Basic Radical Detection — Semi-Micro Qualitative Analysis First Year Chemistry Practical

BASIC RADICAL DETECTION

Semi-Micro Qualitative Analysis

Complete Step-by-Step Guide · All 6 Groups · Reactions & Viva Tips

Group II
Group I Group III
2+ 3+ 2+ 3+ 3+
Cu , Bi , Cd , As , Sb ,
Ag+, Hg22+, Pb2+ Al3+, Fe3+, Cr3+
Sn2+/4+

Group IV Group V Group VI

Co2+, Ni2+, Mn2+, Zn2+ Ba2+, Sr2+, Ca2+ Mg2+, Na+, K+, NH4+

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Basic Radical Detection — Semi-Micro Qualitative Analysis First Year Chemistry Practical

BEFORE YOU START — PREPARE YOUR SOLUTION

■ Important: Dissolve your salt before any group test. Always go from mildest to strongest solvent to
preserve evidence.

Steps to prepare your sample solution:

• Take a small amount of the unknown salt in a semi-micro test tube.
• Add 1–2 mL of distilled water first and shake. Heat if needed.
• If undissolved → try dilute HCl. (Group I ions precipitate here — that IS your Group I test!)
• If still undissolved → try dilute HNO3.
• Last resort → aqua regia (3 parts conc. HCl + 1 part conc. HNO3). Use only in fume hood.

■ Always start mildest first. Strong acids can destroy Cl– or CO32– evidence needed for Group I/acid radical
tests.

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Basic Radical Detection — Semi-Micro Qualitative Analysis First Year Chemistry Practical

★ GROUP I — Ag+, Hg22+, Pb2+

Group Reagent: Dilute Hydrochloric Acid (dil. HCl)

Principle: Group I cations form insoluble white chloride precipitates with dil. HCl. No other group does
this — making HCl a perfect selective separator.

Add dil. HCl to the stock solution

1 Take ~2 mL of sample. Add 5–10 drops dil. HCl. Centrifuge if precipitate forms. Save centrifugate
for Group II.
Why HCl? Ag+, Hg22+ and Pb2+ have very low Ksp chlorides; Fe3+, Cu2+ etc. form soluble chlorides.
Ag+ + Cl- -> AgCl (down, white)
Hg2(2+) + 2Cl- -> Hg2Cl2 (down, white)
Pb(2+) + 2Cl- -> PbCl2 (down, white)
Observation: White ppt = Group I present. No ppt = absent, proceed to Group II.

Heat residue with hot water — test for Pb2+

2 Wash white ppt with cold water. Heat with 1 mL hot distilled water. PbCl2 dissolves in hot water;
AgCl and Hg2Cl2 do not. Divide hot solution into 2 parts.
Why hot water? PbCl2 is more soluble at higher temperatures — physical property used to separate
Pb2+.
Part 1 + K2CrO4 -> PbCrO4 (down, bright yellow) [LEAD CONFIRMED]
Part 2 + KI -> PbI2 (down, golden yellow) [LEAD CONFIRMED]
Observation: Yellow/golden precipitate in either part = Lead (Pb2+) confirmed.

Shake residue with dil. HNO3 — separate Hg22+ and Ag+

3 Take the residue (HgCl2 + AgCl) after hot water. Shake with 5 mL dil. HNO3. Centrifuge.
Why HNO3? AgCl dissolves in HNO3. Hg2Cl2 disproportionates to Hg (black) + HgCl2.
Hg2Cl2 -> Hg (down, black) + HgCl2 [disproportionation]
HgCl2 + SnCl2(excess) -> Hg (down, white->grey) + SnCl4 [MERCURY CONFIRMED]
AgCl + 2NH3 -> [Ag(NH3)2]+ + Cl- (AgCl dissolves in NH3)
[Ag(NH3)2]+ + Cl- + 2HNO3 -> AgCl (down, white) + 2NH4NO3 [SILVER CONFIRMED]
Observation: Black residue = Mercury. White ppt re-appearing on acidification of NH3 solution =
Silver.

