US2489575A

US2489575A - Production of chlorates and chlorites of different metals

Info

Publication number: US2489575A
Application number: US659043A
Authority: US
Inventors: Clifford A Hampel
Original assignee: Cardox Corp
Current assignee: Cardox Corp
Priority date: 1946-04-02
Filing date: 1946-04-02
Publication date: 1949-11-29
Anticipated expiration: 1966-11-29

Description

Nov. 29, 1949 C. A. HAMPEL PRODUCTION OF CHLORATES AND CHL ORITES OF DIFFERENT METALS Filed April 2, 1946 Cl 02. C L 02. 2 W Aesoease -H Aasoeane K6103 /(CL 0;

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"4 [VAPOR/1 role 3; l/RRY I'll use awe/whom (ll/fifd/Zflhlfi l Patented Nov. 29, 1949 PRODUCTION OF CHLORATES AND CHLO- RITES OF DIFFERENT METALS Clifford A. Hampel, Harvey, Ill., assignor to Cardox Corporation, Chicago, Ill., a corporation of Illinois Application April 2, 1946, Serial No. 659,043

13 Claims. 1

: This invention relates to a new process for the production of a chlorate and a chlorite.

It has been known heretofore that a chlorate and a chlorite of the same metal can be produced by the absorption of chlorine dioxide by an alkaline compound of that metal. For example, if potassium chlorate and potassium chlorite 'are to be produced, potassium hydroxide has been employed as the alkaline compound. The equation which illustrates this reaction is:

This prior known process has possessed several inherent disadvantages. For example, there may be numerous commercial and economic reasons why a particular manufacturer may want to produce for use or sale a chlorate and a chlorite of a different metal. To accomplish this desired result with the prior known process, it isnecessary to carry out this process twice, using one metal alkali to produce-the. desired chlorate in one process operation and usinganother metalalkali in the second process operation to produce the desired chlorite of that metal. Therefore, four products are formed, although only two really are desired. f

Another inherent disadvantage of the prior known process is that it is often extremely difilcult or even impossible to efiect by practical commercial means the separation of the chlorate and the chlorite of the same metal. fConsequently, after practising two different processes to obtain four products, only two of which'are really desired, the manufacturer has been confronted with the additional problem of separating out the two desired products.

Still another disadvantage of the prior known process is that the metal introduced appears half as the chlorate and half as the chlorite. This is objectionable .if the metal is an expensive one as potassium, because it may be desired that all of it appear as the chlorate. I

It is a primary object of this invention to provide a process for the production of a chlorate and a chlorite of a different metal in which the chlorate and the chloritecan be selected in accordance with the particular commercial needs of a given manufacturer.

It is a further important object of this invention to provide a process by means of which a desired chlorate and a desired chlorite can be produced, and in which the chlorate and the' chlorite thus produced can be obtained by the use of less expensive materials than the correspending metal base or bases.

A further primaryobject of this invention is to provide a process by means of which a chlorate and a. chlorite of a different metal are pro-.-

duced and which are readily separable by known commercial facilities. 1A specific object of this invention is to provide amethod of producing a chlorate and a chlorite of a different metaLjin which one or the other is considerably, less soluble in the same system, thus making them more readily separable. Another specific object of the invention is to provide a process for producing a chlorate and a chlorite of a different metal in which substantially all of a-particular cation introduced into the, system, and which is capable of forming the chlorate or chlorite, is utilized in the production of the chlorate or chlorite which is desired.

Another specific object of the invention is to provide aprocess for the production of a chlorate and a chlorite of adifierent metal by which cer-- tain raw materials can be employed for producing one of the desiredproducts which are different. from and less expensive than the base which is normally employed to produce that product. The use of less expensive materials is made possible by employing the salt of the metal of the desired chlorateon-chlorite, which salt is less expensive than the corresponding base, and the base of the metal of the chlorate or chlorite de-' sired, whereby the .thus combined salt and base materials will introduce only a foreign anion, which anion will form a salt with the base cation which is less soluble in the system than the chlorate and/or chlorite produced. Other objectsand. advantages of the inven tion will become'apparent during the course ofthe following-description:

' ,As has been pointed out above, and as is specifically illustrated in Equation a, it has been known that thechlorate and chlorite of a given metal can be produced by reacting chlorine di oxide with the baseof that metal. In accordance with thepres'ent invention, substantially equivalent quantities of a chlorate and a chlorite of difierent metals areproduced. For example,

potassium, sodium, lithium, barium, calcium} salt or salts to the products of the first reaction. The process may be carried out in different ways, but they have in common the fact that the salt or salts which are added, are introduced into the system after the interaction between the chlorine dioxide and the metal base is substantially completed and before any separation of the prod-- ucts of that interaction is effected. Also, although different procedures and ingredients may be employed in practicing the invention, they have the common advantage that all or substan-, tially all of one of the metals which is introduced... appears either as the chlorate or the chlorite.

