Professional Documents
Culture Documents
. Copper is reddish coloured metal, takes on a bright metallic luster, and is soft,
malleable, ductile, and a good conductor of heat and electricity (second only to silver
in electrical conductivity). It melts at 1083 C. It is only superficially oxidised in air,
sometimes acquiring a green coating of hydroxo carbonate and hydroxo sulphate.
Silver. Pure silver has a brilliant white metallic luster. It is a little harder than
gold and is very ductile and malleable, being exceeded only by gold and perhaps
palladium. Pure silver has the highest electrical and thermal conductivity of all
metals. It melts at 962 C. It is stable in pure air and water, but tarnishes when
exposed to ozone, hydrogen sulphide, or air containing sulphur.
Gold is a heavy metal with its characteristic yellow colour when in a mass. In
powderous form it is usually reddish-brown, but when finely divided it may be black,
ruby, or purple. It melts at 1064 C. Gold is the most malleable and ductile metal, it is
soft and a good conductor of heat and electricity, and is unaffected by air and most
reagents.
Hot, concentrated sulphuric acid dissolves copper and silver, but gold is
resistant against it.
2+ 2
Cu + 2 H2SO4 Cu + SO4 + SO2 + 2 H2O
+ 2
2 Ag + 2 H2SO4 2 Ag + SO4 + SO2 + 2 H2O
Medium-concentrated (8M) nitric acid also dissolves copper and silver, but
gold is resistant.
2+
3 Cu + 8 HNO3 3 Cu + 6 NO3 + 2 NO + 4 H2O
+
6 Ag + 8 HNO3 6 Ag + 6 NO3 + 2 NO + 4 H2O
2+
3 Cu + 6 HCl + 2 HNO3 3 Cu + 6 Cl + 2 NO + 4 H2O
Au + 4 HCl + HNO3 H[AuCl4] + NO + 2 H2O
78
Silver and gold are resistant against alkalis.
Copper is hardly soluble in strong alkalis in the presence of oxygen, but it is
soluble in concentrated ammonia solution in the presence of oxygen:
+
4 Cu + 8 NH3 + 2 H2O + O2 4 [Cu(NH3)2] + 4 OH
Copper, silver, and gold is soluble in alkali cyanide solutions in the presence
of oxygen:
+
4 Cu + 8 KCN + 2 H2O + O2 8 K + 4 [Cu(CN)2] + 4 OH
+
4 Ag + 8 KCN + 2 H2O + O2 8 K + 4 [Ag(CN)2] + 4 OH
+
4 Au + 8 KCN + 2 H2O + O2 8 K + 4 [Au(CN)2] + 4 OH
+
Au-Au = +1.69 V
Compare the 3+
Au-Au = +1.50 V
standard redox potentials
NO-NO3 = +0.96 V
Au-[AuCl4] = +1.00 V
+
Ag-Ag = +0.80 V
+
Cu-Cu = +0.52 V
OH -O2= +0.40 V
2+
Cu-Cu = +0.34 V
+
H2-H = 0.0 V
+
Cu-[Cu(NH3)2] = -0.12 V
Ag-[Ag(CN)2] = -0.31 V
Cu-[Cu(CN)2] = -0.43 V
Au-[Au(CN)2] = -0.60 V
Au Be Al C Si Pb
cc HNO3
79
Principal cations of copper, silver, and gold
+ + +
(Cu ) * Ag (Au ) **
2+ 2+ 3+
Cu (Ag )*** Au
* Copper(I) ions are unstable in aqueous solution. Copper(I) compounds are colourless and most of
them are insoluble in water.
** Au+ ions are exceedingly unstable with respect to the disproportionation to Au and Au3+.
*** The ion is unstable to water (reduced by water into Ag+).
2+
Reactions of copper(II) ions, Cu
80
1. Hydrogen sulphide gas: black precipitate of copper(II) sulphide. Solubility
36
product: Ksp(CuS, 25 C)= 1.27x10 .
2+ +
Cu + H2S CuS + 2 H
Hot, concentrated nitric acid dissolves the copper(II) sulphide, leaving behind sulphur
as a white precipitate:
2+
3 CuS + 8 HNO3 3 Cu + 6 NO3 + 3 S + 2 NO + 4 H2O
When boiled for longer, sulphur is oxidised to sulphuric acid and a clear, blue
solution is obtained:
+ 2
S + 2 HNO3 2 H + SO4 + 2 NO
3 2
2 CuS + 8 CN 2 [Cu(CN)4] + S2
2+ 2 +
2 Cu + SO4 + 2 NH3 + 2 H2O Cu(OH)2.CuSO4 + 2 NH4
the precipitate is soluble in excess reagent, when a deep blue coloration is obtained
owing to the formation of tetraamminocuprate(II) complex ions:
2+ 2
Cu(OH)2.CuSO4 + 8 NH3 2 [Cu(NH3)4] + SO4 + 2 OH
If the solution contains ammonium salts, precipitation does not occur at all, but the
blue colour is formed right away. (The reaction is characteristic for copper(II) ions in
the absence of nickel.)
2+
Cu + 2 OH Cu(OH)2
The precipitate is insoluble in excess reagent, but soluble in ammonia solution when a
deep blue coloration is obtained:
2+
Cu(OH)2 + 4 NH3 [Cu(NH3)4] + 2 OH
81
When heated, the precipitate is converted to black copper(II) oxide by
dehydration:
Cu(OH)2 CuO + H2O
2+
2 Cu + 5 I 2 CuI + I3
Adding an excess of sodium thiosulphate to the solution, tri-iodide ions are reduced to
colourless iodide ions and the white colour of the precipitate becomes visible:
2 2
I3 + 2 S2O3 3 I + S4O6
2+
Cu + 2 CN Cu(CN)2
The precipitate quickly decomposes into white copper(I) cyanide and cyanogen
(highly poisonous gas):
The complex is so stable (i.e. the concentration of copper(I) ions is so low) that
hydrogen sulphide cannot precipitate copper(I) sulphide from this solution.
48
(Solubility product: Ksp(Cu2S, 25 C)= 2.26x10 .)
2+
Cu + 2 SCN Cu(SCN)2
2 +
2 Cu(SCN)2 + SO2 + 2 H2O 2 CuSCN + 2 SCN + SO4 +4H
82
8. Iron: if a clean iron nail is immersed in a solution of a copper salt, a red deposit
of copper is obtained and equivalent amount of iron dissolves:
2+ 2+
Cu + Fe Cu + Fe
The electrode potential of the copper-copper(II) system is more positive than that of
the iron-iron(II) system.
