US3363985A - Preparation of chlorine pentafluoride - Google Patents
Preparation of chlorine pentafluoride Download PDFInfo
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- US3363985A US3363985A US310970A US31097063A US3363985A US 3363985 A US3363985 A US 3363985A US 310970 A US310970 A US 310970A US 31097063 A US31097063 A US 31097063A US 3363985 A US3363985 A US 3363985A
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- US
- United States
- Prior art keywords
- bomb
- fluorine
- chlorine
- clf
- preparation
- Prior art date
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- KNSWNNXPAWSACI-UHFFFAOYSA-N chlorine pentafluoride Chemical compound FCl(F)(F)(F)F KNSWNNXPAWSACI-UHFFFAOYSA-N 0.000 title claims description 7
- 238000002360 preparation method Methods 0.000 title description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 4
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 16
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 12
- 239000011737 fluorine Substances 0.000 description 12
- 229910052731 fluorine Inorganic materials 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000376 reactant Substances 0.000 description 6
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 4
- 239000011698 potassium fluoride Substances 0.000 description 4
- AHLATJUETSFVIM-UHFFFAOYSA-M rubidium fluoride Chemical compound [F-].[Rb+] AHLATJUETSFVIM-UHFFFAOYSA-M 0.000 description 4
- JOHWNGGYGAVMGU-UHFFFAOYSA-N trifluorochlorine Chemical compound FCl(F)F JOHWNGGYGAVMGU-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 235000003270 potassium fluoride Nutrition 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WZSIPZWRVNMBAO-UHFFFAOYSA-N Cl(=O)(=O)F.Cl(=O)(=O)F.Cl(=O)(=O)F.Cl(=O)(=O)F.[Cs] Chemical compound Cl(=O)(=O)F.Cl(=O)(=O)F.Cl(=O)(=O)F.Cl(=O)(=O)F.[Cs] WZSIPZWRVNMBAO-UHFFFAOYSA-N 0.000 description 1
- YQKNEFQFLCGVIH-UHFFFAOYSA-N Cl(=O)(=O)F.Cl(=O)(=O)F.Cl(=O)(=O)F.Cl(=O)(=O)F.[K] Chemical compound Cl(=O)(=O)F.Cl(=O)(=O)F.Cl(=O)(=O)F.Cl(=O)(=O)F.[K] YQKNEFQFLCGVIH-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- AXCBHWGTRNNXKG-UHFFFAOYSA-N fluorochlorane oxide Chemical compound FCl=O AXCBHWGTRNNXKG-UHFFFAOYSA-N 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/24—Inter-halogen compounds
Definitions
- ClF is an extremely highenergy oxidizer of greater oxidizing potential than chlorine trifluoride which finds utility as an oxidizer for rocket propellant fuels.
- the boiling point of ClF is about -14 C.
- the bomb was then immersed in a bath of liquid nitrogen and the excess fluorine was pumped off.
- the bomb was connected to a train of traps at temperatures not above -112 C., and the liquid nitrogen bath was removed from the bomb.
- a total of 0.04 gram (.003 mole) of ClF was found in the traps along with traces only of impurities, e.g., FClO and C10
- the yield of CIF was calculated to be 0.33 percent on the basis of the amount (0.09 mole) of ClF which reacted with the cesium fluoride, which basis has its equivalent in terms of cesium tetrafluorochlorate initially formed and thereafter fluorinated.
- EXAMPLE 2 0.1 mole (5.8 g.) of potassium fluoride was placed in a 150 ml. stainless steel bomb containing small nickel rods and 0.13 mole (3,000 cc.) chlorine trifluoride was condensed into the bomb. The bomb was rotated overnight at room temperature. Thereafter the excess (about 0.08 mole) ClF was removed, showing the KF reacted with the ClFg in a ratio of 1 to .5, thus indicating that the tetrafiuorochlorate was a double salt, represented as 4,000 cc. of fluorine were then condensed into the bomb. The bomb was maintained at about 200 C. for about 27 hours, the initial pressure in the bomb at 200 C. being about 800 p.s.i. A total of 0.39 gram of ClF was recovered and the yield was calculated to be 6 percent.
- Example 23 was periorme completion of Example 22 without regeneration with CiFg.
- the chemical action or speed of chemical change involved in the reactions of the process of this invention is affected, as is usual for chemical reactions, by the factor of temperature at which the reactions are run.
- the above examples show generally that an increase in temperature of the reactants results in an increase in the yield of ClF Performing the reactions of this invention at a temperature or at temperatures in the range of from room temperature to about 80 C. is impractical from a commercial standpoint because the yields are low.
- the temperature of about 300 C. is selected because above that temperature severe corrosion of the containers results.
