Вы находитесь на странице: 1из 39

Analytical of Qualitative Chemistry

Chemical Engineering

International Class


Andari Rahmadhani
Systematic qualitative analysis, cations agree on five classes based on the
properties of cations for some reagents. By using the so-called special group
reagents, we can determine whether there are no groups of cations, and can also
contain these groups by further examination. The group reagents used for the
most common cations are hydrochloric acid, hydrogen sulfide, and ammonium
carbonate. This classification is based on what is requested with these reagents
by forming a precipitate or not. So we may say that the classification of cations is
the most common, based on the differences in the chlorides, sulfides and
carbonates of the cations (Vogel, 1990: 203).


a) Group I: This cation consists of Ag+ ions, Hg+ and Pb2+,this cation will
precipitate when
diluted hydrochloric acid is reused.
b) Group II: This cation consists of Cu2+,Cd2+, Hg2+, Sn4+ ions, Sb3+ and
Bi3+. This cation does not react to hydrochloric acid but will form a precipitate if
given a hydrogen react sulfide in a runny atmosphere. In group cations
subdivided into sub-groups IIA consisting of ions Cu2+,Bi3+ , Cd2+ and
subclass IIB consisting ofions, Hg2+,Sn4+, Sb3+ . Besides sulfides from
sub-groups IIA will not dissolve in ammonium polysulfide,while sub-group IIB
will dissolve.
c) Group III: This cation consists of Al2+ ions,Cr2+, Cu2+, Fe2+, Ni2+, Mn2+,
Zn3+. Cations of this class do notreact with dilute hydrochloric acid or
hydrogensulfide in the precipitate if it is acidic, but this cation willforming a
precipitate if given ammonium sulfide reagentsin an alkaline atmosphere.
d) Group IV: Cations of this group do not react with the reagents of Groups
I, II, and III. They form precipitates with ammonium carbonate in the
presence of ammonium chloride in neutral or slightly acidic medium.
Cations of this group are: calcium, strontium, and barium. Some systems of
group classification exclude ammonium chloride besides ammonium
carbonate as the group reagent; in such cases magnesium must also be included
in this group. Since, however, in the course of systematic analysis considerable
amounts of ammonium chloride will be present when the cations of the
fourth group are to be precipitated, it is more logical not to
include magnesium into Group IV.
e) Group V: This cation consists of K + ions, NH4 +, Mg +, and Na +. Cation
this will not react with reagents like the previous group is therefore to distinguish
the ions contained in the group here are held flame test The test for each ion will
be coloreddifferent flame when tested.
The things that must be considered in studying ion
1. Reagents are more or less toxic, so use them must be carefully
2. It is better not to add as many reagents as calculated at once to the solution,
but the final amount must be the same or more than the equivalent

Group I : Ag+ , Hg+ and Pb2+

Group reagents: dilute hydrochloric acid (2M)
Group reactions: white lead chloride (PbCl2), mercurium (I) chloride (Hg2Cl2),
and AgCl silver chloride precipitates.
The first group cations,form insoluble chlorides.However, lead chloride is
slightly soluble in water and therefore lead never settles completely when dilute
hydrochloric acid is added to a sample; the remaining lead ions are deposited
quantitatively with hydrogen sulfide and in an acidic atmosphere together with
second group cations.
Nitrate from this cation is very soluble.Between the properties of lead sulfate
practically insoluble while silver sulfate dissolves much more mercurium(I)
sulfate solution is located between the two substances. And iodide is also
insoluble while lead halide is imperfect and the precipitate is very easy into hot
water.insoluble acetic acid is more soluble even though silver acetate may
precipitate from a slightly concentrated solution of hydroxide and carbonate will
be precipitated with an equivalent, amount of reagents but excessive reagents can
act in various ways also there are differences in the nature of the substances this
substance against ammonia

 Dilute hydrochloric acid (or soluble chloride): white precipitate in a cold, not
too runny solution

 Hydrogen sulfide in a neutral or aqueous atmosphere: lead sulfide black

 Ammonia solution: lead hydroxide white precipitate

 Sodium hydroxide: white lead hydroxide precipitate

 Dilute sulfuric acid (or dissolved sulfates): white precipitate, lead sulfate

 Potassium chromate in neutral solution, acetic acid or ammonia: yellow

precipitate, lead chromate

 Potassium iodide: yellow precipitate, lead iodide

 Sodium sulfite in neutral solution: lead sulfite white precipitate

 Sodium carbonate: white precipitate a mixture of lead carbonate and lead


 Disodium hydrogen phosphate: white lead phosphate deposition

 Potassium cyanide (poison): lead cyanide white precipitate

 Tetramethildiamino-diphenylmethane (or ‘tetrabasa’) (0.5%) : oxidation

results are blue
 Benzidine (0.05%) (danger: this reagent is carcinogenic (can cause cancer) :
the so-called 'benzidine blue' is produced upon oxidation with
lead dioxide.
 Galosianina (1%) : deep-violet precipitate of unknown
 Diphenylthiocarbazone (or dithizone) (0.005%) :brick-red complex salt
in neutral, ammoniacal, alkaline, or alkalicyanide solution.
 Dry test :
a. Blowpipe test. When a lead salt is heated with alkali carbonate upon
charcoal, a malleable bead of lead, (which is soft and will mark paper),
surrounded with a yellow incrustation of lead monoxide is obtained.
b. Flame test. Pale blue (inconclusive).

