Analytical Chemistry
Qualitative Analysis
1-1
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Qualitative Analysis
Qualitative analysis reveals the
identity of the elements and
compounds in a sample.
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Solubilities of some ionic compounds in water
Ions Mainly Water Soluble
NO3- All nitrates are soluble.
C2H3O2- All acetates are soluble.
ClO3- All chlorates are soluble.
Cl- All chlorides are soluble except AgCl, Hg2Cl2, and PbCl2. (*)
Br- All bromides are soluble except AgBr, Hg2Br2, and PbBr2, and HgCl2.(*)
I- All iodides are soluble except AgI, Hg2I2, and PbI2, and HgI2.
SO42- All sulfates are soluble except CaSO4, SrSO4, BaSO4 , PbSO4, Hg2SO4 and
Ag2SO4.(*)
(*) considered IA and IIA families: NH4+, Ag+, Al3+, Cd2+, Co2+, Cr3+, Cu2+,
Fe2+, Fe3+, Hg22+, Hg2+, Mn2+, Ni2+, Pb2+, Sn2+ and Zn2+
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Solubilities of some ionic compounds in water
Ions Mainly Water –Insoluble
S2- All sulfides are insoluble except those of the IA and IIA elements and
(NH4)2S.
CO32- All carbonates are insoluble except those of the IA elements and
(NH4)2CO3 .
SO32- All sulfites are insoluble except those of the IA elements and
(NH4)2SO3 .
OH- All hydroxides are insoluble except those of the IA elements, Ba(OH) 2,
Sr(OH)2, and Ca(OH)2.
PO43- All phosphates are insoluble except those of the IA elements and
(NH4)3PO4.
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Rules of the formation of some common gases
by metathesis reactions.
Ions Gas
H2S Any sulfide (salt of S2-) and any acid form H2S(g) and a salt.
CO2 Any carbonate (salt of CO32-) and any acid form CO2(g), H2O, and a salt.
SO2 Any sulfite (salt of SO32-) and any acid form SO2(g), H2O, and a salt.
NH3 Any ammonium salt (salt of NH4+) and any soluble strong hydroxide
react upon heating to form NH3(g), H2O, and a salt.
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Qualitative Analysis
Qualitative analysis involves attempting to
identify what materials are present in a sample.
Answering the question: "What is it?"
Wet chemistry (precipitation, extraction and
distillation)
Chemical tests
Analysis of cations
Analysis of anions
Flame tests
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Qualitative Analysis
Cation Analysis
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Group 1
SILVER Group
(Ag , Pb , Hg2 )
+ 2+ 2+
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Pb²⁺ (Lead) GROUP I
A. Pb(NO₃)₂ , add HCl and boil
Solubility of the ppt. with boiling H₂O SOLUBLE
Solubility of the ppt. with NH₄OH SOLUBLE
B. Pb(NO₃)₂ , add K₂CrO₄ (potassium chromate)
Pb(NO₃)₂ + K₂CrO₄ PbCrO₄ + 2KNO₃
yellow ppt.
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GROUP I
Ag⁺ (Silver)
A. AgNO₃ , add NH₄OH (ammonium hydroxide)
AgNO₃ + NH₄OH AgOH + NH₄NO₃
white ppt.
B. Add excess NH₄OH
AgOH + 2NH₄OH Ag(NH₃)₂OH + 2HOH
ppt. dissolves
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GROUP I
Hg₂²⁺ (Mercurous mercury)
Hg₂(NO₃)₂ , add HCl and 2NH₄OH
Hg₂(NO₃)₂ + 2HCl Hg₂Cl₂ + 2HNO₃
Hg₂Cl₂ + 2NH₄OH HgNH₂Cl + Hg + 2H₂O + NH₄Cl
metallic black ppt.
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Group 2
HYDROGEN SULFIDE Group
• Group IIA – Copper Subgroup
(Hg , Pb , Bi , Cu , Cd )
2+ 2+ 3+ 2+ 2+
• Group IIB – Tin Subgroup
(As3+, As5+, Sb3+, Sn2+, Sn4+)
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Cd²⁺ (Cadmium) GROUP II
Cd(NO₃)₂ , add K₄Fe(CN)₆ (potassium ferrocyanide)
Cd(NO₃)₂ + K₄Fe(CN)₆ Cd₂Fe(CN)₆ + 4KNO₃
white ppt.
