Group 12 the zinc group

•These elements all have a d10S2 electronic arrangement and

they typically form M2+ ions.
•Many of their compounds are appreciably covalent.
•Hg( + II) compounds are more covalent and its complexes are
more stable than is the case for Zn and Cd.
•Because these ions have a complete d shell, they do not behave
as typical transition metals
•the
1
ions are divalent, they show only slight similarity with
 • Zn shows some similarities to Mg. However, Zn is more
dense and less reactive due to its smaller radius and
higher nuclear charge.

• Zn has a much stronger tendency to form covalent

compounds. Zn and Cd are broadly similar in most of
their properties.
• Hg differs appreciably from that of Zn and Cd.

• In many ways Hg is unique.

• It is a liquid at room temperature it is noble, and it

forms 'apparently univalent' mercury(I) compounds.

• Mercury is the only element in the group with a well

2 established (+1) oxidation state.
 ABUNDANCE AND OCCURRENCE

• Zn occurs in the earth's crust to the

extent of 132ppm by weight It is the
twenty fourth most abundant element
• Cd and Hg are quite rare
• In spite of this the elements are
familiar because their extraction and
purification are simple

3
 USES
• Uses of zinc
• Zn is used is large amounts for coatmg iron to prevent
from rusting
• A thin coating of Zn may be apphed electrolytzcally
(galvanlzing)
• With molten Zn Large amounts of Zn are used to make
alloys
• The most common alloy is brass Cu/Zn alloy with 20-
50% Zn) ZnO is sometimes useed as a white pigment in
pamt It is particularly bright as It absorbs UV light and
re emits It as white light
4
 Uses of cadmium

oMost of the Cd produced IS used for protecting steel

from corrosion

oCd absorbs neutrons very well and is used to make control

rods for nuclear
Usesreactors
of cadmium
o
oCd also used for alkalin e Zn/Cd storage batteries
o
oCdS is an Important but expensive yellow pigment used
in paint

5
 Uses of mercury
o The largest use of mercury IS m electrolytic cells for the
production of ( NaOH and O2

o The electrical industry uses Hg to mercury vapour street

Lights.

o Historically Hg has been, and still used in the extraction of

precious metals (particularly silver and gold) as amalgams

o Pheny1 mercury(l1) acetate and other organomercury

compounds have fungicidal and germicidal properties
o They are in agriculture for treating seeds
o Small scale uses of mercury include thermometers,
6 barometers
 OXIDATION STATES
 The elements in this group all have two s electrons beyond a
completed d shell. Removal of the s electrons results in divalent
compounds, and the (+ II) oxidation state is characteristic of
the group.
• Hg( + 1) compounds are important. The univalent ion Hg + does
not exist, as mercury(I) compounds are dimerized.
MercuryMercury(I) chloride is therefore Hg2Cl2 and contains
[Hg-Hg]2+ ions. In these, the two Hg+
• species which have a 6s1 configuration are bonded together
using their s electrons. Thus mercury(l) compounds are
diamagnetic.
• Oxidation states higher than ( + II) do not occur. This is
because removal
• of more electrons would destroy the symmetry of a completed
d shell.
7
 SIZE
• The ionic radii of the M2+ ions of Group 12 are
appreciably smaller than for the corresponding
elements in Group 2.
• This is because Zn, Cd and Hg have 10 d
electrons which shield the nuclear charge
rather poorly.
• The difference in size accounts for the lack of
similarity in properties between the two groups.

8
 Physical properties

9
10
 IONIZATION ENERGIES
• The first ionization energy for Group 12 elements is considerably
higher than for the corresponding Group 2 elements
• This is because the atoms are smaller and the filled d orbital is
poorly shielding The filled 4f shell in Hg further increases the
binding energy of the outer electrons. and
• the first ionization energy for Hg is greater than for any other
metal
• The second ionization energies are high, but +11 Ions are known for
all three elements as the solvatton or lattice energy is sufficient to
offset this
• Mercury tends to form covalent compounds The third ionization
energtes
• are so high that (+IIl) compounds do not exist
11
 General properties
• Zn. Cd and Hg show few of the properties
associated With typical transition
elements This is because they have a
complete d shell.
• Therefore not available for bonding
• Zn and Cd do not show variable valency
• They have a d10 electronic configuration
and so cannot produce d .. D spectra
12
 General properties continued

Thus many of their compounds are white

However. some
compounds of Hg( + II) and a smaller
number of Cd( + II) are hghly
coloured due to charge transfer from the
ligands to the metal metals of this group
are smaller and thus have a greater
polarizingpower than Group 2 metals.
13 This increases the chance of covalency
 The metals are relatively soft compared with the other
transition
metals. This is probably because the d electrons do not
participate in metallic bonding.

