X-Ray Powder Diffraction Patterns of Phosphorus Compounds with Nitrogen ARNO H. HERZOG and MORRIS
L.
NIELSEN
Research and Engineering Division, Monsanto Chemical Co., Dayton, Ohio
b X-ray powder diffraction data are given for the identification of 41 phosphorus-nitrogen compounds including phosphoramidates, phosphorodiamidates, trimetaphosphimates, and tetrametaphosphimates. Eleven new compounds are reported.
X
powder diffraction patterns have been made for the identification of 41 phosphorus-nitrogen compounds. They are particularly useful for differentiating betn-een compounds having the same empirical formulafor example, magnesium ammonium orthophosphate hexahydrate, RIgSH,POa 6H20, and magnesium phosphoramidate heptahydrate, M g P 0 3 S H 2 . -RAY
iH20. PROCEDURE
The compounds were made by procedures described in the literature or by general reactions ryhich were modified as necessary t o give satisfactorily pure products. The methods are sum-
Pattern No.
1 2
3 4
5 6 7 8 9 10
marized in Table I, where 11 nevi compounds are identified. Where compounds differ in their degree of hydration, the conditions for preparing them are given. As a routine procedure, the crystals were filtered from their mother liquor, rinsed with ethyl alcohol and again with ether, and dried quickly in air t o constant weight. The o-tolidine salts were prepared by modification of the method of abel, Eolas, and Busch for precipitating poly- and metaphosphates ( 3 ) . These salts, which are rather insoluble in water, crystallized in distinctiye crystalline forms which proved useful for rapid qualitative identification ( I S ) . Phosphorodiamidic acid did not yield a crystallizable salt with o-tolidine. For comparison, o-tolidine orthophosphate is included in this series. Samples were prepared by grinding in a n agate mortar and screening through a 325-mesh sieve. Preferred orientation of crystallites was minimized by loading a bottomless sample holder against a ground glass plate.
The x-ray equipment consisted of t h e General Electric XRD-3 x-ray diffraction unit, with CuK. radiation filtered through nickel foil (A = 1.5418 A). Intensities measured with a Geiger tube are reported on a basis of 100 t o 1, where 100 represents the most intense line. DISCUSSION
The compounds, with their eleniental analyscs, are listed in Table I. Each is assigned a code number, t o assist the reader in relating the data of Tables I and 11. The three most intense diffraction lines are given in Table I, with complete data for interplanar spacings and intensities giren in Table 11. For the more stable phosphorus-nitrogen compounds, such as the cyclic metaphosphiniates derived from the phosphonitrilic chlorides, elemental analyses were sufficient t o establish their identity. Others such as the phosphoramidates, which may decompose on standing to form isomeric ammonium
Table I. Analyses and Three Most Intense Diffraction Lines of Phosphorus-Nitrogen Compounds Phosphorus, Other Elements Sitrogen, Three 70 % Preparation Strongest % % Lines Calcd. Found Calcd. Found calcd. found Method Ref. Comaound K H salt f (10) Phosphoramidicacid 3.18 4.85 3.34 14.44 1 3 . 8 31.93 29.TO HClOi K H salt (10) Phosphoramidic acid 3.83 4.08 3.36 12.18 12.31 26.93 26.72 HC1O4 monohydrate (kept ice cold) 12.28 12.82 Acid+ (12) 5.77 4.22 4.30 24.56 24.66 27.16 27,12 SH3Ammonium nitrogen ",OH monohydrogen phosphoramidate 19 32 19 3 Phenplester (15) Sodium monohydrogen 3.84 2.89 2.58 11.77 11.64 26.03 25.28 Sodium XH1Sone 0.43 NaOH phosphoramidate nitrogen Phenylester (11) Disodium phosphoram5.63 4.89 3.13 5.62 5.73 12.43 12.61 XaOH idate hexahydrate Phenyl ester ( 1 5 ) 5.68 2.87 2.23 10.37 10.07 22.93 21.62 Potassium KOH monohydrogen phosphoramidate Sone 0.52 K H salt (15) Magnesium 5.70 4.35 6.02 5.71 5.77 12.62 12.74 "1nitrogen magnesia phosphoramidate mixture heptahydrate KHsalt f (16) Barium monohydrogen 12.1 3.27 3.49 7.67 7.55 16.95 16.76 BaC12 phosphoramidate monohydrate KHsalt 4- (15) 5.13 2.96 2.59 6.87 6.65 15.19 14.72 Silver monohydrogen phosphoramidate K H salt f (16) Disilver 2.77 2.93 2.69 4.46 4.72 9.87 11.06 AgSOs phosphoramidate ( Continued)
1490
+
+
+ +
+
ANALYTICAL CHEMISTRY
Table I.