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Basic Radical Detection — Semi-Micro Qualitative Analysis First Year Chemistry Practical

★ GROUP II — Cu2+, Pb2+, Bi3+, Cd2+, As3+, Sb3+, Sn2+/Sn4+

Group Reagent: H2S gas in Acidic Medium (dil. HCl)

Principle: Group II sulphides have extremely low Ksp — they precipitate even in acidic medium where
[S2–] is low. Group III–VI need alkaline conditions (higher [S2–]) to precipitate.

Sulphide precipitate colour guide:

Ion Sulphide Colour Sub-group

Cu2+ CuS Black IIA – Copper group

Pb2+ PbS Black IIA – Copper group

Bi3+ Bi2S3 Brown/Black IIA – Copper group

Cd2+ CdS Yellow IIA – Copper group

As3+ As2S3 Yellow IIB – Arsenic group

Sb3+ Sb2S3 Orange IIB – Arsenic group

Sn2+ SnS Brown IIB – Arsenic group

Pass H2S through hot acidic solution

4 Make centrifugate from Group I acidic with dil. HCl. Heat to near boiling. Pass H2S for 2–3 min.
Centrifuge. Save centrifugate for Group III.
Why acidic + hot? Acid keeps [S2–] low enough to NOT precipitate Groups III–VI, but still exceeds
Ksp of Group II sulphides. Heat speeds kinetics.
Cu(2+) + H2S -> CuS (down, black) + 2H+
Cd(2+) + H2S -> CdS (down, yellow) + 2H+
As(3+) + (3/2)H2S -> (1/2)As2S3 (down, yellow) + 3H+

Separate IIA and IIB — yellow ammonium sulphide

5 Wash sulphide ppt. Treat with 1 mL yellow ammonium sulphide [(NH4)2Sx]. Warm and centrifuge.
Why (NH4)2S? IIB sulphides (As, Sb, Sn) form soluble thioanion complexes. IIA sulphides (Cu, Pb,
Bi, Cd) do not — they remain as residue.
As2S3 + 3(NH4)2S -> 2(NH4)3AsS3 (soluble)
Sb2S3 + 3(NH4)2S -> 2(NH4)3SbS3 (soluble)
Residue = IIA (Cu2+, Pb2+, Bi3+, Cd2+) | Centrifugate = IIB (As, Sb, Sn).

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Basic Radical Detection — Semi-Micro Qualitative Analysis First Year Chemistry Practical

Group IIA — dissolve in dil. HNO3 + conc. H2SO4 to isolate Pb2+

6 Add 10 drops dil. HNO3 to IIA residue, heat 3 min. Then add 2 drops conc. H2SO4, evaporate till
SO3 fumes. Cool, dilute, centrifuge.
Why H2SO4? PbSO4 is insoluble (Ksp ~10–8); CuSO4, Bi and Cd sulphates are soluble.
Pb(2+) + SO4(2-) -> PbSO4 (down, white)
PbSO4 + CH3COONH4 -> Pb(CH3COO)2 (dissolve for confirmatory test)
Pb(2+) + CrO4(2-) -> PbCrO4 (down, yellow) [LEAD CONFIRMED]

Group IIA — add NH4OH to separate Bi3+, Cu2+, Cd2+

7 To centrifugate (Cu2+, Bi3+, Cd2+), add NH4OH dropwise till smells of NH3. Centrifuge.
Why NH4OH? Bi3+ precipitates as Bi(OH)3 (no amine complex). Cu2+ and Cd2+ form soluble
[M(NH3)4]2+ complexes.
Bi(3+) + 3NH4OH -> Bi(OH)3 (down, white) + 3NH4+
Bi(OH)3 + Na2SnO2 -> 2Bi (down, black) + Na2SnO3 [BISMUTH CONFIRMED]
2Cu(2+) + [Fe(CN)6](4-) -> Cu2[Fe(CN)6] (down, chocolate brown) [COPPER
CONFIRMED]
Cd(2+) + H2S -> CdS (down, yellow) [CADMIUM CONFIRMED] (after masking Cu with
NaCN)

