QUALITATIVE

ANALYSIS OF ANIONS
MIDTERM
Qualitative analysis

üdetermination of the presence or absence of a

particular chemical compound or element

üdetermines the amount of that compound present in a

sample
 INTRODUCTION TO ANION ANALYSIS
The purpose of this experiment is to determine what anions are present in an unknown sample.

Arsenate AsO43- Iodide I- Nitrate NO3-

Arsenite AsO2- Borate BO2- Bromide Br-

Carbonate CO3- Chlorate ClO3- Chloride Cl-

Chromate CrO4- Ferricyanide Fe(CN)6 3- Ferrocyanide Fe(CN)6 4-

Fluoride F- Nitrite NO 2 - Oxalate C2O4-

Phosphate PO4 3- Sulfate SO4- Sulfide S-

Sulfite SO3- Thiocyanate CNS - Thiosulfate S2O3-

 ANIONS
• negatively charged ions produced by the
ionization of acids and salts.
• ions are separated into groups based upon the
solubilities of the calcium, barium, cadmium,
and silver salts
 ANIONS GROUP
• GROUP 1 includes ions whose calcium salts are insoluble in slightly basic
solution.
• GROUP 2 includes ions whose calcium salts are soluble but whose barium
salts are insoluble in slightly basic solution.
• GROUP 3 is composed of anions whose calcium and barium salts are soluble
but whose cadmium salts are insoluble in slightly basic solution.
• GROUP 4 is composed of anions whose calcium, barium, and cadmium salts
are soluble but whose silver salts are insoluble in solution slightly acid with
nitric acid.
• GROUP 5 contains anions whose calcium, barium, cadmium, and silver salts
are soluble in water and acids.
GROUP 1 ANIONS
carbonate ion (CO3-)
sulfite ion (SO3-)
arsenite ion (AsO2-)
arsenate ion (AsO43-)
phosphate ion (PO4 3-)
oxalate ion (C2O4-)
fluoride ion (F-)
 PRE-LAB QUIZ
1. What is the positive indicator that carbonate ion is present?
2. What reagent used to confirm the presence of sulfite ions?
3. What solid reagent added in the solution to confirms the
presence of phosphate ions?
4. What type of glassware used to produce etching reaction?
5. What is the chemical name of Na2CO3?
 GROUP I ANIONS
• This group of anions forms insoluble salts of calcium in slightly basic
solution. The precipitating agent is calcium acetate ion.

• Why basic? Take for example CO3-2 + Ca2+ ↔ CaCO3

Addition of H+ (acid) gets rid of the CO3-2 forming H2CO3, meaning the
reaction will shift to the left forming more of CO3-2 ions.

If base is added, it will react with Ca2+, but since Ca(OH)2 is a strong
base, it will not precipitate. Thus amplify the formation of CaCO3.
 First procedure involves detection of carbonate ions.
• Carbonate ions should be analyzed first because carbonate
reagent is always use in the whole analysis of anions thus
creating false positive result.
• Dilute HCl decomposes carbonate ion and forms carbon
dioxide gas thus, the effervescence.
CaCO3 + H3O+↔ Ca2+ + CO2 + H2O
NOTES:
• Effervescence is the escape of gas from an aqueous
solution and the foaming or fizzing that results from
that release.
• PURPOSE: Carbonate ions remove the presence of
cations (Na+, K+, NH4+)
Second procedure involves removal of heavy metals
(common: Mercury, Lead, Chromium, Zinc and Copper)

• Sodium carbonate p re c i p i tate s t h e m i n t h e i r

carbonate and hydroxide salts with Ksp ranging from x
10-14 to 10-20. This can be separated from calcium salts
since calcium salts have solubility of 10-9 or less.
Precipitation of Group I anion
Calcium Acetate
PROCEDURE 3:
• Separation of Group I anions into subgroups.
• Addition of Acetic acid dissolves all calcium salts except CaF2
and CaC2O4.
• NOTE:
add more than 15 drops of acetic acid as long as the
precipitate appears to dissolve
 PROCEDURE 4A: TEST FOR CENTRIFUGATE
Identification of Sulfite ions (SO3-2)
• confirmatory reagent:
Hydrogen peroxide (H2O2)
• positive indicator:
white precipitate
• chemical reaction:
H2SO3 +H2O2 + H2O ↔ SO4- + 2H3O+
SO4- + Ba++ ↔ BaSO4

First is oxidation to sulphate (SO4-2) by hydrogen peroxide. Then sulfate is insoluble as BaSO4, thus the
white precipitate.
 PROCEDURE 4B: TEST FOR CENTRIFUGATE
Identification of Arsenite ions (AsO2-3)
• confirmatory reagent:
thioacetamide (C2H5NS)
• positive indicator:
yellow precipitate
• chemical reaction:
2H3AsO3 + 3H2S ↔ As2S3 + 6H2O