2+
Cu
3+
Bi
+
Reactions of silver(I) ions, Ag
+
Ag + Cl AgCl
With concentrated hydrochloric acid precipitation does not occur. Decanting the
liquid from over the precipitate, it dissolves in concentrated hydrochloric acid, when a
dichloroargentate complex is formed:
AgCl + Cl [AgCl2]
83
By diluting with water, the equilibrium shifts back to the left and the precipitate
reappears.
+
AgCl + 2 NH3 [Ag(NH3)2] + Cl
Dilute nitric acid or hydrochloric acid neutralises the excess ammonia, and the
precipitate reappears because of the equilibrium is shifted back towards the left.
AgCl + 2 CN [Ag(CN)2] + Cl
2 3
AgCl + 2 S2O3 [Ag(S2O3)2] + Cl
Hot, concentrated nitric acid decomposes the silver sulphide, and sulphur
remains in the form of a white precipitate:
+
3 Ag2S + 8 HNO3 6 Ag + 6 NO3 + S + 2 NO + 4 H2O
If the mixture is heated with concentrated nitric acid for a considerable time, sulphur
is oxidised to sulphate and the precipitate disappears:
+ 2
S + 2 HNO3 2 H + SO4 + 2 NO
+
Ag2O + 2 HNO3 2 Ag + 2 NO3 + H2O
+
Ag2O + 4 NH3 + H2O 2 [Ag(NH3)2] + 2 OH
84
4. Sodium hydroxide: brown precipitate of silver oxide:
+
2 Ag + OH Ag2O + H2O
+
Ag2O + 4 NH3 + H2O 2 [Ag(NH3)2] + 2 OH
+
Ag2O + 2 HNO3 2 Ag + 2 NO3 + H2O
+
Ag2O + H2O 2 AgOH 2 Ag + 2 OH
AgI + 2 CN [Ag(CN)2] + I
2 3
AgI + 2 S2O3 [Ag(S2O3)2] + I
+ 2
2 Ag + CrO4 Ag2CrO4
+ 2
Ag2CrO4 + 4 NH3 2 [Ag(NH3)2] + CrO4
+ + 2
2 Ag2CrO4 + 2 H 4 Ag + Cr2O7 + H2O
+
Ag + CN AgCN
When potassium cyanide is added in excess, the precipitate disappears owing to the
formation of dicyanoargentate ions:
AgCN + CN [Ag(CN)2]
85
8. Sodium carbonate solution: yellowish-white precipitate of silver carbonate.
12
Solubility product: Ksp(Ag2CO3, 25 C)= 8.45x10 .
+ 2
2 Ag + CO3 Ag2CO3
+
Ag2CO3 + 2 HNO3 2 Ag + 2 NO3 + CO2 + H2O
+ 2
Ag2CO3 + 4 NH3 2 [Ag(NH3)2] + CO3
When heating, the silver carbonate precipitate decomposes and brown silver oxide
precipitate is formed:
+ 2 +
3 Ag + HPO4 Ag3PO4 + H
+
Ag3PO4 + 3 HNO3 3 Ag + 3 NO3 + H3PO4
+ 3
Ag3PO4 + 6 NH3 3 [Ag(NH3)2] + PO4
Fe Zn Sn Cu
2+
Cu
+
Ag
2+
Standard redox potentials: Fe-Fe = -0.44 V; Zn-Zn2+= -0.76 V; Sn-Sn2+= -0.14 V;
Cu-Cu2+= +0.34 V; Ag-Ag+= +0.80 V.
86
The Group IIb Elements (Zn, Cd, Hg) and
Their Principle Ions
2+ 2
Zn + 2 H2SO4 Zn + SO4 + SO2 + 2 H2O
+ 2+ +
4 Zn + 10 H + NO3 4 Zn + NH4 + 3 H2O
With increasing concentration of nitric acid, dinitrogen oxide (N2O) and nitric oxide
(NO) are formed:
+ 2+
4 Zn + 10 H + 2 NO3 4 Zn + N2O + 5 H2O
2+ 2
3 Zn + 8 HNO3 3 Zn + 2 NO + 6 NO3 + 4 H2O
Concentrated nitric acid has little effect on zinc because of the low solubility of zinc
nitrate in such a medium.
87
Cadmium dissolves slowly in dilute acids with the evolution of hydrogen,
owing to its negative standard electrode potential of 0.40 V:
+ 2+
Cd + 2 H Cd + H2
It dissolves in hot, concentrated sulphuric acid with the evolution of sulphur dioxide,
and in medium concentrated nitric acid with the evolution of nitrogen monoxide.
2+
Mercury, owing to its positive standard potential (Hg/Hg = +0.85 V;
2+
Hg/Hg2 = +0.80 V), is unaffected when treated with hydrochloric acid or dilute (2M)
sulphuric acid.
Hot, concentrated sulphuric acid dissolves mercury. The product is mercury(I)
ion if mercury is in excess, while if the acid is in excess, mercury(II) ions are formed:
2+ 2
Hg in excess: 2 Hg + 2 H2SO4 Hg2 + SO4 + SO2 + 2 H2O
2+ 2
acid in excess: Hg + 2 H2SO4 Hg + SO4 + SO2 + 2 H2O
It reacts readily with nitric acid. Cold, medium concentrated (8M) nitric acid
with an excess of mercury yields mercury(I) ions, and with and excess of hot
concentrated nitric acid mercury(II) ions are formed:
2+
Hg in excess: 6 Hg + 8 HNO3 3 Hg2 + 2 NO + 6 NO3 + 4 H2O
2+
acid in excess: 3 Hg + 8 HNO3 3 Hg + 2 NO + 6 NO3 +
4 H2O
2
Zn + 2 OH + 2 H2O [Zn(OH)4] + H2
Ag Pb Zn
cold, concentrated
HNO3
medium conc.
(8M) HNO3
88
Oxides of zinc, cadmium, and mercury:
ZnO CdO Hg2O HgO
white brown black yellow or red
The oxides are practically insoluble in water; ZnO and HgO are a very little soluble,
and the solubility at 25 C is 0.00016 g and 0.0053 g/100 ml of water, respectively.
CdO and Hg2O are insoluble.
They all are soluble in acids (Hg2O only in nitric acid).
2+
Reactions of zinc(II) ions, Zn
1. Hydrogen sulphide gas: no precipitation occurs in acidic solution (pH about 06),
only partial precipitation of zinc sulphide in neutral solutions. In alkaline solution,
e.g. adding alkali acetate, the precipitation of white zinc(II) sulphide (solubility
25
product: Ksp(ZnS, 25 C)= 2.93x10 ) is almost complete.
