DE1036231B - Process for the preparation of salts of anhydrous linear phosphoric acids - Google Patents
Process for the preparation of salts of anhydrous linear phosphoric acidsInfo
- Publication number
- DE1036231B DE1036231B DEH25645A DEH0025645A DE1036231B DE 1036231 B DE1036231 B DE 1036231B DE H25645 A DEH25645 A DE H25645A DE H0025645 A DEH0025645 A DE H0025645A DE 1036231 B DE1036231 B DE 1036231B
- Authority
- DE
- Germany
- Prior art keywords
- salts
- phosphorus
- acids
- anhydrous
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 150000003839 salts Chemical class 0.000 title claims description 13
- 238000000034 method Methods 0.000 title claims description 6
- 235000011007 phosphoric acid Nutrition 0.000 title claims description 6
- 150000003016 phosphoric acids Chemical class 0.000 title claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 14
- 239000011574 phosphorus Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 4
- 125000004122 cyclic group Chemical class 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000007900 aqueous suspension Substances 0.000 claims description 2
- AZSFNUJOCKMOGB-UHFFFAOYSA-K cyclotriphosphate(3-) Chemical compound [O-]P1(=O)OP([O-])(=O)OP([O-])(=O)O1 AZSFNUJOCKMOGB-UHFFFAOYSA-K 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 4
- 230000003301 hydrolyzing effect Effects 0.000 description 4
- 235000019832 sodium triphosphate Nutrition 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 description 3
- 239000011736 potassium bicarbonate Substances 0.000 description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- UGTZMIPZNRIWHX-UHFFFAOYSA-K sodium trimetaphosphate Chemical compound [Na+].[Na+].[Na+].[O-]P1(=O)OP([O-])(=O)OP([O-])(=O)O1 UGTZMIPZNRIWHX-UHFFFAOYSA-K 0.000 description 2
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- GXWZIFBGFYTFQK-UHFFFAOYSA-K [K+].[K+].[K+].[K+].[O-]P([O-])([O-])=O Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])([O-])=O GXWZIFBGFYTFQK-UHFFFAOYSA-K 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- -1 cyclic phosphoric acids Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- TVZISJTYELEYPI-UHFFFAOYSA-N hypodiphosphoric acid Chemical compound OP(O)(=O)P(O)(O)=O TVZISJTYELEYPI-UHFFFAOYSA-N 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011158 quantitative evaluation Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 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
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/38—Condensed phosphates
- C01B25/40—Polyphosphates
- C01B25/41—Polyphosphates of alkali metals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
Description
Verfahren zur Herstellung von Salzen anhydrischer linearer Phosphorsäuren Es ist bekannt, daß Salze anhydrischer ringförmiger Säuren des Phosphors durch alkalische wäßrige Lösungen in Salze anhydrischer Phosphorsäuren aufgespalten werden, die linear gebaut sind. So ergibt z. B. die Einwirkung von Natronlauge auf Natriumtrimetaphosphat Natriumtripolyphosphat.Process for the preparation of salts of anhydrous linear phosphoric acids It is known that salts of anhydrous cyclic acids of phosphorus by alkaline Aqueous solutions are split into salts of anhydrous phosphoric acids, which are linear are built. So z. B. the action of sodium hydroxide on sodium trimetaphosphate Sodium tripolyphosphate.
Gleichung: Na, P309 + 2NaOH = Na, P,Olo + H20. Es wurde gefunden, daß Salze anhydrischer ringförmiger Säuren des Phosphors auch mit Salzen anderer nicht ringförmig aufgebauter Säuren des Phosphors in Reaktion treten können, wenn man wäBrige Lösungen bzw. wäßrige Suspensionen beider Verbindungsklassen zur Reaktion bringt. Reaktionsgeschwindigkeit und Ausbeute werden durch das Arbeiten in möglichst hoher Konzentration begünstigt.Equation: Na, P309 + 2NaOH = Na, P, Olo + H20. It was found, that salts of anhydrous cyclic acids of phosphorus also with salts of others Non-cyclic acids of phosphorus can react if one aqueous solutions or aqueous suspensions of both classes of compounds for the reaction brings. The reaction rate and yield are reduced by working in the best possible way high concentration favors.
Löst man z. B. Trikaliumtrimetaphosphat gemeinsam mit Tetrakaliumsubphosphat in wenig 60°C warmem Wasser und läßt die Lösung bei gleicher Temperatur einige Tage stehen, so ist nur noch ein Teil des eingesetzten Subphosphates nachweisbar.If you solve z. B. tripotassium trimetaphosphate together with tetrapotassium subphosphate in a little 60 ° C warm water and leaves the solution at the same temperature for a few days only a part of the subphosphate used can be detected.
