONH-to the 3-position cf the pyrazole
ring which residue may contain substituents C O N I Sa N and (b)
Pyrazolones free from -SONH 2 group's, such as 1-( 7 or
P-naphthyl)-3methyl 5 -pyrazolone, 1 ( 21 naphthyl)
-3me;thyl-5-pyrazolon-6 '-sulphoni c acid methyl amide, 1-(ocrtho-,
mzta or para-benzylphenyl)-3-mnthyl-5-pyrazolone or
1-diphenyl3-m:thyl-5-pyrazolone.
As ortho-oxy-diazo compounds of the benzeno series there come into
consideration for making thz dyestuffs used as starting materials in
the present process diazo compounds of ortho-Gxy-amines of the benzene
series of which the benzen'e nucleus may contain, in addition to the
hydroxyl group and the amino grcup, further substituents, such as
halogen atoms (for example, chlorine), alkyl groups (for example,
miethyl), alkoxy groups (for examiple,methoxy),niftro groups,
-CO-Alkyl groups (for example CO-CH 3) and acylamino groups (for

example, acetylamino) As examples of amines free from sulphonic acid
amide groups, the diazo compounds of which are coupled only with the
pyrazolones mentioneld under (a) above, there may be mentioned:
6-Nitro-4-methyl or -4-chloro-2aminc-l-cxybenzene, 6-chiloro-4-methyl
or rrmthyl-, 4-chloro or 4-acetylamino-2-aminol-oxybenzene, 5 or
6-nito-2-amino-1-oxybenzene, 4 methyl or
4-chloro-5-nitro'-2amino-l-oxybenzene, 4-nitro-6-acetylamino-2amin
o:-1-oxybznzene, 6-nitro -4-acetylamino-2amino-1-oxybenzene, 4:
6-dinitro-2-amino-1oxybenzene, 4: 6 dichloro 2 -amino 1 -oxybenzene, 4
tertiary-amyl-6-nitro-2-aminoloxybenzene, 3-amino-4-oxyacetophenone,
5ritro-3-amino-4-oxyacetophenone, 4-methoxy2-amino-l-oxybenzerne or
6-acetylamino-4chlore 2 -amino-1-lxybenzene, and also
2amino-l-oxybenzen-; 4-carboxylic acid amide.
Especially valuable results are obtained with compounds containing a
sulphonic acid amide group, such as 4-nitro or
4-chloro-2anmino-1-oxybenzene-5 or -6-sulphonic acid amide, 6-nitro or
6-chloro-2-amino-1-oxyand which contains a -SONH group if such a
group, is not present in the diazo comFound.
The aforesaid pyrazolones can be made by rathods in themselves known
As examples of such pyrazolones there may be mentioned:
(a) Components containing a -SO 2,NH, group, such as 1 i -naphthyl 3
-methyl-5pyrazclone-4 '-, -5 '-, -6 '-, -7 ' or -8 ' sulphonic acid
amide, 1-fi-naphthyl-3-methyl-5-pyrazolone-6 '-sulphonic acid amide,
and also the pyrazolones of the formula #2 <I CO-J/h M 9
benzene-4-sulphonic acid amide, and especially 2-amrino-l-oxybenzene-4
or -5-sulphonic acid antide The diazo compounds of these amnines may
be coupled either with the pyra 75 zolones mentioned under (a) above
or under (b) above.
Coupling of the ortho-oxy-diazo-compounds with the pyrazolones can be
carried out by the usual known methods, for example, in a 80 weakly
acid to alkaline medium.
When the coupling reaction is finished the dyestuffs, for the purpose
of metallisation, can easily be separated from the reaction mixture by
filtration after the addition of sodium 85 chloride, as they are only
sparingly soluble in water They are advantageously used for the
metallisation in the form of filter cakes without intermediate drying
In some cases it is also possible to carry out the metallisa 90 tion
directly in the coupling mixture without intermediate isolation.
