c
 c c


Anions are negatively charged ions produced by the ionization of acids and salts.

In 1878, Bunsen divided the ³acid radicals´ into related groups for the purpose of identification.

a



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The solution being analyzed is kept slightly basic to prevent or minimize the interaction of
oxidizing and reducing anions. It identifies 21 commonly occurring anions.

Groups Description
Anions whose Calcium salts are insoluble in neutral or slightly basic
I
solution.
Anions whose Calcium salts are soluble but whose Barium salts are
II
insoluble in slightly basic solution.
Anions whose Calcium and Barium salts are soluble but whose Cadmium
III
salts are insoluble in slightly basic solution.
Anions whose Calcium, Barium and Cadmium salts are soluble but whose
IV
Silver salts are insoluble in a solution slightly acid with nitric acid.
Anions whose Calcium, Barium, Cadmium, and Silver salts are soluble in
V
water and acids.

In precipitating the insoluble anion groups, the acetates of Ca, Ba, Cd and Ag are used.

The presence of cations other than Na+, K+ or NH4+ may interfere with the anion analysis. These
cations are removed by adding an excess of sodium carbonate solution.

unwanted cations + Na2CO3 insoluble carbonates + basic carbonates + hydroxides

The prepared solution will contain an excess of carbonate ions.

Advantage: CO32- maintains alkalinity sufficient to prevent unwanted redox reactions
Disadvantage: CO32- causes precipitation in Group I (of CaCO3)

Π
c
 


  Anions whose Calcium salts are insoluble in neutral or slightly basic solution.
   Calcium acetate solution

Ô  

 

3 F HCl + H2O + KClO3 + original sample - - - - vigorous effervescence

*** KClO3 oxidizes the sulfite, sulfide, and thiosulfate ions, in an acid solution, to the sulfate ion
or free sulfur.

 
 



 

sample + 1.5 F Na2CO3 - - - - centrifugate + ppt (discard)

  
     

centrifugate of sample + 2 F Ca(Ac)2 - - - - C [anions of G II-V] + R [insoluble calcium salts]

p

       p  

R + 3 F HAc - - - - C [G IIA: SO32-, AsO2-, AsO43-, PO43-] + R [G IIB: CaC2O4, CaF2]

 
     

1st portion (SO32-): C + conct HCl + Ba(Ac)2 - - - - C + R [discard]

C + H2O2 - - - - white ppt [BaSO4]
*** H2O2 oxidizes the sulfite ion to the sulfate.

2nd portion (AsO2-): C + 3 F HCl + H2O + heat + thioacetamide - - - - yellow ppt [As2S3]
*** Yellow ppt formed after 60 sec or more confirms presence of AsO43-.

3rd portion (AsO43-): C + 3 F HCl + heat + KI - - - - brown solution

C + 3 F HCl + heat + KI + CCl4 - - - - pink color in CCl4 layer

4th portion (PO43-): C + conctd HNO3 + tartaric acid + (NH4)2MoO4 + heat - - - - yellow ppt
[(NH4)3PO4‡12MoO3 or ammonium phosphomolybdate]
*** Excess tartaric acid, in strongly acid sol¶n, forms complex with arsenic.
*** White ppt may form due to decomposition of (NH4)2MoO4 (disregard).

 
     


1st portion (C2O42-): R [CaC2O4, CaF2] + 1 F H2SO4 + heat + KMnO4 - - - - disappearance of
pink color

2nd portion (F-): R [CaC2O4, CaF2] + heat (until dry) + conctd H2SO4 - - - - glass etch

*** Water interferes with the etching test for fluoride ion by forming
insoluble salicic acid with volatile silicon tetrafluoride
*** Conctd H2SO4 reacts with CaF2 to form HF.
*** HF etches glass by producing gaseous SiF4.

 c 

    