PatternXO.
Analyses and Three Most Intense Diffraction Lines of Phosphorus-Nitrogen Compounds (Continued) Three Nitrogen, Phosphorus, Other Elements Strongest % % % yo Preparation Lines Calcd. Found Calcd. Found calcd. found Method Ref. Compound
11 o-Tolidine phosphoramidatea
14.3
4 . 9 8 4 . 1 5 13.79 13.32 15.24 14.47 Carbon Hydrogen
12 Phosphorodiamidic acidb 4.29 3 . 9 1 13 Ammonium phosphorodi- 3 . 2 1 5 . 0 7 amidate 5.01 2.84 14 Silver phosphorodiamidate 15 Trimeric phosphonitrilic 5 . 6 6 3 . 6 9 chloridec 16 Trimetaphosphimic acid. 6.41 3 . 3 1
2.65 29.17 29.18 32.26 32.11 3 . 5 1 37.17 37.02 27.40 27.44
41.38 42.50 o-Tol. ace- ( 13) 5.95 6.58 tate KH salt Phenyl ester ( 16)
+
4 . 5 1 13.81 13.93 15.26 15.11 4.65 12.09
...
26.73
., .
17.73 17.91 39.21 38.30 Potassium
Sone
17 Trimetaphosphimic acid dihydrate"
5 . 4 4 4.65 6 . 9 7 15.39 15.40 34.03 33.89 Hydrogen
3 69
18 Triammonium trimetaphosphimate monohydrate 19 Monosodium dihydrogen trimetaphosphimate dihydratea 20 Disodium monohydrogen trimetaphosphimate 2.5-hydrate" 21 Trisodium trimetaphosphimate monohydrate
7 . 2 0 0.00
4.78 27.46 27.19 30.36 29.40
8.12 4.46
6 . 1 5 14.24 14.20 31.50 31.37 Sodium
6.11
7 79
+
Sone
K,salt (12) EIClO, 3 33 * h i drecryst. ( 1 2 ) from wateralcoholhexane a t 10" c.
7 i
Acid+ XaOH
(12)
9.80 5 . 4 5 3 . 7 5 12.95 12.86 28.52 28.38 Sodium 7.40 3 . 7 1 3.10 13.09 13.09 28.95 29.00 Sodium
21 49
22 Trisodium trimetaphos7.47 5.68 2 . 8 3 11.22 11.01 24.77 24.99 Sodium phimate tetrahydrate 23 Compound of trisodium 5 9 1 2 . 9 1 8.67 8 . 9 6 9 . 2 2 19.81 19.70 Sodium trimetaphosphimate with sodium hydroxidc heptahydrate
19.61 1 8 . 9
24 Tripotassium trimetaphosphimate
3 . 1 5 3.74 3 . 2 2 11.96 11.71 26.45 26.26 Potassium
33.39 31 3
25 Trisilver trimetaphosphimate
3 06
2 . 9 3 2.89
26 Bis(o-tolidine) trimetaph0sphimat.e dihydrate"
15.5 14.4
27 Bis(benzidine) trimetaphosphimate dihydratea
16.5
7.54
18.40 1S.2
S a 3salt, re- ( 1 7 ) cryst. from water a t 95' C. (PSCL), (17) SaOAc
+ S a 3salt + SaOH (PSC1z)a KOAc
+
+
7.18 16.66 16.40
3 . 4 7 14.05 14.11 13.32 13.52 Carbon Hydrogen
8.20 4 . 6 1 15.28 15.04 14.48 14.41 Carbon Hydrogen
28 Bis(ethy1enediamine) trimet.aphosphimate monohydratea
8.30 3.44 4 . 4 0 26.13 25.88 24.76 24.68 Carbon Hydrogen
29 Tetrameric phosphonitrilic chlorided
3 . 4 3 3 . 8 3 7.63
