EXPERIMENT NO: 3

EXPERIMENT TITLE: OXO-ACIDS AND OXO-ACIDS SALTS: THE

PREPARATION OF SODIUM PEROXOBORATE
HEXAHYDRATE.

SURNAME:

FIRST NAME:

ID NUMBER:

DAY: THURSDAY

DATE OF THE EXPERIMENT: 25 AUGUST 2016

AIM
The aim of the experiment was to prepare sodium peroxoborate hexahydrate from sodium
tetraborate decahydarete.
ABSTRACT
For this experiment a crystalline compound of sodium peroxoborate was prepared from the
common detergent, Borax, Hydrogen Peroxide, and Sodium Hydroxide. Borax has an ability
to be an acid when accepting a hydroxyl ion or base if in solution with strong alkalis. The
compound was tested for purity with two compounds, potassium permanganate and Potassium
iodide.
INTRODUCTION
Oxoacids are acids that contain a hydrogen atom bonded to an oxygen atom. These acids
dissociate in water by breaking this bond and forming hydronium ions and a polyatomic anion.
Borax is a naturally occurring mineral of boron with a general chemical formula ofNa2B4O7.
Atkins, P., & Overtin, T. (2010) The universal characteristic to this boron substance is a dual
peroxide bond bridge characteristic with linked oxygens and hydrogens. The hydrogens
undergo adjacent bonding to oxygens which makes large extended sheet layers. The structure
can become a Lewis acid or base because of its incomplete octet. This leaves a vacant orbital
so OH-can be inserted to form a Lewis base or the H+ for a Lewis acid. Peroxoborate in its
simplest form has a cyclic dimer anion B2O4(OH)42–, where dual boron atoms are joined by
two of the peroxidesize, several other formulations of peroxoborate exist: heptahydrate,
monohydrate, tetrahydrate, and trihydrate
The principal oxide of boron is boric oxide, B2O3 (mp 450°, bp (extrap) 2250°C). It is one of
the most difficult substances to crystallize and, indeed, was known only in the vitreous state
until 1937 Greenwood, N. N., & Earnshaw, A. (1997). It is generally prepared by careful
dehydration of boric acid B(OH)3. The normal crystalline form (d 2.56 g cm -1) consists of a
3D network of trigonal BO3 groups joined through their 0 atoms, but there is also a dense form
(d 3.11 g cm-3) formed under a pressure of 35 kbar at 525°C and built up from irregular
interconnected BO4 tetrahedra. In the vitreous state (d 1: 1.83gcmP3) B2O3 probably consists
of a network of partially ordered trigonal BO3 units in which the 6- membered (BO)3 ring
predominates; at higher temperatures the structure becomes increasingly disordered and above
450°C polar -B=O groups are formed Housecroft C.E and Sharpe A.G (2012). Fused B2O3
readily dissolves many metal oxides to give characteristically coloured borate glasses. Its major
application is in the glass industry where borosilicate glasses (e.g. Pyrex) are extensively used
because of their small coefficient of thermal expansion and their easy workability. Orthoboric
acid, B(OH)3, is the normal end product of hydrolysis of most boron compounds and is usually
made (-160000 tonnes pa) by acidification of aqueous solutions of borax.

It forms flaky, white, transparent crystals in which a planar array of BO3 units is joined by
unsymmetrical H bonds. In contrast to the short 0-H . . .O distance of 272 pm within the plane,
the distance between consecutive layers in the crystal is 3 18 pm, thus accounting for the
pronounced basal cleavage of the waxy, plate-like crystals, and their low density (1.48 g ~ m -
~B) (.O H)3 is a very weak monobasic acid and acts exclusively by hydroxyl ion acceptance
rather than proton donation:
 B(OH), + 2H20 H3O+ + B(OH)4-;

pKa = 9.25

Figure 1.1 Layer structure of B(OH)3. Interatomic distances are B-0 136pm. 0-H 97pm, 0-H.. .O 272pm. Angles
at B are 120” and at 0 126“ and 114“. The H bond is almost linear

Greenwood, N. N., & Earnshaw, A. (1997) Orthorhombic HB02 consists of trimeric units
B3°3(0H)3 which are linked into layers by H bonding (Fig. 6.26); all the B atoms are 3-
coordinate. Monoclinic HBO2 is built of chains of composition [B304(OH)(H20)] in which
some of the B atoms are now 4-coordinate, whereas cubic HB02 has a framework structure of
tetrahedral BO4 groups some of which are H bonded. The increase in CN of B is paralleled by
an increase in density and mp.

