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Calcium Fluoride scale
4

Calcium Fluoride scale

Calcium Fluoride scale

(OP)
We are trying to dissolve calcium fluoride scale in a pvc pipeline with hydrochloric acid and it is a very slow process.  We have been told that boric acid added to the hydrochloric solution will speed up the process.  Can anyone tell us if this is true, and if so, why?  Why is the hydrochloric so slow?
Muth
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RE: Calcium Fluoride scale

3
The reaction with of CaF2 with HCl is slow because the free energy of the displacement reaction is  +, so the equilibrium constant is small. Using DF25oC values from Perry’s, 6th Edn.,

CaF2 + HCl(aq) = CaCl2(aq) + HF(aq)

DFRxn = -195.36 –73.7(approx.) + 260.1(approx.) + 31.33 kcal/mol
           =  +22.37 kcal/mol

The addition of boric acid drives the reaction to the right by Le Chatelier’s Principle.  The boric acid reacts with and thereby removes the HF product.  Either the reaction
HBO2 + 3 HF = BF3 + 2 H2O

or the formation of fluoboric acid HBF4 are possible, but the thermodynamic data aren't in Perry’s so I won’t predict which is more likely.

RE: Calcium Fluoride scale

To add a bit of information to the excellent explanation by Kenvlach: HCl is used because the line is of pvc make. Altough HCl is a stronger commercial acid than sulfuric as measured by its pKa, the industrial common way to produce HF is to treat fluorspar (calcium fluoride aka fluorite) with sulfuric acid obtaining gypsum as by-product. Not applicable in this case.

The fluorine anion in fluorite holds strongly to its calcium cation. Thus the reaction is slow. Besides, the solubility product of fluorite in water at 25oC is very low, in the order of 3.5 x 10-11.

Released HF is captured by combining with boric acid B(OH)3, to form F3B a gas that complexes swiftly to [BF4]- in solutions containing F-. F3B is toxic TLV: 0.3 ppm. I assume that F3B may react with water to form other products.

Released HF can also be reacted with alumina trihydrate to produce solid F3Al, with a solubility of 4.1 g/L water.

RE: Calcium Fluoride scale

As a matter of record HBO2 is metaboric acid.
Boric acid is B(OH)3.

RE: Calcium Fluoride scale

Using IUPAC conventions, boric acid is H3BO3

RE: Calcium Fluoride scale

Old chemistry books speak of hydrates of boron oxide B2O3 (aka boric anhydride) with various molecules of water. With 3 H2O we get orthoboric H3BO3. When heated, boric acid losses water becoming metaboric acid BO2H = B2O3.H2O.

Boric acid is essentially monomeric when highly diluted, but in solutions above 0.1 M may form polymeric species. The tetrahydroxyborate anion B(OH)4- is the conjugate base of boric acid. Together they act as pH buffer.

RE: Calcium Fluoride scale


Out of curiosity, how do you get floride deposition.

All of the waterlines I've worked with produces Ca/Mg sulfate type deposits. Floride solubility (in most water systems) is so low that it is never a problem to begin with.

RE: Calcium Fluoride scale

Semiconductor/chip manufacturers like Intel, AMD, Micron, IBM, Motorola, etc. use HF to clean the silicon substrates (it's the only acid that dissolves SiO2.  I once did some consulting where such a firm had a problem meeting F- effluent limit; the local POTW recycles water and had strict limits. Had them use lime Ca(OH)2 to precipitate it as CaF2.

RE: Calcium Fluoride scale

Kev~,

No problem with that, it is just that the solubility of CaF2 in water (as orig. stated) is so low as to beg the question of having to remove it.





RE: Calcium Fluoride scale

The semiconductor people rinse off the HF etchant with lots of high purity DI water. It's the fluoride that needs removal, ergo adding Ca to form CaF2.

RE: Calcium Fluoride scale




Kenvlach,

understand the usage of HF in the front-end.

the CaF2 deposition in the pipe strikes me as a matter of modifying the waste treatment process to better control the crytallization process. there has got to be a better way than re-creating soluable F-.


RE: Calcium Fluoride scale

muth,
can you enlighten us as to the source of the CaF2? If there was a substantial amount, it may be easier to just replace the PVC pipe.

hacksaw,
for the wastewater treatment case I mentioned, the CaF2 was created in a neutralization tank & removed (along with a few heavy metals) by filter pressing.

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