 Dilute hydrochloric acid or soluble chlorides: mercurium (I) chloride
(calomel) precipitate

 Hydrogen sulfide in neutral or dilute acid atmosphere: black precipitate,

which is a mixture of mercurium (II) sulfide and mercurium metal

 Ammonia loch: black precipitate which is a mixture of mercurium and

mercurium (II) in the middle of the base, (which is itself a white precipitate)

 Sodium hydroxide: black deposits of mercurium (I) oxide

 Potassium chromate in hot solution: mercurium (I) red crystalline precipitate


 Potassium iodide, added slowly in a cold solution: green precipitate of

mercurium (I) iodide

 Sodium carbonate in cold solution: yellow precipitate mercurium (I)


 Disodium hydrogen phosphate: white precipitate of mercurium (I) hydrogen


 Potassium cyanide (poison) produces a solution of mercurium (II) cyanide

and mercurium deposits
 Tin (II) chloride reduces mercurium (I) ions to mercurium metal in the form
of grayish black deposits

 Potassium nitrite reduces metal mercurium from a solution of mercurium ion

(I) in a cold state, in the form of black-gray deposits

 Copper sheet or shiny copper coin, if a drop of mercurium (I) nitrate is

placed on top a clean aluminum surface, formed aluminum amalgam, and
dissolved aluminum ions

 Aluminium sheet If a drop of mercury(I) nitrate is placed on a clean

alu• minium surface, aluminium amalgam is formed and aluminium
ions pass into solution:

 Diphenylcarbazide (1% in alcohol) forms a violet-coloured compound

with mercury(I) or mercury(II) ions, the composition of which is not
quite understood
 Dry test All compounds of mercury when heated with a large excess (7--8
times the bulk) of anhydrous sodium carbonate in a small dry test-tube
yield a grey mirror, consisting of fine drops of mercury, in the upper
part of the tube. The globules coalesce when they are rubbed with a glass


 Dilute hydrochloric acid (or soluble chlorides): silver-white chloride


 Hydrogen sulfide (gas or water-saturated solution) in a neutral or acidic

atmosphere: silver sulphide black deposits

 Ammonia solution: silver oxide silver deposits

 Sodium hydroxide: brown silver oxide deposits

 Potassium iodide: yellow silver iodide precipitate

 Potassium chromate in neutral solution: silver chromate red precipitate

 Potassium cyanide (poison) when added dropwise to neutral silver nitrate

solution: silver white cyanide precipitate

 Sodium carbonate: yellowish white precipitate, silver carbonate

 Disodium hydrogen phosphate in neutral solution: yellow silver phosphate


 Hydrazine sulfate (saturated): when added to the solution of the

diamineargentate ion, silver metal is formed in the form of a fine powder,
while nitrogen gas is released

 p-Dimethylaminobenzylidene-rodanina (briefly: rodanina reagents, 0.3%

solution in acetone): reddish-colored precipitate in a slightly acidic solution :
reddish-violet precipitate in slightly acidic solutions
 Dry test : When a silver salt is heated with alkali carbonate on charcoal, a
white malleable bead without an incrustation of the oxide results; this is
readily soluble in nitric acid. The solution is immediately precipitated by
dilute hydrochloric acid, but not by very dilute sulphuric
acid (difference from lead)

Pereaksi Pb 2 Hg+ Ag+

HCl Putih, PbCl2 ↓ Putih, Hg2Cl2 ↓ Putih, AgCl2 ↓
Tdk ada prubahan Hitam, Hg ↓ + Larut, [ Ag(NH3)2]2+
+ NH3
HgNH2 ↓
Tdk ada prubahan
Tdk ada perubahan
+ air panas
H2S (+ HCl) Hitam, PbS ↓ Hitam, Hg ↓ + HgS ↓ Hitam, Ag2S ↓
Putih, PbSO4 Putih, Hg2(NO3)2S ↓ Larut, Ag +
+cc. NHO3
Putih, Pb(OH)2 ↓ Coklat, Ag2O ↓
NH3 sedikit Hitam, Hg+HgO,
Tdk ada perubahan HgNH2NO3 ↓ Larut, [ Ag(NH3)2]+
Tdk ada perubahan
+ berlebihan
NaOH, sedikit ↓putih, Pb(OH)2 Hitam, Hg+HgO2, ↓ coklat, Ag2O
↓ HgNH2NO3
berlebih Larut, [Pb(OH4)]2- Tdk ada perubahan Tdk ada perubahan
KI sedikit ↓ kuning PbI2 ↓ hijau HgI ↓ kuning HgI
+ berlebihan Tdk ada perubahan ↓ abu-abu Tdk ada perubahan
K2CrO4 ↓ kuning PbCrO4 ↓ merah Hg2CrO4 ↓ merah Ag2CrO4
Tdk ada perubahan Larut,[Ag(NH3)]+
kj+ NH3 ↓ hitam
KCN, sedikit ↓ Putih Pb(CN)2 ↓ Hitam Hg + ↓ Putih AgCN
Tdk ada perubahan
+ berlebihan Tdk ada perubahan Larut, [Ag(CN)2]-
Na2CO3 ↓ Putih PbO, PbCO3 ↓ Putih kekuningan ↓ Putih kekuningan
Hg2CO3 Ag2CO3
↓ Hitam Hg + ↓ HgO ↓ Coklat Ag2O
+ mendidih Tdk ada perubahan
Na2HPO4 ↓ Putih Pb3(PO4)2 ↓ Putih Hg2HPO4 ↓ Kuning Ag3PO4
Reaksi spesifik Benzidina (+Br2) Difenil karbazida p-dimetilamino-
Warna biru Warna ungu benzilidena rodamina
Warna lembayung
Group II : Cu2+,Cd2+, Hg2+, Sn4+, Sb3+ and
Group reagent: hydrogen sulphide (gas or saturated aqueous solution).
Group reaction: precipitates of different colours; mercury(II)
sulphide HgS (black), lead(II) sulphide PbS (black), copper(II) sulphide
CuS (black), cadmium sulphide CdS (yellow), bismuth(III)
sulphide Bi,S, (brown), arsenic(III) sulphide As,S (yellow), arsenic(V)
sulphide (yellow), antimony(II) sulphide Sb,S, (orange), antimony(V) sulphide
(orange), tin(II) sulphide SnS (brown), and tin(IV) sulphide SnS, (yellow).
The basis of this division is the solubility of the sulphide precipitates in
ammonium polysulphide. While sulphides of the copper sub-group are
insoluble in this reagent, those of the arsenic sub-group do dissolve under the
formation of thiosalts.
The copper sub-group consists of mercury(II), lead(II),
bismuth(III),copper(II), and cadmium(II)
The arsenic sub-group consists of the ions arsenic(III), arsenic(V),
antimony(III), antimony(V), tin(II) and tin(IV).

 Hydrogen sulfide (gas or saturated water solution): in the presence of dilute
hydrochloric acid, a white precipitate of mercurium (II) chlorosulfide is
formed, which decomposes when further hydrogen sulfide is added, and
finally a black precipitate of mercurium (II) sulfide is formed.