2+ +
Zn + H2S ZnS + 2 H
2
[Zn(OH)4] + H2S ZnS + 2 OH + 2 H2O
89
The precipitate is insoluble in excess reagent, in acetic acid, and in solutions of
caustic alkalis, but dissolves in dilute mineral acids.
The precipitate obtained is partially colloidal; it is difficult to wash and tends
to run through the filter paper, particularly on washing. To obtain the zinc sulphide in
a form which can be ready filtered, the precipitation is carried out in boiling solution.
2+
Zn + 2 OH Zn(OH)2
The precipitate is soluble in acids and also in the excess of the reagent:
+ 2+
Zn(OH)2 + 2 H Zn + 2 H2O
2
Zn(OH)2 + 2 OH [Zn(OH)4]
2+ 2 +
3 Zn + 2 HPO4 Zn3(PO4)2 + 2 H
2+ + 2 +
Zn + NH4 + HPO4 Zn(NH4)PO4 + H
Both precipitates are soluble in dilute acids, when the reaction is reversed.
Also, both precipitates are soluble in ammonia:
2+ 3
Zn3(PO4)2 + 12 NH3 3 [Zn(NH3)4] + 2 PO4
2+ 2
Zn(NH4)PO4 + 3 NH3 [Zn(NH3)4] + HPO4
2+ + 4
3 Zn + 2 K + 2 [Fe(CN)6] K2Zn3[Fe(CN)6]2
The precipitate is insoluble in dilute acids, but dissolves readily in sodium hydroxide.
This reaction can be used to distinguish zinc from aluminium.
90
7. Dithizone test. Dithizone (diphenyl thiocarbazone) forms complexes with a
number of metal ions, which can be extracted with carbon tetrachloride. The zinc
complex, formed in neutral, alkaline, or acetic acid solutions, is red:
NH NH NH N N N
2+
2 S C + Zn S C Zn C S + 2 H+
N N N N N HN
Acidify the test solution with acetic acid, and add a few drops of the reagent
(dithizone dissolved in carbon tetrachloride). The organic phase turns red in the
2+ 2+ 2+ +
presence of zinc. (Cu , Hg2 , Hg , and Ag ions interfere.)
F Cl Br
2
S SO4
2
CrO42 CO3
2
OH
2+
Zn
3+
Al
2+
Ca
2+
Pb
2+
Reactions of cadmium(II) ions, Cd
91
E.g.: Compound Solubility ( g / 100 ml H2O)
at 20 C: CdCl2 140
0 C: Cd(NO3)2 109
25 C: CdF2 4,35
26 C: Cd(OH)2 0,00026
Cd3(PO4)2 -----
The reaction is reversible; if the concentration of a strong acid in the solution is above
0.5M, precipitation is incomplete. Concentrated acids dissolve the precipitate for the
same reason.
The precipitate is insoluble in potassium cyanide (difference from copper ions).
The precipitate dissolves in acid when the equilibrium shifts towards the left.
An excess of the reagent dissolves the precipitate, when colourless
tetramminecadminate(II) complex ions are formed:
2+
Cd(OH)2 + 4 NH3 [Cd(NH3)4] + 2 OH
2+
Cd + 2 OH Cd(OH)2
2+
Cd + 2 CN Cd(CN)2
92
2 +
[Cd(CN)4] + H2S CdS + 2 H + 4 CN
The marked difference in the stabilities of the copper and cadmium tetracyano
complexes serves as the basis for the separation of copper and cadmium ions, and also
for the identification of cadmium in the presence of copper.
2+ 2+ 3+
Cu Cd Bi
H2S
in acidic solution
NaOH
NH3
in excess
KI
Fe nail
2+
Reactions of mercury(I) ions, Hg2
93
2+
Hg2 + 2 Cl Hg2Cl2
+
Hg2Cl2 + 2 NH3 Hg + Hg(NH2)Cl + NH4 + Cl
This reaction can be used to differentiate mercury(I) ions from lead(II) and silver(I).
53
Owing to the extremely low solubility product of mercury(II) sulphide (6.44x10 )
the reaction is very sensitive.
Aqua regia dissolves the precipitate, yielding undissociated mercury(II) chloride and
sulphur:
3 Hg + 3 HgS + 12 HCl + 4 HNO3 6 HgCl2 + 3 S + 4 NO + 8 H2O
When heated with aqua regia, sulphur is oxidised to sulphuric acid and the solution
becomes clear:
2 +
S + 6 HCl + 2 HNO3 SO4 + 6 Cl + 8 H + 2 NO
2+ +
2 Hg2 + NO3 + 4 NH3 + H2O 2 Hg + HgO.Hg(NH2)NO3 + 3 NH4
This reaction can be used to differentiate between mercury(I) and mercury(II) ions.
2+
Hg2 + 2 OH Hg2O + H2O
The precipitate is insoluble in excess reagent, but dissolves readily in dilute nitric
acid.
When boiling, the colour of the precipitate turns to grey, owing to
disproportionation, when mercury(II) oxide and mercury metal are formed:
Hg2O HgO + Hg
94
5. Potassium chromate in hot solution: red crystalline precipitate of mercury(I)
chromate:
2+ 2
Hg2 + CrO4 Hg2CrO4
If the test is carried out in cold, a brown amorphous precipitate is formed with an
undefined composition. When heated the precipitate turns to red, crystalline
mercury(I) chromate.
Sodium hydroxide turns the precipitate into black mercury(I) oxide:
2
Hg2CrO4 + 2 OH Hg2O + CrO4 + H2O
When boiling the mercury(I) iodide precipitate with water, disproportionation takes
place again, and a mixture of red mercury(II) iodide precipitate and finely distributed
black mercury is formed:
Hg2I2 HgI2 + Hg
2+ 2
Hg2 + CO3 Hg2CO3
The precipitate turns slowly to blackish grey, when mercury(II) oxide and mercury
are formed:
Hg2CO3 HgO + Hg + CO2
95
10. Tin(II) chloride solution: reduces mercury(I) ions to mercury metal, which
appears in the form of a greyish-black precipitate:
2+ 2+ 4+
Hg2 + Sn 2 Hg + Sn
11. Copper sheet or copper coin: deposit of mercury metal is formed on the copper
surface.
2+ 2+
Hg2 + Cu 2 Hg + Cu
2+ + 2+
Hg2 Ag Pb
HCl
H2S
NH3
NH3
in excess
KI
KI
in excess
NaOH
Na2CO3
K2CrO4
Cu
96
2+
Reactions of mercury(II) ions, Hg
2+ +
3 Hg + 2 Cl + 2 H2S Hg3S2Cl2 + 4 H
+
Hg3S2Cl2 + H2S 3 HgS + 2 H + 2 Cl
The HgS precipitate is insoluble in water, hot dilute nitric acid, alkali hydroxides, or
ammonium sulphide.