The melting and boiling points are very low.

Mercury is the only metal which is liquid at room
temperature.

The reason for this is that the very high ionization

energy makes it difficult for electrons to participate in
metallic bonding

14
 Similarities between Group 2 elements with an outer
electronic structure S2 and the zinc group an outer
electronic structure d10s2 are slight.
Both groups are divalent.

zinc group is more noble. more covalent, has a much

greater ability to form complexes and is less basic.

15
 • The reactivity of the metals decreases going
down the group; although zinc and cadmium
have high first ionization energies, their
redox potentials are quite large and negative
owing to the high solvation energy that drives
the reaction
• Consequently they readily dissolve in non-
oxidizing acids. In contrast, mercury will only
dissolve in oxidizing acids, such as nitric acid.
16
 OXIDES
• The metals react directly with oxygen on
heating; however, above 400 ⁰C,
• HgO decomposes back to the metal plus
oxygen.
• ZnO is amphoteric, dissolving in both
acids and bases.
• whiles CdO and HgO are basic illustrating
metallic nature increasing down the group
17
 Oxides continued
• ZnO(s) + 2H+ (aq) → Zn 2+ (aq) +H2O(l)
• ZnO(s) + 2OH- (aq) + H2O(l → Zn (OH)4 2- (aq)
• ZnO is white when cold and hence used as pigment in paint.
It however changes color when hot to pale yellow this is
due to change in lattice structure or lattice defect.
However, when the heating is stopped and on cooling it
goes back to the white color.
• Oxides of Zn and Cd sublime when heated those of oxygen
on the other hand decompose to give Hg on heating.
• ZnO and CdO yield precipitates of Zn(OH)2 and Cd(OH)2
respectively. Hg on the other hand gives a yellow color

18
 HYDROXIDES
• Addition of hydroxide to solutions of M2+ ions
precipitates Zn(OH)2, and Cd(OH)2, however,
Hg(OH)2, does not exist and instead yellow HgO
is formed and cadmium hydroxides also dissolve in
aqueous ammonia solutions by the formation of
ammonia complexes Addition of alkali to a salt of
Zn yields a white gelatinous precipitate.
• Zn2+(aq) + 2OH- (aq) → Zn (OH)2 (s) The
solution will dissolve in excess alkali to give to give
soluble Zn (OH)4 2- ions
19
 HYDROXIDES continued
• Zinc hydroxide is also precipitated in Aqueous ammonia and will
dissolve in excess ammonia
• However, this time it is the complex in Zn (NH3)4 2+ which is
formed.
• The reactions of Hg 1 and Hg 11 are remarkably different to
those of Zn and Cd a Mercury (ii) solution will give a yellow ppt of
Mercury (ii) oxide
• Hg2+ (aq) + 2OH- (aq) → HgO(s) + H2O(l)
• (YELLOW)
• Dimercury (i) ion give a black ppt of Mercury (ii) oxide
• Hg22+ (aq) + 2OH- (aq) → Hg2O(s) + H2O(l)
• (BLACK)
20
 SULFIDES

• Each of the sulfides are highly

insoluble ZnS, CdS and HgS there is
no Hg2S

21
 HALIDES
• Halides of Zn and Cd are mainly ionic while those
of Hg are covalent. Mercury halides are insoluble
in water where as it is only ZnF2 which is insoluble
Hg(ii) Chloride is sufficiently covalent to have the
individual molecules identified.
• Dimercury (i) chloride(Hg2Cl2) is used as an
ingredient in calomel electrode. In addition the
halides are usually hydrated and in water form
Zn(H2O)6]2+ which is an octahedral complex
(sp3d2)
• Cd salts are less hydrated than Zn salts Hg11 salts
are normally anhydrous

22
 CARBONATES
• Zinc and cadmium carbonates are rather unstable to
heat as a result of the polarizing effect of the small
Zn2+ and Cd2+ ions, causing decomposition to the
oxide. In this way they resemble magnesium carbonate
• CdCO3, → CdO + CO2
• ZnCO3 and CdCO3 when heated give metal oxide and
CO2 This occurs at about 350 ⁰C
• MCO3(s) → MO(s) + CO2(g) (M= Cd or Zn)
• ZnCO3 Important medicinally calamine lotion used to
treat spot and other skin ailments. It is insoluble but
has the characteristics of other carbonates

23
 NITRATES
• The nitrates of Zn and Cd decompose in the
normal way giving off nitrogen dioxide the
metal oxide and oxygen
• 2M(NO3)2(s) → 2MO(s) + 4NO2(g) + O2(g)

• Mercury however decomposes to the metal

nitrogen dioxide and oxygen.