Pb²⁺ (Lead)
Pb(NO₃)₂ , add K₂CrO₄ (potassium chromate)
Pb(NO₃)₂ + K₂CrO₄ PbCrO₄ + 2KNO₃
yellow ppt.
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GROUP II
Bi³⁺ (Bismuth)
a. Bi(NO₃)₂ , add NaOH & NaSnO₂ (sodium stannite)
Bi(NO₃)₂ + 3NaOH Bi(OH)₃ + 3NaNO₃
b. 2Bi(OH)₃ + 3NaSnO₂ 2Bi + 6NaNO₃ + 3NaSnO₃ + 3H₂O
black ppt.
Cu²⁺ (Copper)
Cu(NO₃)₂ , add K₄Fe(CN)₆ (potassium ferrocyanide)
2 Cu(NO₃)₂ + K₄Fe(CN)₆ Cu₂Fe(CN)₆ + 4KNO₃
reddish brown ppt.
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Hg²⁺ (Mercuric mercury) GROUP II
HgCl₂ , add SnCl₂ (stannous chloride)
a. 2HgCl₂ + SnCl₂ Hg₂Cl₂ + SnCl₄
white ppt.
b. Hg₂Cl₂ + SnCl₂ 2Hg + SnCl₄
black ppt.
Sb³⁺ (Antimony)
SbCl₃, add Sn
2SbCl₃ + 3Sn 2Sb + 3SnCl₂
black ppt
In the ppt., add sodium hypobromite to test the solubility:
INSOLUBLE
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GROUP II
Sn²⁺ (Stannous)
SnCl₂ , add HCl and magnesium ribbon, then boil. Add HgCl₂
a. H₂SnCl₆ + 2Mg SnCl₂ + 2MgCl₂ + H₂
b. SnCl₂ + 2HgCl₂ Hg₂Cl₂ + SnCl₄
white to gray ppt.
As³⁺ (Arsenic)
H₃AsO₄ , add distilled water and saturate with H₂S . Dissolve
with NH₄OH. Add AgNO₃.
H₃AsO₄ + 3NH₄OH + 2AgNO₃ Ag₃AsO₄ + 3NH₄NO₃ + 3H₂O
chocolate brown ppt.
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Group 3
AMMONIUM SULFIDE Group
• Group IIIA – Aluminum Subgroup
(Al , Cr , Zn ) 3+ 3+ 2+
• Group IIIB – Iron Subgroup
(Fe2+, Fe3+, Mn2+, Co2+, Ni2+)
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GROUP III
Al³⁺ (Aluminum)
Al(NO₃)₃ , add NH₄OH, NH₄Ac and aluminum reagent
Al(NO₃)₃ + NH₄OH Al(OH)₃ + 3NH₄NO₃
bright red lake formed
Cr³⁺ (Chromium)
Cr(NO₃)₃ , add NaOH, H₂O₂ or Na₂O₂
2NaCrO₂ + 2Na₂O₂ 2Na₂CrO₄ + 4NaOH
yellow green solution
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GROUP III
Fe³⁺ (Ferric)
Fe(NO₃)₃ , add KCNS
Fe(NO₃)₃ + 3KCNS Fe(SCN)₃ + 3KNO₃
blood red ppt.
Zn²⁺ (Zinc)
Zn(NO₃)₂ , saturate with H₂S in alkaline solution
Zn(NO₃)₂ + H₂S ZnS + 2HNO₃
white metallic ppt.
Zn(NO₃)₂ , K4Fe(CN)6
Zn(NO₃)₂ + K4Fe(CN)6 Zn2Fe(CN)6 + 2KNO₃
3Zn2Fe(CN)6 + K4Fe(CN)6 2Zn3K2[Fe(CN)6]2
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white ppt.
GROUP III
Mn²⁺ (Manganese)
Mn(NO₃)₃ , add HNO₃ and sodium bismuthate
2Mn(NO₃)₃ + 5NaBiO₃ + 16HNO₃ 2HMnO₄ + 5NaNO₃
+ 5Bi(NO₃)₃ + 7H₂O pink or violet solution
Co²⁺ (Cobalt)
Co(NO₃)₂ , add KNO₂ and CH₃COOH. Heat it.
