D AND F BLOCK ELEMENTS

CHEMISTRY

BY – SAGAR VARJATIA SIR

The d and f-Block Elements
The P-Block Elements
Sture
INTRODUCTION
Transition Definition
Elements
Incomplete d subshell in ground state or in its common oxidation state . Zn, Cd and Hg-are
d-block but non-transition elements.

General Electronic Configuration

ns0–2 (n–1)d1–10

Cr = 4s1 3d5 0 10

Exceptions  1 10 ,Pd = 5s 4d
Cu = 4s 3d

Transition Series
1. 3d series Sc21-Zn30
2. 4d series Y39-Cd48
3. 5d series La57 Hf 72-Hg80
4. 6d series Ac59, Unq104-Uub112
Atomic Radius
3d series Sc > Ti > V > Cr > Mn  Fe  CO  Ni  Cu < Zn
In a group 3d to 4d series increases but 4d and 5d series nearly same due
to poor shielding of f electron. (Lanthanide contraction)
[3d < 4d = 5d]

Melting point; s-block metals < d-block metals

In a series on increasing number of unpaired e– mpt increases upto Cr

then decreases.
Sc < Ti < V < Cr > Mn < Fe > Co > Ni > Cu > Zn
 
Half filled d5 Fully filled d10
weak metallic bond. weak metallic bond
Density: s-block metals < d-block metals

3d series
Sc < Ti < V < Cr < Mn < Fe < Co < Ni < Cu > Zn

Density in a Group 3d < 4d < < 5d

Metallic character: They are solid, hard, ductile, malleable, good
conductor of heat and electricity and exhibit metallic lusture. high
tensile strength. Hg is liquid
Oxidation State
Transition elements exhibit variable oxidation state due
to small energy difference of ns and (n–1)d electrons.
➢ Sc(+3) and Zn(+2) exhibit only one oxidation state
➢ Common oxidation state is +2
➢ 3d series highest oxidation state is +7 (Mn)
➢ In d-block series highest oxidation state is +8 (Os,
Ru)
➢ In carbonyl compound oxidation state of metals is
zero due to synergic effects.
➢ Their higher oxidation states are more stable in
fluoride and oxides.
➢ Higher oxidation states in oxides are normally more
stable than fluorides due to capability of oxygen to
form multiple bonds.
eg. stable fluoride in higher ox. st. of Mn is MnF4
white oxide is Mn2O7
 Oxidation State

Cu+ compounds are unstable in aqueous solution and

undergo disproportionation Some more stable oxidation state of d-block elements
Cu + 2 Mn + 2 Pt + 4 Ag + 1
Cr + 3 Sc = 3 Au + 3 Ni + 2

Common oxidation states

Ti(+4) V(+5) Cr(+3, +6) Mn(+2, +4,
+7)
Fe(+2, +3) Co(+2, +3) Ni(+2) Pt(+2, +4)

In p-block lower oxidation states of heavier elements are

more stable while in d-block heavier element, higher
oxidation state are more stable.

eg. In VIB gp Mo(+6) and W(+6) are more stable than

Cr(+6)
Magnetic Property
All transition elements are paramagnetic due to presence of unpaired electrons. They attract when magnetic field is applied.
Magnetic moment of unpaired electron is due to spin and orbital angular momentum.

"Spin only" magnetic moment can be calculated by using formula  = (𝑛 = 2) Bohr magneton. (n is number of unpaired e–.)
If n is 1  = 1.73 BM n is 2  = 2.84 BM
n is 4  = 4.90 BM n is 5  = 5.92 BM
Substances that are not attracted by applied magnetic field are diamagnetic. They have all the electrons paired. d-block element and ions having d0 and d10
configuration are diamagnetic.

Colour

Colour in transition metal ions is associated with d-d transition of unpaired electron from t2g to e set of energies. This is achieved by absorption of light in
the visible spectrum, rest of the light is no longer white.
Colourless: Sc3+, Ti4+, Zn2+ etc.
Coloured: Fe3+ yellow . Fe2+ green. Cu2+ blue. Co3+ blue etc.
Interstitial compounds: When less reactive nonmetals of small atomic size eg. H. B. N. C. Trapped in the interstitial space of transition metals, interstitial
compounds are formed, like TiC. Mn N. Fe H etc.
They are nonstoichiometric compounds. They have high melting point than metals. They are chemically inert.

Alloys Catalyst

Solid mixture of metals in a definate ratio (15% difference in metallic Transition metals and their compounds act as catalyst due to-
radius) ➢ Variable oxidation state
They are hard and having high melting point. ➢ Tendency to form complex
Eg. Brass (Cu + Zn) Eg., V2O5 - Contact process
Bronze (Cu + Sn) etc. Fe - Haber process
Hg when mix with other metals form semisolid amalgam except Fe,Co, Ni. Ni - Catalytic hydrogenation
Li.
ELECTRODE POTENTIAL (E0):

• Stability of oxidation state in the aqueous solution is determined by electrode potential.