• Hg(NO3)2(s) → Hg(l) + 2NO2(g) + O2(g)

24
 SULPHATES
• All the Sulphates are soluble in water
and are hydrated crystals ZnSO4.
7H2O, SrSO4 6H2O
• They are useful sources of the metal
but dissolve in water to form acidic
solutions through hydrolysis
• [Zn(H2O)4]2+ (aq) →
[Zn(H2O)3OH]2+ (aq) + H+ (aq)
25
 COMPLEXES
• Zn 2+ and Cd 2+ forms complexes with O donor
with N and sufur donor ligands
• The stability of Hg complexes is much greater
than that of the other two elements Zn 2+ and
Cd 2+ occur largely as 4 coordination
tetrahedral compounds
Zn and Cd do form complexes with CN-, e.g.
[Zn(CN)4]2-. Zn complexes are
usually colorless, but Hg complexes (and to a
lesser extent Cd complexes)
26 arc often colored because of charge transfer.
 Hg (+1) COMPOUNDS
• Only few Hg(I) compounds are known.
They contain the ion (Hg-Hg)2+ not Hg +
• The Hg atoms are bonded using 6s
orbitals Mercury is unique in forming
dinuclear ions. Cd and Zn also forms
dinuclear ions but they are less stable
Hg(I) compounds
• Are prepared by reducing Hg(II) with
the metal
27
 Evidences that mercury(I) ion
thus has the structure [Hg-Hg]+

28
29
30
 Raman spectra
• The Raman spectrum for mercury(I) nitrate
contains the lines characteristic of the NO;
group. Similar lines appear in the spectra of
many other nitrates. Mercury(I) nitrate has an
extra line in the spectrum at 171.7 cm-1
• which is attributed to the Hg-Hg bond.
HomonucIear stretching of a diatomic species is
Raman active but not infra-red active. This was
the first example of Raman spectra identifying a
new species.
31
 Magnetic properties

• All mercury(I) compounds are diamagnetic

both in the solid state and in solution. Hg+
would have an unpaired electron and would
be paramagnetic,
• but in [Hg-Hg]+ the electrons are all paired
and it should therefore be diamagnetic.

32
 Cryoscopic measurements

• The depression of freezing point produced

depends on the number of particles
dissolved in the liquid.

• The observed depression fits for mercury(l)

nitrate ionizing into Hg2+ and two NO;
ions, not into Hg+ and N03

33
 BIOLOGICAL ROLE OF ZINC
 Zinc plays a biological role in both plants and animals

 There are about 20 elements containing Zn some of

which are
 Alkaline phosphatase (energy release)

 Alcohol dehydrogenase (metabolism of alcohol)

 Carbonic anhydrase (present in red blood cells

involved in respiration)

 Carboxypeptidase (present in pancreatic juice is

involved in the digestion of proteins by animals)
34
 TOXICITY OF CADMIUM AND
MERCURY
• Zn is an essential element for life
• But the other two elements in the group Cd and
Hg are both extremely toxic
• There concern at the amount of Cd in
cigarette smoke
• If Cd is ingested It accumulates in the kidneys
causing fatal function of the kidneys and also
replaces Zn in some enzymes thus preventing
them from working
35
 TOXICITY OF CADMIUM
AND MERCURY
• Mercury vapour IS toxic and if inhaled can cause
giddiness tremors lung damage and brain damage
• In the laboratory mercury should be
• covered With oil or toluene and spillages should
be treated with flowers of Sulphur forming HgS
• Inorganic compounds such HgCl2, Hg2Cl2 and
HgO are also poisonous if eaten

36
 TOXICITY OF CADMIUM
AND MERCURY
• Alkyl mercury compounds such as dimethyl
mercury are much more toxic than
inorganic mercury compounds.
• Aryl mercury compounds are even more
dangerous.
• They cause brain damage giving numbness,
loss of vision. deafness, madness and death.

37