Das Verfahren beruht auf einer Aufspaltung des Trimetaphosphatringes unter gleichzeitiger Bildung anhydrischer linearer Verbindungen mit den zugesetzten Salzen anderer nicht ringförmiger Phosphorsäuren.The process is based on splitting the trimetaphosphate ring with simultaneous formation of anhydrous linear compounds with the added ones Salts of other non-cyclic phosphoric acids.
Gleichung: K,P308 -i- K,P208 = K7P6015.Equation: K, P308 -i- K, P208 = K7P6015.
Während der Reaktion können hydrolytische Spaltungen eintreten, so daß im Reaktionsgemisch auch Sauerstoffsäuren vorliegen können, die durch Abspaltung von einem oder mehreren Molen Orthophosphorsäure entstehen. Nicht nur mit Unterphosphorsäure, sondern auch mit anderen nicht ringförmig aufgebauten Säuren des Phosphors tritt die gleiche Reaktion ein, deren Ergebnis durch Chromatographie festgestellt werden kann.Hydrolytic cleavage can occur during the reaction, see above that oxygen acids can also be present in the reaction mixture, which by splitting off from one or more moles of orthophosphoric acid. Not only with hypophosphoric acid, but also occurs with other non-ring-shaped acids of phosphorus enter the same reaction, the result of which will be determined by chromatography can.
Es ist ein Verfahren bekannt, Natriurntrimetaphosphat in Gegenwart von Wasser mit Natriumhydroxyd durch hydrolytische Aufspaltung des Ringes in Natriumtripolyphosphat zu verwandeln. Zu diesem Zweck sollen auch Natriumsalze aus schwachen Säuren brauchbar sein. Das einzige zu diesem Zweck verwandte Salz ist das sehr stark alkalische Natriumsulfid. Hieraus mußte der Fachmann den Schluß ziehen, daß die Aufspaltung des Trimetaphosphatringes eine rein hydrolytische Reaktion ist, an der sich das Anion des gegebenenfalls verwandten Natriumsalzes nicht beteiligt. Beim erfindungsgemäßen Verfahren können aber auch sehr viel weniger stark alkalisch reagierende Salze linearer Säuren des Phosphors verwandt werden, und dasAnion des verwandten linearen Salzes des Phosphors beteiligt sich an der Reaktion, indem es sich an den aufgespaltenen Metaphosphatring anlagert. Es handelt sich demnach um eine ganz spezielle Reaktionsweise, die auf Grund des Bekannten nicht vorherzusehen war.There is a known method of using sodium trimetaphosphate in the presence of water with sodium hydroxide by hydrolytic splitting of the ring into sodium tripolyphosphate to transform. Sodium salts from weak acids should also be useful for this purpose be. The only salt used for this purpose is the very strongly alkaline sodium sulfide. From this the expert had to draw the conclusion that the splitting of the trimetaphosphate ring is a purely hydrolytic reaction in which the anion of the possibly related Sodium salt not involved. In the method according to the invention, however, can also Much less strongly alkaline reacting salts of linear acids of phosphorus and the anion of the related linear salt of phosphorus involved participates in the reaction by attaching itself to the split metaphosphate ring. It is therefore a very special way of reacting due to the Acquaintances could not have been foreseen.
Beispiele: 1. 1 Mol Tetrakaliumsubphosphat, 1 Mol Trikaliumtrimetaphosphat und 100 g Kaliumbicarbonat wurden in 31 60°C warmem Wasser gelöst und 4 Tage bei dieser Temperatur belassen. Das p$ der Lösung betrug nach dieser Zeit 8,2. Durch bromometrische Titration in bicarbonatalkalischer Lösung (Z. anorg. Chem., 215 [1933], S. 33 bis 43: Bruno Blaser und Paul Halpern) waren nur noch 0,78 Mol Subphosphat nachzuweisen. 0,22 Mol des Subphosphats waren in eine Verbindung übergegangen, die unter den Bedingungen der bromometrischen Titration resistent gegen Brom ist.Examples: 1. 1 mole of tetrapotassium phosphate, 1 mole of tripotassium trimetaphosphate and 100 g of potassium bicarbonate were dissolved in 31 60 ° C warm water and 4 days at leave this temperature. The p $ of the solution after this time was 8.2. By bromometric titration in bicarbonate-alkaline solution (Z. anorg. Chem., 215 [1933], P. 33 to 43: Bruno Blaser and Paul Halpern) were only 0.78 mol of subphosphate to prove. 0.22 mol of the subphosphate had gone into a compound that is resistant to bromine under the conditions of bromometric titration.