That the results of the present invention. can be obtained by this subsequent addition of oer-- tain ingredients to the system, is surprising because of the large number of components which;- are in the system. It would be expected that due to the large number of components in the system, it would not be possible to obtain a defini-te setof products, but in carrying out the present invention it hasz been found that the same high percentage of products is formed which would be formed if a prior separation'hadbeen carried out with respect to. the products immediately resulting from the chlorine dioxide absorption.

One mode of carrying out the process of the present invention is to first absorb chlorinedioxide in an alkali which" has the-metal of the desired chlorite but not that of the desired chlorate, the metal of the desired chlorate beingintroduced as a salt. It may be pointed out here that an important advantage of this procedure is that an alkali may be employed which is considerably less expensive than the alkali which would have to be employed if the desired chlorate were to be produced by the process represented by equation (a). For example, if it is desired to produce potassium chlorate, instead of utilizing a relatively expensive potassium. alkaline compound, the invention comprehends the employment of a sodium alkaline compound forthe production of the chlorate ion. After thereaction has proceeded until the alkali has been neutralized and sodium chlorate and sodium chlo-- rite have been produced, a potassium salt is added to these mixed reactionproducts and this will result in the formationof" the desired potassium chlorate. by theequations:

In equation (b), sodium hydroxide is used, but? it is to be understoodthat any alkali; as an oxide,- hydroxide, or carbonate may be. employed-the hydroxide being used for illustrative purposes.

The term hydroxide as used in the claims embraces the introduction of; oxides of the named metals into the system since oxides will inherently form the hydroxides of the named metals in an aqueous medium. Also, it is to. be understood that the metal of this alkali should be that of the desired chlorite and for this reason it may be any one of the alkali metals, alkaline earth metals, or magnesium, sodium being selected merely to illustrate one exampleof the invention; Inaddition, it should be understood that the salt used to introduce the metal of the desiredchlorate need not be a chlorite as shown in equaetion 0, but may have another anion as, for: example, the sulfate, phosphate, or nitrate ion. The metal of this salt. should,.however, be that; of the desired chlorate and this may be a dif- These reactions are represented 4 ferent metal selected from the above class from which the metal of the alkali is selected.

It will be observed from Equations b and c that the salt which is added for the purpose of introducing the metal ion, whose chlorate is desired, should be added in an amount equivalent to one-half of the alkali which is reacted. By adding this relative quantity of the salt having the metal whose chlorate is desired, its cation is present in an amount equivalent to the amount 7 of chlorate ion which is formed from the chlorine dioxide. Thus, as will appear from a combination of Equations b and c, all of the potassium ion andall of the chlorate ion which is in the system will be'combinedtoform potassium chlorate.

None of this metal of the introduced salt will, therefore, appearv as the chlorite, and none of the chlorate ion which is formed will carry with it a cation other than that of the introduced salt. In obtaining certain chlorates, it is necessary to observe certain precautions in the selectionof the ingredients. For example, the potassium ion should not be introduced into the system, if the chlorate of. some other metal is desired. Also,- the salt used should not be a sulfate, for example, if. the chlorate desired is. that. of calcium or. barium.

If a chlorite is to, be utilized in carrying out the process represented by Equations b and c, this. chlorite may beobtainedi by carrying out a sepa... rate chlorine dioxide absorption reaction. After the alkali used in this separate absorption reaction isneutralized,-and before any separation of the reaction products is effected, they are combined with the reaction products resulting from the first absorption reaction. This is represented by the equations:

FromEquations d, e, and it will be observed. that. equal-amounts. on. an equivalent basis of thewtwo alkalis. are employed. This results'in the productionof. equivalent amounts of chlorate? and chlorite. ions in the separate absorption re.-- actions, so that all of the one metal will. appear: asrthe chlorate and all of the other metal will appear as. thechlorite- It is not necessary that. thealkalis. employedv in Equations (1 and. e have; the same anion, as, for example, one may be a. hydroxide and. the. other may be a carbonate; The precaution referred to in connection with: Equations. b, andc should, however, be observed: in,the. selection of the anions and cations.