- inert gasses e.g., nitrogen and helium
- inert gasses e.g., nitrogen and helium
- the tetrafiuorochlorates are solids while the other reactant, fluorine, is a gas, and through the reaction between them resulting in the formation of C11 occurs immediately upon bringing the reactants together, the fact that one of the reactants is in the solid phase makes it desirable from a practical standpoint that the tetrafluorochlorates be agitated throughout the time allowed for the reaction to run.
- a process for preparing chlorine pentafluoride comprising the steps of reacting fluorine with at least one tetrafluorochlorate of an alkali metal of the group consisting of potassium, cesium and rubidium, and collecting chlorine pentafluoride.
- a proces for preparing chlorine pentafluoride comprising the steps of reacting at least one fluoride of the group consisting of potassium, cesium and rubidium fluoride with chlorine trifluoride, and thereafter subjecting the products of said reaction to reaction with gaseous fluorine, and collecting the chlorine pentafiuoride evolved.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
' Frank C. Gunderloy,
United States Patent 3,363,985 PREPARATION 0F CHLORINE PENTAFLUORIDE Jr., Woodland Hills, Walter Maya, Los Angeles, and Richard D. Wilson, Canoga Park, Califi, assignors to North American Aviation, Inc. No Drawing. Filed Sept. 17, 1963, Ser. No. 310,970 4 Claims. (Cl. 23--205) This invention relates to a process for preparation of chlorine pentafluoride (Cl-F by reaction of fluorine with tetrafluorochlorates of certain alkali metals.
A method for the preparation of ClF by subjecting a mixture of fluorine and chlorine, for example, to a glow discharge is described in patent application, Ser. No. 253,521, filed Jan. 21, 1963, by Walter Maya and Hans P. Bauer. As therein mentioned, ClF is an extremely highenergy oxidizer of greater oxidizing potential than chlorine trifluoride which finds utility as an oxidizer for rocket propellant fuels. The boiling point of ClF is about -14 C.
By the above-mentioned glow discharge process, the yields of ClF are relatively low and various resultants are produced requiring cryogenic fractionation for separation, whereas according to the process of the instant invention only one coudensable gaseous resultant (GR) is produced.
There are three known alkali metal tetrafluorochlorates, they being the potassium, cesium and rubidium species. Lithium and sodium tetroiiuorochlorates are not known to have been produced. The reactions of the process of this invention may be represented by the equation:
EXAMPLE 1 0.1 mole (15.2 g.) of cesium fluoride was placed in a 150 ml. stainless steel bomb and 0.13 mole (3,000 cc.) of
group consisting of chlorine trifluoride was condensed into the bomb with cooling of the bomb in a bath of liquid nitrogen. The bomb was then heated to C. for 4 hours and was then evacuated through a l96 C. trap for collecting the unreacted CIF which was measured and found to be about 0.04 mole. 4,000 cc. of fluorine were then condensed into the bomb and the contents of the bomb was maintained at about 80 C. for six hours, the initial pressure in the bomb being about 520 p.s.i.
The bomb was then immersed in a bath of liquid nitrogen and the excess fluorine was pumped off. The bomb was connected to a train of traps at temperatures not above -112 C., and the liquid nitrogen bath was removed from the bomb. A total of 0.04 gram (.003 mole) of ClF was found in the traps along with traces only of impurities, e.g., FClO and C10 The yield of CIF was calculated to be 0.33 percent on the basis of the amount (0.09 mole) of ClF which reacted with the cesium fluoride, which basis has its equivalent in terms of cesium tetrafluorochlorate initially formed and thereafter fluorinated.
EXAMPLE 2 0.1 mole (5.8 g.) of potassium fluoride was placed in a 150 ml. stainless steel bomb containing small nickel rods and 0.13 mole (3,000 cc.) chlorine trifluoride was condensed into the bomb. The bomb was rotated overnight at room temperature. Thereafter the excess (about 0.08 mole) ClF was removed, showing the KF reacted with the ClFg in a ratio of 1 to .5, thus indicating that the tetrafiuorochlorate was a double salt, represented as 4,000 cc. of fluorine were then condensed into the bomb. The bomb was maintained at about 200 C. for about 27 hours, the initial pressure in the bomb at 200 C. being about 800 p.s.i. A total of 0.39 gram of ClF was recovered and the yield was calculated to be 6 percent.
EXAMPLE 3 The same technique as that described in Example 2 was followed, using rubidium fluoride in the place of potassium fluoride and 5.3 percent yield of ClF was recovered.
EXAMPLES 4-26 The same technique as that described in Example 2 was followed for the examples contained in Tables I and II.
TABLE I.-FLUORINATION OF POTASSIUM TETRAFLUOROCHLORATE Example KClFyKF Fluorine Initial Temp, Time, 011%,
No. in moles in liters Pressure 0. Hours percent in p.s.i. yie
See Notes at end of Table II.