The monoazo dyestuffs obtainable as described above are in general not
especially easily soluble in water when in the form of 95 their alkali
metal compounds However, some of them' are sufficiently soluble in
that form to enable them' to be used from dyebaths which require noe
addition of acid The treatm:ent with an agent yielding chromium or 100
cobalt in accordance with the present invention is carried out in such

manner that a metalliferous dyestuff is obtained which contains less
than one atom of chromium or cobalt in complex union per molecule of
mono 105 azc-dyestuff Accordingly, the metallisation is advantageously
carried out with such an agent yielding chromium or cobalt ard by such
a method that a complex chromium or cobalt compound of the desired
constitution is oh 110 tained In general, it is of advantage to use
less than one, but at least a half, atomic proportion of chromium or
cobalt per molecule of monzoazo-dyestuff and/or to carry out the
m:etallisation in a weakly acid to alkaline 115 medium Therefore,
there are especially suitable these agents yielding chromium or cobalt
785,026 wet fastness and very gobd fastness to light.
Specification No 637,404 describes and claims a process for the
manufacture of metalliferous dyestuffs free from sulphonic acid groups
by the action of agents yielding metal upon azo-dyestuffs which are
free from sulphonic acid groups and from carboxylic acid -groups
standing in ortho-position to hydroxyl groups and which contain the
atomic grouping /0 01/ which are stable in alkaline media, for
example, complex chromium or cobalt compounds of aliphatic or aromatic
ortho-oxycarboxylic acids, such as lactic acid, citric acid, tartaric
acid 4-, 5 or 6-methyl-1-Gxybenzenre-2-carboxylic acid and above all
1-oxybenzene-2-carboxylic acid itself As agents yielding cobalt there
are advantageously used simple cobalt salts such as cobalt sulphate or
cobalt acetate.
Conversion of the dyestuffs into the conmplex metal compounds is
advantageously carried out at a raised temperature, under atmospheric
or superatmospheric pressure, if desired in the presence of suitable
additions, for example, salts of organic acids, bases, organic
solvents or other agents assisting the formation of complexes.
In one form of the process of the invention a mixture of two different
metallisable mono azo-dyestuffs is used as starting material, which
dyestuffs both correspond to the formula ( 1).
Inl this form of the process it will be understood that the treatment
with the agent yielding metal is carried out under conditions such
that metalliferous dyestuffs are obtained which contain at least one
atom of chromium or cobalt bound in complex union per molecule cf
monoazo-dyestuff.
The new products of the present process are chromium or cobalt
compounds which contain one or two monoazo-dyestuffs in a complex in
which the ratio of the number of chromium or cobalt atoms bound in
complex union to the number of monoazo-dyestuff molecules bound in
complex union to the chromium or cobalt is smaller than 1: 1, and
advantageously about 1:2, and in which the meonazo-dyestuff or
dyestuffs or ortho:ortho L dioxy-monoazo-dyestuffs free from sulphonic
acid and carboxylic acid groups, which correspond to the general

formula ( 1) above.
Especially valuable are those chromium and cobalt compounds of this
kind which contain two monioazo-dyestuffs of the same constitution,
and those wherein the monoazo-dyestuffs correspond to the formula (
2), and still more so are those chromium and cobalt compounds which
contain 2-monoazo-dyestuf Es of the formula ( 3).
The new chromiferous and cobaltiferous dyestuffs are soluble in water,
and are indeed more soluble than the metal-free dyestuffs used for
making them They are suitable for dyeing and printing a very wide
variety of materials, but especially fo, dyeing nitrogenous natural
materials such as silk, leather and especially wool, and also for
dyeing and printing synthetic fibres of super polyamides, super poly
urethanes or polyacrylonitrile They are suitable above all for dyeing
from a weakly alkaline, neutral or acid, especially acetic acid, bath
The wool dyeings so obtained are distinguished by their level
character and very good properties of wherein the treatment with the
agent yielding metal is conducted in a neutral to alkaline medium and
the aforesaid agent is a metal compound which contains an aromatic
ortho, oxycarboxylic acid in complex union, and with the use of a
proportion of the complexforming metal corresponding to less than one
atom for each group, in the dyestuff capable of leading to the
formation of complexes.
As compared with the pyrazolone dyestuffs disclosed in Specification
No 637,404, which are at most sparingly soluble in water, the
dyestuffs of the present invention are distinguished by a much better
solubility and consequently a greater suitability for dyeing wool from
aqueous baths As compared with the dyestuffs of Specification 637,404
whose solubility is sufficient that they are suitable for dyeing wool
from aqueous baths, the dyestuffs of the present invention are
distinguished by the fact that they yield wool dyeings of much better
wet fastness properties.