If, in. carryingout the process according to Equations b and.c,.. the introduced salt is not. a chlorite,. but has another anion, it is convenient. so to select. it so thatthe foreign salt product which; is formed will be, of. a .quitedifierent solubility: from; the. chlorate. and chlorite. Thus, if the alkaliemployed is a calcium compound, it would be advisable to add potassium sulfate to intro-- duce thepotassiu-m ion. The calcium sulfate which is then formed may be easily separated from the chlorite and chlorate. It should be understood, however, that if this foreign salt product is more soluble than calcium sulfateJ-t may still be separated from the chlorate and" chlorite-by appropriateseparation means.

However, the. invention. contemplates the selection; of such ingredients that the foreign salt product whichis'formed' will be recoverable with: .25 either the chlorate ,or the chlorite. This will be advantageous in some instances as this foreign salt will serve as a diluent. For example, by employing sodium hydroxide and potassium sulfate, the sodium chlorite recovered can be left diluted with sodium sulfate, if desired.

In carrying out the process of the invention according to asecond mode, the alkali is used of the metal whose chlorate is desired, and after its absorption of chlorine dioxide until neutrality is reached, a salt of a different metal is added to the system. The cation of this salt should. be

the metal whose chlorite is desired. It is of'particular benefit in carrying out this procedure to employ a chlorate as the salt since this will result in the appearance of all, or substantially all, of the metal of the alkali as the final chlorate product. For example, if it is desired to obtain potassium chlorate :by the use of potassium hydroxide, all of the potassium introduced into the system as the hydroxide may be caused to appear as the chlorate by adding sodium chlorate in an amount equivalent to the chlorite formed. This process takes place according to the equations: I

In equation g, a hydroxide is employed as the alkali, but instead, an oxide, or carbonate may be employed. Also, in Equation 71. sodium has been introduced by the added salt, but this metal may be selected from the alkali metals, alkaline earth metals, or magnesium, it being understood that this metal should be selected so as to form the desired chlorite. The precautions discussed above in reference to Equations 12 and c as to the selection of the cations and anions in the system must, however, be observed.

It has been noted that the salt used to introduce the metal of the desired chlorite need not be a chlorate. If it is not a chlorate, the foreign salt product which is formed may be separately recovered or it may be recovered with the chlorate or chlorite.

The salt which is added should be introduced in an amount which is equivalent to half of the alkali reacted. With this relationship, an amount of metal ion is introduced which is equal to the amount of chlorite ion which is formed so that all of this introduced cation appears as the chlorite.

If a chlorate is to be utilized in carrying out the process according to the mode represented by Equations 9 and it, one possible source of the chlorate ion is the .products resulting from carrying out a separate chlorine dioxide absorption reaction. The products of this second chlorine dioxide absorption reaction, after the alkali has been neutralized, are-combined with the products resulting from the absorption by the first alkali of chlorine dioxide. This is represented :by the It will be observed from Equations z, i, and k that an equivalent amount of alkali is consumed in the two reactions represented byEquations i and 7'. It is not necessary that the alkalis employed in the reactions of Equations 2 and 7' have the same anion, as the one may be a hydroxide and the other may be a carbonate, for example.

b and. c, the process may be carried out employing any two different metals of the alkali metals, alkaline earth metals or magnesium, the stated precautions as :to the selection of the cations and the anions in the system being observed.

According to a third mode of carrying out the invention, the metal of the alkali chosen to carry out the absorption reaction is not the metal of either. the desired chlorate or the desired chlorite, but is chosen principally because of the inexpensiveness of this alkali. The metal of the desired chlorate is introduced by one salt and the metal of the desired chlorite is introduced by another salt. Both Of these salts are added to the products of the absorption reaction after the alkali is neutralized and before those products of the absorption reaction are separated.

