Sodium metaborate

Hydrates and solubility

The following hydrates crystallize from solutions of the proper composition in various temperature ranges:

• tetrahydrate from −6 to 53.6 °C
• dihydrate from 53.6 °C to 105 °C
• hemihydrate from 105 °C to the boiling point. Early reports of a monohydrate have not been confirmed.

Structure

Anhydrous

Solid anhydrous sodium metaborate has the hexagonal crystal system with space group R\bar3 c. It actually contains a six-membered rings with the formula , consisting of alternating boron and oxygen atoms with one negatively charged extra oxygen atom attached to each boron atom. All nine atoms lie on a plane. The six oxygen atoms are evenly divided into two distinct structural sites, with different B–O bond lengths: B–O(external) 128.0 pm and B–O(bridge) 143.3 pm. The density is 2.348 ± 0.005 g/cm3. The approximate dimensions of the hexagonal cell are a = 1275 pm, c = 733 pm. However, the true unit cell is rhombohedral and has dimensions: ar= 776 pm, α = 110.6°, Z = 6 (5.98) molecules KB0

Dihydrate

The dihydrate crystallizes in the triclinic crystal system, but is nearly monoclinic, with both α and γ very close to 90°. The cell parameters are a = 678 pm , b = 1058A pm, c = 588 pm, α = 91.5°, β = 22.5°, γ = 89°, Z = 4, density 1.905 g/cm3. The refractive indices at 25°C and wavelength 589.3 nm are α = 1.439, β = 1.473, γ = 1.484. The dispersion is strong, greater at red than at violet.

The transition temperature between the dihydrate and the hemihydrate is 54 °C. However, the crystalline dihydrate will remain metastable until 106 °C to 110 °C, and change slowly above that temperature.

Vapor

Infrared spectroscopy of the vapor from anhydrous sodium metaborate, heated to between 900 °C and 1400 °C, shows mostly isolated clusters with formula , and some dimers thereof. Electron diffraction studies by Akishin and Spiridonov showed a structure with linear anion and angle of 90-110°. The atomic distances are : 120 pm, : 136 pm,: 214 pm

Preparation

Sodium metaborate is prepared by the fusion of sodium carbonate and boron oxide or borax . Another way to create the compound is by the fusion of borax with sodium hydroxide at 700 °C:

:

The boiling point of sodium metaborate (1434 °C) is lower than that of boron oxide (1860 °C) and borax (1575 °C) In fact, while the metaborate boils without change of composition, borax gives off a vapor of sodium metaborate with a small excess of sodium oxide .

The anhydrous salt can also be prepared from the tetraborate by heating to 270 °C in vacuum.

Although not performed industrially, hydrolysis of sodium borohydride with a suitable catalyst gives sodium metaborate and hydrogen gas: : (ΔH = −217 kJ/mol)

Reactions

With water

When sodium metaborate is dissolved in water, the anion combines with two water molecules to form the tetrahydroxyborate anion .

Electrochemical conversion to borax

Electrolysis of a concentrated aqueous solution of 20% with an anion exchange membrane and inert anode (such as gold, palladium, or boron-doped diamond) converts the metaborate anion to tetraborate , and the sodium salt of the later (borax) precipitates as a white powder. :

Reduction to sodium borohydride

Sodium metaborate can be converted to sodium borohydride by several methods, including the reaction with various reducing agents at high temperatures and pressure, or with magnesium hydride by ball milling at room temperature, followed by extraction of the with isopropylamine.

:

Another method is the electrolytic reduction of a concentrated sodium metaborate solution, namely

:

However, this method is not efficient since it competes with the reduction of hydroxide: :

Nanofiltration membranes can effectively separate the borohydride from the metaborate.

Reaction with alcohols

Anhydrous sodium metaborate refluxed with methanol yields the corresponding sodium tetramethoxyborate (melting point: 253-258 °C, CAS number: 18024-69-6): : The analogous reaction with ethanol yields the sodium tetraethoxyborate.

Uses

Current and proposed applications of sodium metaborate include:

• Manufacture of borosilicate glasses, which are resistant to uneven or fast heating because of their small coefficient of thermal expansion.
• Composition of herbicides.
• Raising the pH of injected fluids for oil extraction.

References

References

1. (1963). "The bond lengths in the sodium metaborate structure". Acta Crystallographica.
2. "Product".
3. (1962). "Electron diffraction study of the structure of LiBO2 and NaBO2 metaborate molecules in the vapor state". Journal of Structural Chemistry.
4. Alfred Büchler and Edward P. Marram. (1963). "Gaseous Metaborates. II. Infrared Spectraof Alkali Metaborate Vapors". Journal of Chemical Physics.
5. (2007). "Separation of sodium metaborate from sodium borohydride using nanofiltration membranes for hydrogen storage application". International Journal of Hydrogen Energy.
6. (2013). "Evaluation the performance of sodium metaborate as a novel alkali in alkali/Surfactant/Polymer flooding". Journal of Industrial and Engineering Chemistry.
7. (1951). "Crystallographic Data. 44. Sodium Metaborate Dihydrate". Analytical Chemistry.
8. "[https://www.pro-serveinc.com/_files/ugd/048165_be0900f366474955b6d34ac2569a2877.pdf BareSpot Monobor-Chlorate]". Product safety data sheet at the BareSpot company website.Retrieved 2022-06-28.
9. "[http://chemister.ru/Database/properties-en.php?dbid=1&id=752 Sodium metaborate]" Substance page at the Chemister website. Accessed on 2022-06-28.
10. (2003). "Protide compounds in hydrogen storage systems". Journal of Alloys and Compounds.
11. (2009). "Regeneration of sodium borohydride from sodium metaborate, and isolation of intermediate compounds". International Journal of Hydrogen Energy.
12. (2009). "Mechanochemical Synthesis of Sodium Borohydride by Recycling Sodium Metaborate". Energy & Fuels.
13. (2007). "Recycling of sodium metaborate to borax". International Journal of Hydrogen Energy.
14. (1967). "Solubility isotherms in the system sodium oxide-boric oxide-water. Revised solubility-temperature curves of boric acid, borax, sodium pentaborate, and sodium metaborate". Journal of Chemical & Engineering Data.
15. (1938). "The Crystal Structure of Sodium Metaborate Na₃ (B₃ O₆)". Zeitschrift für Kristallographie - Crystalline Materials.
16. (1935). "THE SYSTEM Na₂O-B₂O₃, IV Vapor Pressures of Boric Oxide, Sodium Metaborate, and Sodium Diborate between 1150°C and 1400°C". Journal of the American Ceramic Society.
17. (1937). "The Crystal Structure of Potassium Metaborate, K3(B3O6)". The Journal of Chemical Physics.