Specification No 678,492 describes and claims monoazo-dyestuffs of the
pyrazolone series which are free from carboxylic acid and from
sulphonic acid groups and correspond to the general formula 04 ' -4 /
I 2 o in which R represents an aromatic residue of 105 the benzene
series containing a single sulphonamide group of the formula -5 2 a <'
in which R 1 and R 2 each represent hydrogen, an alkyl or an oxyalkyl
residue, and which aromatic residue may contain other substituents.
785,026 Specification No 709,495 describes and claims
monoazo-dyestuffs of the general formula or X #_l-R A O a in which X
represents a sulphonic acid amide group, and R represents the residue
of an azo component which is free from sulphonic acid and carboxylic
acid groups and is bound to the azo linkage in a position vicinal to a
hydroxyl group.

The following Examples illustrate the invention, the parts being by
weight:
EXAMPLE 1.
47.1 parts of the sodium salt of the dyestuff from diazotised 2 amino
1 oxybanzene-4sulphonic acid amide and 1-( 4
phenylphenyl)-3-methyl-5-pyrazolone are dissolved in 1000 parts of
water and 13 3 parts of sodium hydroxide solution of 30 per cent
strength After the addition of 120 parts of a solution of sodium
chromosalicylate having a chromium content of 2 6 per cent, the whole
is boiled for 3 hours under reflux The metallised dyestuff is isolated
by evaporating the solution in vacuo It is a water-soluble brown
powder which dyes wool from a neutral or acetic acid bath orange tints
having very good properties of fastness.
The metal-free dyestuff described above is dissolved in 1000 parts of
water and 26 6 parts of a sodium hydroxide solution of 30 per cent
strength, and, after the addition of 300 parts of a cobalt sulphate
solution having a cobalt content of 1 3 Fer cent and heating the
mixture for hour at 80-85 C, the cobalt compound of the dyestuff is
obtained.
It dyes wool from neutral or acetic acid baths brown yellow tints
having very good properties of fastness.
Similar dyestuffs are obtained by treating the monoazo-dyestuffs,
obtained from the diazo: and coupling compcnents mentioned in Columns
I and II of the following Table, in the mrnanner described above with
an agent yielding thez metal named in Column III In Column IV are
given the tints produced on wool with the chromium and cobalt
complexes so obtained:
785,026 785,026 II rv red-orange scarlet yellowish brown red-orange
yellowish brown, bluish red orange OU S Ox Y, or .a 0,.5/ 1 yea 0,q -2
0,15, 1 8 % OH ll, 602 % OH lll 30, NY, OH .112 S 0, Nt, OR IY,4 S o',
NY, III chromium chromium cobalt chromium cobalt chromium #0 1 C-IV.
UC.0 p C., I_k Mb #0 W-/V elf Ilellc 1 COEXAMPLE 2.
parts of well wetted wool are entered at 40-50 C into; a dyebath which
contains in 4000 parts of water i part of the chromiferous dyestuff
obtainable as described in the first paragraph of Example 1 2 parts of
aewtic acid of 40 per cent strength are added, the bath is raised to
the boil in the course of hour and dyeing is carried on at the boil
for 43 hour Finally the wool is rinsed, with cold water and dried
There is obtained an cralnge dyeing of very good fastness to washing
and light.
The same result is obtained when no acetic acid is added to the
dyebath.
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* GB785027 (A)
Description: GB785027 (A) ? 1957-10-23
Improvements in or relating to high frequency current supply arrangements
for use intelecommunication systems
Inventoir: JOHN BOURA Date of filing Complete Specification April 19,
1955.
Application Date April 20, 1954.
7859027 No 11396/54.
Complete Specification Published Oct 23, 1957.
Index at Acceptance: -Classes 40 ( 4), R 3 D; and 40 ( 5), L 14 B.
International Classification: -H 04 j.