For example, it may be desired to obtain potassium chlorate and sodium chlorite, WithOllt the use of an alkali of either of these metals. This may be accomplished by using as the alkali, an inexpensive compound as calcium hydroxide and, after the hydroxide is neutralized, adding the salts which are to introduce the metals of the desired chlorate and chlorite. This is represented by the equations:

From Equations Z and m, it will be noted that an amount of each salt is added which is equivalent to half of the alkali employed. This results in the addition of one metal in an amount equivalent to the chlorate ion formation so that all of this metal is used in the formation of the desired chlorate. Also, it results in the addition of another metal in an amount equivalent to the chlorite ion formation so that all of this other metal is used in the formation of the desired chlorite.

It is not necessary that the two added salts have the same anion, as, for example, one may be a sulfate and the other a nitrate. If it is desired that the foreign salt product be separated from the chlorate and chlorite, it is preferable that the anion or anions of the added salts be such as to form with the metal of the alkali, a salt product of quite different solubility from the chlorate and chlorite. However, this salt product may be left with either the chlorate or the chlorite and if this is to be done, it may or may not have a solubility close to the solubility of the chlorate or chlorite with which it is to appear.

The above stated precautions as to the anions and cations in the system, should be observed to assure the formation of the desired products. For example, if sodium chlorate is desired, the potassium ion should not be ntroduced into the system.

It will be appreciated that a mixture of chlorites, for example, rather than a single chlorite, could be produced .by this invention simpl by the use of two or more alkaline compounds, or .by the use ofone alkaline compound and the salts of two or more metals. In this way, the necessary metals for the formation of the mixture of chlorites are introduced.

Although the oxides, hydroxides, and carbonates of the alkali metals, the alkaline earth metals, and magnesium have been mentioned as the alkaline compounds useful for the operation of the invention, the reaction rate is much slower when carbonates are used than it is when oxides llilso, as explained in connection, with Equations g-5 or hydroxides are employed. It is for this rec-.-

assume 7 son thatthe oxides and hydroxides are therpreferred alkaline materials.

In .carring out the process of this invention in the preferred manner, chlorine dioxide as :a dilute gas in the presence of such a diluent as :air or .nitrogen, is reacted with an aqueous slurry or solution, as the case may be, of the desired al-.- kaline .material. This chlorine dioxide is .introdnced as a dilute gas to prevent the decomposition of the chlorine dioxide. .Asuitable concentration of chlorine dioxide in the gas phase is. about by volume. This concentration .depends somewhat upon the temperature employed in the reaction, the lower the temperature, the higher the safe concentration of chlorine dioxide which can be allowed. The temperature of the reaction can be varied from the freezing point to 100 C., a, suitable temperature being 50 C. The .reaction rate increases -with higher temperatures.

The quantity of water used for the reacting slurry .or solution is not vital to the operation of the invention and may be varied over a wide range. .In general, sufficient water should be present at the end of the operation, and before the products are separated, to keep the chlorate and chlorite in solution and thereby prevent their precipitation along with the precipitation of the third compound, if present, providing that it be desired to allow the third compound to be precipitated for removal from the chlorate-chlorite solution. If the invention is to be operated so that only a chlorate and a 'chlorite are produced, and no foreign salt'is to be produced, it will be evident that it is only necessary to have suflicient water present to keep these two compounds in solution. However, if potassium -chlorate be one of the compounds produced, for example, the amount of water present may be reduced so as to cause the precipitation of some of the potassium chlorate. It further will be realized that should a compound, which it is desired to keep in solution, be inadvertently precipitated, additional water may be added to redissolve it.

In general, the amount of water in the re- :action vessel, wherein chlorine dioxide is being absorbed, should be enough to make the gasiiq-uid contact efiicient. If too thick a slurry is used, difficulty may be experienced in retaining a. uniform suspension and in obtaining proper contact between the chlorine dioxide gas and the absorbing medium. Design of the appara- :tus for the absorption of chlorine dioxide-will dictate to a large degree the optimum thickness of slurry and, therefore, the quantity-of water to be used. For most purposes, a suitable concen- 'tration of reactants is about by weight in the water slurry or solution. This quantity .of water, for example, will keep all of the potassium chlorate of a solution containing equal moles of potassium chlorate and sodium chlorite solution at C.

