@ashumerez : BSMT-1G 2019 | ANALYTICAL CHEMISTRY LECTURE 1

analysis of cations
CHAPTER 2
Elements are classified according to their:
(1) Atomic numbers (in the periodic table)
(2) Reaction and properties of their ions, which lead to their analytical separation and detection.
• Ions, which form compounds, having similar properties are placed in a single group.
ANALYTICAL CLASSIFICATION OF CATIONS
# GROUP EXAMPLES CHARACTERISTIC PRECIPITANT
V Alkali/Soluble K+, Na+, NH4+ (Li+, Rb+, Cs+, Fr+) Remain in solution
2+ 2+ 2+ 2+ Form insoluble carbonates (NH4)2CO3,
IV Alkaline Earth/Ammonium Carbonate Ba , Sr , Ca , Mg
except Mg2+ NH4, NH4OH
3+ 3+ 2+
Aluminum Group Al , Cr , Zn Will form amphoteric hydroxide 5M NH4Cl,
Aluminum-Iron/Alkali
III Will form non-amphoteric 15M NH4OH,
Insoluble Sulfide Iron Group 2+ 2+ 2+
Co , Ni , Mn , Fe , Fe 2+ 3+
hydroxide CH3CSNH2
Copper-Arsenic Copper Group Cu2+, Cd2+, Pb2+, Hg2+, Bi3+ Do not form amphoteric sulfides
0.2-0.3M H+
II Group/Acid Insoluble *
Arsenic Group As3+, As5+, Sb3+, Sb5+, Sn2+, Sn4+ Form amphoteric sulfides TAH2O2
Sulfide
First represented from unknown
I Silver Group Ag+, Pb2+, Hg22+ 6M HCl
sol’ns in general cation analysis
*TA, where TA = thioacetamide (C₂H₅NS)

group v cations
ALKALI/SOLUBLE
Test solutions: 0.2M NaNO3, 0.2M KNO3, 0.2M NH4NO3
FLAME TEST
Na+ Persistent yellow
• Reliable test for Na+ and K+
K+ Fleeting lavender
o Should be done using the original solution
o Identification of K+ should be done through an optical filter (cobalt glass) to eliminate any possible interfering ions
§ Presence of these ions (Sr2+, Ba2+, Ca2+, Na+) will make K+ invisible.
NaNO3 + HCl à NaCl (more volatile; chlorides impart brighter flames) + HNO3

CHEMICAL / PRECIPITATION TEST

Yellow crystals of sodium zinc uranyl acetate à Na(ZnUO2(CH3COO)4)
Na+
White crystals of sodium pyroantimonate à C5H4Na3O6Sb
K+ Precipitated by sodium cobaltinitrite à potassium sodium cobaltinitrite à K2NaCo(NO2)6
Addition of strong base (NaOH) à converts ion to molecular ammonia (red litmus paper to blue)
Heating alkaline solution to expel NH3 gas (urine-like odor)
NH4+
NH4+ + OH- ➝ NH3 + H2O
• Test for NH4+ should be done on the original sample.
• Should be carried out in the absence of NH4+ à will form a similar ppt. with the reagent
o Can be destroyed by oxidation with hot conc. HNO3
NH4+ + NO3- ➝ N2O­ + H2O

group iv cations
ALKALINE EARTH/AMMONIUM CARBONATE
these ions from insoluble carbonates except Mg2+
PRECIPITANT CHARACTERISTICS
1 (NH4)2CO3 Source of CO32- to ppt.
To make the solution basic
2 NH4OH
To prevent hydrolysis of CO32-
3 NH4Cl Reduces the OH- concentration of the NH4OH à prevents precipitation of Mg(OH)2

PROPERTIES FLAME TEST PRECIPITATES CONFIRMATORY EQUATIONS

Ba2+ Yellow green Ba2+ + SO4- à BaSO4¯
Resemble each other very closely in
Ca2+ Orange/brick red SO2+ + CO32- à SrCO3¯
their physical and chemical properties Formation of white
Sr2+ Deep/crimson red Ca2+ + C2O42- à CaC2O4¯
solids
Differs chemically because of its Mg + 2OH- à Mg(OH)2¯
2+
Mg2+ x
greater electronegativity and small size S & O rgt. à Mg(OH)2¯ + blue-lake
@ashumerez : BSMT-1G 2019 | ANALYTICAL CHEMISTRY LECTURE 2

REAGENT CHARACTERISTICS / REASONS

HAc To acidity but not to an extent of acidity à BaCrO4 is soluble
NH4Ac To buffer excess HAc by ¯H+
TEA More stable complex ion with Ca2+ > Sr2+ à SrSO4 precipitates out
MgNH4PO4 Not reliable for Mg2+ à all cations, except alkali metals, precipitate as P from alkaline solution
HCl Dissolves ppt.; converts salt into more volatile form
Buffer Solution weak acid/base + its salt; maintains near H+ ion concentration if appreciable acid/base + à solution
S & O reagent Para-nitrobenzeneazoresorcinol; Suitzu and Okuma

group iii cations

ALKALI-INSOLUBLE | AMMOUNIUM SULFIDE | BASIC HYDROGEN SULFIDE
SOLUTIONS PRECIPITATES
Al3+ Al(OH)3
Colorless White
Zn3+ Zn(OH)3
Mn2+ Colorless à faint pink MnS Peach
Cr3+ Blue green Cr(OH) 3 Dirty green/grayish green
Ni2+ Green NiS
Co2+ Reddish pink CoS Black
FeS
Fe2+ Pale green
Fe(OH)2 Pale green
Fe3+ Reddish brown to yellow Fe(OH)3 Reddish brown