30 Tetrametaphosphimic acid dihydrate
8.04 4.00 3 . 4 2 15.92 15.89 35.20 34.99
(12)
S a s salt AgNOJ
(17)
48 20 48 13 o-Tol. 6 07 5 85 acetate trimeta acid 44 93 44 22 Benzidine 5 34 5 32 acetate sodium salt
+ (13) + (12)
12 80 12 60 Ethylene(12) 6 45 5 04 diamine sodium salt
+
12.09 12.25 26.73 26.42
(SH4hHz (12) salt ion exchange IR-120 31 Diammoniumdihydrogen 7.20 3 . 2 3 3 . 5 1 23.97 23.50 35.34 34.28 SH36.00 7 00 -4g4salt + ( 1 7 ) tetrametaphosphimate nitrogen (THAS 4H0.4~ 32 Tetrammonium 8 . 2 7 2 . 8 8 3 . 4 1 24.56 24.55 27.16 26.95 SH,12.27 11 7 ilg4salt (13) tetrametaphosphimate nitrogen (SH4)VS tetrahydrate 33 Disodiumdihydrogen 3 . 7 8 2.92 2.90 15.56 15.47 34.42 34.22 Sodium 12.78 13.4 Sacsalt (19) tet>rametaphosphimate HOhc
+
+
+
VOL. 30, NO. 9, SEPTEMBER 1958
1491
Table 1.
Analyses and Three Most Intense Diffraction Lines of Phosphorus-Nitrogen Compounds (Continued) Three Nitrogen, Phos horus, Other Elements Strongest % Preparation % % Compound NO. calcd. found Method Ref. Lines Calcd. Found Calcd. Found (12) 3.51 3.58 7.97 12.74 12.69 28.16 28.23 Sodium 20.91 22.2 Recrystd. 34 Tetrasodium tetrametatrihydrate phosphimate dihydrate from hot water 8 . 5 1 2.87 8.26 12.48 12.44 27.60 27.39 Sodium 20.49 20.1 Dehydrated (18, 18) 35 Tetrasodium tetrametatrihydrate phosphimate 2.5at 68' C. hydratee 8.27 2.80 4 . 1 1 12.23 12.11 27.05 26.84 Sodium 20.08 19.0 36 Tetrasodium tetrametaphosphimate but not' trihydrate",f dried in vacuum K, salt (18) 37 Dipotassium dihydrogen 3 . 4 8 3.13 6.94 14.29 13.94 31.59 30.19 HOAc tetrametaphosphimate 3.20 4.11 3.16 11.55 11.61 25.55 25.36 Acid ( 2 , 12) 38 Dirubidium dihydrogen RbOH tetrametaphosphimate n'asHzsalt (13) 7.22 3.24 2.41 7 . 5 4 8.00 16.66 16.94 39 Tetrasilver tetrametaAgNOa phosphimate 17.2 8.72 4.98 12.70 12.91 14.00 14.14 Carbon 38.00 37.49 o-To~. (13) 40 Bis(o-to1idine)tetraacetate Hydrogen 6.35 6.35 metaphosphimate K?Hnsalt octahydrate" 1 3 . 8 4.37 3.47 9.03 9.05 9.98 9.89 Carbon 54.19 54.21 o-To~. 41 o-Tolidine orthophos(13) acetate Hydrogen 6.17 6.39 phate" XaHz salt, ice cold a New compound. * M. p. 117-19" C., corr. 11.p. 112-13" C. (lit., 114" C.). M.p. 123.5-124.5" C. (lit., 123.5OC.). 8 Transition temperature for 2.5 to 2 HzO, about 120" C. (11). f Transition temperature for 3 to 2.5 H ~ 0 , 5 2 'C. (12).
Pattern-
k-------
+ +
+
+
+
Table 11. d, 9.
