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THE USE OF VANADIUM OXIDE IN NAVAS´ QUANT FUSION PROCESS

Vanadium has an unusually large number of stable oxidation states (+2, +3, +4,
+5) each of which is characterized by a unique color in solution. Vanadium
oxide is a yellow to red crystalline powder. Decomposition of Vanadium oxide
occurs at 1750 C.

In NAVAS INSTRUMENTS we use vanadium (V) oxide as an oxidizing catalyst,


converting between the various vanadium oxidation states.

Vanadium oxide exhibits poor thermal stability and mechanical strength. The
catalytic oxidation properties of vanadia can be improved by depositing on an
appropriate support, such as alumina, silica, titania, zirconia, etc. The activity
and selectivity of supported metal oxide catalysts are significantly affected by
the properties of the support oxide material, which is generally known as the
metal oxide-support effect. Supported vanadium oxides show chemical and
electronic properties, which are entirely different from those found for
unsupported vanadium pentoxide (V2O5), in aqueous media and in the solid
state.

Upon heating, it reversibly loses oxygen, successively forming V2O4, V2O3, VO,
and metallic vanadium. At normal temperature and pressure, vanadium oxide is
thermodynamically most stable among the oxides of vanadium. Equilibration of
gas phase oxygen with vanadium oxides results in the formation of the intrinsic
defect structure of V2O5 consisting of oxygen vacancies. Vanadium oxide is a
well-established catalyst for the partial oxidation of hydrocarbons to oxygenated
products.

The electron configuration of V is [Ar] 3d3 4s2 and the main oxidation states are
+2, +3, +4 and +5. V5+ (d0) can be present in tetrahedral (VO4), pentahedral
(VO5) and octahedral (VO6) coordination environment and tends to form
polyoxoanions. V4+ (d1) is also stable and is mostly present in square pyramidal
or pseudo-octahedral coordination as an isolated cation. Other oxidation states
such as V3+ (d2) and V2+ (d3) are less stable and only present under reducing
conditions. The melting point of vanadium is 1915 C and boiling point is 3350 C.

Being a d-transition metal, vanadium has different oxidation states capable of


existing in both single as well as mixed valence state on forming oxides. The
vanadium oxides such as VO, V2O3, VO2 and V2O5 exist in a single oxidation
state whereas many others, for instance: V3O5, V4O7, V6O11, V6O13, V7O13,
V8O15 etc., remain in mixed valence state.

V5+ and V4+ are the most important oxidation states in aqueous solution. The
nature of vanadium oxide species present in solution depends on the pH and
the vanadium oxide concentration of that solution.

Oxidizers generally supply all or most of the oxygen present in the system. For
example, strontium and barium or lithium nitrates are easy to obtain in the
anhydrous state and are good oxidizers. Alkali metal nitrates, chlorates and
perchlorates are other useful oxidizers when combined at a high-temperature.
But out of all possible oxidizing agents, NAVAS INSTRUMENTS has found the
vanadium oxide to be the best one when working with ferro alloys, other hard
reducing ore concentrates or mixed polymeric substances, mainly because it
can coexist in various oxidation states. All technically interesting reactions
carried out with vanadium oxide catalysts are marked by their highly exothermic
character.

Here are some examples:

Using, for example, a sample of Zinc as the reducing agent

Let's look at the first stage of the reduction - from VO2+ to VO2+. The redox
potential for the vanadium half-reaction is given by:

The corresponding equilibrium for the Zinc is:

The simple principle is that if we couple two of these half-reactions together, the
one with the more positive E° value will move to the right; the one with the more
negative (or less positive) E° moves to the left. If we mix together zinc and
VO2+ ions in the presence of acid to provide the H+ ions:

That converts the two equilibria into two one-way reactions.


Here are the E° values for all the steps of the reduction from vanadium(V) to
vanadium(II):

and here is the Zinc value:

We have to remember that for the vanadium reactions to move to the right
(which is what we want), their E° values must be more positive than whatever
you are reacting them with. In other words, for the reactions to work, zinc must
always have the more negative value - and that's the case. Zinc can reduce the
vanadium through each of these steps to give the vanadium(II) ion.