Addition of hydrogen sulphide (from thioacetamide) produces yellow precipitate (As2S3)

NOTES:

• If a yellow precipitate does not form immediately, the

arsenite ion is absent.
• The arsenite ion will give a yellow precipitate of arsenic
pentasulfide after a period of 60 seconds or more.
• If arsenite ion is present must be destroyed by heating ian
acid solution. Otherwise, this ion will react with free iodine
liberated in the arsenate test.
 PROCEDURE 4C: TEST FOR CENTRIFUGATE
Identification of Arsenate ions (AsO4-3)
• confirmatory reagent:
Potassium iodide (KI)
• positive indicator:
Brown solution
• chemical reaction:
H2AsO4- + 3H3O+ + 2I- ↔ As2S6 + 10H2O

Same as arsenite, addition of hydrogen sulphide (from thioacetamide) produces yellow precipitate (As2S5) but action is
very slow.
Instead, addition of KI is used which reduces arsenate to arsenite and liberates iodine compound which is color brown.
 PROCEDURE 4D: TEST FOR CENTRIFUGATE
Identification of Phosphate ions (PO4-3)
• confirmatory reagent:
ammonium molybdate solution ((NH4)6Mo7O24)
• positive indicator:
yellow precipitate
• chemical reaction:
H2PO4- + 12MoO4- + 22H3O+ + 3NH4+
↔ (NH4)3 PO4 . 12MoO3 + 34H2O

Phosphate ions react with ammonium molybdate in a nitric acid forming yellow precipitate of ammonium
phosphomolybdate [(NH4)3PO4∙12MoO3]. Tartaric acid should be added to make solution strongly acidic so as not to
precipitate arsenate ions with molybdate.
NOTES:

• The excess tartaric acid, in strongly acid solution (HNO 3 ),

forms a complex with arsenic. Otherwisem the arsenate ion
would precipitate with ammonium molybdate in the
confirmatory test for the phosphate.
• Do not boil, the soluble complex between tartaric acid and
arsenic may be broken down with heat.
• Absence of phosphate ion turns to white precipitate.
 PROCEDURE 5: TEST FOR PRECIPITATE

Thorough washing of the residue is necessary to

remove traces of reducing ions (sulfite and arsenite),

which interfere with the test for the oxalate ion.

 PROCEDURE 5A: TEST FOR PRECIPITATE
Confirmation of Oxalate ions (C2O4-2)
• confirmatory reagent:
Potassium permanganate ( KMnO4 )
• positive indicator:
disapperance of pink color
• chemical reaction:
5H2C2O4 + 2MnO4- + 6H3O+
↔ 2Mn2+ + 10CO2 + 14H2O

Addition of sulphuric acid dissolves CaC2O4 producing oxalic acid. Oxalic acid is a reducing agent reducing permanganate ions to manganous ions,
thus color changes from purple to colorless. MnO4- ↔ Mn+2
 PROCEDURE 5B: TEST FOR PRECIPITATE
Confirmation of Fluoride ions (F-)
• corfimatory reagent:
Sulfuric acid ( H2SO4 )
• positive indicator:
etching (cut)
• chemical reaction:
CaF2 + 2H3O+ ↔ Ca++ + 2H2 + 2HF
NOTES:
- Thorough washing of the residue is necessary to
remove traces of reducing ions (sulfite and arsenite), which interfere
with the test for the axalate ion.
- The pink colored MNO4- ion is reduced by oxalic
acid (produced by calcium oxalate in acid solution) to the manganous
ion which is colorless in this dilution.
- The presence of water interference with the etching
test for the fluoride ion by forming insoluble silicic acid with volatile
silicon tetrafluoride.
 GROUP II ANIONS
MIDTERM

Sulfate ions (SO4-2) Chromate ions (CrO4-2)

BACKGROUND:

• It contains only the chromate and sulfate ions.

• These ions are precipitated by the group reagent -- barium

acetate --- in slightly basic solution.

• The analysis of this group involves no difficulties because the
presence of chromate ions shows yellow color.
 PROCEDURE 1:
• Precipitation of Group II anions
ü REAGENT: barium acetate ---- Ba (Ac)2

SO4-2 + Ba2+ ↔ BaSO4

CrO4-2 + Ba2+ ↔ BaCrO4

notes: 1M Ba(Ac)2 = maximum of 15 drops must be complete precipitation

PROCEDURE 2
• Precipitate may composed:
1. BaCrO4 2. BaSO4
• Separation of Group II anions:
üAddition of HCl dissolves BaCrO4.
üThus precipitate is BaSO 4 while centrifugate is solution with
CrO4-2 ions

notes:
PROCEDURE 2A: Test for Residue
• Identification of Sulfate ions (SO4-2)
: White precipitate in the precipitation
with Barium acetate
üFirst is oxidation to sulphate (SO4-2) by hydrogen peroxide.
Then, sulfate is insoluble as BaSO 4 , thus the white
precipitate.

notes:
Identification of Sulfate ions (SO4-2)
• confirmatory reagent:
Hydrochloric acid (HCl)
• positive indicator:
white precipitate
• chemical reaction:
SO4- + Ba++ ↔ BaSO4
PROCEDURE 2B: Test for Centrifugate

• Identification of Chromate ions (CrO4-2)

ü The addition of sodium acetate to the acidic chromic solution

lowers the Hydrogen ion concentration sufficiently to permit

reprecipitation of BaCrO4, the yellow precipitate.