1/11
1. Phosphoramidic acid HzP03NHz
d, A. 1/11 1. Phosphoramidic acid (Continued) 1.258 2 1.193 3 1.167 2
Powder Diffraction Data
d , A. 1/11 2. Phosphoramidic acid monohydrate (Continued) 1.571 5 1.530 2 1.510 2 1.497 4 1.469 2 1.453 3 1.440 5 1.427 4
58 6.68 94a 4.85 52 4.62 26 4.35 2. Phos hor 23 3.83 amidic a c i z mono27 3.77 ' hydrate 21 3.65 70 3.34 HzPOaNHs.Hz0 28 3.22 17 3. Ammonium 5 47 100 3.18 monohydrogen 20 4 33 41 3.05 phosphoramidate 58 4 08 2.94 10 100 3 83 NH4HPOaNH2 8 2.77 33 3 69 32 2.54 5.77 100 13 3 58 20 2.50 6 5.53 52 3 36 2.42 25 5.44 5 25 3 24 15 2.40 5.34 5 7 2 98 2 2.27 35 4.30 13 2 85 4 2.18 4.26 35 2 74 9 2 2.12 46 4.22 29 4 2 68 2.08 3.53 16 2 55 13 1.985 10 3.48 20 2 44 8 7 1.937 3.41 20 2 31 10 6 1.887 3.25 2 6 2 24 9 1.838 3.18 9 2 19 10 4 1.755 3.13 7 6 2 11 4 1.736 3.08 6 2 04 3 1.716 3 3.01 10 1 967 7 1.642 6 2.89 16 5 1 914 1.613 3 2.86 6 3 1 848 6 1.585 2.81 7 1 804 8 1.566 5 2.67 2 1 740 1 3 1.519 2.62 2 1 698 8 1.449 2 2.48 1 4 2 1 658 1.402 2.34 1 2 1 642 1.389 3 2.29 1 2 1 623 3 1.308 2.23 17 4 1 597 1.284 4 a Three strongest lines for each compound are underlined.
d , A. 1/11 3. Ammonium monohydrogen phosphoramidate ( Continued)
1.994 1.886 1.828 1,778 1.746 1.733 1.686 1.650 1.629
3 1 2 1 2 1 2 2 1
L
-
1492
ANALYTICAL CHEMISTRY
4. Sodium monohydrogen p hosphoramidate NaHPOaNHz 3.84 100 3.00 10 40 2.89 18 2.58 2.50 3 2.31 8 2.08 3 1.925 15 1.892 4 1.866 9 1.804 7 1.667 5 1.603 3 1.566 2 1.506 1 1.443 7 1.375 2 1.381 3 1.336 1
-
d, A. IIII 4. Sodium monohydrogen phosphoramidate (Continued) 1.261 2 1.179 2 1 1.155 1.142 2 1.128 2 1,091 1 1.073 1 5. Disodium phosphoramidate hexahydrate NhPOJHz.6HzO 6.68 6 6.30 19 5.63 5.22 72 4.89 86 4.59 15 4.11 4 3 73 66 3.58 9 3.41 38 3.34 30 3.30 10 3.18 14 79 3.13 8 3.08 3.03 25 2.97 65 2.93 5 2.85 34 2.81 52 2.78 51 2.68 15 2.60 11 2.56 7 2.49 7
2
AL 1/11 5 , Disodium phosphoramidate hexahydrate (Continued) 2.44 11 2.42 7 d,
2.18 2.13 2.10 2.07 2.05 2.03 1.994 1.979 1.973 i .941 1.916 1.884 1,870 1.841 1.816 1.765 1.737 1.728 1,704
3 14 49 3 2 9 4 13 19 9 3 4 3 9 5 3 4 3 12
6. Potassium monohydrogen phosphoramidate KHPOSNHZ 5.68 4.17 4.09
3.40 3.24 3.05
9 56 55 55 8 30
Table II. Powder Diffraction Data (Continue
