Sodium paratungstate is known commercially as "tungstate of soda" and may be prepared on a large scale by fusing wolframite with soda ash and lixiviating the fused mass. On nearly neutralising the boiling solution with hydrochloric acid and allowing to crystallise, large triclinic crystals of the salt separate.
The salt may be formed in solution by any of the following methods:
1.Saturation of a solution of sodium hydroxide, carbonate, or tungstate, with anhydrous tungstic acid.
2.Treatment of a sodium tungstate solution with hydrochloric acid at boiling-point (as described above) until only faintly alkaline to litmus.
3.Addition of a solution of sodium metatungstate (containing 5.8 grams Na2O.4WO3.10H2O) to one of the normal tungstate (containing 2 grams Na2O.WO3.2H2O).
4.Saturation of a solution of normal sodium tungstate with carbon dioxide.
5.Electrolysis of sodium tungstate solution in a cell in which the electrodes are separated by a diaphragm (see above).
2015年9月27日星期日
Sodium Tungstate as Mordant
The production of colloidal tungsten hydroxide by the electrolysis of a solution of sodium tungstate has already been described. If precautions are taken to prevent the sodium hydroxide formed at the cathode from reaching the anode, for example, by means of a porous partition, it is possible to prepare the paratungstate, or other complex tungstate, from the anode solution.
The use of sodium tungstate has been recommended as a mordant, and it has been used as a fire-proofing material for flannelette, but owing to its solubility it cannot be considered satisfactory and it is not now used.
Sodium ditungstate, Na2O.2WO3, may be obtained by fusing together tungstic anhydride and sodium hydroxide or sodium carbonate, the mixture containing lNa2O:2WO3. On cooling, long needles separate, which on prolonged heating with water dissolve, yielding an alkaline solution which contains metatungstate. The dihydrate, Na2O.2WO3. 2H2O, is described by Rammelsberg as a crystalline precipitate obtained by addition of hydrochloric acid to a solution of the normal tungstate. The hexahydrate, Na2O.2WO3.6H2O, is stated by Lefort to crystallise from a solution containing the normal tungstate (2 molecules) and acetic acid (1 molecule); von Knorre, however, could only obtain the paratungstate from such a solution. The hydrate,Na2O.2WO3.12H2O, has also been described.
Sodium paratungstate is known commercially as "tungstate of soda" and may be prepared on a large scale by fusing wolframite with soda ash and lixiviating the fused mass. On nearly neutralising the boiling solution with hydrochloric acid and allowing to crystallise, large triclinic crystals of the salt separate.
The use of sodium tungstate has been recommended as a mordant, and it has been used as a fire-proofing material for flannelette, but owing to its solubility it cannot be considered satisfactory and it is not now used.
Sodium ditungstate, Na2O.2WO3, may be obtained by fusing together tungstic anhydride and sodium hydroxide or sodium carbonate, the mixture containing lNa2O:2WO3. On cooling, long needles separate, which on prolonged heating with water dissolve, yielding an alkaline solution which contains metatungstate. The dihydrate, Na2O.2WO3. 2H2O, is described by Rammelsberg as a crystalline precipitate obtained by addition of hydrochloric acid to a solution of the normal tungstate. The hexahydrate, Na2O.2WO3.6H2O, is stated by Lefort to crystallise from a solution containing the normal tungstate (2 molecules) and acetic acid (1 molecule); von Knorre, however, could only obtain the paratungstate from such a solution. The hydrate,Na2O.2WO3.12H2O, has also been described.
Sodium paratungstate is known commercially as "tungstate of soda" and may be prepared on a large scale by fusing wolframite with soda ash and lixiviating the fused mass. On nearly neutralising the boiling solution with hydrochloric acid and allowing to crystallise, large triclinic crystals of the salt separate.
Na2WO4 Refractive Indices
The densities and refractive indices of solutions of various concentrations have been determined as follows:
The equivalent conductivities of solutions containing ½Na2WO4 in v litres at 25° C. are as follows:
The vapour pressures of solutions have been determined.
Grams Na2WO4 in 100 Grams Solution.
|
Density, d4°20°
|
Refractive Index, nD20°
|
2.21
|
1.0184
|
1.33586
|
10.08
|
1.0949
|
1.34516
|
16.56
|
1.1667
|
1.35376
|
20.59
|
1.2148
|
1.35933
|
25.46
|
1.2789
|
1.36648
|
32.68
|
1.3854
|
1.37934
|
38.43
|
1.4828
|
1.38890
|
The equivalent conductivities of solutions containing ½Na2WO4 in v litres at 25° C. are as follows:
v =
|
32
|
64
|
128
|
256
|
512
|
1024
|
Λ =
|
95.9
|
101.8
|
105.4
|
110.3
|
112.9
|
116.4
|
The vapour pressures of solutions have been determined.
Solubility of Sodium Tungstate
The heat of formation of sodium tungstate has been found to be:
Na2O + WO3 = Na2WO4 + 94,700 calories.
The aqueous solution, which is alkaline, when allowed to crystallise at temperatures above 6° C., yields slender nacreous crystals of the dihydrate, Na2WO4.2H2O, in the form of rhombic bipyramidal scales, a:b:c = 0.8002:1:0.6470, of density 3.259 at 17.5° C. and 3.231 at 19° C. This hydrate is stable in the air, and it is in this form that the salt is generally used. When heated, it loses water at 200° C., becomes opaque, and finally melts. It dissolves readily in hot water, but may be precipitated by means of alcohol. The solution yields white tungstic acid on the addition of mineral acids.