 Ammonia solution: white precipitate with mixed composition; basically

consists of mercurium (II) oxide and mercurium (II) amidonitrate

 Sodium hydroxide when added in small amounts: red-brown precipitate with

different composition; if added in stoichiometric amounts, the deposits turn
yellow when mercurium (II) oxide is formed
 Potassium iodide when added slowly to solution: mercurium (II) iodide red

 Potassium cyanide (poison): does not cause any changes in aqueous solution
(difference from other ions from the copper sub-group)
 Tin (II) chloride: when added in moderation: white and silky precipitate,
mercurium (I) chloride (calomel)

 Copper sheets or coins reduce mercurium (II) ions to their metals

 Reagentia dienkuprato (II) sulfate * in the presence of potassium iodide:

dark blue violet deposition in neutral or amoniacal solution. First
tetraiodomercurat (II) ions are produced

 Diphenylcarbazide reacts with mercurium (II) ions in a manner similar to

mercurium (I)
 Cobalt (II) thiocyanate test. To the test solution, add the same volume of
reagents (about 10%, freshly made), and rub the walls of the vessel with a
glass rod. Dark blue crystalline deposits, namely cobalt
tetratiocyanatomerkurat (II)

 Dry test : All mercury compounds, irrespective of their valency state, form
mercury metal when heated with excess anhydrous sodium carbonate.

 Hydrogen sulfide (saturated water solution gas): bismuth sulfide black
 Ammonia solution: white base salt with various compositions. Insoluble
precipitates in excessive reagentia difference from copper or cadmium)

 Sodium hydroxide: white bismuth (III) hydroxide precipitate

 Potassium iodide when added dropwise: black precipitate, bismuth (III)


 Potassium cyanide (poison): white precipitate, bismuth hydroxide

 Sodium tetrahydroxostanate (II): in a cold solution, it reduces bismuth (III)

ions to bismuth metal which separates in the form of black deposits. At first

 sodium hydroxide in regensia reacts with bismuth (III) ions, then bismuth
(III) hydroxide is reduced by tetrahydroxostanate (II) ions, bismuth metal
and hexahydroxostanate ions are formed.


 Hydrogen sulfide (gas or saturated water-solution): black precipitate, copper (II) sulfide

 Ammonia solution if added in very small amounts: blue precipitate of a basic salt (copper sulphate base)

 Sodium hydroxide in cold solution: copper (II) hydroxide blue precipitate

 Potassium iodide: precipitates white copper (I) iodide, but the solution is dark brown due to the formation of
tri-iodide ions

 Potassium cyanide (poison): when very little is added, a yellow copper (II) cyanide precipitate is formed

 Potassium hexasianoferate (II): reddish-brown precipitate, ie copper hexacyanoferate (II) in a neutral or

acidic atmosphere

 Potassium thiocyanate: black copper (II) thiocyanate deposits

 Iron. If a clean piece of iron nail or folding blade is dipped in a solution of a

copper salt: a red precipitate of solid copper is obtained

 Benzoinoxima (or kupron) (5% in alcohol): forms a copper (II)

benzoinoksima green precipitate
 Salcylaldoxima (1%): forms salisilaldoxima copper-yellowish-green
 A rubeanate acid (or ditio-oxamide): copper rubeanate black deposits
 Ammonium tetratiosianatomerkurat (II): dark purple crystal deposits in the
presence of zinc or cadmium ions

 Catalytic Test : (a) is fairly rapid; reaction (b) is a slow one, but is
enormously acceler• ated by traces of copper.

 Dry test
a. Blowpipe test When copper compounds are heated with
alkali carbonate upon charcoal red metallic copper is obtained but
no oxide is visible.
b. Borax bead Green while hot, and blue when cold
after heating in the oxidizing flame; red in the reducing flame, best
obtained by the addition of a trace of tin.
c. Flame test Green especially in the presence of halides, e.g. by
moistening with concentrated hydrochloric acid before heating.

 Hydrogen sulfide (gas or saturated water solution): yellow cadmium sulfide

 Ammonia solution when added dropwise: cadmium (II) white hydroxide


 Sodium hydroxide: white cadmium (II) hydroxide precipitate

 Potassium cyanide (poison): a white precipitate of cadmium cyanide

 Potassium thiocyanate: does not form deposits

 Potassium iodide: does not form deposits
 Dinitro-p-diphenyl carbazide (0.1%): forms a brown product with cadmium
hydroxide, which turns greenish-blue with formaldehyde
 4-Nitronaphthalene-diazoamino-azo-benzene: cadmium hydroxide forms a
red dye with reagents, which contrasts with the blue hue of the reagents
 Dry test :
a. Blowpipe test All cadmium compounds when heated with
alkali carbonate on charcoal give a brown incrustation of cadmium oxide
b. Ignition test Cadmium salts are reduced by sodium oxalate to
elementary cadmium, which is usually obtained as a metallic mirror
surrounded by a little brown cadmium oxide. Upon heating with sulphur, the
metal is converted into yellow cadmium sulphide.

 Hydrogen sulfide: arsenic (III) sulfide yellow precipitate

 Silver nitrate: Yellow deposition of arsenite in a nitrate solution

 Magnesia mixture (solution containing MgCl2, NH4Cl and a little NH3: no

 Copper sulphate solution: arnesite copper green precipitate
 Potassium tri-iodide: oxidizes arsenite ions while losing color

 Tin (II) chloride and concentrated hydrochloric acid solutions (Bettendorff


 Hydrogen sulfide, does not occur immediately precipitate in the presence of
dilute hydrochloric acid.

 Silver nitrate solution; red-brown precipitate, silver arsenate Ag3AsO4, from

a neutral solution.

 Magnesium mixture; white crystalline precipitate magnesium ammonium

arsenate, Mg (NH4) AsO4.6H2O, from neutral or amoniacal solutions.
 Ammonium molybdate solution; if this reagentia and nitric acid are added in
excess to a solution of an arsenic, it will produce ammonium

 Potassium iodide solution; if there is concentrated hydrochloric acid, the

iodine will be precipitated, by shaking the mixture with 1-2 ml of
chloroform or carbon tetrachloride, the latter will be colored purple by

 Uranyl Acetate Solution; deposits such as light yellow gelatin, uranyl

ammonium arsenate UO2 (NH4) AsO4.XH2O, in the presence of excessive
ammonium acetate.