d, A. I/li 6. Potassium monohydrogen phosphoramidate (Continued) 2.99 36 2.87 100 2.73 8 2.28 8 2.23 83 2.18 6 6 2.15 2.09 20 2.05 7 2.01 4 1.965 10 1.899 8 2 1.834 1.821 2 8 1.801 1,759 4 4 1.743 1.728 4 1.713 4 1.689 10 1.660 10 12 1.642 1.626 23 1,570 4 2 1.530 1.435 3 1.423 2 1 1.388 1.304 3 7. Magnesium phosphoramidate heptahydrate MgPOaNH2.7HzO 68 6.02 5.70 lo0 29 5.45 5 4.67 96 4.35 4.19 53 15 3.56 50 3.35 3.08 15 2.98 63 2.84 70 2.79 11 2.71 71 2.58 6 2.53 6 2.43 6 2.39 12 2.32 3 2.28 3 2.21 6 2.16 8 2.09 13 2.05 19 2.01 9 1.985 14 1.910 5 1.831 11 1.817 9 1,778 12 1.746 11 1.698 4 1.676 3 1.616 12 1.585 3 1.572 3 1.537 5 1.497 4 1.435 3 1.408 3 1.373 3 1.332 4 1.285 4
-
d, A. I/Il 8. Barium monohydrogen phosphoramidate monohydrate Bal12HP03"2. H2O 12 1 100 4 4 15 4 3 80 12 3 67 3 49 13 6 3 36 16 3 27 3 14 5 6 3 10 3 01 6 4 2 93 2 77 5 2 2 66 2 59 2 2 41 5 3 2 33 2 19 2 2 14 3 2 05 5 2 00 4 3 1 899 2 1 834 2 1 664
-
9. Silver monohydrogen phosphoramidate AgHP03NHz 5.13 3.91 26 2.96 66 2.76 5 2.66 4 66 2.59 2.56 14 2.35 3 2.11 23 1.953 26 1.937 20 1.870 4 1.841 3 1.707 7 1.626 13 1.480 7 1.445 6 1.421 3 1.344 3 1.300 3 1.285 6 1.190 5 1.179 2 1.117 4 1.095 3
100
10. Disilver phosphoramidate AgzPOaNHz 4.67 53 3.68 30 3.51 30 3.47 30 2.93 70 2.77 __ 1% 2.69 70 2.67 37 2.55 35 2.52 43 2.42 22 2.35 16 2.33 26 2.03 6 1.945 9 1.929 9
d , A. 1/11 10. Disilver phosphoramidate (Continued) 1.866 11 1.840 7 1.801 10 1.755 21 1.737 20 1.725 20 1.637 16 1.598 4 1.560 14 1.467 i 1 441
A
11. +Tolidine phosphoramidate
14.3 7.14 4.98 4.85 4.69 4.61 4.15 3.87 3.58 3.41 3.24 3.21 3.16 2.96 2.87 2.65 2.56 2.42 2.39 2.30 2.15 2.01 1.973
100 -
1.623 1.584 1.566 1.510
1 1 2 1
12.
25
75 15 13 8 50 7 22 11 8 7 16 25 23 7 2 2 7 1 9
1 1
Phosphorodiamidic acid HPOz(NH2)z 5.50 13 4.29 100 3.91 72 3.69 7 3.61 20 3.39 19 3.33 13 3.08 5 2.85 3 2.76 17 2.65 27 2.47 13 2.40 6 2.32 2 2.24 * 7 2.21 4 2.14 6 2.05 6 2.00 10
d , A. I/Ii 12. Phosphorodiamidic acid (Continued) 1.965 3 1.930 3 1.841 2 1.765 5 1.752 8 1.701 2 1.670 10 1,600 1 1 537 3 1.490 3 1.427 2
1.291 1.250 1.230
3 1 2
13. Ammonium phosphorodiamidate NHdP02(NH2)1 6.42 33 5.94 28 5.07 92 4.37 36 4.25 36 4.19 21 3.87 42 3.79 52 3.51 77 3.21 1% 3.06 13 3 03 19 2.98 19 2.86 8 2.68 11 2.66 11 2.55 24 2.46 7 2.34 7 2.29 10 2.26 6 2.21 6 2.06 9 2.00 25 1.929 6 1.895 3 1.768 4 1.750 5 1.725 6 1.656 5 1 600 2 1.570 3 1.486 3 1.447 2 1.391 2 1.326 1 1.308 2 1.274 2
-
14. Silver phosphorodiamidate AgPOz("z)z 5.01 100 4.51 60 3.60 46 3.45 9 2.89 14 2.84 67 2.78 29 2.52 29 2.50 29 2.43 27
