ANALYSIS OF ANIONS

Reference:
Petrucci, General Chemistry with qualitative analysis,

Holtzelaw, HE; Robinson, WR; Odom, JD. 1991.

General Chemistry with Qualitative Analysis, 9th Ed. DC
Heath and Co. Lexington.
 Anion groups of
qualitative analysis
Group number Group reagent

1 Dilute H2SO4
(Volatile acid)
2 Alkaline Ba(NO3)2
(Barium group) and Ca(NO3)2
3 Acidic AgNO3
(Silver group)
4 -
(Soluble group)
 Anion Groups
Group number Anions

1 CO32-, S2-,SO32-,S2O32-,NO2-
(Volatile acid)
2 SO42-,CrO42-, PO43-,C2O42, BO2-
(Barium group)
3 I-, SCN-, Br-, Cl-
(Silver group)
4 NO3-,C2H3O2-
(Soluble group)
 Anion Groups
Group number Anions Product
1 CO32-, S2-,SO32-,S2O32- A gas (if the sample is
(Volatile acid) ,NO2- treated with H2SO4)
2 SO42-,CrO42-, PO43-,C2O42, Precipitates when
(Barium group) BO2- Ba(NO3)2, and
Ca(NO3)2 are added to
an amoniacal solution
3 I-, SCN-, Br-, Cl- Precipitates in dilutes
(Silver group) nitric acid with added
AgNO3
4 NO3-,C2H3O2- No general test for the
(Soluble group) anions
 Detection of Anion Group I
Anion Group I are weak acid, volatile or
decompose into volatile oxides
Cyanida ion also is a member (poisonous).
 Detection of Anion Group II

Ba2+ + SO42- ---- BaSO4 (white)

(will not disslove in strong acid)

Ba2+ + CrO42- ---- BaCrO4 (yellow)

(in strong acid to produce an orange
solution ----- dichromate ion)

3Ba2+ + 2PO43- ---- Ba3(PO4)2 (white)

Ca2+ + C2O42- ---- CaC2O4 (white)
Ba2+ + 2BO2- ---- Ba(BO2)2 (white)
The confirmation test for the
anions of Barium Groups are
summerized in scheme 33-5
(844) (Book 1)
 Identification of SO42-
Based on the precipitation of barium
sulfate, which only very slightly soluble in
acid
BaSO4 + H+ ---- Ba2+ + HSO4- + H2O
K= 1,1 x 10-8
 Identification of chromate ion
Based on the precipitation of yellow
barium chromate.
Ba-chromate dissolve in acid to yield
yellow dichromate
 Identification of Phosphate ion
Based on the precipitation of bright yellow
amonium molibdophosphate, when
amonium molybdate is added to an acidic
solution
HPO42- + NH4+ + MoO42- + H+
(NH4)3(P(Mo3O10)4 + H2O
 Identification of Oxalate ion
Oxalate :
strong diprotic acid,
successive ionizations
moderately strong reducing agent
Identification :
with permanganate ion in solution acid
H2C2O4 + MnO4- + H+ CO2 + Mn2+ + H2O
Other reducing ions : SO 2-, S O 2-, S2-, NO -, I-, SCN-,
3 2 3 2
- -
Br , and Cl ---- will interfere with this reaction
 Identification of Borate Ion
Boric acid, boron trioxide (B2O3) contain tetraborate ion (B4O72-),
metaborate ion (BO2-), or orthoboric acid (H3BO3);

How is the characteristic of them?

Based on a yellow-green flame test

When methanol added to boric acid in the presence of concentrated

sulfuric acid, produce trimethyl borate (volatile) :

H3BO3 + CH3OH + H+ B(OCH3) + H2O

What is the function of concentrated sulfuric acid?

 Identification of Silver group
- - -
(Cl , Br , I )
Silver nitrate is added to precipitate the halides as
AgCl (white), AgBr (pale yellow), and AgI (yellow)
 Identification of iodide ion :

I- + HNO2 + H+ ---- I2 + 2NO + H2O

Iodine is extracted and concentrated by CCl4

I2 I2 (CCl4)

alternatively : iodine produced can be detected by the reaction of

iodine with strach to produce a deep blue adsorption complex.