 Hydrogen sulfide: orange-red stibium trisulfide deposit, Sb2O3, from
not-so-acid solutions.

 Water: when the solution is poured into water, a white precipitate of

antimonyl chloride, SbOCl is dissolved in hydrochloric acid and in a
solution of tartrate.
 Sodium hydroxide or ammonia solution: white stibium (III) oxide hydrated
Sb2O3.XH2O, which dissolves in concentrated alkaline alkaline solutions to
form antimony.

 Zinc: black sediment is produced, i.e. stibium.

 Iron wire: stibium black deposits.

 Potassium iodide solution: the color becomes red due to the formation of
complex salts.
 Reagentia rodamina-B: blue staining with quintuevalent stibium (validated
 Reagents of phosphomolybdic acid: blue molybdenum is produced by
stibium (III) salts.

 Hydrogen sulfide: red-orange precipitate stibium pentasulfide, Sb2S5, in an
acidic solution

 Water: white deposits of alkaline salts with varying compositions, eventually

forming antimonic acids.

 Potassium iodide solution: in an acidic solution, iodine separates.

 Zinc or lead: stibium black deposits in the presence of hydrochloric acid.

 Reagents of rodamide-B: see stibium (III) compounds.

 Hydrogen Sulfide: lead (II) sulphide brown deposition, SnS, from a solution
that is not too acidic

 Sodium hydroxide solution: white precipitate tin (II) hydroxide which

dissolves in excessive alkali.

 Mercurium (II) chloride solution: white precipitates of mercurium (II)

chloride are formed, if large amounts of reagents are added quickly.
 Bismuth nitrate and sodium hydroxide solutions: black bismuth metal
 Metal zinc: tin that resembles foam rubber settles and attaches to zinc.
 Dimethylglyoxima-iron (III) chloride test: no staining when iron (III) ion is
mixed with dimethylglyoxima reagents and a small amount of ammonia
solution, but if there is a small amount of iron (II) a dark red color occurs,
which is caused by the iron (II) dimethylglyoxima complex .
 Cocoteline reagents (cacotheline, nitro derivatives from the C12H21O7N3
brusir): staining violet with stano salts.
 Diazine green reagents (dyes formed by coupling reaction between azazized
safranania and dimethilanilina): lead (II) chloride reduces green diazina in
blue to red safranina
 4-methyl-1,2-dimercapellenzene reagents: red precipitate when heated with
lead salts (II) in acidic solutions

 Hydrogen Sulfide: Yellow sulphide (IV) sulfide, SnS2, from dilute acid

 Sodium hydroxide solution: white precipitate such as gelatin, namely lead

(IV) hydroxide, Sn (OH) 4, which dissolves in excessive precipitating
substances, by forming hexahydroxostanate (IV).

 Mercurium metal (II) chloride: no deposits (difference from lead (II)).

 Ferrous metals: reducing tin (IV) ions to tin (II).

 Dry test
Blow pipe test, all lead compounds when heated with sodium carbonate, pref
erably accompanied by potassium cyanide, on top of the charcoal give
granules of tin which are white and forged, which do not stain paper.
The borax bead test, the borax bead that has been colored light blue by
copper salts, becomes clear red colored in a flame of reduction, if only very
little lead is added.

Pereaks Hg2+ Sn2+ Bi3+ Cu2+ Cd2+

H2S ↓ Putih Hg3S2Cl2 Coklat ↓ Hitam ↓ Hitam CuS ↓ Kuning
Bi2Sr3 CdS
↓ Hitam HgS
↓ SnS
NH3, ↓ Putih ↓Bi(OH)2NO ↓ Biru ↓ Putih
HgO.Hg(NH)2NO 3 Cd(OH)2
sedikit Cu(OH)2CuSO
3 4
NaOH, ↓ Merah Putih ↓ Putih ↓ Biru Cu(OH)2 ↓ Putih
sedikit kecoklatan Bi(OH)3 Cd(OH)2
+ ↓ Sedikit larut Tidak larut Tidak larut
berlebih Larut 2
KI ↓ Merah HgI2 ↓ Putih Putih, CuI2
Berlebi Larut Larut, (BrI)2-
KCN Tdk ada ↓ Putih Kuning, ↓ Putih
perubahan Bi(OH)3 Cu(CN)2 Cd(CN)2

Tdk ada Tdk larut Larut Larut
perubahan [Cd(CN)4]2
SnCl2 ↓ Putih ↓ HgCl2
Berlebi ↓ Hitam Hg
Air ↓ Putih

Reaksi Uji kobalt (II) Kalium Asam tionat Dinitro-P

spesifik iodida depensi ↓
Tiosianat → biru → hitam warbadida
tua → (0,1%) →
n merah dari coklat
Uji Biru Hijau
nyala abu-abu kebiran

Pereaksi As3+ As5+ Sb3+ Sb5+ Sn4+

H2S Suasana Kuning Merah Coklat Kuning
asam kuning As2S5 jingga Sb5S2 SnS2
(As2S3) Sb2S3
Tidak larut Larut
Tidak larut Larut Larut, SnS2
+ HCl pelarut,
AgNO3 + Kuning Merah
HNO3/NH4OH Ag3AsO3 coklat
Larut, Larut
SnCl2 + 2 mL HCl
0,5 mL
SnCl2 ↓
Coklat tua
NH4-molibolat Kristalin
KI + HCl pekat, Merah
ungu, I2 ↓ (SbI)3-
kuning muda

Air Putih, Putih SbO4

NaOH/NH4OH Putih, Putih Putih,
SbO3 Sb(OH)2 Sn(OH)4
Zink ↓ Hitam, Sb ↓ Hitam Sb Mereduksi
ion Sn4+
HgCl2, sedikit Putih, Tdk ada
berlebih HgCl2 endapan
Reaksi spesifik ↓ kuning Barutan Reagensia Reagensia
muda utanil rodamin-B Rodamin-B
asetat: ↓ Warna
kuning muda biru