Aqua regia dissolves the precipitate:
2+ +
2 Hg + NO3 + 4 NH3 + H2O HgO.Hg(NH2)NO3 + 3 NH4
97
3. Sodium hydroxide (added in small amounts): brownish-red precipitate with
varying composition; if added in stoichiometric amounts the precipitate turns to
yellow when mercury(II) oxide is formed:
2+
Hg + 2 OH HgO + H2O
The precipitate is insoluble in excess sodium hydroxide. Acids dissolve the precipitate
readily.
2+
Hg + 2 I HgI2
2+ 2+ 4+
2 Hg + Sn + 2 Cl Hg2Cl2 + Sn
If more reagent is added, mercury(I) chloride is further reduced and black precipitate
of mercury is formed:
2+ 4+
Hg2Cl2 + Sn 2 Hg + Sn + 2 Cl
2+
Hg2
2+
Hg
98
Compare the characteristic reactions of arsenic(III)(arsenite), antimony(III),
tin(II), tin(IV), copper(II), cadmium(II), bismuth(III), and mercury(II) ions.
3+ 3+ 2+ 4+ 2+ 2+ 3+ 2+
As Sb Sn Sn Cu Cd Bi Hg
HCl
H2S
precipitate
+
(NH4)2SX
+
HCl
NaOH
KI
KCN
NH3
SnCl2
Fe
99
Titanium (Group IVb) and Its Common Ions
Titanium, when pure, is a lustrous, white metal. It has a low density, good strength,
is easily fabricated, and has excellent corrosion resistance (melting point: 1660 C).
The metal is not attacked by mineral acids at room temperature or even by hot
aqueous alkali.
Solubility in acids
The titanium metal is not soluble in mineral acids at room temperature, but
soluble in hot, concentrated hydrochloric acid and sulphuric acid, and in hydrogen
fluoride:
3+
2 Ti + 6 HCl 2 Ti + 6 Cl + 3 H2
4+ 2
Ti + 4 H2SO4 Ti + 2 SO4 + 2 SO2 + 4 H2O
The best solvents of the metal are HF and acids to which fluoride ions have been
added; such media dissolve titanium and hold it in solution as fluoro complexes.
Titanium is insoluble in hot, concentrated nitric acid, like tin, because of the
formation of titanic acid (TiO2.xH2O) on the surface of the metal, which protects the
rest of the metal from the acid.
The white titanium(IV) oxide, TiO2, is used as a pigment and is far the most
important titanium oxide, which occurs also in the nature. The solubility of TiO2
depends considerably on its chemical and thermal history; strongly roasted specimens
are chemically inert.
Titanium(IV) ions exist only in strongly acid solutions; they tend to hydrolyse.
In strong acid the Ti4+ (aquated) ions are in equilibrium with Ti(OH)22+, Ti(OH)3+ and
TiO2+ ions (aquated); the main species is Ti(OH)22+ and if the acidity of the solution is
lowered titanium(IV) hydroxide is precipitated.
100
4+
Reactions of titanium(IV) ions, Ti
2+
Ti(OH)2 + 2 OH Ti(OH)4
2+ 2
Ti(OH)4 + H2SO4 Ti(OH)2 + 2 H2O + SO4
2+
Ti(OH)4 + 3 HCl Ti(OH)Cl + 3 H2O + 2 Cl
If precipitation takes place from hot solution, white TiO(OH)2 (or metatitanic acid,
H2TiO3) is formed, which is sparingly soluble in dilute acids.
2+
Ti(OH)2 + 2 OH TiO(OH)2 + H2O
2+
Ti(OH)2 + 2 OH TiO(OH)2 + H2O
2+
Ti(OH)2 + 2 H2PO4 Ti(HPO4)2 + 2 H2O
4. Zinc or tin metal: when any of these metals is added to an acid solution of a
titanium(IV) salt, a violet coloration is produced, due to reduction to titanium(III)
ions:
4+ 3+ 2+
2 Ti + Zn 2 Ti + Zn
2+ +
Ti(OH)2 + H2O2 + OH Ti(O2)OH + 2 H2O
OH2 OH2
H2O OH2 O OH2
Ti 4+ Ti 4+
- O
HO OH- OH-
OH2 OH2
101
Vanadium (Group Vb) and Its Common Ions
Vanadium is a bright, white metal, and is soft and ductile (melting point: 1890 C). It
has good corrosion resistance to alkalis, sulphuric and hydrochloric acid, and salt
waters. The metal has good structural strength.
Solubility in acids
The vanadium metal is not soluble in hydrochloric, nitric, or sulphuric acids
or in alkalis at room temperature due to passivation (thin protective oxide layer
forms).
It dissolves readily in aqua regia, in hot nitric acid, hot and concentrated
sulphuric acid, or in a mixture of concentrated nitric acid and hydrogen fluoride:
2+
3 V + 4 HNO3 + 6 HCl 3 VO + 6 Cl + 4 NO + 5 H2O
2+
3 V + 10 HNO3 3 VO + 6 NO3 + 4 NO + 5 H2O
2+ 2
V + 3 H2SO4 VO + SO4 + 2 SO2 + 3 H2O
* The orange decavanadate ion can exist in several protonated form, and with increasing
acidity of the solution rapidly gives the dioxovanadium(V) ion, VO2+.
Vanadium(II) and vanadium(III) ions are instable in aqueous solution, and easily
oxidised to vanadium(IV), due to their small standard reduction potentials:
3+ 2+
[VO2(H2O)4] + [VO(H2O)5] 2+ [V(H2O)6] [V(H2O)6] V
+0.999 V +0.359 V -0.256 V -1.186 V
102
Vanadium(V) oxide, V2O5, is the most stable and is far the most important vanadium
oxide. It is an orange (or brick red) powder, which is insoluble in water, but soluble
in both mineral acids and alkalis.
Vanadium(V) is moderately strong oxidising agent, thus if the oxide is dissolved in
hydrochloric acid chlorine gas is evolved and vanadium(IV) is produced. The oxide is
also reduced by warm sulphuric acid.
Vanadium pentoxide dissolves in sodium hydroxide to give colourless solutions and
3
in the highly alkaline region, pH>13, the main ion is VO4 . As the basicity is
reduced, a series of complicated reactions occurs with the formation of various
vanadates (mono, di, meta, deca, etc.).
