INTERFERING ACID

RADICALS AND THEIR

ELIMINATION

BY
Meghna Manuel
Albin Antony
Prasanth
Doris Maria
 Interfering Acid Radicals

1. Oxalate
2. Tartrate
3. Fluoride
4. Borate
5. Phosphate
Why are they called Interfering Acid
Radicals?
• The salt of interfering radicals are soluble in acidic medium and become
insoluble in alkaline medium.
• As long as the analysis remains under the grip of acidic medium, they remain
soluble and get no chance to interfere.
• But, after the 2nd group, the solution is made alkaline.
• Group reagent for 3rd group : NH4Cl & NH4OH.
• This leads to incomplete precipitation of IIIrd group cations as hydroxides and
causes immature precipitation of IVth ,Vth , VIth group cations as oxalates ,
borates, fluorides , phosphates and tartrates.
• That’s why they are called as interfering acid radicals.
 Cause Of Interference :
• In acidic medium these salts produce their corresponding acids like oxalic acid,
phosphoric acid, hydrofluoric acid, boric acid and tartaric acid.

H3BO3 ⇌ 3H+ + BO33-

H2C2O4 ⇌ 2H+ + C2O42-
H3PO4 ⇌ 3H+ + PO43-
HF ⇌ H+ + F-
Acid medium HCl ⇌ H+ + Cl-
Thus H+ ions causes common ion effect . According to Le- Chatelier’s principle ,
equilibrium shifts in the backward direction to neutralize the effect of increase in
conc.
• Higher concentration of H+ suppresses the ionization of interfering acids.
• Ionic product < Solubility product. Hence no precipitation takes place.
• For example, barium oxalate reacts with HCl and produces oxalic acid.

• BaC2O4 + 2HCl ⟶ BaCl2 + H2C2O4

• H2C2O4 ⇌ 2H+ + C2O42-
• HCl ⟶ H+ + Cl-
• Hydrogen ions acts as common ion among them and higher concentration of H+ suppresses
the ionization of oxalic acid.
• Therefore, ionic product of C2O42- and Ba2+ doesn’t exceed the solubility product of barium
oxalate which is why Ba2+ remains in the solution as barium oxalate.
• Interfering radicals do not interfere as long as the medium remains acidic .
• By adding 3rd group reagent ammonium hydroxide NH4OH, the solution becomes
alkaline

• NH4OH ⇌ NH4+ + OH-

• H2C2O4 ⇌ 2H+ + C2O42-

• OH- ions combine with H+ and neutralize them to form water.

• This decreases the concentration of H+ ions which shifts the equilibrium of dissociation
of interfering acid forward and increases the concentration of C2O42- .

• Ionic product > Solubility product . Hence precipitation occurs.

• Thus the ionic product of C2O42- and Ba2+ exceeds the solubility product of barium
oxalate and Ba2+ gets precipitated in the 3rd group, which actually belongs to the
4th group.
 Elimination Of Interfering Acid
Radicals
• The interfering acid radicals interfere with the analysis of cations. Hence these

are to be eliminated before proceeding for the analysis of cations.

• Elimination of Oxalate.

• Oxalate is eliminated by dry ignition. The substance is heated in a broken china

dish with occasional stirring with glass rod till the whole mass chars. It is then

extracted with dil.HCl and centrifuged.

Elimination of fluoride

• A little of the substance is boiled with 2ml Conc.HCl in a china dish and

evaporated nearly to dryness. The process is repeated three to four times. The

fluoride volatilize as HF. The residue is extracted with water and centrifuged , the

centrifugate is used for analysis of the metal .