-
d , A. 1/11 14. Silver phosphorodiamidate (Continued) 2.25 14 18 2.21 2.02 6 1.926 7 1.914 7 1.892 7 1.863 28 1,800 6 1.781 21 1.728 3 1,684 6 1.661 6 1.631 4 1.590 10 1.526 9 15. Trimeric phosphonitrilic chloride (Psc12)3 7.03 22 6.51 10 6.19 9 5.66 100 5.19 8 4.77 8 4.65 39 4.28 16 4.13 4 3.82 20 89 3.69 3.60 17 3.52 26 3.45 13 3 24 3 3.16 18 3.09 14 3.06 39 3.03 26 2.83 6 2.80 8 2.74 8 2.56 7 2.53 6 2.48 7 2.22 7 2.17 5 2.14 5 2.04 4 2.01 4 1.961 9 1,895 7 1.801 4 1.784 7 1.459 4
-
16. Trimetaphosphimic acid Ha( P02NH)a 6.41 100 6.11 52 5 11
4.75 4.19 4.08 3.99 3.57 3,45 3.31 3.25 3.21 3.16 3.08
9 10 48 25 43 40 26 57 26 37 9 7
d , A. 1/11 16. Trimetaphosphimic acid (Continued) 3.04 5 2.93 16 2.86 8 2.67 4 2.58 12 2.56 12 17 2.48 2.40 2 2.33 14 2.29 6 5 2.26 2.21 6 6 2.18 2.14 12 2.08 5 2.05 Ll 1.943 2 1.877 5 1,845 4 3 1 ,791 1.759 5 1.731 5 1.705 4 1.639 2 1.623 4 5 1.603 1.570 2 1.551 5 1.524 3 1 480 4 1.461 6 1.401 3 1.383 3 17. Trimetaphosphimic acid dihydrate H~(P0z"h. 2H20 6.97 72 5.81 30 5.44 100 5.04 14 4.96 11 4 65 92 4.40 18 4.29 22 4.15 11 3 87 22 3 63 26 3.53 26 3 48 30 3 43 60 3.27 37 3.15 45 3.05 35 3.00 21 2.93 59 2.76 14 2.71 36 2.52 12 2.48 7 2.39 6 2.33 6 2.23 9 2.14 12 2.07 10 2.01 5 1,953 ci 1.918 :3 1.881 I , 1.855 1,791 a 1,743 (i 1.647 Ij 1.600 5 (Continued)
VOL. 30, NO. 9, SEPTEMBER 1 9 5 8
-
T
1493
T‘able II. d , A. 1/11 18. Triammonium trimetaphosphimate monohydrate (SH4)3(POJH),. Hz0 7 20 100 -_ 6 00 41 4 78 17 15 4 67 4 51 9 4 17 11 3 43 4 3 25 7 2 90 6 2 86 7 2 76 12 5 2.56 2.49 4 2.39 2 2 31 3 2 24 4 2 12 4
d, -1. 1/11 20. Diaodium monohydrogen trimetaphosphimate 2.5-hydrate Na2H(P02XH),. 2.5H20 9.80 7.50 11 24 7 08 5.95 9 58 5 45 5 28 49 4.90 45 4.84 41 4 73 29 4 11 20 3 95 16 3 75 53 3.65 26 40 3 55 3.48 36 3 39 19 3 27 27 3 20 27 3 12 42 2 92 32 19. hIonosodium 2 78 28 dihydrogen 2 69 37 trimetaphos2 67 37 phimate dihydrate 2 64 30 SaH,( PO,”),. 2 61 28 2H20 2 57 25 2 44 15 8 12 100 -~ 2 40 12 7 7 50 8 2 36 6 15 54 2 30 6 4 93 33 2 14 18 4 80 14 2 09 7 4 62 23 1.973 8 4 46 70 1 877 9 13 4 04 1 814 10 3 93 1i 1 79-4 10 3.77 19 1 771 8 3 53 32 1 752 9 3 36 34 1,698 9 3.22 22 1 631 6 3.13 27 3 08 14 3 02 22m 2 92 21. Trisodium 2 88 9 trimetaphosphi2 85 12 mate monohydrate 2 75 10 Nal( PO??;H j3.H20 2 56 9 2 47 10 7 40 100 2 43 6 6 07 14 2 30 19 4 62 16 2 24 -4 -4 70 12 2 20 3 4 55 8 2 09 3 3 75 11 2 04 4 3 71 34 2 01 3 3 62 17 1 965 4 3 48 13 1 914 3 1 903 6 1 804 7 1.713 3 1 670 1 1 642 2 1 626 3 1 585 2 1 508 2 2 54 3 1.484 4 2 50 11 2.47 11 2.42 7n 2 2 26 6 2.22 12 2.13 2 2 04 5