Metavanadates, VO3
To study these reactions use a 0.1 M solution of ammonium metavanadate,
NH4VO3, or sodium metavanadate, NaVO3. The addition of some sulphuric acid
keeps these solutions stable.
+ 2+
2 VO3 + H2S + 6 H 2 VO + S + 8 H2O
2 3
VO3 + 4 S + 3 H2O VS4 + 6 OH
3 +
2 VS4 + 6 H V2S5 + 3 H2S
103
4. Hydrogen peroxide: A red coloration is produced when a few drops of hydrogen
peroxide solution are added dropwise to an acid (15-20 per cent sulphuric acid)
solution of a vanadate; excess hydrogen peroxide should be avoided.
The red colour is due to the formation of the
mono- and diperoxovanadium(V) ions, O
+
VO(O2) and VO(O2)2 : O OH 2
+ + V 5+
VO3 + 2 H + H2O2 VO(O2) + 2 H2O O
OH2
VO3 + 2 H2O2 VO(O2)2 + 2 H2O
OH2
If the solution is made alkaline and more
hydrogen peroxide is added, the colour
changes to yellow, due to the formation of
diperoxoorthovanadate(V) ions: O
O
+ 3 O
VO(O2) + H2O2 + 4 OH VO2(O2)2 + 3 V 5+
H2O O
3
O
VO(O2)2 + 2 OH VO2(O2)2 + H2O
OH2
The reaction is reversible; on acidification the
solution again turns red.
5. Lead acetate solution: yellow precipitate of lead vanadate, turning white or pale
yellow on standing; the precipitate is insoluble in dilute acetic acid but soluble in
dilute nitric acid.
8. Iron(III) chloride:
+ 2+ 2+ 3+
VO3 + 4 H + Fe VO + Fe + 2 H2O
The reaction proceeds from left to right in acid solution and in the reverse direction in
2+ 3+
alkaline solution. ((Fe /Fe )= +0.771 V)
104
Chromium (Group VIb) and Its Common Ions
Chromium is a silver-white, lustrous, hard, and brittle metal that takes a high polish
(melting point: 1857 C). Chromium is extremely resistant to ordinary corrosive
agents, which accounts for its extensive use as an electroplated protective coating.
Solubility in acids
The metal, if it is passivated (probably due to a thin protective oxide layer), is
not soluble in mineral acids, but the metal is rather active when not passivated.
2+ 3+
Redox potentials: (Cr/Cr )= 0.913 V; (Cr/Cr )= 0.744 V.
Redox potential(V)
2+ 0.0
Cr + 2 HCl Cr + 2 Cl + H2 -0.1 H2/H+
-0.2
Even if the solution is protected from air, chromium(II) ions decompose at rates
2+ 3+
varying with acidity, by reducing water with liberation of hydrogen ((Cr /Cr )=
0.407 V).
Chromium(II) ions are stable only in neutral and pure solutions at the exclusion of air.
3+ 2
2 Cr + 6 H2SO4 2 Cr + 3 SO4 + 3 SO2 + 6 H2O
Both dilute and concentrated nitric acid render chromium passive, as does
cold, concentrated sulphuric acid and aqua regia.
105
The green chromium(III) oxide, Cr2O3, and its hydrous form, Cr2O3.nH2O, are
amphoteric, dissolving readily in acids and in concentrated alkali, but if ignited too
strongly Cr2O3 becomes inert toward both acid and base.
2 2
Chromate (CrO4 ) and dichromate (Cr2O7 ) ions
In basic solutions above pH 7, the yellow chromate ion CrO42 is the main
species; between pH 1 and 6, HCrO4 and the orange-red dichromate ion Cr2O72 are
in equilibrium; and at pH<0 the main species are H2CrO4 and HCr2O7.
The equilibria are the following:
+
H2CrO4 HCrO4 + H
2 + 2 +
HCrO4 CrO4 + H HCr2O7 Cr2O7 + H
2
2 HCrO4 H2O + Cr2O7
CrO 42-
0.04
HCr2O 7-
0.03
Cr2O 72-
0.02
HCrO 4-
0.01
0.00
H2CrO 4
0 2 4 6 8 10 12 14
pH
The chromates of the alkali metals and of magnesium and calcium are soluble
in water.
Strontium chromate is sparingly soluble in water, and most other metallic chromates
are insoluble.
Sodium, potassium, and ammonium dichromates are well known and they are
soluble in water.
3+
Reactions of chromium(III) ions, Cr
106
Hydrated chromium(III) sulphate, nitrate, chloride, bromide, iodide, and
acetate are soluble in water.
Chromium oxide, hydroxide, phosphate, and anhydrous halogenides (fluoride,
chloride, bromide, iodide) are hardly soluble or not soluble in water.
3+
Cr + 3 OH Cr(OH)3
The solution is green. On adding hydrogen peroxide to the alkaline solution, a yellow
solution is obtained, owing to the oxidation of chromium(III) to chromate:
2
2 [Cr(OH)4] + 3 H2O2 + 2 OH 2 CrO4 + 8 H2O
After decomposing the excess of hydrogen peroxide by boiling, chromate ions may be
identified in the solution by one of their characteristic reactions.
3+ 2
2 Cr + 3 CO3 + 3 H2O 2 Cr(OH)3 + 3 CO2
3+ 2
2 Cr + 3S + 6 H2O 2 Cr(OH)3 + 3 H2S
107
5. Chromate test.
Chromium(III) ions can be oxidised to chromate, and than chromate ions can
be identified on the basis of their characteristic reactions.
Oxidation of chromium(III): adding an excess of sodium hydroxide to a
solution of chromium(III) salt followed by a few ml of hydrogen peroxide.
2
2 [Cr(OH)4] + 3 H2O2 + 2 OH 2 CrO4 + 8 H2O
The excess of H2O2 can be removed by boiling the mixture for a few minutes.
2+ 2
Ba + CrO4 BaCrO4
2 2
Reactions of chromate (CrO4 ) and dichromate (Cr2O7 ) ions
The chromates of metal ions are usually coloured solids, yielding yellow
solutions when dissolved in water. In the presence of dilute mineral acids chromates
are partially converted into dichromates; the latter yield orange-red aqueous solutions.
2 + 2
2 CrO4 + 2 H Cr2O7 + H2O
2 2+
CrO4 + Ba BaCrO4
The precipitate is insoluble in water, sodium hydroxide, and acetic acid, but soluble in
mineral acids.