If the aqueous solution is allowed to crystallise at temperatures below 6℃, the decahydrate,Na2WO4·10H2O, is obtained.
The solubility of sodium tungstate has been determined by Funk as follows:
These results are shown graphically in fig.
Na2O + WO3 = Na2WO4 + 94,700 calories.
The aqueous solution, which is alkaline, when allowed to crystallise at temperatures above 6° C., yields slender nacreous crystals of the dihydrate, Na2WO4.2H2O, in the form of rhombic bipyramidal scales, a:b:c = 0.8002:1:0.6470, of density 3.259 at 17.5° C. and 3.231 at 19° C. This hydrate is stable in the air, and it is in this form that the salt is generally used. When heated, it loses water at 200° C., becomes opaque, and finally melts. It dissolves readily in hot water, but may be precipitated by means of alcohol. The solution yields white tungstic acid on the addition of mineral acids.
If the aqueous solution is allowed to crystallise at temperatures below 6℃, the decahydrate,Na2WO4·10H2O, is obtained.
The solubility of sodium tungstate has been determined by Funk as follows:
Solid Phase Na2WO4.10H2O.
|
|
Temperature,° C.
|
Grams Na2WO4 in 100 Grams Solution.
|
-5
|
30.60
|
-4
|
31.87
|
-3.5
|
32.98
|
-2
|
34.52
|
0
|
36.54
|
+3
|
39.20
|
+5
|
41.02
|
Solid Phase Na2WO4.2H2O.
|
|
Temperature,° C.
|
Grams Na2WO4 in 100 Grams Solution.
|
-3.5
|
41.67
|
+0.5
|
41.73
|
+21
|
42.27
|
+43.5
|
43.98
|
+80.5
|
47.65
|
+100
|
49.31
|
These results are shown graphically in fig.
Binary Systems Na2WO4 - Na2SiO3 and Na2WO4 - K2WO4
The anhydrous normal tungstate, Na2WO4, is prepared by the fusion method described for potassium tungstate, or by complete dehydration of the hydrates at 100° C. or over sulphuric acid. It may be obtained from the mineral wolframite by fusion with alkali as already described.
The anhydrous salt exists as white crystals, of density 4.1833 at 18.5° C. and 4.1743 at 20.5° C., which melt at 698° C. On heating it undergoes two transformations, the first with considerable development of heat, and finally boils. The transition temperatures between the polymorphic forms thus indicated have been determined from the cooling and heating curves as follows:
The binary systems Na2WO4 - Na2SiO3 and Na2WO4 - K2WO4, and the properties of aqueous solutions of the mixtures, have been investigated.
The anhydrous salt exists as white crystals, of density 4.1833 at 18.5° C. and 4.1743 at 20.5° C., which melt at 698° C. On heating it undergoes two transformations, the first with considerable development of heat, and finally boils. The transition temperatures between the polymorphic forms thus indicated have been determined from the cooling and heating curves as follows:
Method
|
Transition Point ° C
|
Melting point of β Form
|
|
δ⇔γ
|
γ⇔β
|
||
Cooling curve
|
570
|
. . .
|
698
|
Cooling curve
|
564
|
588
|
698
|
Cooling curve
|
568
|
585
|
698
|
Cooling curve
|
572
|
589
|
700
|
Heating curve
|
587
|
591
|
694
|
The binary systems Na2WO4 - Na2SiO3 and Na2WO4 - K2WO4, and the properties of aqueous solutions of the mixtures, have been investigated.
Sodium Tungstate Applications
Sodium Tungstate has applications
as a catalyst, analytical reagent, fire proofing agent. It features a high
degree of chemical purity and outstanding water solubility with no residue. It
can be used in the manufacture of metal tungsten, tungsten acid, tungsten
salts, and dyes, galvanic coatings, and the manufacture of X-ray contrast
agents.
Sodium tungstate is Colorless or
white crystalline powder and widely used as catalyst in paint
industries, dyes industries, pigments and pharmaceuticals and many more chemical
reactions like epoxidation of alkenes and oxidation of alcohols into aldehydes
or ketones, it also used in Manufacture of heteropolyacid color lakes used in
printing inks, plants, waxes, glasses, and textiles, Analytical reagent,
Reagent for alkaloids, uric acid and plasma proteins, Fuel-cell electrode
material, and Fire proofing agent, Manufacture of metal tungsten, tungstic acid
and tungsten salts.
Sodium
tungstate is an effective Antidiabetic agent when administered orally. It
improves pancreatic function and beta cell proliferation. It activates glycogen
synthesis through an insulin receptor-independent pathway.
There are
dual effects of sodium tungstate on adipocyte biology: inhibition of
Adipogenesis and stimulation of cellular oxygen consumption. Sodium tungstate
inhibits adipocyte differentiation and regulates the mitochondrial oxygen
consumption of adipose cells. These effects contribute to the anti-obesity
activity of sodium tungstate and confirm its potential as a powerful
alternative for the treatment of obesity.
Sodium
tungstate is used for slurry sampling electro thermal atomic absorption
spectrometric determination of indium in soils.
Typical
applications include catalysis, pigment production, galvanic coatings, and the
manufacture of X-ray contrast agents.
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