Powder Diffra ction Data (Continuedl d, A. 1/11 d , A. 1!11 d , A. 1/11 24. Tripotassium 21. Trisodium 22. Trisodium trimetaphostrimetaphosphitrimetaphosphimate phimate mate monohydrate tetrahydrate (Continued) (Continued) 1 980 1 gal
1.892 1.811 1.774 1,722 1 656 1.603 1.588 1 526 1,486 1.451 1.431 1 ,420
8 4 1
6 5 3 3 2 4
7
~
~
( Continued) 1.645 1 1.608 1 1.590 1
1.5 7 9 3
22. Trisodium trimetaphosphimate tetrahydrate Na3(POzNH)3. 4Hz0 8.34 11 7.44 100 7.08 7 5.68 23 n 5.41 5.01 5 4.61 2 4 55 2 4 42 0 4 20 12 3 92 2 3.82 4 3.71 2 3.65 2 3.53 5 3.35 10 3.29 18 3.23 8 3.21 8 3 09 G3 00 2.96 2 93 9 2.83 23 2 77 13 2 71 I 2 66 9 2 61 3 2 51 5 2 48 8 2 45 1 2 40 2 2 36 4 2 32 1 2 28 3 2 25 11 2.21 5 2 19 6 2 17 2 2 15 3 2 12 3 2.08 5 2 05 1 2 03 1 1 961 1 1.926 3 1.895 3 1,841 1 1.817 3 1.765 4 1.734 3 1.707 2 1.681 3
A
r
23.
Compound of trisodium trimetaphosphimate with sodium hydroxide heptahydrate Sal( PO*SH),. SaOH.iH*O 8.67 82 7.38 13 6.42 20 6.11 13 5.91 100 5.47 I 4.82 10 4.62 24 4.42 11 3.92 30 3.75 I 3.66 11 ” 3.48 3.39 33 3.22 9 3.13 14 2.91 100 2 78 17 2 72 11 2 67 42 2 60 12 2 47 35 2.34 20 2 30 91 2 01 1 961 11 ( 1 910 1 831 6 1 817 12 1 800 13 1 737 18
-
-
~~
~
-
24. Tripotassium trimetaphosphimate K(POz”)3 7.44 10 6.33 21 4.82 36 4.62 58 3.83 11 3 7-4 97 3 40 19 3 22 94 3 15 loo 3 00
1.903 1.866 1 834 1 791 1 698 1 647 1.609 1.588 1 559 1 544 1 497 1 541 1 386 1.336 1.245
18 6 10 38 7 8 8 19 7 14 8 22 15 6 8
25. Trisilver trimetaphosphimate i4g,(PO,?;H), 7.08 12 6.42 22 6.03 54 5.54 40 4.90 23 4.17 I 4.06 27 3.71 12 3 62 10 3.56 21 3 45 21 3 21 30 3 15 20 3 06 100 83 2 93 2 89 73 2 78 45 2 75 43 2 67 23 2 62 21 2 54 39 2 47 31 2.42 13 2 36 21 2 23 11 2 14 9 11 2 09 I 2 02 1.985 13 1 926 17 1 873 19 1 791 11 1 734 13 1 667 16
-
-
-
26. Bis(o-tolidine) trimetaphosphimate dihydrate
19 49 14 24 13 12
27. Bis( benzidine) trimetaphosphimate dihydrate
16.5 11 5 8 20 6 05 5 95 5 71 5 44 5 19 4 87 4 61 4 48 4 37 4 02 3 92 3 79 3 59 3 49 3 27 3 11 3 04 2 96 2 91 2 75 2 71 2 64 2 50 2 32 2 28 2.18
100 13 39 13 14 8 20 11 4
39 -
31 .~
18 6 10 5 14 38 5 12 8 9 9 6 6 3
5 3 4
6
28.