108
Dichromate ions produce the same precipitate, but as strong acid is formed,
precipitation is only partial:
2 2+ +
Cr2O7 + 2 Ba + H2O 2 BaCrO4 + 2 H
2 +
CrO4 + 2 Ag Ag2CrO4
The precipitate is soluble in dilute nitric acid and in ammonia solution, but is
insoluble in acetic acid. Hydrochloric acid converts the precipitate into silver
chloride, Ksp(AgCl)= 1.77x1010:
+ + 2
2 Ag2CrO4 + 2 H 4 Ag + Cr2O7 + H2O
+ 2
Ag2CrO4 + 4 NH3 2 [Ag(NH3)2] + CrO4
2
Ag2CrO4 + 2 Cl 2 AgCl + CrO4
2 2+
CrO4 + Pb PbCrO4
The precipitate is insoluble in acetic acid, but soluble in dilute nitric acid and sodium
hydroxide solution:
+ 2+ 2
2 PbCrO4 + 2 H 2 Pb + Cr2O7 + H2O
2 2
PbCrO4 + 4 OH [Pb(OH)4] + CrO4
2 + 3+
2 CrO4 + 3 H2S + 10 H 2 Cr + 3 S + 8 H2O
2 + 3+
2 CrO4 + 6 I + 16 H 2 Cr + 3 I2 + 8 H2O
109
7. Iron(II) sulphate: reduces chromates or dichromates in the presence of mineral
acid smoothly:
2 2+ + 3+ 3+
CrO4 + 3 Fe + 8 H Cr + 3 Fe + 4 H2O
3+ +
2 K2CrO4 + 16 HCl 2 Cr + 3 Cl2 + 4 K + 10 Cl + 8 H2O
3+ +
K2Cr2O7 + 14 HCl 2 Cr + 3 Cl2 + 2 K + 8 Cl + 7 H2O
O OH + HCl O Cl + HOH
Cr Cr
O OH + HCl O Cl + HOH
+ 2+ 2+
Ag Ba Pb
2
CrO4
solubility in
acetic acid
HNO3 soln.
NaOH soln.
NH3 soln.
110
Manganese (Group VIIb) and Its Common Ions
Manganese is grey-white, resembling iron, but is harder and very brittle (melting
point: 1244 C). Manganese is roughly similar to Fe in its physical and chemical
properties, the chief difference being that it is harder and more brittle. The metal is
reactive, and slowly reacts even with cold water.
Mn + 2 H2O Mn(OH)2 + H2
Dilute mineral acids and also acetic acid dissolve the metal with the
production of manganese(II) salts and hydrogen ((Mn/Mn2+)= 1.185 V):
+ 2+
Mn + 2 H Mn + H2
2+ 2
Mn + H2SO4 Mn + SO4 + SO2 + 2 H2O
+2 2+
Mn
3+
+3 (Mn )*
4+ 4 2
+4 (Mn )* (MnO4 or MnO3 )*
+5 3
(MnO4 )**
+6 2
MnO4 ***
+7
MnO4
* manganese(III) and manganese(IV) cations, and manganate(IV) anion are unstable
in aqueous solutions, they are easily reduced to manganese(II).
** unstable in aqueous solution, disproportionates to Mn(VII) and Mn(IV).
*** stable in alkaline solutions, but upon neutralisation a disproportination reaction
takes place:
2
3 MnO4 + 2 H2O MnO2 + 2 MnO4 + 4 OH
111
Permanganate ions, MnO4 , can be reduced step by step, e.g. with perborate
solution, to study the colour of the different oxidation state of manganese:
7+ 6+ 5+ 4+
2 3
MnO4 MnO4 MnO4 MnO44
+0.564 V +0.27 V
MnO2 is inert to most acids except when heated, but it does not dissolve to
give Mn(IV) in solution; instead it functions as an oxidising agent, the exact manner
of this depending on the acid. With concentrated hydrochloric or sulphuric acid,
chlorine and oxygen gas are evolved, respectively, and manganese(II) ions are
produced:
2+
MnO2 + 4 HCl Mn + Cl2 + 2 Cl + 2 H2O
2+ 2
2 MnO2 + 2 H2SO4 2 Mn + O2 + 2 SO4 + 2 H2O
112
2+
Reactions of manganese(II) ions, Mn
2+
Mn + 2 OH Mn(OH)2
2 Mn(OH)2 + O2 2 MnO2.H2O
The precipitate is soluble in ammonium salts, when the reaction proceeds towards the
left.
2+ 2
Mn + S MnS
The precipitate is readily soluble in mineral acids and even in acetic acid.
+ 2+
MnS + 2 H Mn + H2S
113
4. Disodium hydrogen phosphate solution: in the presence of ammonia (or
ammonium ions), pink precipitate of manganese ammonium phosphate:
2+ 2
Mn + NH3 + HPO4 Mn(NH4)PO4
2+ 2 +
3 Mn + 2 HPO4 Mn3(PO4)2 + 2 H
2+ 2
Mn + CO3 MnCO3
The precipitate is soluble in dilute mineral acids and even in acetic acid.
2+ + 2+
5 PbO2 + 2 Mn + 4 H 2 MnO4 + 5 Pb + 2 H2O
Permanganates, MnO4
To study these reactions use a 0.01 M solution of potassium permanganate,
KMnO4.
+ 2+
2 MnO4 + 5 H2O2 + 6 H 5 O2 + 2 Mn + 8 H2O
2+
2 MnO4 + 16 HCl 5 Cl2 + 2 Mn + 6 Cl + 8 H2O
114
3. Hydrogen sulphide: in the presence of dilute sulphuric acid the solution
decolourizes and sulphur is precipitated: (H2S/S)= +0.142 V
+ 2+
2 MnO4 + 5 H2S + 6 H 5 S + 2 Mn + 8 H2O
2+ + 3+ 2+
MnO4 + 5 Fe + 8 H 5 Fe + Mn + 4 H2O
The solution becomes yellow because of the formation of iron(III) ions. The yellow
colour disappears if potassium fluoride is added; it forms colourless complex with
iron(III).
+ 2+
2 MnO4 + 10 I + 16 H 5 I2 + 2 Mn + 8 H2O
2 MnO4 + I + H2O 2 MnO2 + IO3 + 2 OH
2
4 MnO4 + 4 OH 4 MnO4 + O2 + 2 H2O
When the manganate solution is poured into a large volume of water or is acidified
with dilute sulphuric acid, the purple colour of the potassium permanganate is
2
restored, and manganese dioxide is precipitated. (MnO4 /MnO2)=
+0.60 V
2
3 MnO4 + 2 H2O 2 MnO4 + MnO2 + 4 OH
115
Summarise the reactions of CrO42, Cr2O72, and MnO4 ions.