CHARACTERISTICS CONFIRMATORY EQUATIONS

MnS – most soluble sulfide of the group
KClO3 in hot conc. HNO3 à oxidizes Mn2+ à MnO2
• Separates Mn from all other ions of the Al-Fe
Mn2+ + 2ClO3- à MnO2¯ + 2ClO2­ 2Mn2+ + 5NaBiO3 + 14H+ à
Mn2+
NaBiO3 (sodium bismuthate) à HNO3 solution à oxidizes Mn2+ à MnO4- 2MnO4- + 5Bi3+ + 5Na+ + 7H2O
• Formation of purple MnO4- à sensitive test for detection of Mn
• Reducing agents (e.g. Cl-, S2-) will interfere with confirmatory test in Mn2+ à reduces
MnO4- to Mn2+
Fe(OH)3 à less soluble than 2
Fe2+,
• Differs from hydroxides of Co, Ni, Zn because it is insoluble in NH4OH Fe3+ + KSCN à FeSCN2
Fe3+
SCN (thiocyanate ion) à no color with Fe2+; blood red with Fe3+
Oxidation of its compounds in NH3(aq) gives hexamine cobalt (III) ion à Co(NH3)62+
Co2+ + 7NO2- + 2HAc + 3K+ à
Co(OH)2 à blue in cold, pink in warm, brown in exposure to air à oxidizes to Co3+ or
K3Co(NO2)6¯ + NO + 2Ac- + H2O
Co(NH3)42+ (cobalt tetraamine)
Co2+
K3Co(NO2)6¯ (potassium cobaltinitrite) ß precipitated when KNO2 is added to slightly
acidic sol’n of Co2+ Co2+ + 4SCN- à Co(SCN)42
• Not formed in alkaline or strongly acidic solutions
does not form ppt. + KNO2 in HAc sol’n
Ni2+ + 2NH3 + 2CH3(CONH)2CH3
Ni2+ Forms red ppt. with DMG (dimethylglyoxime) [CH3(CONH)2CH3]
à Ni[CH3(CONH)2CH3]2¯ + 2NH4+
• Formed in slightly alkaline solution + NH3… buffered with NaAc
Only element of the Al-Fe group not a transition element
Salts have a strong tendency to hydrolyze
Al(OH)4- + NH4+
Al3+ Acidity decreases à extensive hydrolysis at pH 4 à white gelatinous ppt.
à Al(OH)3¯ + NH3 + H2O
pH ≥ 10 àAl(OH)3 redissolves à it is amphoteric
• Fe3+ and Cr3+ give the same red ppt., but can be destroyed with (NH4)2CO3.
Acidic solutions: Oxidized only by very strong oxidants (KClO3 in conc. HNO3) Cr2O72- + H2O2 + 2H+
Cr3+
Basic solutions: readily oxidized by H2O2 à 2CrO5 + H2O
Dissolves in excess of OH- Zn(OH)42- + H2S à
Zn2+
Precipitation of ZnS is complete in the presence of acetate (CH3COO-) ZnS¯ + 2OH- + 2H2O

group ii cations
COPPER-ARSENIC GROUP | ACID INSOLUBLE SULFIDE
1 Cu2+ Cu2+ + 4NH3 à Cu(NH3)4+
2 Pb2+ HPbO2- + CrO42- + 3HAc à PbCrO4¯ + 3Ac- + 2H2O
Cd(NH3)22+ + HS- à CdS¯+ NH4+ + 3NH3
3 Cd2+
Cd2+ + H2S + 2NH3 à CdS¯ + 2NH4+
@ashumerez : BSMT-1G 2019 | ANALYTICAL CHEMISTRY LECTURE 3

4 Bi3+ 2Bi(OH)3 + 3HSnO2- à 2Bi + 3HSnO3- + 3H2O

5 Hg2+ 2HgCl2 + Sn2+ + 4Cl- à Hg2Cl2(s) + SnCl62-
6 Sn2+, (4+) Hg2Cl2 + Sn2+ + 4Cl- à 2Hg(l) + SnCl62-
7 As3+, (5+) AsH3(g) + 6Ag+ + 3H2O à H3AsO3 + 6Ag + 6H+
8 Sb3+, (5+) 2Sb3+ + 2S2O32- + 3H2O à Sb2OS2(s) [antimony sulfide] + 2SO42- + 6H+
Group II-A: Copper; Group II-B: Arsenic Group

group i cations
SILVER GROUP
• During precipitation, [H+] must be maintained at a relative high value à prevent precipitiation of sparingly soluble oxychlorides
of Bi and Sb, provided that Group II is also in the unknown.
Ag(NH3)2+ + I- à AgI¯ + 2NH3
1 Ag+
Ag(NH3)2+ + Cl- + 2H+ à AgCl + 2NH4+
2 Pb2+ HPbO2- + CrO42- + 3HAc à PbCrO4¯ + 3Ac- + 2H2O
3 Cd2+ Hg2Cl22+ + 2NH3 à Hgº(l) + Hg(NH2)Cl {amino mercuric chloride] +NH4+ + Cl-