Group IIB — acidify, pass H2S → As2S3; then test Sb and Sn

8 Acidify IIB centrifugate with dil. HCl, warm, pass H2S.
2(NH4)3AsS3 + 6HCl -> As2S3 (down, yellow) + 3H2S + 6NH4Cl [ARSENIC CONFIRMED]
Boil centrifugate to expel H2S. Divide in 2 parts:
Part A + Al/Fe metal + HgCl2 -> Hg2Cl2 (down, white -> grey) [TIN (Sn4+)
CONFIRMED]
Part B + NH4OH (alkaline) + oxalic acid + H2S -> Sb2S3 (down, orange) [ANTIMONY
CONFIRMED]
Why Fe/Al for Sn? Reduces Sn4+ → Sn2+, which then reduces HgCl2 giving white→grey Hg
precipitate.

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Basic Radical Detection — Semi-Micro Qualitative Analysis First Year Chemistry Practical

★ GROUP III — Al3+, Fe3+, Cr3+

Group Reagent: NH4Cl + NH4OH (Ammoniacal Buffer at pH ~9)

Principle: NH4Cl + NH4OH creates a buffer at pH ~9. Al3+, Fe3+, Cr3+ precipitate as hydroxides. Group IV
ions (Co2+, Ni2+ etc.) do NOT precipitate at this pH — that is the key selectivity.

Add NH4Cl + NH4OH to Group III centrifugate

9 Boil centrifugate from Group II to remove H2S. Add 2–3 drops solid NH4Cl then NH4OH dropwise
till smells of NH3. Centrifuge.
Why NH4Cl first? Provides NH4+ common ion. By Le Chatelier's principle this suppresses [OH–],
preventing Group IV precipitation.
Al(3+) + 3OH- -> Al(OH)3 (down, white gelatinous)
Fe(3+) + 3OH- -> Fe(OH)3 (down, reddish brown)
Cr(3+) + 3OH- -> Cr(OH)3 (down, greyish green)

Treat ppt with 4N NaOH + Br2 water

10 Wash ppt. Add 4 drops 4N NaOH + boil. Add 5–10 drops Br2 water. Centrifuge.
Why NaOH + Br2? Al(OH)3 and Cr(OH)3 are amphoteric — dissolve in NaOH. Br2 oxidises Cr3+ →
Cr6+ (chromate, yellow). Fe(OH)3 stays as residue.
Al(OH)3 + NaOH -> NaAlO2 + 2H2O (aluminate — centrifugate)
2Cr(OH)3 + 3Br2 + 10NaOH -> 2Na2CrO4 + 6NaBr + 8H2O (chromate — centrifugate)
NaAlO2 + HNO3 + H2O -> Al(OH)3 (down, gelatinous) + NaNO3 [ALUMINIUM CONFIRMED]
Pb(2+) + CrO4(2-) -> PbCrO4 (down, yellow) [CHROMIUM CONFIRMED]
Fe(3+) + 3CNS- -> Fe(CNS)3 (deep blood red colour) [IRON CONFIRMED]
For Fe: Dissolve Fe(OH)3 residue in dil. HCl + 3 drops NH4CNS → deep blood red.

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Basic Radical Detection — Semi-Micro Qualitative Analysis First Year Chemistry Practical

★ GROUP IV — Co2+, Ni2+, Mn2+, Zn2+

Group Reagent: H2S in Ammoniacal (Alkaline) Medium

Principle: In alkaline medium, [S2–] is very high (H2S + 2OH– → S2– + 2H2O). This exceeds Ksp of CoS,
NiS, MnS and ZnS — which would NOT precipitate in Group II's acidic conditions.