Na(Ac) serve as the buffer solution.

notes:
Identification of Chromate ions (CrO4-2)
• confirmatory reagent:
Sodium Acetate -- Na(Ac)
• positive indicator:
yellow precipitate
• chemical reaction:
Ba++ + HCRO4- + Ac- ↔ HAc + BaCRO4
 SHORT QUIZ
1. What reagent used to precipitate the Group II Anions?

2. What is the confirmatory reagent of sulfate ions?

3. What is the confirmatory reagent of chromate ions?

4. What is the positive indicator of sulfate ions?

5. What is the positive indicator of chromate ions?

 GROUP III ANIONS
MIDTERM

Fe(CN)6-4 Fe(CN)6-3
S-2
BACKGROUND:

• Group III anions are those ions whose calcium and barium salts
are soluble but whose cadmium salts are insoluble in neutral or
slightly basic solutions.
• No separation is involved in the analysis of this group.
• The tests for the three anions are made on separate portions of
the group precipitate since they offer no interference with each
other.
 PROCEDURE 1
• Precipitation of Group III anions
üREAGENT: Cadmium acetate --- Ca (Ac)2

S-2 + Cd2+ ↔ CdS ( )

Fe(CN)6-4 + Cd2+ ↔ Cd2Fe(CN)6 ( )

Fe(CN)6-3 + Cd2+ ↔ Cd3[Fe(CN)6]2 ( )

notes:
PROCEDURE 2:

üT h e p r e c i p i t a t e i s w a s h e d t h o r o u g h l y t o r e m o v e a n y
contamination of the thiocyanate ion from Group IV anions.

üREASON: To remove that will interefere with the

test for the ferrocyanide since both ions react with ferric ion,
which is the identification reagent.
PROCEDURE 2A: Detection of Sulfide ions (S-2)
• Glassware:
Test tube
• Confirmatory reagent:
Hydrochloric acid (HCl)
• positive indicator:
brown or black coloration
• chemical reaction:
Cds + 2H3O+ ↔ Cd++ + H2S + 2H2O
Pb(Ac)2 + H2S ↔ PbS + 2HAc
PROCEDURE 2B: Identification of Ferrocyanide Ion [Fe(CN)6-4]

• Glassware:
spot plate
• Confirmatory reagent:
Hydrochloric acid (HCl)
• positive indicator:
dark blue precipitate (prussian blue)
• chemical reaction:
Cd2Fe(CN)6 + 2H3O+ ↔ H2Fe(CN)6- + 2Cd++ + 2H2O
3H2Fe(CN)6- + 4Fe3+ 6H2O ↔ Fe4[Fe(CN)6]3 + 6H3O+
PROCEDURE 2C: Confirmation of Ferricyanide Ion [Fe(CN)6-3]

• Glassware:
spot plate
• Confirmatory reagent:
ferrous sulfate
• positive indicator:
dark blue precipitate (Turnbull's blue)
• chemical reaction:
Cd3[Fe(CN)6]2 + 2H3O+ ↔ 2HFe(CN)6- + 3Cd++ + 2H2O
HFe(CN)6- + Fe++ + H3O+ ↔ H2Fe(CN)6- + Fe3+ + H2O
NOTES:

• Dilute HCl should be added until the precipitate is dissolved

and the solution is barely acid.
• If the solution is made too acid, the identifying blue
precipitate may not be obtained, because of its stability in
HCl.
• If green solution is obtained upon the addition of ferric
chloride, the presence of ferricyanide is indicated!
 SHORT QUIZ
1. What reagent used to precipitate the Group III Anions?

