2015年9月27日星期日

Tungstate of Soda

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).


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.


Na2WO4 Refractive Indices

The densities and refractive indices of solutions of various concentrations have been determined as follows:

Grams Na2WO4 in 100 Grams Solution.
Density, d20°
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:

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:

Method
Transition Point ° C
Melting point of β Form
δγ
γβ
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.