Figure 1.2 Layer structure of orthorhombic metaboric

acid HBOz(III), comprising units of formula B303(OH)3

The reaction of the hexahydrate with sodium hydroxide and hydrogen peroxide occurs as
written in the chemical equations below and with the mechanism shown, NaBO2 is a sodium
metaborate and NaBO3.4H2O is the perborate tetrahydrate

Na2B4O7 (s) + 2NaOH (l)  4NaBO2 (l) + H2O2

NaBO2 (l) + H2O2 + 3H2O  NaBO3.4H2O (s)

Overall reaction

Na2B4O7 (s) + 2NaOH (aq) + 4H2O2 (l)  4NaBO3 (s) + 5H2O (l)

Structure of sodium perborate tetrahydrate [1]

PROCEDURE

APPARATUS USED CHEMICALS USED

 Petri dish Sodium tetraborate decahydrate

 100 ml beaker Hydrogen peroxide

 Buchner funnel Sulphuric acid

 Stirring rod Titanium (IV) oxosulphate

 Buchner flask Potassium permanganate

 Filter paper Sodium hydroxide

Potassium iodide

Sodium fluoride

ether

Alcohol

In the preparation of sodium peroxoborate hexahydrate, 3.0754 g of sodium tetraborate

decahydrate was dissolved in 20 cm3 of 3.3% NaOH solution. The solution was cooled in ice
with stirring while adding 20 cm3 of 6% hydrogen peroxide solution slowly until crystallization
was complete. The solution was filtered by suction, alcohol and then ether were used to wash
the crystals. The crystals were dried on filter paper.

5 cm3 aliquots of freshly prepared aqueous solution of the product were in the following:

i. To it was added 2 M sulphuric acid and 0.02 M potassium permanganate solution.

ii. To it was added 2 M sulphuric acid and 10% w/v potassium iodide solution

iii. To it was added 1 cm3 of 1% titanium (IV) oxosulphate solution followed by excess
sodium fluoride solution.
OBSERVATION/RESULTS
To the 5cm3 aqueous solutions prepared from the product;
ACTION OBSERVATION
Addition of 2M sulphuric No observable change,
acid and 0.02M of because as KI was added
potassium permanganate the purple colour
solutiondisappeared. Solution
remained colourless.
Effervescence was also
noted.
Addition of 2M sulphuric A brick red solution
acid and 10% w/v formed after adding the
potassium iodide solution potassium iodide solution
CONCLUSION
The reaction formed dihydrogen
monoxide which is a colourless
and odourless compound.
Na2[B2(OH)4(O2)2] + 4 KI
+ 3 H2SO4  Na2SO4 + 2 K2SO4 +
B2O3 + 5 H2O + 2 I2
The iodine ion was oxidized,
peroxoborate ion is a strong
oxidizing agent, while the
peroxoborate ion was reduced to
the borate ion. The dark brown
colour was due to the presence
of the Iodine ion.

Addition of 1cm3 of 1% A dark orange solution The light orange colour was due
titanium (IV) oxosulphate formed after adding 1% to the formation of aqueous
solution followed by titanium(IV) oxosulphate titanium sulphide. After adding
excess sodium fluoride solution. The solution excess sodium fluoride, a small
solution turned pale yellow after precipitate sodium sulphate
the excess sodium appeared.
fluoride solution was
added.