2-
CO3 HCl (decomposing) effervescence
2- H2O2 (oxidizing)
SO3 white ppt of BaSO4
Ba(Ac)2 (ppting)
-
AsO2 Thioacetamide (ppting) yellow ppt of As2S3
AsO43- Iodine ion (reducing) brown solution due to liberation of iodine when oxidized
PO43- (NH4)2MoO4 (ppting) yellow ppt of (NH4)3PO4‡12MoO3
H2SO4 (forming) disappearance of pink color due to the reduction of
C2O42-
oxalic acid (reducing) permanganate ions to manganous ions
- H2SO4 (liberating)
F glass etch
HF (etching)
Π

c
 


  Anions whose Calcium salts are soluble but whose Barium salts are insoluble in
slightly basic solution.
   Barium acetate

 
     

C [anions of G II-V] + 1 F Ba(Ac)2 - - - - C [anions of G III-V] + R [BaSO4, BaCrO4]

p

 
 
    

R [BaSO4, BaCrO4] + 3 F HCl - - - - C [CrO42-] + R [BaSO4]

C [CrO42-] + 2.5 F NaAc - - - - yellow ppt [BaCrO4]

*** NaAc buffers the H3O+ concentration of the solution sufficiently to permit pption of BaCrO4.

R [BaSO4] + 3 F HCl - - - - white ppt [BaSO4]

 c 

    

CrO42- NaAc (buffering, ppting) yellow ppt of BaCrO4
SO42- Ba(Ac)2 (ppting) white ppt of BaSO4

Π


c
 


  Anions whose Calcium and Barium salts are soluble but whose Cadmium salts
are insoluble in slightly basic solution.
   Cadmium acetate

The sulfide and ferricyanide ions cannot exist together in solution. The ferricyanide will oxidize
the sulfide ion to free sulfur, being reduced to the ferrocyanide in the course of the reaction.

 
    

C [anions of G III-V] + 1 F Cd(Ac)2 - - - - C [anions of G IV-V] +

P { CdS, Cd2Fe(CN)6, Cd3[Fe(CN)6]2 }

*** Cadmium hydroxide may precipitate since solution is slightly alkaline.

*** Color of ppt - - - - - sulfide: bright yellow
ferrocyanide: pale yellow (almost white)
ferricyanide: orange





 
    

P { CdS, Cd2Fe(CN)6, Cd3[Fe(CN)6]2 } + wash ....

*** The ppt is washed to remove any contamination of thiocyanate ion. This ion will interfere with
the test for the ferrocyanide.

1st portion ( S2- ): P + 3 F HCl + 0.5 F Pb(Ac)2 on filter paper - - - - brown / black coloration
caused by formation of PbS

2nd portion ( Fe(CN)64- ) P + 3 F HCl + 1 F FeCl3 - - - - dark blue ppt Fe4[Fe(CN)6]3

(Prussian blue)

*** If the sol¶n is made too acid, the identifying blue ppt may not be obtained, because of its
solubility in HCl.

3rd portion ( Fe(CN)63- ) P + 3 F HCl + water + FeSO4 - - - - dark blue ppt Fe3[Fe(CN)6]3
(Turnbull¶s blue)

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S2- Pb(Ac)2 (forming) brown / black coloration on test paper
Fe(CN)64- FeCl3 (ppting) dark blue ppt Fe4[Fe(CN)6]3 (Prussian blue)
Fe(CN)63- FeSO4 (ppting) dark blue ppt Fe3[Fe(CN)6]3 (Turnbull¶s blue)

Π

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  Anions whose Calcium, Barium and Cadmium salts are soluble but whose Silver
salts are insoluble in a solution slightly acid with nitric acid.
   Silver acetate

 
    
 

C [anions of G IV-V] + AgAc + 3F HNO3 - - - - ppt changes color from white, yellow, orange,
brown to black

*** The solution must be acid.

*** Ag2S2O3 is unstable in acid solution and undergoes a series if color changes.
*** Ag2S2O3 is a white ppt when first formed. It undergoes hydrolysis to black Ag2S.