Co(NO₃)₂ + 7KNO₂ + 2CH₃COOH K₃Co(NO₂)₆
+ 2CH₃COOK + NO + 2KNO₃ + H₂O yellow ppt.
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Ni²⁺ (Nickel) GROUP III
Ni(NO₃)₂ , add concentrated ammonium hydroxide and
alcoholic dimethylglyoxime (DMG)
Ni(NO₃)₂ + 2NH₃ + 2C₄H₆N₂O₂H₂ Ni(C₄H₆N₂O₂H₂)₂
+ 2NH₄NO₃ red ppt.
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Group 4
ALKALINE EARTH Group
(Ba2+, Ca2+, Sr2+, Mg2+)
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GROUP IV
Ba²⁺ (Barium)
Ba(NO₃)₂ , add acetic acid and K₂CrO₄
Ba(NO₃)₂ + K₂CrO₄ BaCrO₄ + 2KNO₃
yellow ppt.
Flame color: green or yellowish-green
Sr²⁺ (Strontium)
Sr(NO₃)₂ , add (NH₄)₂SO4
Sr(NO₃)₂ + (NH₄)2SO4 SrSO4 + 2NH₄NO₃
white ppt.
Flame color: crimson red
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GROUP IV
Ca²⁺ (Calcium)
Ca(NO₃)₂ , add water, potassium oxalate & acetic acid
Ca(NO₃)₂ + K₂C₂O₄ CaC₂O₄ + 2KNO₃
white ppt.
Flame color: brick red
Mg²⁺ (Magnesium)
Mg(NO₃)₂ , add ammonium hydroxide and sodium
biphosphate
Mg(NO₃)₂ + NH₄OH + Na₂HPO₄ MgNH₄PO₄ + 2NaNO₃
+ H₂O white crystalline ppt.
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Group 5
ALKALI Group
(NH4 , K , Na , Li )
+ + + +
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GROUP V
NH₄⁺ (Ammonium)
In test solution NH₄Cl, add NaOH and heat the mixture
NH₄Cl + NaOH NaCl + H₂O + NH₃
ammonia gas
K⁺ (Potassium)
In test solution KCl, add H₂C₄H₄O₆ (tartaric acid)
KCl + H₂C₄H₄O₆ KHC₄H₄O₆ + HCl
white crystalline ppt.
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Na⁺ (Sodium) GROUP V
In NaCl, add potassium antimonate or pyroantimonate
2NaCl + K₂H₂Sb₂O₇ Na₂H₂Sb₂O₇ + 2KCl
white crystalline ppt.
Flame color: intense yellow
In LiCl , add Na₂HPO₄ and NH₄OH to render alkaline
3LiCl + Na₂HPO₄ + NH₄OH Li₃PO₄ + 2NaCl + NH₄Cl
white ppt.
Flame color: carmine red or crimson red
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Qualitative Analysis
Anion Analysis
1-28
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Group 1 Anions
(Cl-, Br-, I-, CN-, Fe(CN)64-,
Fe(CN)63-, SCN-)
Forms ppt. AgNO3; no ppt. formed
with BaCl2; ppt. is insoluble in HNO3
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Name of Anion Color of precipitate Reagents used Confirmatory Test
formed with AgNO3
Ferricyanide Orange Ferrous Sulfate TS + ferrous sulfate = Blue ppt.
Bromide Yellow Chloroform, HNO3, KMnO4 TS + chloroform + 10 drops 6N HNO3
+ KMnO4 = Orange to brownish red
chloroform layer
Iodide Yellow Chloroform, HNO3, TS + chloroform + 10 drops HNO3 +
KMnO4 KMnO4 = Violet chloroform layer
Reddish-brown ppt. Conc. HCl, KI, Starch TS + 5 drops conc. HCl + 5 drops KI +
solution 2-3 drops Starch solution = Blue
coloration
Ferrocyanide White Ferric chloride TS + 1 -2 drops ferric chloride = Blue
coloration
Thiocyanate White Ferric chloride TS + 1 -2 drops ferric chloride = Blood
red coloration
Hypochlorite White Acetic acid, Lead acetate TS + 6N acetic acid + 1ml lead acetate
= Brown ppt.