Group III : Al2+ ions,Cr2+, CO2+, Fe2+, Ni2+, Mn2+,

Group reagent: hydrogen sulphide (gas or saturated aqueous solution)
inthe presence of ammonia and ammonium chloride, or ammonium
sulphide solution.
Group reaction: precipitates of various colours: iron(II) sulphide
(black),aluminium hydroxide (white), chromium(III) hydroxide (green), nickel
sulphide(black), cobalt sulphide (black), manganese(II) sulphide
(pink), and zinc sulphide (white).
The metals of this group are not precipitated by the group
reagents for Groups I and II, but are all precipitated, in the presence of
ammonium chloride,by hydrogen sulphide from their solutions made
alkaline with ammonia solution. The metals, with the exception of aluminium
and chromium which are precipitated as the hydroxides owing to the complete
hydrolysis of the sulphides in aqueous solution, are precipitated as the
sulphides. Iron, aluminium, and chromium (often accompanied by a little
manganese) are also precipitated as the hydroxides by ammonia solution in
the presence of ammonium chloride, whilst the other metals of the group
remain in solution and may be precipitated as sulphides by hydrogen sulphide.
It is therefore usual to subdivide the group into the iron group (iron,
aluminium, and chromium) or Group IIIA and the zinc group (nickel,
cobalt, manganese, and zinc) or Group IIIB.

 Sodium hydroxide solution: white precipitate iron (II) hydroxide

 Ammonia Solution: precipitation of iron (II) hydroxide occurs

 Hydrogen sulfide: no precipitation occurs in acidic solutions

 Ammonium sulfide solution: black deposits of iron (II) sulfide

 Potassium cyanide solution (POISON): a yellowish brown precipitate

 Passium hexasianoferate (II) solution: white potassium iron (II)

hexasianoferate precipitate

 Passium hexacyanate (III) solution: dark blue precipitate is obtained

 Ammonium thiocyanate solution: no staining with pure iron (II) salts

(difference from iron (III) ions)
 Reagent - Dipyridyl: dark red complex of bivalent cations [Fe (C5H4N) 2]
2+ with iron salts (II) in a mineral acid solution
 Dimethylglyoxima reagent: iron (II) red methyl dimethylglyoxima and
ammonia solution
 Reagentia o-Fenantrolina red staining, caused by cation complex [Fe
(C18H8N2) 3] 2+ in a solution that is slightly acidic

 Ammonia solution: red brown deposits such as gelatin from iron (III)

 Sodium hydroxide solution: reddish copper (III) hydroxide precipitate

 Hydrogen sulfide gas: in acidic solutions reduce iron (III) ions to iron (II)
and form sulfur as a milky-white precipitate

 Ammonium sulfide solution: a black precipitate is formed consisting of iron

(II) sulfide and sulfur

 Potassium cyanide (POISON) when added slowly, produces a reddish-brown

precipitate of iron (III) cyanide

 Potassium hexasianoferate (II) solution: dark blue precipitate, iron (III)

hexasianoferate (Prussian blue)

 Potassium hexacyanate (III): a brown stain is produced, by the formation of

an undissociated complex, namely iron (III) hexacyanation (III)

 Disodium hydrogen phosphate solution: a yellowish-white precipitate of iron

(III) phosphate is formed

 Sodium acetate solution: reddish brown staining obtained, which is caused

by the formation of complex ions with the composition [Fe3 (OH) 2
(CH3COO) 6] +
 Reagentia Kupferon, ammonium salt from nitrofenihydroxylamine, C6H5
(NO) ONH4 reddish-brown precipitate is formed when there is hydrochloric

 Ammonium thiocyanate solution: in a slightly acidic solution, a deep red

staining is produced, which is due to the formation of an undissociated iron
(III) thiocyanate complex

 7-iodo-8-hydroxyquinoline-5-sulfonic acid green staining or blue-greenish

with iron salts (III) in a slightly acidic solution (pH 2.5-3.0)

 The reduction of iron (III) ions to iron (II) in acidic solutions can be
achieved with various substances

 Oxidation of iron (II) ions to iron (III) oxidation occurs slowly when exposed to air

 Distinction determination tests for iron (II) and iron (III) ions

 Dry tests

a. Blowpipe test When iron compounds are heated on charcoal

with sodium carbonate, grey metallic particles of iron are produced; these are ordinarily
difficult to see, but can be separated from the charcoal by means of a magnet.

b. Borax bead test With a small quantity of iron, the bead is yellowish-brown while
hot and yellow when cold in the oxidizing flame, and pale green in the reducing flame;
with large quantities of iron the bead is reddish-brown in the oxidizing flame.

 Ammonia solution: face like a green gray to blue gray

 Sodium hydroxide solution: chromium (III) hydroxide precipitate

 Sodium carbonate solution: chromium (III) hydroxide deposit

 Ammonium sulfide solution: chromium (III) hydroxide precipitate

 Sodium acetate solution: no deposits, even with boiling

 Sodium phosphate solution: chromium (III) phosphate green precipitate

 7. Chromate Test. Chromium (III) ions can be oxidized to chromate in several ways

 8.Identification of chromium after oxidation to chromate

 Barium Chloride Test : a yellow precipitate of barium chromate is formed

 Chromium pentoxide test

 Diphenylcarbazide test In dilute mineral acid solution diphenylcarbazide produces a

soluble violet colour, which is a characteristic test for chromium.

 9. Dry test

a. Blowpipe test AU chromium compounds when heated with sodium

carbonate on charcoal yield a green infusible mass of chromium(III) oxide

b. Borax bead test The bead is coloured green in both the oxidizing
and reducing flames, but is not very characteristic

c. Fusion with sodium carbonate and potassium nitrate in a loop of platinum wire
or upon platinum foil or upon the lid of a nickel crucible results in the formation of a
yellow mass of alkali chromate.


