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ANALYSIS OF ANIONS

Reference:
Petrucci, General Chemistry with qualitative analysis,
Holtzelaw, HE; Robinson, WR; Odom, JD. 1991.
General Chemistry with Qualitative Analysis, 9
th
Ed. DC
Heath and Co. Lexington.
Anion groups of
qualitative analysis
Group number Group reagent
1
(Volatile acid)
Dilute H
2
SO
4
2
(Barium group)
Alkaline Ba(NO
3
)
2
and Ca(NO
3
)
2
3
(Silver group)
Acidic AgNO
3
4
(Soluble group)
-
Anion Groups
Group number Anions
1
(Volatile acid)
CO
3
2-
, S
2-
,SO
3
2-
,S
2
O
3
2-
,NO
2
-
2
(Barium group)
SO
4
2-
,CrO
4
2-
, PO
4
3-
,C
2
O
4
2
, BO
2
-
3
(Silver group)
I
-
, SCN
-
, Br-, Cl
-
4
(Soluble group)
NO
3
-
,C
2
H
3
O
2
-
Anion Groups
Group number Anions Product
1
(Volatile acid)
CO
3
2-
, S
2-
,SO
3
2-
,S
2
O
3
2-
,NO
2
-
Agas (if the sample is
treated with H
2
SO
4
)
2
(Barium group)
SO
4
2-
,CrO
4
2-
, PO
4
3-
,C
2
O
4
2
,
BO
2
-
Precipitates when
Ba(NO
3
)
2
, and
Ca(NO
3
)
2
are added to
an amoniacal solution
3
(Silver group)
I
-
, SCN
-
, Br-, Cl
-
Precipitates in dilutes
nitric acid with added
AgNO
3
4
(Soluble group)
NO
3
-
,C
2
H
3
O
2
-
No general test for the
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
Ba
2+
+ SO
4
2-
---- BaSO
4 (white)
(will not disslove in strong acid)
Ba
2+
+ CrO
4
2-
---- BaCrO
4 (yellow)
(in strong acid to produce an orange
solution ----- dichromate ion)
3Ba
2+
+ 2PO
4
3-
---- Ba
3
(PO
4
)
2 (white)
Ca
2+
+ C
2
O
4
2-
---- CaC
2
O
4 (white)
Ba
2+
+ 2BO
2
-
---- Ba(BO
2
)
2 (white)
The confirmation test for the
anions of Barium Groups are
summerized in scheme 33-5
(844) (Book 1)
Identification of SO
4
2-
Based on the precipitation of barium
sulfate, which only very slightly soluble in
acid
BaSO
4
+ H
+
---- Ba
2+
+ HSO
4
-
+ H
2
O
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
HPO
4
2-
+ NH
4
+
+ MoO
4
2-
+ H
+

(NH
4
)
3
(P(Mo
3
O
10
)
4
+ H
2
O
Identification of Oxalate ion
Oxalate :
strong diprotic acid,
successive ionizations
moderately strong reducing agent
Identification :
with permanganate ion in solution acid
H
2
C
2
O
4
+ MnO
4
-
+ H
+
CO
2
+ Mn
2+
+ H
2
O
Other reducing ions :
SO
3
2-
, S
2
O
3
2-
, S
2-
, NO
2
-
, I
-
, SCN
-
,
Br
-
, and Cl
-
---- will interfere with this reaction
Identification of Borate Ion
Boric acid, boron trioxide (B
2
O
3
) contain tetraborate ion (B
4
O
7
2-
),
metaborate ion (BO
2
-
), or orthoboric acid (H
3
BO
3
);
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) :
H
3
BO
3
+ CH
3
OH + H
+
B(OCH
3
) + H
2
O
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
-
+ HNO
2
+ H
+
---- I
2
+ 2NO + H
2
O
Iodine is extracted and concentrated by CCl
4
I
2
I
2
(CCl
4
)
alternatively : iodine produced can be detected by the reaction of
iodine with strach to produce a deep blue adsorption complex.