2. What is the confirmatory reagent of sulfide ions?

3. What is the confirmatory reagent of ferricyanide ions?

4. What is the positive indicator of sulfide ions?

5. What is the positive indicator of ferrocyanide ions?

GROUP IV ANIONS
MIDTERM
BACKGROUND:
• The group reagent is silver acetate, which is only soluble to the extent
of approximately 0.07 F.
• Silver thiosulfate is unstable acid solution and undergoes a series of
characteristics color changes- which serve to identify this ion during
the process of group precipitation.
• Silver chloride has the largest solubility product of any of the
precipitating anions of Group IV and more soluble in ammonia.
• Silver thiocyanate will react with a solution of ferric chloride to
give the characteristic color of the complex ion, Fe (CNS) 6 3-.
• The iodide and bromide anions, in the form of the insoluble
silver salts, are brought into solution by the action of zinc dust
in a slightly acid solution. This is a redox reaction in which silver
ions are reduced to metallic silver, and zinc is oxidized to zinc
ions.
 PROCEDURE 1: Preliminary Group Test
• REAGENT: Silver acetate (AgAc) with Nitric Acid (HNO3)
S2O3- + 2Ag+ ↔ Ag2S2O3 (BLACK)
CI- + Ag+ ↔ AgCl (WHITE)
CNS- + Ag+↔ AgCNS (WHITE)
I- + Ag+ ↔ AgI (YELLOW)
Br- + Ag+ ↔ AgBr (CREAM-colored)

note: In the preliminary test, the solution must be acid - test with litmus paper.
REMINDERS:

Silver acetate (AgAc), the group

reagent, precipitates Ag2S2O3
which is a white precipitate when
first formed. It rapidly undergoes
hydrolysis, with possible
intermediate color changes, to
black Ag2S.
PROCEDURE 2: Identification of Thiosulfate Ion (S2O3-).

• Reagent: Silver acetate (AgAc)

• Positive indicator: Color changes from white precipitate
through yellow, orange, brown to black.
• Chemical reaction: Ag2S2O3 + 2H2O ↔ Ag2S + H3O+ + HSO4-

note:
PROCEDURE 3: Precipitation of Group IV Anions
• Reagent: saturated AgAc solution with acetic acid

- Centrifugate contains anions of Group V.

- Precipitate may contain Ag2S, AgCl, AgCNS, AgI, and AgBr.

notes:
PROCEDURE 4: Separation and Identification of Group IV Anions
• Solvent action of Ammoniacal Silver Nitrate upon Group IV
Anion Precipitates.
üIn a solution of ammonia: If silver ions are added to ammonia
water (MIller's reagent), the
- Ag2S and AgI are insoluble solubilities of the precipitates are
decreased because of the
- AgBr is slightly soluble
common-ion effect of the complex
- AgCNS fairly soluble ion, Ag(NH3)2+. Only AgCl will
dissolves that permits the
- AgCl quite soluble separation of chloride ions.

note:
 TEST FOR CENTRIFUGATE
Confirmatory Test for Chloride ions (Cl-)

• confirmatory reagent:

Nitric acid (HNO3)

• positive indicator:

white precipitate

• chemical reaction:

Ag(NH3)2+ + Cl- + 2H3O+ ↔ AgCl + 2NH4+ + 2H2O

https://slideplayer.com/slide/4385416/14/im
ages/26/TEST+FOR+CHLORIDE+IONS+add+sil
ver+nitrate+solution+followed+by.jpg
 TEST FOR RESIDUE
Identification of Thiocyanate Ion (CNS-)

• confirmatory reagent:

Hydrochloric Acid (HCl) and Ferric Chloride (FeCl3)

• positive indicator:

red coloration

• chemical reaction:

AgCNS + Cl- ↔ AgCl + CNS-

General Chemistry 101/102 Laboratory
Fe3+ + 6CNS- ↔ Fe (CNS)6 3- Manual University of North Carolina
Wilmington
 Action of Zinc upon Residue of Group IV Analysis

• This residue contains Ag2S, AgCNS, and AgBr.

• If an acid solution containing this residue is treated with zinc dust,
metallic silver precipitates from solution.
• Zinc, being higher in the potential series, replaces silver ions in its
compounds.
• In this redox reaction the anions are brought into solution, although
the thiocyanate is destroyed in the process.
• With Ag 2 S, produced by the hydrolysis of the thiosulfate ion, zinc
releases hydrogen sulfide.
Ag2S + Zn + 2H3O+ ↔ Zn ++ + 2Ag + H2S + 2H2O
 TEST FOR RESIDUE
Identification of Iodide ions (I-)

• confirmatory reagent:

Carbon tetrachlodride (CCl4) and Sodium

Nitrate(NaNO2)

• positive indicator:

Violet in color

• chemical reaction:

NO2- + H3O+ ↔ HNO2 + H2O

2HNO2 + 2H3O+ +2I ↔ 2NO + I2 + 4H2O

https://image.slidesharecdn.com/chemlab2-
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Identification of Bromide ions (Br-) TEST FOR RESIDUE

• confirmatory reagent:

Nitric Acid (HNO3) and Carbon tetrachlodride (CCl4)

• positive indicator:

Yellow or orange in color

• chemical reaction:

6Br- + 2NO3- + 8H3O+ ↔ 3Br2 + 2NO + 12H2O

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