Halides
Magnetic Properties
• Diamagnetic substances are repelled by the applied field
• Paramagnetic substances are attracted by the applied field
• Ferromagnetic substances are attracted very strongly by the applied field
• Most of transition metals are Paramagnetic in nature
• Paramagnetism arises due to the presence of unpaired electrons, each such
electron are associated with a magnetic moment(µ).
• Magnetic moment is determined by the number of unpaired electrons and is
calculated by
• where n is the number of unpaired electrons and µ is the magnetic moment
units of magnetic moment is Bohr magneton (BM).
• A single unpaired electron has a magnetic moment of 1.73 Bohr magnetons
(BM).
Magnetic Properties
• The magnetic moment increases with the increasing number of unpaired
electrons
1. Calculate the magnetic moment of a divalent ion in aqueous solution if its
atomic number is 25.
• With atomic number 25, the divalent ion in aqueous solution will have d5
configuration (five unpaired electrons). The magnetic moment,
Transition elements
2. Calculate the ‘spin only’ magnetic moment of M2+ (aq) ion (Z = 27).
• Atomic number (Z)=27
The valence electronic configuration of cobalt ( Co) is 3d7,4s2.
M2+(aq) ion means, it loses two electrons.
Hence, valence electronic configuration becomes 3d7.
Now, Number of unpaired electrons =3
Substitute n=3
Formation of Coloured Ions
• When an electron from a lower energy d orbital is excited to a higher
energy d orbital,
• The energy of excitation corresponds to the frequency of light
absorbed. This frequency generally lies in the visible region. The
colour observed corresponds to the complementary colour of the light
absorbed.
Formation of Complex Compounds
• Complex compounds are those in which the metal ions bind a number of
anions or neutral molecules giving complex species with characteristic
properties.
• Examples are: [Fe(CN)6]3-, [Fe(CN)6]4- , [Cu(NH3 )4]+2and [PtCl4]2-.
• The transition metals form a large number of complex compounds. This is due to
• Comparatively smaller sizes of the metal ions,
• High ionic charges
• Availability of d orbitals for bond formation.
Transition elements
Catalytic Properties
• The transition metals and their compounds are known for their catalytic activity.
• This is due to their ability to adopt multiple oxidation states and ability to form
complexes.
• Ex:- Vanadium(V) oxide (in Contact Process)
• finely divided iron (in Haber’s Process)
• nickel (in Catalytic Hydrogenation)
• As transition metal ions can change their oxidation states, they become more
effective as catalysts.
• For example, iron(III) catalyses the reaction between iodide and persulphate ions.
• The over all reaction is
Formation of Interstitial Compounds
• Interstitial compounds are formed when small atoms like H, C or N are
trapped inside the crystal lattices of metals.
• They are usually non stoichiometric and are neither typically ionic nor
covalent,
• for example, TiC, Mn4N, Fe3H, VH0.56 and TiH1.7, etc.
• physical and chemical characteristics of these compounds are
as follows:
i. They have high melting points, higher than those of pure metals.
ii. They are very hard, some borides approach diamond in hardness.
iii. They retain metallic conductivity.
iv. They are chemically inert.
Transition elements
Alloy Formation
• Alloys are homogeneous mixture of more than one metal that can displace
another metal in the crystal lattice due to their comparable sizes
• Alloys are hard and have high melting point
• chromium, vanadium, tungsten, molybdenum and manganese are used for the
production of a variety of steels and stainless steel.
• brass (Cu-Zn) and bronze (Cu-Sn), stainless steel (Fe +Cr + Ni)
3. Explain why Cu+ ion is not stable in aqueous solutions?
The hydration energy of Cu2+ is highly negative and compensated the 2nd
I.E.Therefore Cu+ (aq) is unstable and it
oxidizes and reduces simultaneously in aqueous solution to give Cu(II)
and Cu ions.
Some Important Compounds of Transition
Elements
• Oxides are generally formed by the reaction of metals with oxygen at
high
temperatures.
• All the metals except scandium form MO oxides and are ionic in nature
• As the oxidation number of a metal increases, ionic character
decreases
• In these higher oxides, the acidic character is predominant.
• Thus, Mn2O7 gives HMnO4 and CrO3 gives H2CrO4 and H2Cr2O
• V2O5 is, amphoteric V2O5 reacts with alkalies as well as acids to give
VO43- and VO4+ respectively. The well characterized CrO is basic but
Cr2O3 is amphoteric.
Some Important Compounds of
Transition Elements
i. Potassium dichromate K2Cr2O7
Potassium dichromate is a very important chemical used in leather industry and
as an oxidant for preparation of many azo compounds.
Dichromates are generally prepared from chromate,
Step 1: At 1st the fusion of chromite ore (FeCr2O4) takes place with sodium or
potassium carbonate in excess of air.
Step 2: sodium chromate solution is filtered and acidified with sulphuric acid to
give orange colour sodium dichromate, Na2Cr2O7 solution
K2Cr2O7
Step 3: sodium dichromate solution is then treated with potassium chloride to
get potassium dichromate
Properties of K2Cr2O7
• Orange-red coloured crystalline compound.
• Moderately soluble in cold water but freely soluble in hot water.
• It melts at 398°C.
• K2Cr2O7 is preferred over Na2Cr2O7 as a primary standard in volumetric
estimation because Na2Cr2O7 is hygroscopic in nature but K2Cr2O7 is not.
K2Cr2O7
The oxidation state of chromium in chromate and dichromate is the same.
The chromate ion is tetrahedral and the dichromate ion consists of two tetrahedra
sharing one corner with Cr–O–Cr bond angle of 126°
Oxidizing property:
K2Cr2O7 is a powerful oxidizing agent in an acidic medium
(i) It oxidizes iodides to iodine
Cr2O72- + 14H+ + 6I- → 2Cr3+ + 7H2O + 3I2
K2Cr2O7
ii. It oxidizes ferrous salts to ferric salts
2- + + +
Cr2O7 + 14H + 6Fe2 → 2Cr3 + 7H2O + 6Fe3+
iii. It oxidizes stannous salt to stannic salt
Cr2O72- + 14H+ + 3Sn2+ → 2Cr3+ + 7H2O + 3Sn++
iv. It oxidizes H2S to Sulphur
Cr2O72- + 8H+ + 3H2S → 2Cr3+ + 7H2O + 3S
Action of heat:-
Application of heat leads to the decomposition of K2Cr2O7 leading to formation of
K2Cr O4, chromic oxide and oxygen.
4 K2Cr2O7 + heat → 4 K2Cr O4 + 2Cr O3 + 3O2
Effect of pH
• The chromates and dichromates are interconvertible in aqueous solution
depending upon pH of the solution