Improvrements in or relating to High l'requency Current Supply
Arrangernents for use in Telecommunication Systems We, BRITISH
TELECOMMUNICATIONS RESEARCH LIMITED, a British Company, of Taplow
Court, Taplow, Buckinghamshire, do hereby declare the invention, for
which we pray that a patent may be granted to us, and the method by
which it is to be performed, to be particularly described in and by
the following statement: -
The present invention is concerned with the supply of carrier current
in telecommunication systems, for instance so-called broad-band
multi-channel carrier systems where a comparatively large number of
different frequencies may be employed corresponding to the various
channels.
As a matter of convenience and in order to simplify the maintainence
of the desired relationship between the different carrier frequencies,

it is usual to derive a number of them from a single master oscillator
the frequency of which is very carefully controlled, for instance by
the use of a quartz crystal in a special oven maintaining the
temperature accurately constant In these circumstances it is obviously
very important that the carrier supplies should have the utmost
reliability as otherwise there is a danger that a large number of
channels might be thrown out of action simultaneously It is
accordingly usual practice to provide a stand-by master oscillator
together with automatic changeover arrangements to bring in the
stand-by supply if any trouble should develop on the normal supply The
chief object of the present invention is to provide an arrangement of
this type whereby the changeover from one supply to the other is made
so rapidly that any loss of signal is negligible.
According to the invention, in a carrier current supply arrangement
for use in a telecommunication system, two sources of supply are
provided from which currents of a plurality of different frequencies
are normally available each source being capable of supplying all the
frequencies required but being arranged lPrice 3 s 6 dl normally to
supply some only of such frequencies, the remainder being normally
supplied by the other source, the two sources for each frequency being
connected to a common output circuit by way of rectifier networks
arranged to be biassed respectively under the control of the common
output circuit so that only one source is effective but that on
failure of the output the bias is altered so as to render the other
source effective.
The invention will be better understood from the following description
of a preferred method of carrying in into effect which should be taken
in conjunction with the drawings accompanying the provisional
specification comprising Figs 1 and 2.
Fig 1 is block schematic showing the general layout of the carrier
supply arrangements, while Fig 2 shows detailed circuits of the
changeover arrangements for one particular frequency.
Referring now to Fig 1, the supplies for source A and source B are
obtained from individual oscillators OA and OB respectively, each of
which as mentioned above may be a crystal having its temperature
accurately controlled In each case the output of the oscillator is fed
to a harmonic generator HGA or HGB arranged to produce the required
harmonics and as illustrated it is assumed that five different
frequencies a?-e are required from the generator These are separated
by the use of suitable filters F Al-FA 5 and FB 1-FB 5 of which only
those for frequecies b and e are shown The outputs from the two
sources for any one frequency are then extended to linked electronic
switches E Al-EA 5 and E Bi-EB 5, details of which are shown in Fig.
2 The linkage between the corresponding members of each pair of

switches is such that at any time one of the switches will be closed
and the ohter open, so that the supply is being obtained from one
source only The output is then fed to a dual path amplifier such as DP
2 or DP 5 i e an amplifier employing two valves in parallel which, in
order to obtain 785,027 enhanced reliability, may be of the type
disclosed in Specification No 732,567.
The arrangement of the electronic switches is such that certain of the
harmonic frequencies are normally supplied from source A and the
remainder from source B and conveniently the division can be alternate
over the frequency range Thus for instance source A will normally
supply frequencies b and d, while source B will provide frequencies a,
c and e, If the supply of any one frequency should fail, changeover
will immediately take place to the other source The fault may be due
to trouble in the equipment relating to that frequency alone or may be
due to the failure of the source in which case all the frequencies
which it is supplying will fail but the changeover will be made
satisfactorily in either case.
Considering now Fig 2, it will be assumed that the normal supply
extends to input transformer TI and passes by way of the electronic
switching or gate circuit to output transformer T 2 and thence to the
carrier supply amplifier CSA The stand-by supply is fed to input
transformer T 3 and extended by way of its gate to output transformer
T 4 and thence to the amplifier The gate circuits each comprise
networks of rectifiers and resistors and transformer Ti is
centre-tapped with a connection extending to terminal A and similarly
transformer T 3 is centre-tapped with a connection extending to
terminal B Connections from these terminals extend to terminals A' and
B' in the control circuit shown in the lower portion of the figure
This comprises essentially two cold cathode gas discharge tubes which
are normally extinguished and an electromagnetic relay which is
normally released.