2 2
CrO4 Cr2O7 MnO4
colour
(alkali metal salt)
H2S
acid solution
H2O2
acid solution
KI
acid solution
FeSO4
acid solution
cc HCl
116
The Group VIIIb Elements (Fe, Co, Ni) and
Their Principle Ions
Iron is a relatively abundant element in the universe. Its nuclei are very
stable. The metal is the fourth most abundant element on earth, by weight, making up
the crust of the earth. The use of iron is prehistoric. Iron is a vital constituent of plant
and animal life, and appears in haemoglobin.
The chemically pure iron is a silver-white, tenacious, and ductile metal. It melts at
1535 C. The pure metal is very reactive chemically, and rapidly corrodes, especially
in moist air or at elevated temperatures. Iron can be magnetised. It has four allotropic
forms, from which only the -form is magnetic.
The commercial iron is rarely pure and usually contains small quantities of carbide,
silicide, phosphide, and sulphide of iron, and some graphite. These contaminants play
an important role in the strength of iron structures. Other additives such as nickel,
chromium, vanadium, etc. are also used to produce alloy steels. Iron is the cheapest
and most abundant, useful, and important of all metals.
Solubility in acids
Dilute or concentrated hydrochloric acid and dilute sulphuric acid dissolve
iron, cobalt, and nickel, when iron(II), cobalt(II), and nickel(II) salts and hydrogen
gas are produced.
+ 2+
Fe + 2 H Fe + H2 (Fe/Fe2+)= 0.447 V
+ 2+
Co + 2 H Co + H2 (Co/Co2+)= 0.28 V
+ 2+
Ni + 2 H Ni + H2 (Ni/Ni2+)= 0.257 V
Hot, concentrated sulphuric acid yields iron(III), cobalt(II), and nickel(II) ions
and sulphur dioxide:
+ 3+
2 Fe + 3 H2SO4 + 6 H 2 Fe + 3 SO2 + 6 H2O
+ 2+
Co + H2SO4 + 2 H Co + SO2 + 2 H2O
+ 2+
Ni + H2SO4 + 2 H Ni + SO2 + 2 H2O
Cold, concentrated nitric acid and sulphuric acid renders iron passive.
117
Cold, dilute nitric acid, yields iron(II) and ammonium ions:
+ 2+ +
4 Fe + 10 H + NO3 4 Fe + NH4 + 3 H2O
Medium concentrated nitric acid, or hot, concentrated nitric acid dissolves iron
with the formation of nitrogen oxide gas and iron(III) ions:
+ 3+
Fe + HNO3 + 3 H Fe + NO + 2 H2O
Like iron, cobalt and nickel does not dissolve in concentrated nitric acid
because it is rendered passive by this reagent.
Iron(III) oxide, Fe2O3, is soluble in dilute acids at room temperature, but if heated too
strongly it is almost insoluble even in hot concentrated hydrochloric acid.
Iron(II,III) oxide, Fe3O4=FeIIFe2IIIO4, is very resistant to attack by acids and alkalis.
Cobalt(II) oxide, CoO, and cobalt(III) oxide, Co2O3, are soluble in mineral acids.
Cobalt(II,III) oxide, Co3O4=CoIICo2IIIO4, is very slightly soluble in mineral acids.
118
2+
Reactions of iron(II) ions, Fe
Solubility of the most common iron(II) compounds
The chloride, bromide, iodide, chlorate, perchlorate, nitrate, sulphate, and
acetate are soluble in water.
The fluoride is very slightly soluble, and oxide, carbonate, sulphide, and phosphate
are practically insoluble.
2+
Fe + 2 OH Fe(OH)2
4 Fe(OH)2 + 2 H2O + O2 4 Fe(OH)3
2 Fe(OH)2 + H2O2 2 Fe(OH)3
If, however, larger amounts of ammonium ions are present, precipitation does not
occur.
119
+ 2+
FeS + 2 H Fe + H2S
4 FeS + 9 O2 2 Fe2O(SO4)2
2+ + 4
Fe + 2 K + [Fe(CN)6] K2Fe[Fe(CN)6]
2+ 3
Fe + [FeIII(CN)6] Fe3+ + [FeII(CN)6]4
3+ 4
4 Fe + 3 [Fe(CN)6] Fe4[Fe(CN)6]3
III II
FeII CN
-
Fe CN
-
Fe
The structure of Turnbull's blue is CN
-
CN
- -
CN
based on a three-dimensional cubic Fe III CN Fe - II
CN
-
Fe III
- - -
framework with FeII and FeIII atoms at
-
CN CN CN CN
- CN
II - III - II
Fe CN Fe CN Fe
the corners of a cube and with FeIIN- - -
- CN
CFeIII links. CN
III
CN
- II - III
-Fe CN -Fe CN Fe
CN
- CN
- CN
CN - -
CN CN
II III -
Fe CN
-
Fe CN Fe II
- - - -
CN CN - CNCN- CN
III
CN
II
Note, that the composition of this Fe CN
-
Fe CN
-
Fe III
-
- -
CN CN
precipitate is identical to that of CN
III II
Prussian blue (see below at the reaction -
FeII CN
-
-Fe CN
-
Fe
CN - CN
CN - - -
of iron(III) ions). III
CN - CN CN
Fe CN Fe II CN
-
Fe III
- - -
CN CN CN
II - III - II
Fe CN Fe CN Fe
120
3+
Reactions of iron(III) ions, Fe
Solubility of the most common iron(III) compounds
The chloride, bromide, iodide, chlorate, perchlorate, nitrate and sulphate are
soluble in water.
The fluoride is very slightly soluble, and oxide, carbonate, sulphide, and phosphate
are practically insoluble.
Iron(III) hydroxide can be converted on strong heating to iron(III) oxide; the heated
oxide is soluble with difficulty in dilute acids, but dissolves on vigorous boiling with
concentrated hydrochloric acid.
39
The solubility product of iron(III) hydroxide is so small (2.64x10 ) that complete
precipitation takes place even in the presence of ammonium salts.
The finely distributed sulphur cannot be readily filtered with ordinary filter papers.
By boiling the solution with a few torn pieces of filter paper the precipitate coagulates
and can be filtered.
121
The black iron(II) sulphide precipitate dissolves in hydrochloric acid and the white
colour of sulphur becomes visible:
+ 2+
FeS + 2 H Fe + H2S
3+ 2
2 Fe + 3S Fe2S3
On acidification with hydrochloric acid iron(III) ions are reduced to iron(II) and
sulphur is formed:
+ 2+
Fe2S3 + 4 H 2 Fe + 2 H2S + S
3+ 4
4 Fe + 3 [Fe(CN)6] Fe4[Fe(CN)6]3
3+ 3
Fe + [Fe(CN)6] Fe[Fe(CN)6]
Upon adding some tin(II) chloride solution, the hexacyanoferrate(III) part of the
compound is reduced and Prussian blue is precipitated.