~
2.31 2.25 2.18 2.11 2.01 1.957
d, A. I/Ii 26. Bis(o-tolidine) trimetaphosphimate dihydrate (Continued) 5 47 40 5 15 14 5 07 16 4 86 42 4 65 32 4.44 40 3.95 20 3.55 17 3.53 20 3.47 60 3.33 28 3 03 11 2 95 10 2 83 9 2 67 7 2 56 4 2 49 3 D 2 43 2 37 5 2 32 5 2 22 7
15 5 14 4 11 2 9 93 7 70 7 13 6 86 6 61 6 24 5 87 5 61
100 100 40 40 27 7 11 19 29 14 29
Bis(ethy1enediamine j trimetaphosphimate monohydrate
8 30 6.92 6.07 5.81 5.61
100 4 2
-
h
(Continued)
1494
ANALYTICAL CHEMISTRY
Table II. Powder Diffraction Data (Continued)
d , A. 1/11 28. Bis(ethg1enediamine) trimetaphosphinate monohydrate (Continued) 5.50 12 4.91 4 4.77 4 4 58 6 4 40 28 4.19 3 3.99 5 3.88 5 3 60 3 3.47 26 3 44 31 3 33 21 3.27 18 3 16 14 3 03 6 2.93 4 2 84 10 2.75 6 2 56 5 2.44 6 2.38 9 2.28 5 2.19 1 2.16 2 2.14 1 2.09 2 2 05 2
-
20. Tetrameric phosphoni trilic chloride (PSCl,), 7 63 39 5.75 26 4.72 2 4 00 5 3.83 55 .~ 3.77 11 3.43 100 3.23 8 3 10 8 2.08 18 2.88 6 2 71 0 2.68 13 2.54 7 2.47 3 2.42 6 2.40 6 2.35 5 2.30 2 2 25 1 2.12 8 2.04 2 2.01 2 1.953 1 1.910 1 1 .8bR 1 1.759 3 1,713 13 1.670 3 1.631 3 ~
30. Tetrametaphosphimic acid dihydrate
8.04 6.86
100 14
d , A. 1/11 30. Tetrametaphosphimic acid dihydrate (Continued) 5 75 14 38 4 72 18 4 18 65 4 00 3 95 27 3 77 5 3 45 7 62 3 42 62 3 37 20 3 21 3 15 30 3 01 8 2 95 14 3 2 87 2 77 11 2 67 16 2 55 2 2 51 2 2 40 13 2 36 11 2 31 6 2 28 4 2 17 5 2 10 3 2 08 3 2 03 2 2 01 2 1 973 3 1 949 2 31.
Diammonium dihydrogen t etrame t aphosphimate (S‘H412H2( P O J S H)J 7 20 100 -_ 7 01 22 11 5 0; 4 31 3 4 19 18 4 13 18 4 00 18 3 68 3 20 3 59 26 3 51 3 2: 43 __ 3 18 12 3 14 8 2 92 8 2 88 5 2 72 5 2 68 10 2 58 13 2 53 2 2 40 4 2 33 7 2 25 2 2 17 3 2 12 0 2 oc, 3 2 05 3 2 00 4 1 914 2 1 886 2 1 859 2 1 841 5 1 791 2 1 689 2 1 650 1 1 616 2 1 590 2 1 571 2 1 542 2
d, A. 1/11 32. Tetrammonium tetrametaphosphimate tetrahydrate
8.27 6.24
100 __
4.13 3.95 3.87 3.54 3.41 3 31 3.21
11 2 3 9 17 3 8
7
d , A. I/I, d , A. 1/11 33. Disodium 35. TetraEodium dihydrogen tetrametaphostetrametaphimate phosphimate 2.5-hydrate (Continued) Sa4(P02NH)4. 2.5H20 2.20 6 2 16 6 8 51 100 -~ 2 08 2 8 26 85 2 01 4 7 14 49 1 9% 1 6 81 57 1,907 I 5 01 21 1 881 6 5 72 14 1 848 8 4 82 58 1.817 3 4 69 14 1.766 4 4 42 11 1.710