Pass H2S through ammoniacal centrifugate from Group III

11 The Group III centrifugate is already ammoniacal. Pass H2S and centrifuge. Save centrifugate for
Group V.
Co(2+) + S(2-) -> CoS (down, black)
Ni(2+) + S(2-) -> NiS (down, black)
Mn(2+) + S(2-) -> MnS (down, buff/pink)
Zn(2+) + S(2-) -> ZnS (down, white)

Dissolve CoS/NiS in aqua regia — confirm Co2+ and Ni2+

12 Treat residue with aqua regia. Divide in 2 parts.
Part 1 + CH3COONa + KNO2 -> K3[Co(NO2)6] (down, bright yellow) [COBALT
CONFIRMED]
Part 2 + NH4OH (basic) + dimethylglyoxime -> Ni-DMG (down, bright red) [NICKEL
CONFIRMED]
Why DMG? Dimethylglyoxime (DMG) is a bidentate chelating agent. Forms a square-planar Ni2+
complex of brilliant red colour — one of the most specific tests in qualitative analysis.

Centrifugate — confirm Zn2+ and Mn2+

13 Add 10 drops NaOH. Centrifuge.
Zn(2+) + 4OH- -> [Zn(OH)4](2-) (soluble zincate — goes to centrifugate)
[Zn(OH)4](2-) + H2S -> ZnS (down, white) + 4OH- [ZINC CONFIRMED]
2Mn(2+) + 5PbO2 + 4H+ -> 2MnO4- (violet/purple) + 5Pb(2+) + 2H2O [MANGANESE
CONFIRMED]
For Mn: Residue + conc. HNO3 + PbO2, heat → violet MnO4– (permanganate colour) is
unmistakable.

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Basic Radical Detection — Semi-Micro Qualitative Analysis First Year Chemistry Practical

★ GROUP V — Ba2+, Sr2+, Ca2+

Group Reagent: (NH4)2CO3 in Ammoniacal Medium

Principle: Ba2+, Sr2+ and Ca2+ form insoluble carbonates with (NH4)2CO3. Mg2+ (Group VI) does NOT
precipitate here. Flame tests are essential for final confirmation.

Add (NH4)2CO3 — precipitate Group V

14 Boil Group IV centrifugate to expel H2S. Add NH4OH + (NH4)2CO3. Heat on water bath.
Centrifuge.
Ba(2+) + CO3(2-) -> BaCO3 (down, white)
Sr(2+) + CO3(2-) -> SrCO3 (down, white)
Ca(2+) + CO3(2-) -> CaCO3 (down, white)

Dissolve in dil. CH3COOH + add K2CrO4 — test for Ba2+

15 Dissolve carbonate ppt in dil. acetic acid. Add 2 drops K2CrO4.
Why acetic acid? BaCrO4 is insoluble in weak acid (Ksp ~10–10); SrCrO4 and CaCrO4 are more
soluble — selective for Ba2+.
Ba(2+) + CrO4(2-) -> BaCrO4 (down, yellow) [BARIUM CONFIRMED]
Flame test: Ba → Apple green flame.
Sr(2+) + SO4(2-) -> SrSO4 (down, white) [STRONTIUM CONFIRMED — crimson red
flame]
Ca(2+) + C2O4(2-) -> CaC2O4 (down, white) [CALCIUM CONFIRMED — brick red flame]
Strontium: Centrifugate from Ba step + (NH4)2SO4, heat, cool 5 min → SrSO4. Calcium: Remaining
centrifugate + (NH4)2C2O4 → CaC2O4.

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Basic Radical Detection — Semi-Micro Qualitative Analysis First Year Chemistry Practical

★ GROUP VI — Mg2+, Na+, K+, NH4+

No Group Reagent — Each Ion Tested Individually

■ CRITICAL: Test NH4+ from the ORIGINAL MIXTURE only — NOT the centrifugate — because NH4Cl,
NH4OH and (NH4)2CO3 were added during the procedure. Testing the centrifugate will always give a false
positive!