• Electrode potential depends upon three enthalpies:

• Cu cannot liberate H2 from acids.

• Mn and Zn are more negative than expected from general trend

• Cr2+ is reducing and Mn3+ is oxidising when both have d4 configuration.

• Cr2+ can liberate hydrogen from dilute acids

OXIDES AND OXOANIONS OF METALS:-

• All the metals except scandium form MO oxides which are ionic.

• Highest oxidation state in the oxides coincides with the group number.

• No higher oxides of iron above Fe2O3 are known.

• As the oxidation number of a metal increases, ionic character decreases.

• Mn2O7 is a covalent green oil.

• CrO is basic oxide, Cr2O3 is amphoteric.

• V2O5 is amphoteric oxide

• V2O4 dissolves in acid to give VO2+

 KMnO4
This is the most important and well known salt of permanganic acid and is prepared from the
pyrolusite ore. It is prepared by fusing pyrolusite ore either with KOH or K2CO3 in presence of
atmospheric oxygen or any other oxidising agent such as KNO3. The fused mass turns green with the
formation of potassium manganate, K2MnO4.
2MnO2 + 4KOH + O2 ⎯→ 2K2MnO4 + 2H2O
2MnO2 + 2K2CO3 + O2 ⎯→ 2K2MnO4 + 2CO2
The fused mass is extracted with water and the solution is now treated with a current of chlorine or
ozone or carbon dioxide to convert manganate into permanganate.
2K2MnO4 + Cl2 ⎯→ 2KMnO4 + 2KCl
2K2MnO4 + H2O + O3 ⎯→ 2KMnO4 + 2KOH + O2
3K2MnO4 + 2CO2 ⎯→ 2KMnO4 + MnO2 + 2K2CO3
(disproportionate in acidic medium)
Commercially it is prepared by fusion of MnO2 with KOH followed by electrolytic oxidation of
manganate.
MnO42– (green) ⎯→ MnO4– (purple) + e–
In the laboratory, a manganese(II) ion salt is oxidised by peroxodisulphate to permanganate
2Mn2+ + 5S2O82– + 8H2O ⎯→ 2MnO4 + 10SO42– + 16H+
(b) Physical property: It is purple coloured crystalline compound. It is moderately soluble in water
at room temperature.
(c) Chemical property:
➢ Effect of heating 2KMnO4 ⎯⎯⎯ 750 K
→ K2MnO4 + MnO2 + O2
➢ On treatment with concentrated H2SO4 (KMnO4 is taken in excess), it forms manganese
heptoxide via permanganyl sulphate which decomposes explosively on heating.
conc. H SO
KMnO 4 ⎯ ⎯ ⎯ 2⎯ 4⎯
→ Mn 2O7 (an explosive)
➢ Potassium permanganate is a powerful oxidising agent. Potassium permanganate acts as an
oxidizing agent in alkaline, neutral or acidic solutions.
➢ In alkaline and neutral medium :
➢ In strongly alkaline medium KMnO4 is reduced to manganate.
2KMnO4 + 2KOH (conc.) ⎯→ 2K2MnO4 + H2O + [O]
Or e– + MnO4– ⎯→ MnO42–
However if solution is dilute then K2MnO4 is converted in to MnO2 which appears as a
brownish precipitate.
2K2MnO4 + 2H2O ⎯→ 2MnO2 + 4KOH + 2[O]
or
2e– + 2H2O + MnO42– ⎯→ MnO2 + 4OH–
This type of behaviour is shown by KMnO4 itself in neutral medium
3e– + 2H2O + MnO4 ⎯→ MnO2 + 4OH–
(D) Other reactions:
Potassium Dichromate (K2Cr2O7)

(a) Preparation: The chromite ore is roasted with sodium carbonate in

presence of air in a reverberatory furnace.
4FeO.Cr2O3 (chromite ore) 8Na2CO3 + 7O2. ⎯ Roasting
⎯in⎯ ⎯→
air
8Na2CrO4 + 2Fe2O3 + 8CO2
2Na2CrO4 + H2SO4 ⎯→ Na2Cr2O7 + Na2SO4 + H2O

Na2Cr2O7 + 2KCl ⎯→ K2Cr2O7 + 2NaCl

➢ K2Cr2O7 is preferred over Na2Cr2O7 as a primary standard in volumetric

estimation because Na2Cr2O7 is hygroscopic in nature but K2Cr2O7 is not.