The oxoanions ofcertain Group III metals, like chromate

are reduced by hydrogen sulphide in hydrochloric acid media to chromium(III) and

manganese(II) ions respectively. In the course of the systematic analysis of an unknown
sample (cf. Chapter V) these anions will already be converted into the
corresponding Group III cations when the separating process reaches this stage. If therefore
chromium(III) and/or manganese(II) are found, the initial oxidation states of these metals
should be tested in the original sample.
 Sodium hydroxide solution: in a cold state, settles a blue base salt, on heating with
excessive alkali the base salt is converted to cobalt (II) hydroxide precipitate which is pink

 Ammonia solution: if there are no ammonium salts, a little ammonia will precipitate
alkaline salt.

 Ammonium sulfide solution: black cobalt (II) sulfide precipitate from a neutral or basic

 Potassium cyanide (poison) solution: cobalt-reddish-brown precipitate (II) cyanide.

 Potassium nitrite solution: yellow precipitate potassium hexanitritocobaltate (III).

 Ammonium thiocyanate test (vogel reaction): by adding a few crystalline ammonium

thiocyanate crystals to a neutral or acid cobalt (II) solution, appearing blue because the
tetratiocyanatocobaltate (II) ion is formed

 Reagents of α-nitroso-β-naphthol: reddish brown cobalt (III) α-nitroso-β-naphthol CO

(C10H6O2N) 3 which is slightly pure, the precipitate can be extracted with carbon
tetrachloride, which will produce a wine red solution.

 Reagents of sodium 1-nitroso-hydroxynaphthalene-3: 6-disulfonate: dark red staining, this

test can be used even if there is disturbing nickel, lead and iron and must be removed, the
color produced by iron can be prevented by adding an alkyl fluoride.

 Rubeanic acid (or ditio-oxamide) reagents: brownish-yellow deposits, nickel salts and
copper give blue and black deposits respectively.

 Dry test

a. Blowpipe test All cobalt compounds when ignited with sodium

carbonate on charcoal give grey, slightly metallic beads of cobalt. If these are
removed, placed upon filter paper, and dissolved by the addition of a few drops of dilute
nitric acid, a few drops of concentrated hydrochloric acid added and the filter paper dried,
the latter is coloured blue by the cobalt chloride produced.

b. Borax bead test This gives a blue bead in both the oxidizing and reducing flames.
Cobalt metaborate Co(BO,),, or the complex salt Na,Co(BO,),, is

formed. The presence of a large proportion of nickel does not interfere.

 Sodium hydroxide solution: green nickel (II) hydroxide precipitate, insoluble precipitate in
excessive reagents.

 Ammonia solution: green nickel (II) hydroxide precipitate, which dissolves in excess
reagency the solution turns dark blue.

 Ammonium sulfide solution: black nickel sulfide precipitate from a neutral or slightly
alkaline solution.

 Hydrogen sulfide (gas or saturated water solution): only a portion of nickel settles slowly as
nickel sulfide from neutral solution.

 Potassium cyanide solution (POISON): nickel green (II) cyanide precipitate, precipitate
dissolved in excessive reagents.

 Potassium nitrite solution: no precipitate in the presence of acetic acid.

 Α-nitroso-β-naphthol reagents: brown deposits with the composition of Ni (C10H6O2N) 2

which are soluble in hydrochloric acid, which results in reddish-brown deposits.

 Dimethylglyoxima reagents: dimethylgliosima nickel red precipitates from the right

solution base with ammonia.

 Α-furil-dioxima reagents: red deposits in a slightly amoniacal solution.

 Rubeanic acid reagents: deposits or blue stain to violet in an ammonia solution.

 Dry test

a. Blowpipe test All cobalt compounds when ignited with sodium

carbonate on charcoal give grey, slightly metallic beads of cobalt. If these are
removed, placed upon filter paper, and dissolved by the addition of a few drops of dilute
nitric acid, a few drops of concentrated hydrochloric acid added and the filter paper dried,
the latter is coloured blue by the cobalt chloride produced.

b. Borax bead test This gives a blue bead in both the oxidizing and reducing flames.
Cobalt metaborate Co(BO,),, or the complex salt Na,Co(BO,),, is

formed. The presence of a large proportion of nickel does not interfere.

 Sodium hydroxide solution: manganese (II) hydroxide precipitate. Firstly white, insoluble
deposits in excess reagency.

 Ammonia solution, deposition of manganese (II) hydroxide which was (originally) white,
precipitation did not occur if there were ammonium salts.

 Ammonium sulfide solution: pink manganese (II) sulfide sediment, the sediment also
contains weakly bound water.

 Sodium phosphate solution: ammonium phosphate pink deposits.

 Lead oxide and concentrated nitric acid: by boiling a dilute solution of manganese (II) ions

 Ammonium or potassium peroxodisulfate

 Sodium bismuthate: when this solid is added to the cold solution of manganese (II) ions in
diluted nitric acid, it produces a permanganate solution.

 Potassium periodate

Potassium periodic test 'retrabasa'

'tetrabasa' solution in chloroform,

 Formaldoxymal reagents: red staining with a solution of manganese (II) salts that are basic.

 Dry Tests :
Borax bead test, a bead produced in flame by small amounts of manganese salt

Melting test, melting each manganese compound with sodium carbonate and an oxidizing

 Sodium hydroxide solution: precipitate like white gelatin, namely zinc hydroxide

 Ammonia solution: white zinc hydroxide precipitate

 Ammonium sulfide solution: white zinc sulphide precipitate

 Hydrogen sulfide: white sulphide precipitate

 Dodium hydrogen phosphate solution: white zinc phosphate deposition

 Potassium hexasianoferate (II) solution: white precipitate with different composition; if the
reagents are added a little too much, the depositional composition is K2Zn3 [Fe (CN) 6] 2

 Quinaldic acid reagents: white precipitate of zinc Zn (C10H6NO2) complex 2.H2O

 Ammonium tetratiosianatomerkurat (II)-sulfate copper test: white precipitate Zn [Hg (SCN)


 Ammonium tetratiosianatomerkurat (II) -cobalr sulfate test: blue precipitate consisting of a

mixture of crystals Zn [Hg (Hg (SCN) 4] + Co [Hg (SCN) 4]

 Potassium hexacyanate (III) p-phenetidine test: zinc hexacyanation (II) precipitate