In the normal conditions of the circuit, terminal A has a higher
potential than terminal B and current flows from terminal A over the
two halves of the secondary of the transformer TI, rectifiers Wi and W
2, two halves of the centre-tapped primary of transformer T 2,
resistor R 2, connection from the junction point of resistors RI and R
2 to the junction point of resistors R 3 and R 4, resistor R 3
rectifiers W 5 and W 6, two halves of the secondary of transformer T 3
to terminal B This current is maintained at a suitable value, for
instance 10 ma, and as a result rectifiers W 1, W 2, W 5 and W 6 are
biassed to the low resistance condition while rectifiers W 3, W 4, W 7
and W 8 are biassed to the higl resistance condition.
Consequently rectifiers W 3 and W 4 form a high impedance shunt and
rectifiers Wi and W 2 a low series impedance so that carrier supply is

extended from transformer Ti to transformer T 2 The gate circuit for
the stand-by supply is closed however since rectifiers W 7 and W 8
form a high series impedance, while rectifiers W 5 and W 6 form a low
impedance shunt across transformer T 3.
It will be appreciated that since the circuit is symmetrical, if the
potentials of terminals A and B are reversed, the conditions of the
gate circuit will be reversed, and the control current will flow by
way of the windings of transformer T 3, rectifiers W 7 and W 8,
resistor R 4, resistor RI, rectifiers W 3 and W 4 and 70 windings of
transformer TI, accordingly there will be a low impedance path between
transformer T 3 and T 4 so that the standby supply will become
operative while the normal supply will be cut off 75 The connections
from the control circuit to terminals A and B may be traced as
follows:
From IIT+ over normal contact RA 1 and resistor RS to terminal A' and
from terminal B' over resistor R 16 and normal contacts 80 RA 3 to HT
or earth Changeover is effected by a momentary positive pulse over
lead P transmitted from the carrier supply amplifier CSA in the event
of failure of the supply This pulse is applied to the grids of the two
gas dis 85 charge tubes V 1 and V 2 by way of capacitors Cl and C 2
and rectifier W 9 included in series with capacitor C 2 The priming
voltages on the grids are normally just below those needed to produce
striking and are determined by the 90 potential dividers comprising
resistors R 6 and P.7 and resistors R 11 and R 12 respectively.
The capacitors Cl and C 2 are necessary to isolate the two different
grid priming voltages and prevent the operating pulse which may 95
have a low impedance source from influencing the priming potentials of
V 1 and V 2 The rectifier W 9 prevents the higher grid potential of V
2 from being transmitted to the grid of Vi which might occur and cause
the 100 unwanted striking of V 1 when the HT power was first switched
on.
If a failure of the supply takes place, monitoring equipment in the
amplifier CSA causes a pulse to the transmitted which effects the 105
striking of both V 1 and V 2 The current flow through V 2 raises the
potential of terminal B' and similarly current flow through V 1 lowers
the potential of terminal A' The combined effect of these two changes
is to reverse the 110 original polarity relationship of terminals A'
and B' and as a consequence current now flows through the gate
circuits in the opposite direction with the results previously
described, namely that the stand-by source is brought into 115
operation Current flow through V 1 also now operates relay RA which
will accordingly change over its contacts Contacts RAI disconnect the
anode supply to tube V 2 which is therefore extinguished but the
polarising 120 current through the gate circuits is maintained by way

of resistor Ri O Contacts RA 3 disconnect resistor R 16 and contacts
RA 2 connect resistor R 13 across tube V 1, this resistor being
sufficiently low in value to extinguish V 1 Con 125 tacts RA 2 also
supply potential by way of resistor R 17 to a cold cathode diode V 3
which acts as a local visual alarm Resistor R 9 is connected up to
provide conditions suitable for the subsequent restoration to normal
130 two sources of supply are provided from which currents of a
plurality of different frequencies 60 are normally available each
source being capable of supplying all the frequencies required but
being arranged normally to supply some only of such frequencies, the
remainder being normally supplied by the other source, 65 the two
sources for each frequency being connected to a common output circuit
by way of rectifier networks arranged to be biassed respectively under
the control of the common output circuit so that only one source is
effective 70 but that on failure of the output the bias is altered so
as to render the other source effective.
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