Führte man den Versuch unter den gleichen Bedingungen durch, jedoch mit dem Einsatz von 2 Mol Trikaliumtrimetaphosphat und 200 g Kaliumbicarbonat, so hatte die Reaktionslösung ein p$ von 7,8. Es waren 0,33 Mal Subphosphat bromometrisch nicht mehr nachweisbar. Bei der Wiederholung des Versuchs mit einem Einsatz von 5 Mol Trikaliumtrimetaphosphat und 500 g Kaliumbicarbonat waren 0,56 Mol Subphosphat bromometrisch nicht mehr nachzuweisen.The experiment was carried out under the same conditions, however with the use of 2 moles of tripotassium trimetaphosphate and 200 g of potassium bicarbonate, so the reaction solution had a p $ 7.8. It was 0.33 times subphosphate bromometric no longer detectable. When repeating the attempt with a bet of 5 moles of tripotassium trimetaphosphate and 500 g of potassium bicarbonate were 0.56 moles of subphosphate bromometrically no longer detectable.
In allen drei Versuchen wurde durch Kochen von Proben der Reaktionslösung mit 4n-Salzsäure durch hydrolytische Spaltung 1,0 Mol phosphorige Säure gebildet, die durch jodometrische Titration bestimmt wurde.In all three experiments, samples of the reaction solution were boiled with 4N hydrochloric acid formed by hydrolytic cleavage 1.0 mol of phosphorous acid, determined by iodometric titration.
2. 1 Mol eines wasserhaltigen K,P30io (P206 Gehalt = 40,17 Gewichtsprozent) und 1 Mol K3 P309 wurden 4 Tage lang in 1 1 Wasser auf 60°C erhitzt. Das Reaktionsprodukt wurde durch alkalische und saure Chromatographie untersucht. Im alkalischen Chromatogramm war Trimetaphosphat nicht mehr mit Sicherheit nachzuweisen. Durch quantitative Auswertung des sauren Chromatogrammes wurde festgestellt, daß sich der angewandte Phosphor in folgender Weise auf die genannten Verbindungen verteilte 5,3 Gewichtsprozent des Phosphors lagen als Pentapolyphosphat vor, 11,9 Gewichtsprozent des Phosphors lagen als Tetrapolyphosphat vor, 13,9 Gewichtsprozent des Phosphors lagen als Tripolyphosphat vor, 33,1 Gewichtsprozent des Phosphors lagen als Pyrophosphat vor, 35,7 Gewichtsprozent des Phosphors lagen als Orthophosphat vor.2. 1 mol of a water-containing K, P30io (P206 content = 40.17 percent by weight) and 1 mole of K3 P309 were heated to 60 ° C. in 1 1 of water for 4 days. The reaction product was examined by alkaline and acidic chromatography. In the alkaline chromatogram was trimetaphosphate can no longer be proven with certainty. By quantitative evaluation of the acidic chromatogram was found to be the phosphorus used was distributed among the compounds mentioned in the following way 5.3 percent by weight of the phosphorus was present as pentapolyphosphate, 11.9 percent by weight of the phosphorus was in the form of tetrapolyphosphate, 13.9 percent by weight of the phosphorus were in the form of tripolyphosphate, 33.1 percent by weight of the phosphorus was in the form of pyrophosphate before, 35.7 percent by weight of the phosphorus was in the form of orthophosphate.
3. 223 g Na4P30, - 1011$O und 207 g Na$P309 - 6H20 wurden 2 Stunden lang in 750 ccm Wasser auf 98°C erhitzt. Im Chromatogramm war außer kleinen Mengen an Trimetaphosphat und den Hydrolyseprodukten des Trimetaphosphates (Tripolyphosphat, Pyrophosphat, Orthophosphat) auch Tetrapolyphosphat und Pentapolyphosphat gut nachzuweisen.3. 223 g Na4P30, - 1011 $ O and 207 g Na $ P309 - 6H20 were 2 hours heated in 750 ccm of water to 98 ° C for a long time. Except for small amounts in the chromatogram of trimetaphosphate and the hydrolysis products of trimetaphosphate (tripolyphosphate, Pyrophosphate, orthophosphate) also tetrapolyphosphate and pentapolyphosphate can be clearly detected.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEH25645A DE1036231B (en) | 1955-12-01 | 1955-12-01 | Process for the preparation of salts of anhydrous linear phosphoric acids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEH25645A DE1036231B (en) | 1955-12-01 | 1955-12-01 | Process for the preparation of salts of anhydrous linear phosphoric acids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1036231B true DE1036231B (en) | 1958-08-14 |
Family
ID=7150072
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEH25645A Pending DE1036231B (en) | 1955-12-01 | 1955-12-01 | Process for the preparation of salts of anhydrous linear phosphoric acids |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1036231B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE734511C (en) * | 1940-07-12 | 1943-04-17 | Ig Farbenindustrie Ag | Production of crystallized sodium tripolyphosphate (Na P O aq) |
-
1955
- 1955-12-01 DE DEH25645A patent/DE1036231B/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE734511C (en) * | 1940-07-12 | 1943-04-17 | Ig Farbenindustrie Ag | Production of crystallized sodium tripolyphosphate (Na P O aq) |
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