After the reaction has been completed, the mixture of final products is removed from the reactor for further treatment to separate the desired products. Inasmuch as the reactants-and the products have been selected, as previously described, because of their mutually different solubilities in any given system, the separation of the various products will entail the use of such common chemical engineering unit operations as evaporation, crystallization, washing, and filtration.

This invention can beill-ustrated further and sorbers as a :5 by volume mixture with air.

E3 explained 'by -the following example, reference be, ing: had to: the accompanying drawing:

In an absorber l isplaced 256.1 parts of potas+ slum. hydroxide, and-in a separate absorber 2 is placed 40 parts of sodium hydroxide, sufficient water being used to bring them into, solution. Chiorine. dioxide-is introduced into both ab- The reaction :is continued in each absorber until the hydroxide is substantially neutralized.

After both absorption reactions are completed their products "are combined into the mixer .It will be appreciated that this may be a sepae rate vessel, or that the products of the oneab- .sorber may as well be delivered into the other absorber. After an intimate intermingling of these products, they :are delivered to the evaporator 4.. Evaporation is continued until the solution is saturated with respect to sodium chlorite at 125- C.

After cooling to about 25 C., the slurry from evaporator 4;is delivered to filter 5. .About oi the 122.5 parts of potassium chlorate formed is recovered in the filter cake, and the filtrate contains all of the sodium chlorite and the residual potassium chlorate. Theseseparatedproducts maybe dried.

Related subject matter is disclosed in my copending cases as follows: Ser. No. 647,403, filed February .13, 1946, directed to perchlorate production; Ser. Nos. 647,404, filed February 3, 1946', and 659,043, filed April 2, 1946, directed to the production of chlorates and chlorites; Ser'. No. 647,396, filed February 13, 1946, directed to the production of perc'hiorates and --involving the production of :chlorates; and :Ser. Nos. 736, 11'3, filed March 20, 1947;756542, 756,543, and 756,544, filed June 23, 1947, directed to the separation of salts salt systems containing a chlorate and a c'hlorite.

Having thus described the invention, I-claim:

1. The process :of iorming achlorate of a metal selected fromthe class consisting of lithium, p0- tassium, sodium, calcium, barium, strontium, and magnesium, and-for forming therewith a chlorite of a:clifh-z rentmetal selected from said class, comprising reacting chlorine dioxide and a compound selected from the group consisting of hydroxides and carbonates, and whose metal is selected from the :class consistingof lithium, potassium, sodium, calcium, barium, strontium, and magnesium, and, after the reaction is substantially completed, combining the reaction products, without separation thereof, with a salt whose metal is adiiferent one selected from said class, whereby substantially all of one of the metals introduced appears as the-chlorate while substantially-all of the'diff-eren-t metal appears as the chlorite, said salt being so selected that the anion thereof does not form an insolublecompound with the metal whose chlorate isdesired, and said compound and said salt being so selected that no potassium ion is present when a chlorate other than that of potassium is desired.

2. The process of forming a chlorate of a metal selected .from the class consisting of lithium, potassium, sodium, calcium, barium, strontium, and magnesium, and for .forming therewith a .chlorite of a diiferent metal selected from said class, com.- prising reacting chlorine dioxide and a compound selected from the group consistin of hydroxides and carbonates, and whose metal is selected from the class consisting of lithium, potassium, sodium, calcium, barium, strontium, and magnesium, and, after the reaction is substantially completed, combining the reaction products, without separation thereof, with a salt of the metal whose chlorate is desired, whereby substantially all of this latter metal appears as the chlorate, said salt being so selected that the anion thereof does not form an insoluble compound with the metal whose chlorate is desired, and said compound and said salt being so selected that no potassium ion is present when a chlorate other than that of potassium is desired. v 1

3. The process of forming a chlorate of a metal selected from the class consisting of lithium, potassium, sodium, calcium, barium, strontium, and magnesium, and for forming therewith a chlorite of a different metal selected from said class, comprising reacting chlorine dioxide and a compound selected from the group consisting of hydroxides and carbonates, and whose metal is selected from the class consisting of lithium, potassium, sodium, calcium, barium, strontium, and magnesium, and, after the reaction is substantially completed, combining the reaction products, without separation thereof, with a salt of the metal whosechlorate is desired, whereby substantially all of this metal appears as the chlorate, said salt being introduced in an amount equivalent to half the compound introduced, said salt being so selected that the anion thereof does not form an insolublecompound with the metal whose chlorate is desired, and said compound and said salt being so selected that no potassium ion is present when a chlorate other than that of potassium is desired.