TABLE II.FLUO RINATION OF GESIUM TET RAFLUO R CHLO RATE Example CsGlF Fluorine Initial Temp, Time, ClFs,
No. in moles in liters Pressure 0. Hours percent in p.s.i. yield contents of the bomb following mole Na]? mixed with the KF. the contents of the bomb used in its Note d-Example 13 was performed using the contents of the bomb following Example 1 and regenerating with GlFg.
Note eExample 23 was periorme completion of Example 22 without regeneration with CiFg.
The chemical action or speed of chemical change involved in the reactions of the process of this invention is affected, as is usual for chemical reactions, by the factor of temperature at which the reactions are run. The above examples show generally that an increase in temperature of the reactants results in an increase in the yield of ClF Performing the reactions of this invention at a temperature or at temperatures in the range of from room temperature to about 80 C. is impractical from a commercial standpoint because the yields are low. For an upper limit of temperature as a factor affecting the process of this invention, the temperature of about 300 C. is selected because above that temperature severe corrosion of the containers results.
With respect to the matter of concentrations of the reactants, inert gasses, e.g., nitrogen and helium, may be present in the reaction zone without affecting the qualitative aspects of the reactions of this invention. Obviously such contaminants Which through combination with fluorine form corrosive products should be avoided. When it is desired to obtain the pure ClF purity of the two reactants avoids the need for separating the desired product from contaminants.
The tetrafiuorochlorates are solids while the other reactant, fluorine, is a gas, and through the reaction between them resulting in the formation of C11 occurs immediately upon bringing the reactants together, the fact that one of the reactants is in the solid phase makes it desirable from a practical standpoint that the tetrafluorochlorates be agitated throughout the time allowed for the reaction to run.
It is apparent from the above examples that changes in pressure are without eifect on the reactions of this invention except insofar as pressure determines eifective concentration of the fluorine gas. In the above examples 150 p.s.i. was the minimum pressure utilized, but such mini d by fiuorinating the contents of the bomb following mum pressure was prescribed only because of the size of the apparatus employed, making it necessary that the fluorine be under pressure in order to provide a sufficient number of fluorine atoms for measurable reactions to occur.
It will be understood that it is intended to cover all changes and modifications of the examples of the invention herein chosen for the purposes of this disclosure, which do not constitute departures from the spirit and scope of the invention.
Having described the invention, what is claimed is:
1. A process for preparing chlorine pentafluoride comprising the steps of reacting fluorine with at least one tetrafluorochlorate of an alkali metal of the group consisting of potassium, cesium and rubidium, and collecting chlorine pentafluoride.
2. The process of claim 1 in which the reaction is run at a temperature in the range of from to 300 C.
3. The process of claim 2 in which the reaction is run at a pressure of at least p.s.i.
4. A proces for preparing chlorine pentafluoride comprising the steps of reacting at least one fluoride of the group consisting of potassium, cesium and rubidium fluoride with chlorine trifluoride, and thereafter subjecting the products of said reaction to reaction with gaseous fluorine, and collecting the chlorine pentafiuoride evolved.
References Cited Science, vol. 141, No. 3585 (Sept. 13, 1963), pp. 1039 and 1040.
MILTON WEISSMAN, Primary Examiner.
OSCAR R. VERTIZ, L. DEWAYNE RUTLEDGE,
Examiners.
G. T. OZAKI, S. TRAUB, Assistant Examiners.
Claims (1)
1. A PROCESS FOR PREPARING CHLORINE PENETAFLUORIDE COMPRISING THE STEPS OF REACTING FLUORIDE WITH AT LEAST ONE ETRAFLUORCHLORATE OF AN ALKLAI METAL OF THE GROUP CONSISTING OF POTASSIUM, CESIUM AND RUBIDUM, AND COLLECTING CHLORINE PENTAFLUORIDE.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US310970A US3363985A (en) | 1963-09-17 | 1963-09-17 | Preparation of chlorine pentafluoride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US310970A US3363985A (en) | 1963-09-17 | 1963-09-17 | Preparation of chlorine pentafluoride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3363985A true US3363985A (en) | 1968-01-16 |
Family
ID=23204826
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US310970A Expired - Lifetime US3363985A (en) | 1963-09-17 | 1963-09-17 | Preparation of chlorine pentafluoride |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3363985A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3441362A4 (en) * | 2016-04-05 | 2020-02-26 | Kanto Denka Kogyo Co., Ltd. | PROCESS FOR SUPPLYING CHLORINE FLUORIDE |
-
1963
- 1963-09-17 US US310970A patent/US3363985A/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| None * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3441362A4 (en) * | 2016-04-05 | 2020-02-26 | Kanto Denka Kogyo Co., Ltd. | PROCESS FOR SUPPLYING CHLORINE FLUORIDE |
| US10899615B2 (en) | 2016-04-05 | 2021-01-26 | Kanto Denka Kogyo Co., Ltd. | Feeding process of chlorine fluoride |
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