3+
Fe + 3 SCN Fe(SCN)3
3
Fe(SCN)3 + 6 F [FeF6] + 3 SCN
3 6
Fe(SCN)3 + 3 PO4 [Fe(PO4)3] + 3 SCN
Upon addition of SnCl2 solution in excess, the red colour disappears due to the
reduction of iron(III) to iron(II):
2+ 2+ 4+
2 Fe(SCN)3 + Sn 2 Fe + Sn + 3 SCN
122
9. Disodium hydrogen phosphate solution: a yellowish-white precipitate of
iron(III) phosphate is formed, Ksp(FePO4.2H2O, 25C)= 9.92x1029:
3+ 2 +
Fe + HPO4 FePO4 + H
4 3
[Fe(CN)6] [Fe(CN)6]
2+
Fe
3+
Fe
2+
Reactions of cobalt(II) ions, Co
Solubility of the most common cobalt(II) compounds
The chloride, bromide, iodide, chlorate, perchlorate, nitrate, sulphate, and
acetate are soluble in water.
The fluoride is very slightly soluble, and oxide, hidroxide, carbonate, sulphide, and
phosphate are practically insoluble.
2+
Co + OH + NO3 Co(OH)NO3
Upon warming with excess alkali (or sometimes merely upon addition of excess
reagent) the basic salt is converted into pink cobalt(II) hydroxide precipitate
Ksp(Co(OH)2, 25C)= 1.09x1015:
123
Co(OH)NO3 + OH Co(OH)2 + NO3
The hydroxide is slowly transformed into the brownish black cobalt(III) hydroxide on
exposure to the air:
2+ +
Co + NH3 + H2O + NO3 Co(OH)NO3 + NH4
The excess of the reagent dissolves the precipitate, when hexamminocobaltate(II) ions
are formed:
2+
Co(OH)NO3 + 6 NH3 [Co(NH3)6] + NO3 + OH
The precipitation of the basic salt does not take place at all if larger amounts of
ammonium ions are present, but the complex is formed in one step.
2+ 2
Co + S CoS
On longer heating the mixture becomes clear because sulphur gets oxidised to
sulphate.
The CoS precipitate dissolves also in the 1+1 mixture of concentrated acetic
acid and 30% hydrogen peroxide:
2+ 2
CoS + 4 H2O2 Co + SO4 + 4 H2O
2+ + +
Co + 7 NO2 + 2 H + 3 K K3[Co(NO2)6] + NO + H2O
124
The test can be carried out most conviniently as follows: to a neutral solution of
cobalt(II) add acetic acid, than a freshly prepared saturated solution of potassium
nitrite.
2+ 2
Co + 4 SCN [Co(SCN)4]
If amyl alcohol or ether is added the free acid H2[Co(SCN)4] is formed and dissolved
by the organic solvent.
2
2 H+ + [Co(SCN)4] H2[Co(SCN)4]
The test is rendered more sensitive if the solution is acidified with concentrated
hydrochloric acid, when the equilibrium shifts towards the formation of the free acid.
2+
Reactions of nickel(II) ions, Ni
Solubility of the most common nickel compounds
The chloride, bromide, iodide, chlorate, perchlorate, nitrate, sulphate, and
acetate are soluble in water.
The fluoride is very slightly soluble, and oxide, carbonate, sulphide, and phosphate
are practically insoluble.
2+
Ni + 2 OH Ni(OH)2
125
2+
Ni(OH)2 + 6 NH3 [Ni(NH3)6] + 2 OH
+ 2+
Ni(OH)2 + 6 NH4 + 4 OH [Ni(NH3)6] + 6 H2O
2 Ni(OH)2 + ClO + H2O 2 Ni(OH)3 + Cl
Hydrogen peroxide solution, however, does not oxidise nickel(II) hydroxide, but the
precipitate catalyses the decomposition of hydrogen peroxide to oxygen and water
without any other visible change.
2+
Ni(OH)2 + 6 NH3 [Ni(NH3)6] + 2 OH
the solution turns deep blue. If ammonium salts are present, no precipitation occurs,
but the complex is formed immediately.
2+ 2
Ni + S NiS
If the reagent is added in excess, a dark-brown colloidal solution is formed which runs
through the filter paper. If the colloidal solution is boiled, the colloidal solution
(hydrosol) is coagulated and can than be filtered.
The precipitate is insoluble in hydrochloric or acetic acids.
Hot, concentrated nitric acid or aqua regia dissolve the precipitate with the separation
of white sulphur:
+ 2+
3 NiS + 2 HNO3 + 6 H 3 Ni + 3 S + 2 NO + 4 H2O
2+
NiS + HNO3 + 3 HCl Ni + S + NOCl + 2 Cl + 2 H2O
On longer heating the mixture becomes clear because sulphur gets oxidised to
sulphate.
2 +
S + 2 HNO3 SO4 + 2 H + 2 NO
2 +
S + 3 HNO3 + 9 HCl SO4 + 6 Cl + 3 NOCl + 8 H + 2 H2O
The NiS precipitate dissolves also in the 1+1 mixture of concentrated acetic
acid and 30% hydrogen peroxide:
2+ 2
NiS + 4 H2O2 Ni + SO4 + 4 H2O
126
4. Potassium nitrite solution: no precipitate is produced in the presence of acetic
acid (difference from cobalt).
2+
Ni + 2 CN Ni(CN)2
The precipitate is readily soluble in excess reagent, when a yellow solution appears
owing to the formation of tetracyanonickelate(II) complex ions:
2
Ni(CN)2 + 2 CN [Ni(CN)4]
H
O O
H3C N N CH3
CH3 C N OH C C
+
Ni 2+ + 2 Ni + 2H
CH3 C N OH C C
H3C N N CH3
O O
H
2+
Cu
2+
Ni
127
Summarise the solubility of sulphides:
colour
HCl
aqua regia
acetic acid +
H2O2
Summarise the reactions of various metal ions with NaOH and NH3 solutions.
2+ 2+ 3+ 2+ 2+ 3+ 3+ 2+
Mn Fe Fe Co Ni Al Cr Zn
NaOH
NaOH
in excess
NH3
NH3
in excess
Summarise the solubility of selected metals in cold concentrated and 1+1 diluted
nitric acid:
Ti V Cr Fe Co Ni
diluted
HNO3
cc HNO3
128