4. The process of forming a chlorate of a metal selected from the class consisting of lithium, po-

tassium, sodium, calcium, barium, stronti um,'and

said chlorate being so selected that no potassium ion is present when a chlorate other than that of potassium is desired.

5. The process of forming a chlorate of a metal selected from the class consisting of lithium,v Dotassium, sodium, calcium, barium, strontium, and magnesium, and for forming therewith a childrite of a different metal selected from said class, comprising reacting chlorine dioxide and. a compound selected from the group consistingof hydroxides and carbonates, and whose metal is selected from the class consisting of lithium, potassium, sodium, calcium, barium, strontium, and magnesium, and, after the reaction is substantially completed, combining the reaction products, without separation thereof, with a chlorate whose metal is a different one selected from said class, whereby the metal of said compound appears as the metal of this introduced chlorate ion, said chlorate being added in an amount equivalent to half the introduced compound, and said compound and said chlorate being so selected that no potassium ion is present when a chlorate other than that of potassium is desired.

6. The process of forming a chlorate of a metal selected from the class consisting of lithium, potassium, sodium, calcium, barium, strontium, and

magnesium, and for forming therewith a chicrite of a different metal selected from said class, comprising reacting chlorine dioxide and a compound selected from the group consisting of hydroxides and carbonates, the metal of the selected compound being that of the desired chlorate, and, after the reaction is substantially completed, combining the reaction products, without separation thereof, with a salt Whose metal is selected from said class and whose chlorite is desired, whereby substantially all of the metal introduced as the salt appears as the chlorite, said salt being so selected that the anion thereof does not form an insoluble compound with the metal whose chlorate is desired, and said compound and said salt being so selected that no potassium ion is present when a chlorate other than that of potassium is desired.

7. The process of forming a chlorate of a metal selected from the class consisting of lithium, po-

tassium, sodium, calcium, barium, strontium, and

magnesium, and for forming therewith a chlorite of a difierent metal selected from said class, comprising reacting chlorine dioxide and a compound selected from the group consisting of hydroxides and carbonates, the metal of the selected com pound being that of the desired chlorate, and, after the reaction is substantially completed, combining the reaction products, without separation thereof, with a salt whose metal is selected from said class and whose chlorite is desired, whereby substantially all of the metal introduced asthe compound appears as the chlorate, said salt being added in an amount equivalent to half the compound introduced, said salt being so selected that the anion thereof does not form an insoluble compound with the metal whose chlorate is desired, and said compound and said salt being so selected that no potassium ion is present when a chlorate other than that of potassium is desired.

' 8. The process of forming a chlorate of a metal selected from the class consisting of lithium, potassium, sodium, calcium, barium, strontium, and magnesium, and for forming therewith a chlorite of a difierent metal selected from said class, comprising reacting chlorine dioxide and a compound selected from the group consisting of hydroxides and carbonates, and whose metal is selected from the class consisting of lithium, po-- tassium, sodium, calcium, barium, strontium, and magnesium, and, after the reaction is substantially completed, combining the chlorate and chlorite, without separation thereof, with the unseparated chlorate and-chlorite resulting from the reaction of chlorine dioxide with a compound whose metal is a different one selected from said class, whereby the major portion of the metal of the one compound appears as a chlorate and the major portion of the metal Of the other compound appears as a chlorite, and said compounds being so selected that no potassium ion is present when a chlorate other than that of potassium is desired.

9. The process of forming a chlorate of a metal selected from the class consisting of litmium, potassium, sodium, calcium, barium, strontium, and magnesium, and for forming therewith a chlorite of a different metal selected from said class, comprising reacting chlorine dioxide and a compound selected from the group consisting of hydroxides and carbonates, and whose metal is selected from the class consisting of lithium, potassium, sodium, calcium, barium, strontium, and magnesium, and, after the reaction is substanaccepts :12 .ot. acdiflerent metal selected from saidclass, com- .ipfis'ingreadtingchlorine dioxide. and a compound selected from the 'groupconsisting of hydroxides and carbonates,- and whose metal is selected from ".the class. consisting oflithium, potassium, sodium, calium, barium, strontium, and magnesium, and, after the reaction is substantially completed, combining .the reaction products, without separation'thereoiwith two salts, the metal of onasalt i q amounts on an equivalent s, a 4 being that, or .the desired chlorate and the metal "said compounds being so selected that no potassiumion is present-when a chlorate other than that of potassium is desired.