 Rinmann green test

 Ditizon Test (diphenyl thiocarbazone) :

 forms complexes with a number of metal ions, which can be extracted with carbon

Pereaksi Fe2+ Fe3+ Al3+ Cr3+

NaOH ↓ Putih ↓ Coklat merah ↓ Putih Al(OH)3 Larut ↓ Hijau
Fe(OH)2 Fe(OH)3 biru Cr(OH)3
Tidak larut
+ berlebih Larut [Al(OH)3]- [Cr(OH)4}-
Tidak larut
NH4OH ↓ Putih ↓ Coklat merah Putih gelatine Hijau biru
Fe(OH)2 Fe(OH)3 Al(OH)3 Cr(OH)3
Tidak larut Larut sedikit Larut sedikit
+ berlebih
Al2S Tdk ada Putih susu
endapan Fe2SO3
(NH4)2S Hitam FeS ↓ Hitam Fe2S3 ↓ Putih Al(OH)3 ↓ abu-abu hijau
biru Cr(OH)3
Asam HCl Larut Larut
KCN Coklat Coklat
kekuningan kemerahan
+ berlebih [(Fe(CN)6]3-
K4F2(CN) Putih, K2F2
K3Fe(CN)6 Biru tua Coklat [Fe
[Fe(CN)6]3 (CN)6]
Dimetil Merah
Mg3HPO4 Putih Putih gelatine Hijau biru
kekuningan AlPO4 CrPO4
NaCH3COOH Coklat Tidak ada Tidak ada
kemerahan endapan putih, perubahan
+ berlebih

Na2CO3 Putih, Al(OH)3 Abu-abu hijau

biru, Cr(OH)3
Reaksi spesifik V- Kuprikan, Alizarin-S
endapan endapan merah
fenamtrolina coklat
warna merah kemerahan
(bila ada HCl)

Pereaksi Co2+ Ni2+ Mn2+ Zn2+

NaOH ↓ Biru ↓ Hijau ↓Putih ↓ Putih gelatin
+ berlebih ↓ Merah jambu Tidak larut Tidak larut larut
NH4OH ↓ Biru ↓ hijau ↓ putih ↓ putih
+ berlebih Larut Larut Tidak larut
(NH4)2S ↓ hitam ↓ hitam ↓ merah jambu ↓ putih
+ HCl encer Tidak larut Larut
+ berlebih Tidak larut
coklat tua
KCN ↓ kuning Tidak ada ↓
NH4(SCN)2 Larutan biru
H2S ↓ hitam Hanya sebagian ↓ ZnS
yg mengendap
Na(HPO4)2 ↓ merah jambu
Na2HPO4 ↓putih
KNO2 ↓ kuning Tidak ada ↓
Warna zat Biru Hijau

Group IV : Ba2+,Sr2+,Ca2+
Group reagent: IM solution of ammonium carbonate.

The reagent is colourless, and displays an alkaline reaction because of hydrolysis:

The reagent is decomposed by acids (even by acetic acid), when carbon dioxide gas is formed:

The reagent has to be used in neutral or slightly alkaline media.

 Ammonia solution: no barium hydroxide deposits occur because of their relatively high
 Ammonium carbonate solution: white deposits of barium carbonate, which are soluble in
acetic acid and in dilute mineral acids.

 Ammonium oxalate solution: white deposits of barium oxalate Ba(COO)2, which are only
slightly soluble in water, but are dissolved easily by dilute acetic acid and by mineral acids.

 Dilute sulfuric acid: white barium sulfate BaSO4, which is fine-grained, heavy, and practices
insoluble in water, almost insoluble in dilute acid and in a solution of ammonium sulfate,
and dissolves quite well in boiling concentrated sulfuric acid.

 Saturated calcium sulfate solution: immediate deposition of white barium sulfate.

 Potassium chromate solution: barium chromate yellow precipitate, which is practically

insoluble in water, insoluble precipitate in dilute acetic acid.

 Sodium rodizonate reagents: reddish-brown deposits, that is, barium salt from rodizonic
acid in neutral solutions.

 Water and ether free ethanol: a 1 + 1 mixture of these solvents does not dissolve barium
nitrate anhydrous or barium chloride.

 Dry test (staining): barium salts, when heated in an incomplete bunsen (bluish) flame, give
the flame a yellowish-green color.

 Ammonia solution: no deposits

 Ammonium carbonate solution: white deposition of strontium carbonate, strontium

carbonate is somewhat less soluble than barium carbonate.

 Dilute sulfuric acid: strontium sulfate white precipitate, solubility of the precipitate cannot
be ignored.
 Saturated calcium sulfate solution: strontium sulphate white precipitate, formed slowly in
a cold state, but faster by boiling.

 Ammonium oxalate solution: strontium oxalate white precipitate, precipitate only slightly
soluble in water.

 Potassium chromate solution: Strontium chromate yellow precipitate, precipitate dissolves

somewhat in water, then no precipitate occurs in dilute strontium solution.

 Sodium rodizonate reagents: reddish-brown deposits of strontium rodizonate in neutral


 Water-free ethanol and ether: a mixture of 1 + 1 of these solvents, does not dissolve
anhydrous strontium nitrate, but dissolves anhydrous strontium chloride.

 Dry test (staining): volatile strontium compounds, especially their chlorides, give a
distinctive red-karmin color to the bunsen flame that is not bright.

 Ammonia solution: no deposits, because calcium hydroxide dissolves quite a lot.

 Ammonium carbonate solution: white amorphous precipitate of calcium carbonate, by

boiling, the precipitate becomes crystalline.

 Dilute sulfuric acid: calcium sulphate white precipitate, CaSO4 is quite significant in water,
which is more soluble than barium or strontium sulfate.

 Saturated calcium sulfate: no sediment (a difference between strontium and barium).

 Ammonium oxalate solution: white calcium oxalate precipitate, immediately from

concentrated solutions and later from dilute solutions.

 Potassium chromate solution: no precipitate from dilute solutions, nor from concentrated
solutions in the presence of acetic acid.

 Potassium hexasianoferate (II) solution: white salt mixture. In the presence of ammonium
chloride, this test will be more sensitive.
 Reagents of sodium dihydroxitartrate osazone: yellow salts of calcium salts that are very
little soluble.