I2 + starch I2 strach complex

 Identification of Thiocyanate ion

Based on the formation of blood-red

complex (Fe(SCN)2+
 THE ANALYSIS
OF ANIONS
Introduction
The anions considered are carbonate, sulfide, sulfite,
nitrite, sulfate, nitrate, phosphate, metaborate,
oxalate, fluoride, chloride, bromide, and iodide.
Among the anion were covered by analytical
scheme for cation are arsenite, arsenate, stannite,
stannate, permanganate, aluminat, chromate, and
zincate.
Preliminary Elimination Test for the Anions
See next page
 ANION ELIMINATION FLOW SHEET
CO2 (g) CO32-
H2SO4
SO2 (g) formed from SO32_ (anions forming volatile acids or anhidrides)
H2S (g) S2-
NO2 (g) NO2-

MnCl2 [MnCl4]-, formed by NO2- or NO3- (oxidizing anions)

CO32- brown or
HCl
SO32_ black
S2- FeCl3 KFe[Fe(CN)6].H2O, formed by S2-, SO32-, NO2-, or I- (reducing
NO2- K3[Fe(CN)6] anions)
NO3- HCl blue
I- CaF2 (white)
CaCl2 CaC2O4 (white) formed by F-, or C2O42- (anions whose calcium salts are
F-
CH3CO2H Solution insoluble in CH3CO2H)
C2O42-
SO42- BaCl2 BaSO4 (white) , SO42- is the only anion
PO43- CH3CO2H Solution remaining whose barium salt
BO2-
is insoluble in CH3CO2H
Cl-
Br- BaCl2 Ba3(PO4)2 (barium salt are
H2SO4 2-
PbS, S is the only anion of NH3 + H2O Ba(BO2)2 insoluble in
Pb(CH3CO2)2 volatil acid that will form a black
aqueous ammonia)
lead salt
AgCl (white) (Cl-, Br-, I-, are the only anions
Co(NO3)2 Co(Halida) AgNO 3 AgBr (pale yellow) remaining whose silver salts
CH3CO2H Solution HNO 3 AgI (yellow) are insoluble in acid solution)
 Elimination of Anions that
Form Volatile Acid Anhydrides
The anions CO32-, SO32-, S2-, and NO3- are derived from weak acids H2CO3,
H2SO3, H2S, and HNO2, respectively.
As acids in solution, H2CO3, H2SO3, and HNO2 are unstable and
decompose, producing gas. H2S does not decompose but has a limited
solubility in water.
The equilibrium are:
CO32- + H+ = HCO3-
HCO3- + H+ = H2CO3
H2CO3 = H2O + CO2(g)
SO32- + H+ = HSO3-
HSO3- + H+ = H2SO3
H2SO3 = H2O + SO2(g)
S2- + H+ = HS-
HS- + H+ = H2S(g)
NO2- + H = HNO2
3HNO2 = H+ + NO3- + 2NO(g) + H2O
2NO + O2 = 2NO2(g)
Elimination of Chloride,
Bromide, and Iodide
Silver nitrate is added to precipitate the halides as
AgCl (white), AgBr (pale yellow), and AgI (yellow)
 Identification of Nitrate (terbentuk
cincin coklat)

3Fe2+ + NO3- + 4H+ 3Fe3+ + NO + H2O

Fe2+ + NO [Fe(NO)]2+
Identification of Nitrite
 Identification of Fluoride

NaF + H2SO4 Na2SO4 + 2HF

SiO2 + 4HF SiF4 + 2H2O
3SiF4 + 4H2O H4SiO4 + 4H+ + 2[SiF6]2-
 Identification of Metaborate
(nyala api warna hijau)
BO2- + H+ + H2O = H3BO3
H3BO3 + 3CH3OH = B(OCH3)3 + 3H2O
B(OCH3)3 + 9O2 = B2O3 + 6CO2 + 9H2O
Identification of Iodide,
Bromide and Chloride
 KMnO4 + H2SO4 + CHCl3

I-, Br-, Cl-

MnO
4 ----- Mn 2+

I- -------- I2 dengan
amilum membentuk kompleks
berwarna biru