Cyanide White NaOH, Ferrous sulfate, TS + 6N NaOH + ferrous sulfate +
Ferric chloride 1drop ferric chloride = Blue ppt.
Chloride White Mercurous nitrate TS + mercurous nitrate = White ppt.
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Group 2 Anions
(S2-, NO2-, H2PO2-, CH3COO-)
Forms ppt with AgNO3; no ppt formed
with BaCl2; ppt is soluble in HNO3
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Name of Anion Color of precipitate Reagents used Confirmatory Test
formed with AgNO3
Sulfide Black HCl TS + HCl = evolution of
Hydrogen Sulfide Gas
Lead acetate TS + lead acetate =
Black ppt.
Hypophosphite White rapidly NaOH, HNO3, TS + 1ml 6N NaOH.
changing to brown Ammonium Boil mixture, acidify
or black molybdate with HNO3 and
ammonium molybdate
= Yellow ppt.
Nitrite White Dilute H2SO4 TS + dilute H2SO4 =
evolution of brown
gas
Acetate White Concentrated H2SO4, TS + conc. H2SO4 + 5
Ethyl alcohol drops ethyl alcohol =
evolution of gas with
fruity odor
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Group 3 Anions
(SO32-, CO32-, BO33-, C2O42-,
C4H4O62-, C6H5O73-)
Produces white precipitate with AgNO3;
produces ppt with BaCl2; both are soluble in
HNO3
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Name of Anion Reagents Used Confirmatory Test
Sulfite BaCl2, HCl, Bromine water TS + 3-5 drops BaCl2 + HCl +
1ml of bromine to the
filtrate = White ppt.
Carbonate Lime water Expose lime water to the
odorless gas using stirring
rod = White ppt.
Borate Concentrated H2SO4, Methyl TS + 1ml of conc. H2SO4 +
alcohol 3ml methyl alcohol. Light
the solution = Green flame
coloration
Oxalate CaCl2, Acetic acid TS + CaCl2 + acetic acid =
White ppt.
Tartrate Potassium acetate, Acetic TS + potassium acetate +
acid acetic acid = White
crystalline ppt.
Citrate CaCl2 TS + CaCl2 = White ppt.
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Group 4 Anions
(PO43-, AsO43-, AsO33-
S2O32-, CrO42-)
Produces colored ppt with AgNO3; forms colored
or white ppt with BaCl2; both ppt are soluble
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Name of Anion Color of precipitate Reagents used Confirmatory test
Arsenite Yellow ppt. with HCl, Thioacetamide TS + HCl + 10%
AgNO3 solution thioacetamide solution =
Yellow ppt.
Chromate Reddish brown ppt. Lead acetate TS + lead acetate = Yellow
with AgNO3 ppt.
Phosphate Yellow ppt. with Ammonium chloride, TS + 10 drops ammonium
AgNO3 Magnesium mixture, chloride + 1ml magnesium
Excess NH4OH mixture and excess NH4OH
= White ppt.
Thiosulfate White ppt. with Iodine TS + iodine = Immediately
AgNO3 rapidly turning discolorized solution of
black iodine
Arsenate Reddish brown ppt. NH4Cl, Magnesia TS + 5 drops 3N NH4Cl + 3
with AgNO3 mixture drops magnesia mixture =
white crystalline ppt.
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Group 5 Anions
(NO3-, ClO3-)
No precipitate is produced with AgNO3 and
BaCl2
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Name of Anion Reagents used Confirmatory Test
Nitrate Concentrated H2SO4, TS + 1ml conc. H2SO4 and
copper wire copper wire = Evolution
of brown gas
Chlorate KNO2, AgNO3, HNO3 TS + 2-3 drops KNO2 and
AgNO3 + HNO3 = White
ppt.
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Group 6 Anions
(SO42-)
Produced no ppt with AgNO3; produces white
ppt with BaCl2, ppt is insoluble in HNO3
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Name of Anion Reagents used Confirmatory Test
Sulfate Lead acetate, Ammonium TS + lead acetate + 1-2 ml
acetate solution ammonium acetate
solution = White ppt.
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THE END
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