Also we can suppose to replace Zinc as the reducing agent by Tin. How far
would the set of reductions go this time?

Here are the E° values:

and here is the Tin value:


For each reduction to happen, the vanadium reaction has to have the more
positive E° value because we want it to go to the right. That means that the Tin
must have the more negative value.

 In the first vanadium equation (from +5 to +4), the Tin value is more
negative. That works OK.
 In the second vanadium equation (from +4 to +3), the Tin value is again
the more negative. That works as well.
 In the final vanadium reaction (from +3 to +2), Tin no longer has the
more negative E° value. Only in this case Tin won't reduce vanadium(III)
to vanadium(II).

Scientific background

 Vanadium is the only element that may be in four different oxidation


states, all of which are stable in aqueous solutions.
 Solution becomes yellow due to the presence of ions VO2+.
 Sulfite anion is a weak reducing agent that can restore V (V) to a V (IV),
giving a solution of a blue color. A stronger reducing agent is Tin. It can
restore to V (III), giving a solution of a green color.
 Finally, most of the strong reductants, step by step restores V (V) to V
(II), giving a violet solution.

IMPROVED QUANTITATIVE FUSION – PREPARATION OF BEADS USING


VANADIUM OXIDE AS THE OXIDIZING AGENT (NAVAS INSTRUMENTS)

0. Close the door of the empty balance, and press tare.

1. Operator will place a clean ceramic crucible (#1) inside the balance. Press
enter.

2. Operator will place a clean moldable inside the balance. Press enter.

3. Operator will distribute 3.5 grams of flux into moldable and 2.5 grams of flux
into the ceramic crucible (#1); close the balance door. Press enter.

4. Operator will remove both the moldable and crucible #1 from the balance,
and set them apart.

5. For additional samples to be processed, operator must repeat steps 1-4.

6. Operator will place the moldable(s) in the autoloader. Then press enter. The
pre-fusion process will start (1000 C for 5 minutes with 5 l/min of air flow) to
create a bed of fused flux in the moldable.

7. Operator will place a new clean ceramic crucible (#2) in the balance. Then
weight (tare). Press enter.
8. Operator will transfer the sample (0.3 grams) to crucible #2 using a clean
spatula. Press enter.

9. Operator will add the oxidizing agent (approximately 0.6 grams of Vanadium
Oxide) to crucible #2; then weight. Press enter.

10. Operator will mix roughly the mixture (sample + oxidizing agent) with a clean
spatula.

11. For additional samples to be processed, operator must repeat steps 7-10.

12. Once the preparation step for pre-fusion is completed (1000 C / 5 minutes)
the moldables will automatically come out of the furnace for cooling. A bed of
fused flux in moldable will then be noticeable.

13. Operator will add the whole mixture (sample + oxidant in crucible #2) into
the moldable (the mixture must be distributed precisely all around the inside of
the moldable so that the oxidizing process is executed correctly); then place the
moldable in the balance and weight. Then press enter.

14. Operator will add the remaining amount of flux (preserved in crucible #1)
into the moldable (the flux must be scattered properly on top covering all the
area). Then press enter.

15. Operator will use a small piece of clean paper (cellulose) with a little amount
of alcohol to clean the inside of both ceramic crucible (#1 y #2) and the spatula
(or spatulas) used previously. Ensure the cleaning is done correctly by bending
the paper and proceed again; then place the washing paper on top of the
moldable.

16. Place the moldable in the autoloader; then light the paper on fire.

17. Repeat steps 13 to 16 for each additional samples.

18. The samples are fused at 1050 C for 60 minutes with 5 l/min of air flow (with
agitation and mixing inside the furnace). The Fusion process is controlled
automatically by Navas software.

19. A small amount of Lithium Bromide (6 to 10 mg, depending on the


constituent) will be added just before the completion of the Fusion time to assist
in the bead release from the moldable once the Fusion process is finished.

20. Finally the beads will come out from the automatic loader for cooling.

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