10.'The process ofjforming a chlorate of a. metal selected from the class consisting of lithium,

potassium, sodium, calcium, barium, strontium,

and magnesium, and for forming therewith a chlorite of a difierent metal selectedfrom said class, comprising-reacting chlorine dioxide and a compound selected. from the-group consisting-of hydroxides and carbonates, and whose metal, is selected from the class consisting of lithium,-potassium, sodium, calcium, barium, strontium, and magnesium, and,. after the reaction issubstantially completed, combining the reaction products, without separation thereof, with .a chlorite .of a metal whose chlorate is desired, whereby .sub- 'stantially all of this .latter .metal appears-as .the chlorate and all of the metal of the compound appearsas achlorite, and said compoundand said chlorite being so selected that nopotassiumionis present when a. chlorate other thanpotassiumis desired.

'11. Theprocess of forminga chlorate ofaimetal selected from the class-consisting oilithium, .po-

tassium, sodium, calcium, barium, strontium, and magnesium, and for forming therewitha chlorite of a differentmetal selected from said class, comprising reacting chlorine dioxide .an'da compound selected from the group consisting of hydroxides and carbonates, and whosemetal is selected from the class consistingofflithium,.potassium, sodium, calcium, barium, strontium and magnesium, and, afterthe reaction is substantially completed combihing the reaction .products, without separation thereof, with achlorite ofvametal whose chlorate is desired, whereby substantially all of this :latter metal appears asthe chlorate anddall-of .the metal of the compound appears asa chlorite,.saidch1orite being introducedv in an amount equivalent to half the compound 'introduced,.and-said compound and said chlorite being so selected that nopotassium'ion ispresentwhen a chlorate-other than potassium is desired.

'12. The process of 'forminga chlorateofiametal 'selectedffrom the. class consisting of lithium,.-potassium, sodium, calcium, barium, strontium and magnesium, and for forming .therewitha chlorite of the other salt'being that of thedesired chlorite, .th'e metalls of-theseisalts'being different from eticlii dthenand from the metal ofv said compound. but beingselec'ted from said class, said salts being-so :selectedthatthe anions thereof do not form insol- "uble compounds with the metal whose chlorate is"desired,,and'said compound and said saltsbeing 'so'selected that Sno potassium ion is present when a -chlorate other thanthatofpotassiumiis desired.

"1'3.".'1he;process of forming a chlorate of a metal selectedfrom the class consisting. of lithium,.potassium, sodium, calciumjbarium, strontium, and

magnesium, and'foriorming therewith a chlorite of a different metal selectedfrom said class, comprising-reacting chlorine dioxide and a compound selected "from theg'roup consisting ofv hydroxides and carbonates, "and whose metal is selected. from the class consisting of lithium, potassium, sodium, calciumjbarium, strontium, andmagnesium, and, after the reaction is substantially completed, combining the reaction products, without separation thereof,'with'two salts, the metal. of one salt being thatof the desired chlorate. andthemetal ofthedther saltbeing that of .the desired chlorite, the metals ofthesesalts being different fromeach "other and "from the .meta1 of said, compound'but being selected fromsa'id class, each of said salts beingdn'troduce'diin an. amount equivalent to half the comp'ound'reacted, said salts being soselected :that 'th'e'ariions thereof. :do not form insoluble compounds with the metal whose chlorate is desired-and said compound and said salts being so selectedth'a't nospo'ta'ssium ion is "present when a chlorate other-"than that'ofpo'tassium. is desired.

CLIFFORD A. HAMPEL.

REFERENCES 'Iheiollowlng references (are .of record in the file of this patent:

UNI I ED STATESPKI'EN I S Number Name Date {2,046,830 .Logan -July 7, .1936 "21.691166 Cunningham and Aug. 8, 1939 :O'ITI-IEIR' REFERENCES "Mllbr, Comprehensive .Treatise 'on Inorganic and Theoretical'Chemistry,vol."2, p. 282 (1922).