Test for NH4+ — from ORIGINAL MIXTURE only

16 Method A: 10 mg original sample + 1 mL NaOH → heat → hold moist red litmus near mouth.
Method B: Pass evolved gas into Nessler's reagent.
NH4(+) + OH- -> NH3 (gas) + H2O (NH3 turns red litmus blue)
NH3 + Nessler s reagent -> [OHg2NH2]I (yellow/brown) [AMMONIUM CONFIRMED]

Test for Mg2+ — ammonium hydrogen phosphate

17 Add 2 drops (NH4)2HPO4. Cool under tap water, scratch with glass rod.
Or: add magneson reagent + NaOH.
Mg(2+) + NH4(+) + HPO4(2-) -> MgNH4PO4 (down, white crystalline) [MAGNESIUM
CONFIRMED]
Mg(OH)2 + magneson dye -> sky blue precipitate [MAGNESIUM CONFIRMED]

Test for Na+ — magnesium uranyl acetate

18 Add 10 drops magnesium uranyl acetate solution to 0.5 mL of sample. Scratch sides.
Na(+) + Mg(2+) + 3UO2(2+) + 9CH3COO- -> NaMg(UO2)3(CH3COO)9 (down, light
yellow) [SODIUM CONFIRMED]
Flame test: Na → Golden yellow flame.

Test for K+ — sodium cobaltinitrite

19 Add a few drops of Na3[Co(NO2)6]. Shake 2–3 minutes.
2K(+) + Na(+) + [Co(NO2)6](3-) -> K2Na[Co(NO2)6] (down, bright yellow)
[POTASSIUM CONFIRMED]
Flame test: K → Violet flame (view through blue glass to eliminate Na yellow).

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Basic Radical Detection — Semi-Micro Qualitative Analysis First Year Chemistry Practical

QUICK REFERENCE — ALL GROUPS

Group Ions Reagent Key Observation Flame

I Ag+, Hg2(2+), Pb(2+) dil. HCl White ppt in acid —

Cu2+, Pb2+, Bi3+, Cd2+,

II H2S in acid Coloured sulphide ppts —
As3+, Sb3+, Sn2+/4+

III Al3+, Fe3+, Cr3+ NH4Cl + NH4OH Gelatinous hydroxide ppts —

IV Co2+, Ni2+, Mn2+, Zn2+ H2S in alkali Sulphide ppts in base —

Ba=Green
V Ba2+, Sr2+, Ca2+ (NH4)2CO3 White carbonate ppts Sr=Crimson
Ca=Brick red

VI Mg2+, Na+, K+, NH4+ Individual reagents Specific ppts Na=Golden K=Violet

VIVA TIPS

Q: Why centrifuge instead of filter?

A: Semi-micro uses tiny amounts — centrifuging is faster, uses less reagent, no loss on filter paper.

Q: Why heat before passing H■S in Group II?

A: Hot solution ensures faster H■S absorption and complete precipitation of Group II sulphides.

Q: Why add NH■Cl BEFORE NH■OH in Group III?

A: NH■Cl provides NH■■ common ion. Le Chatelier's principle suppresses [OH■] to pH ~9, precipitating
only Group III hydroxides without Group IV.

Q: Why test NH■■ from original sample?

A: We add NH■Cl, NH■OH, (NH■)■CO■ during the procedure — the centrifugate is always contaminated.
Only the original mixture gives a valid test.

Q: What is the principle of H■S group separation?

A: Acid controls [S²■]: low [S²■] in acid precipitates only Groups I–II (very low Ksp sulphides). High [S²■] in
alkali precipitates Groups III–IV. Groups V–VI don't form sulphides.

Q: Why does Pb²■ appear in both Groups I and II?

A: PbCl■ is only slightly soluble — not all Pb²■ precipitates in Group I. Remaining Pb²■ precipitates as PbS
in Group II.

Q: H■S safety precaution?

A: H■S is highly toxic (TLV = 1 ppm). Always use in fume hood. Never sniff directly. Dispose by passing
through NaOH solution.

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Basic Radical Detection — Semi-Micro Qualitative Analysis First Year Chemistry Practical

Best of luck for your practical and viva! ■ Observe every colour change carefully and always explain WHY you
use each reagent — that impresses the examiner most.

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