I
2
+ starch I
2
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
CO
3
2-
SO
3
2_
S
2-
NO
2
-
NO
3
-
I
-
F
-
C
2
O
4
2-
SO
4
2-
PO
4
3-
BO
2
-
Cl
-
Br
-
MnCl
2
HCl
[MnCl
4
]
-,
formed by NO
2
-
or NO
3
-
(oxidizing anions)
brown or
black
FeCl
3
K
3
[Fe(CN)
6
]
HCl
KFe[Fe(CN)
6
].H
2
O, formed by S
2-
, SO
3
2-
, NO
2
-
, or I
-
(reducing
anions)
blue
CaCl
2
CH
3
CO
2
H
CaF
2
(white)
CaC
2
O
4
(white) formed by F
-
, or C
2
O
4
2-
(anions whose calcium salts are
Solution insoluble in CH
3
CO
2
H)
BaCl
2
CH
3
CO
2
H
BaSO
4
(white) , SO
4
2-
is the only anion
Solution remaining whose barium salt
is insoluble in CH
3
CO
2
H
H
2
SO
4
CO
2
(g)
SO
2
(g)
H
2
S (g)
NO
2
(g)
CO
3
2-
SO
3
2_
S
2-
NO
2
-
formed from (anions forming volatile acids or anhidrides)
BaCl
2
NH
3
+ H
2
O
Ba
3
(PO
4
)
2
(barium salt are
Ba(BO
2
)
2
insoluble in
aqueous ammonia)
H
2
SO
4
Pb(CH
3
CO
2
)
2
PbS, S
2-
is the only anion of
volatil acid that will form a black
lead salt
Co(NO
3
)
2
CH
3
CO
2
H
Co(Halida)
Solution
AgNO
3
HNO
3
AgCl (white) (Cl
-
, Br
-
, I
-
, are the only anions
AgBr (pale yellow) remaining whose silver salts
AgI (yellow) are insoluble in acid solution)
Elimination of Anions that
Form Volatile Acid Anhydrides
The anions CO
3
2-
, SO
3
2-
, S
2-
, and NO
3
-
are derived from weak acids H
2
CO
3
,
H
2
SO
3
, H
2
S, and HNO
2
, respectively.
As acids in solution, H
2
CO
3
, H
2
SO
3
, and HNO
2
are unstable and
decompose, producing gas. H
2
S does not decompose but has a limited
solubility in water.
The equilibrium are:
CO
3
2-
+ H
+
= HCO
3
-
HCO
3
-
+ H
+
= H
2
CO
3
H
2
CO
3
= H
2
O + CO
2(g)
SO
3
2-
+ H
+
= HSO
3
-
HSO
3
-
+ H
+
= H
2
SO
3
H
2
SO
3
= H
2
O + SO
2(g)
S
2-
+ H
+
= HS
-
HS
-
+ H
+
= H
2
S
(g)
NO
2
-
+ H = HNO
2
3HNO
2
= H
+
+ NO
3
-
+ 2NO
(g)
+ H
2
O
2NO + O
2
= 2NO
2(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)
3Fe
2+
+ NO
3
-
+ 4H
+
3Fe
3+
+ NO + H
2
O
Fe
2+
+ NO [Fe(NO)]
2+
Identification of Nitrite
Identification of Fluoride
NaF + H
2
SO
4
Na
2
SO
4
+ 2HF
SiO
2
+ 4HF SiF
4
+ 2H
2
O
3SiF
4
+ 4H
2
O H
4
SiO
4
+ 4H
+
+ 2[SiF
6
]
2-
Identification of Metaborate
(nyala api warna hijau)
BO
2
-
+ H
+
+ H
2
O = H
3
BO
3
H
3
BO
3
+ 3CH
3
OH = B(OCH
3
)
3
+ 3H
2
O
B(OCH
3
)
3
+ 9O
2
= B
2
O
3
+ 6CO
2
+ 9H
2
O
Identification of Iodide,
Bromide and Chloride
KMnO
4
+ H
2
SO
4
+ CHCl
3
I
-
,
Br
-
, Cl
-
MnO
4
----- Mn
2+
I
- --------
I
2
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