 Reagents of picrolonic acid: typical rectangular crystals and calcium picrolonic in neutral or
acetic acid solutions. Strontium and barium also give deposits but with different crystalline

 Calcium sulphate dihydrate (microscopy) test:

 Water-free ethanol, or a 1 + 1 mixture of water-free ethanol and diethyl ether, dissolves

both calcium chloride and calcium nitrate.

 Dry test (staining): volatile calcium compounds, giving a yellowish red color to the bunsen

Pereaksi Ba2+ Sr2+ Ca2+

NH4OH Keruh (≠↓) Keruh (≠↓)
(NH4)2CO3 ↓ putih ↓ putih Amorf putih
+ CH3COOH Larut
↓ Kristal
Amonium Oksalat ↓ putih ↓ putih
+ CH3COOH Larut
H2SO4 encer ↓ putih ↓ putih ↓ putih
+ H2SO4 Larut Larut
CaSO4 ↓ putih
K2CrO4 ↓ kuning ↓ putih
Larutan jingga
dipanaskan kemerahan
Uji nyala Hijau kekuningan Merah barmin Merah kekuningan
K4Fe(CN)6 ↓ putih

Group V : K +, NH4 +, Mg +, and Na +.

Group reagent: there is no common reagent for the cations of this group.

Group reaction: cations of the fifth group do not react with hydrochloric acid, hydrogen
sulphide, ammonium sulphide or (in the presence of ammonium salts) with ammonium
Mg +
 Ammonia larvae: partial precipitation of white magnesium hydroxide such as gelatin

 Sodium hydroxide solution: a white precipitate of magnesium hydroxide, which is insoluble

in excessive reagents, but easily dissolves in ammonium salts

 Ammonium carbonate solution: in the absence of ammonium salts, white magnesium

carbonate base deposits occur

 Sodium carbonate solution: a white, large-volume precipitate, that is, basic carbonate,
which is insoluble in an alkaline solution, but is easily soluble in acids and ammonium salts

 Dodium sodium phosphate solution: white crystalline precipitate of magnesium

ammonium phosphate

 Diphenylcarbazide reagents: the magnesium saline solution, treated with sodium

hydroxide solution will form magnesium hydroxide precipitate, then the diphenylcarbazide
reagentia will obtain a red-brown color.

 Reagents of 8-hydroxyquinolina or 'oxine': yellow salts of the Mg (C9H6NO) complex 2,


 P-nitrobenzene-azo-resorcinol reagents: blue deposits

 Titan yellow reagents: red sediment

 Quinalizarin reagensia: blue precipitate or blue staining like cornflower with magnesium

 Dry test (dry pipe test) All magnesium compounds when ignited on charcoal
in the presence of sodium carbonate are converted into white mag• nesium oxide,
which glows brightly when hot. Upon moistening with a drop or two of cobalt nitrate
solution and reheating strongly, a pale-pink mass is obtained.

 Sodium hexanitritocobaltate (III) Na3 [Co (NO2) 6] solution: yellow precipitate potassium
hexanitritocobaltate (III)
 Tartaric acid solution (or sodium tartrate hydrogen solution): white crystalline precipitate
potassium hydrogen tartrate

 Perchloric acid (HClO4) solution: a white crystalline precipitate of potassium perchlorate

KClO4 from a solution that is not very thin

 Hexagloroplatinic (IV) (H2 [PtCl6]) acid reagents: yellow potassium hexachloroplatinic (IV)

 Test for sodium hexanitritocobaltate (III) -silver nitrate: insoluble K2Ag [Co (NO2) 6]

 Dipagrilamine (or hexanitrodifenylamine) reagents: crystalline deposits of their orange-red

potassium derivatives

 Sodium tetrafenylborone test: potassium forms a white precipitate in neutral solution or in

the presence of acetic acid

 Dry test (staining on) :Potassium compounds, preferably the chloride, colour the
non-luminous Bunsen flame violet (lilac).

Na +
 Uranyl magnesium acetate solution: Yellow crystalline precipitate, sodium magnesium
Uranyl acetate NaMg (UO2) 3 (CH3COO) 9.9H2O, from concentrated solutions

 Chloroplatinic acid, tartaric acid or sodium hexanitritocobaltate (III): no precipitate with

sodium salt solution

 Uranyl Zinc Acetate Reagensia: Yellow crystals of sodium zinc Uranyl Acetate, NaZn (UO2) 3
(CH3COO) 9.9H2O

 Dry test (staining test) : The colour is not visible when viewed through two
thicknesses of cobalt blue glass.
NH4 +
 Sodium hydroxide solution: ammonia gas released when heated, a mixture of mercurium
(II) amidonitrate and a black mercurium precipitate is formed

 Nessler reagents (base solution of potassium tetraiodomerkurat (II)): brown deposits or

brown or yellow staining are produced according to the amount of ammonia or
ammonium ions contained in mercurium (II) base amidoide deposits

 Sodium hexanitritocobaltate (III): ammonium hexanitritocobaltate (III) yellow precipitate

similar to that produced by potassium ions

 Hexachloroplatinic acid: ammonium hexachloroplatinic yellow precipitate

 Saturated sodium hydrogen tartrate solution: white precipitate ammonium tartrate acid
which is similar but slightly more soluble than the associated potassium salt, from which
the precipitate can be distinguished by the release of ammonia gas, when the precipitate is
heated with a solution of sodium hydroxide

 Perchloric acid or sodium perchloric solution: no precipitation (difference from potassium).

 Tanal-silver nitric acid test, to produce silver black tanic acid precipitates silver in the
presence of ammonia

 Reagents of p-nitrobenzene-diazonium chloride reagents (I) produce red staining with

ammonium salts, if there is a solution of sodium hydroxide

 Ammonia formation test. Put a drop of test solution or a small amount of solid in the micro
test tube, and add a drop of 2M sodium hydroxide solution. attach a small piece of red
litmus paper to the glass hook, and put the cover in place. The paper turns blue

 Dry test All ammonium salts are either volatilized or decomposed when heated
to just below red heat. In some cases, where the acid is volatile, the vapours
recombine on cooling to form a sublimate of the salt, e.g. ammonium chloride.

a.Glass objects

b. Ni-Crc Wire. Litmus paper

d. Bunsen burner
e. Wood clamp

f. Drip plate. Reaction tube rack

h. Spatel