YIELD AND PHYSICAL PROPERTIES

Mass of borax (381.372138 g.mol-1) = 3.0754 g

No. of moles of borax = 3.0754 g/ 381.372138 g.mol-1

= 0.008064 mol

Mass of NaOH (39.997109 g.mol-1) = concentration x volume used

= 3.3 g/ 100 mL x 20 mL

= 0.66 g
No. of moles of NaOH = 0.66 g/ 39.997109 g/mol
= 0.01650 mol
Mass of H2O2 used (34.01468 g.mol-1) = 6.6 g/ 100 mL x 20 mL
= 1.32 g
No. of moles H2O2 = 1.32 g/ 34.01468 g/mol
= 0.03881 mol
From the no. of moles of the reactant it is seen that borax is the limiting reactant.
Molar mass of sodium peroxoborate hexahydrate = 153.860089 g.mol-1
Mass of sodium peroxoborate hexahydrate = 4.0258 g (actual yield)
Reaction equation:
Na2B4O7 (s) + 2NaOH (aq) + 4H2O2 (l)  4NaBO3.4H2O (s) + H2O (l)
No. of mole NaBO3 = 0.0079 mol Na2B4O7 x 4 mole NaBO3 / 1 mole Na2B4O7
= 0.0316 mol
Theoretical yield = 0.0316 mol x 153.860089 g.mol-1
= 4.86 g
Percentage yield = 4.0258 g/ 4.86 g x 100
= 82.8%
DISCUSSION

The equations below give a clear indication and reference to the results obtained when doing
the qualitative tests.

The oxoborate in acidic medium has a bleaching effect and therefore decolourise the
permanganate, the gas that was produced is oxygen.

i. Na2[B2(O2)2(OH)4].6H2O + H2SO4 + KMnO4 --> Na2[B2(O2)2(OH)4].6H2O + Mn2+ +

4H2O

The iodine causes the brick-red colour of the solution.

ii. Na2[B2(O2)2(OH)4].6H2O + H2SO4 + KI2 --> Na2[B2(O2)2(OH)4].6H2O + 2I- + [S2O6]2-

Addition of 1cm3 of 1% titanium (IV) oxosulphate solution followed by excess sodium fluoride
solution will form water as a by-product.

iii. 𝑇𝑖𝑂𝑆𝑂4 (𝑎𝑞) + [𝑁𝑎𝐵𝑂2 (𝑂𝐻)2 . 3𝐻2 𝑂](𝑎𝑞) → 𝑁𝑎2 𝑆𝑂4 (𝑎𝑞) + 𝐻2 𝑂(𝑙) + 𝑇𝑖𝐹4 (𝑎𝑞) +
𝑁𝑎𝐵𝑂2 (𝑎𝑞)

The experiment was conducted under good conditions, although some errors may have
occurred, they were minimised by following the procedure carefully. What the percentage yield
would indicate is how much of the salt recrystallized. This process is highly dependent on how
much of the borax is firstly dissolved in the NaOH in the first process, this would go on further
to play a role in the addition of the hydrogen peroxide. Once after the slow addition in a cold
water bath the salt starts to recrystallize. The longer one slowly mixes and increases the time
spent in the water bath, the more salt forms. Hence experimentally 82.8% was obtained

The sources of error that may have occurred is in addition of impurities from using normal
water and not distilled water, as normal water carries along with it some dissolved salts. Also
one of the errors that would have occurred is the during the dissolvation of the borax salt. Some
of the salt may not have completely dissolved.

RECOMMENDATIONS

Since the borax salt to be dissolved depends on the percentages of the NaOH and hydrogen
peroxides prepared, so that the number molecules to be obtained for each molecule to be
dissolved and recrystallized, it would be recommended to either introduce a way of completely
dissolving the salt with less time consuming method. Temperature could also be an implicating
variable. Also the other recommendation is that students should be properly be

CONCLUSION

Sodium peroxoborate hexahydrate was prepared from sodium tetraborate decahydarete. This
was further proved by the qualitative tests which were done on the product salt. The percentage
yield of the salt was 82.8% which is a fair amount taking into consideration the sources of
error.

REFERENCES

1. Atkins, P., & Overtin, T. (2010). Inorganic Chemistry (5th ed.). Oxford: Oxford
University Press.

2. Greenwood, N. N., & Earnshaw, A. (1997). Chemistry of the Elements, 2nd ed.,
Butterworth-Heinemann, Oxford, UK.

3. Housecroft C.E and Sharpe A.G., Inorganic Chemistry, 4th edition, Pearson Education
Limited, Essex, 2012, p211

4. Sosis P and Zoller U, Handbook of detergents, Part F: Production, 1st edition, CRC
Press, Boca Raton, 2009, p427

5. Wulfsberg, G. (1992). Principles of Descriptive Inorganic Chemistry. Chicago:

University Science Books.