 
    

C [anions of G IV-V] + sat AgAc + HAc - - - - C [anions of GV] +

P [Ag2S, AgCl, AgCNS, AgI, AgBr]

*** Color of ppt - - - - - black ppt: Ag2S cream: AgBr

white ppt: AgCl or AgCNS yellow: AgI
p

 
 
     

P [Ag2S, AgCl, AgCNS, AgI, AgBr] + wash (water + 3F HNO3) until no ppt with HCl
+ wash (water)
+ ammoniacal AgNO3 - - - - C [Cl-] + R [Ag2S, AgCNS, AgI, AgBr]

*** Excess silver ions decrease the solubility of AgCl in ammoniacal AgNO3.

C [Cl-] + 3 F HNO3 - - - - white ppt AgCl

*** In the presence of excess Ag(NH3)2+ ions, AgI and AgBr are insoluble and AgCNS is only
slightly soluble in ammonia water.

R [Ag2S, AgCNS, AgI, AgBr] divide ....

small portion ( CNS- ) + 3 F HCl + FeCl3 - - - - red coloration caused by Fe(CNS)63-

large portion + water + excess 3 F HAc + zinc dust - - - - C [ I- and Br- ] + R [Ag and excess Zn]

*** Zinc reduces Ag+ in AgBr and AgI, depositing Ag and bringing Br- and I- into solution. CNS- is
destroyed in the solution.

R [Ag and excess Zn] discard...

C [ I- and Br- ] + CCl4 + NaNO2 + water - - - - violet color in CCl4 due to liberation of iodine

*** The nitrite ion, in an acid solution, oxidizes the iodide ion to free iodine.

C [ I- and Br- ] + conctd HNO3 + CCl4 + heat (< 20s) - - - - yellow/orange in CCl4 due to bromine

*** Conctd HNO3 oxidizes bromide ion to bromine.

 c 

    

AgAc with HNO3 white ppt Ag2S2O3 changes color through yellow,
S2O32-
(ppting) orange, brown to black Ag2S
Cl- HNO3 (ppting) white ppt AgCl
CNS- FeCl3 (complexing) red coloration caused by Fe(CNS)63-
I- NaNO2 (oxidizing) violet color in CCl4 due to liberation of iodine
Br- conctd HNO3 (oxidizing) yellow/orange in CCl4 due to bromine
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  Anions whose Calcium, Barium, Cadmium, and Silver salts are soluble in water
and acids.
  
  Water-soluble group. 

 
     

C [anions of GV] divide...

1st portion ( ClO3- ) C + conctd HNO3 + 0.5 F AgNO3 - - - - C¶ + R (discard)

C¶ + NaNO2 - - - - white ppt AgCl

2nd portion ( BO2- ) C + conctd H2SO4 + heat (to dryness) + carminic acid + heat (warm)
- - - - change of red color to bluish-violet

*** Hydoxyanthraquinones (alizarin dyes) - organic dyes

*** ClO3- and NO3- interfere with the test for borate .... destroyed by evaporation

3rd portion ( NO2- ) C + urea in HCl solution - - - - vigorous evolution of gas N2 and CO2

4th portion ( NO3- )

Test 1 C + conctd H2SO4 + Į-naphthylamine - - - - purple ring around reagent

*** Į-naphthylamine is oxidized by the NO3-, in sulfuric acid sol¶n.

Test 2 C + FeSO4 + conctd H2SO4 - - - - brown ring around crystal

*** Ferrous ions in high concentration of sulfuric acid reduce nitric acid to nitric oxide.
*** Nitric acid combines with excess ferrous ions to produce the unstable brown complex,
Fe(H2O)5NO2+
*** If nitrite ion is present, it must be removed by adding 1.5 F H2SO4 and 1 F (NH4)2SO4 sol¶n.

 c 

    

HNO2 (reducing)
ClO3- white ppt AgCl
AgNO3 (ppting)
carminic acid dissolved
BO2- change of red color to bluish-violet
in conctd H2SO4
NO2- urea in HCl solution vigorous evolution of gas N2 and CO2
Į-naphthylamine
NO3- purple ring around reagent
(reducing)
FeSO4 in conctd H2SO4
NO3- (reducing and brown ring around crystal
complexing)