➢ Solubility of Na2Cr2O7 is higher than K2Cr2O7

H+
CrO 4−2 Cr2O7−2
OH −
(b) Physical property: It is orange-red coloured crystalline 1. Chromyl chloride test:
compound. It is moderately soluble in cold water but freely NaCl + K2Cr2O7 + H2SO4 ⎯→ CrO2Cl2 (Red orange vapour)
soluble in hot water. It melts at 380°C.  NaOH
Na2CrO4 (Yellow)
(b) Chemical property:
Effect of heating: On strongly heating, it decomposes with 2. Acidified K2Cr2O7 solution reacts with H2O2 in a ethereal
liberating oxygen. solution to give a deep blue solution due to the formation of
3 CrO5.
2K2Cr2O7 ⎯→ 2K2CrO4 + Cr2O3 + O2 Cr2O72– + 2H+ + 4H2O2 ⎯→ 2CrO5 + 5H2O
2

(d) Other reactions: Note:

Reaction with C2H5OH is used in drunken driver test.
F-block Elements
Atomic Element Symbol Outer electronic Configuration
1. INNER TRANSITION FI FMENTS No.
The elements in which the additional electron enters in (n – 2) f
orbitals are called inner transition elements or f-block elements. Atomic +3 ion
58 Cerium Ce 4f15d16s2 4f1
Position in the Periodic Table: 59 Praseodymium Pr 4f36s2 4f2
The lanthanoids resemble with Yttrium in most of their
properties. So it became necessary to accommodate all the fifteen 60. Neodymium Nd 4f46s2 4f3
elements together at one place. This has been done by placing the 61. Promethium Pm 4f56s2 4f4
first element, lanthanum below yttrium and placing the remaining 62. Samarium Sm 4f66s2 4f5
fourteen elements separately in the lower part of the periodic
table. 63. Europium Eu 4f 7 6s2 4f6
Lanthanoid series (Z = 58 – 71) (Ce – Lu) 64. Gadolinium Gd 4f 7 5d1 6s2 4f 7
Actinide series (Z = 90 – 103) (Th – Lr) 65. Terbium Tb 4f9 6s2 4f8
66. Dysprosium Dy 4f106s2 4f9
2. LANTHANIODS (Rare Earths or Lanthanones)
67. Holmium Ho 4f11 6s2 4f10
(i) Lanthanoids are reactive elements so do not found in free
state in nature. 68. Erbium Er 4f126s2 4f11
(ii) Most important minerals for lighter Lanthanoids are 69. Thulium Tm 4f136s2 4f12
-Monazite, cerites and orthite and for heavier lanthanoids 70. Ytterbium Yb 4f14 6s2 4f13
- Gadolinite and Xenotime 71. Lutecium Lu 4f14 5d1 6s2 4f14
(a) Electronic configuration
(i) The general configuration of lanthanoids may be given as
[Xe] 4f1–14 5s2 5p6 5d0–1 6s2.
(b) Oxidation states: (e) Lanthanoid Contraction
(i) In lanthanoids +3 oxidation state is most common. (i) In the lanthanoid series with increasing atomic number, there is
(ii) Except Ce, Tb, Nd, Dy, Pr which also exhibit +4. a progressive decrease in the size from lanthanum to lutecium
(iii) Sm, Eu, Tm, and Yb, also exhibit +2 state. or from La+3 to Lu+3. This contraction in size is known as
(C) Magnetic Properties lanthanoid contraction.
(i) In tripositive lanthanoid ions the number of unpaired (ii) The general electronic configuration of these elements is
electrons regularly increases from lanthanum to 4f1–14 5s2 p6 d0–1 6s2. In these elements the added electron enters
Gadolinium (0 to 7) and then continuously decreases the deep seated f-orbitals and therefore experiences
upto lutecium (7 to 0). considerable pull by the nucleus.
(ii) Lanthanum and lutecium ions are diamagnetic, while all (iii) Due to very poor shielding effect of (n-2)f electrons, they exert
other tripositive lanthanoid ions are paramagnetic. very little screening effect on the outermost 6s2 electrons.
(Exception: Neodymium is the most paramagnetic Hence with increasing atomic number, the enhanced nuclear
lanthanoid). charge leads to contraction in the size of atoms and ions.
(iii) Ce+4 and Yb+2 are also diamagnetic ions.
(d) Colour
(i) The lanthanoid ions have unpaired electrons in their 4f
orbitals. Thus these ions absorbs visible region of light
and undergo f—f transition and hence exhibit colour.
(ii) The colour exhibited depends on the number of
unpaired electrons in the 4f orbitals.
(iii) The ions often with 4fn configuration have similar
colour to those ions having 4f14–n configuration.
(iv) Lanthanoid ions having 4f0, 4f14 are colourless.
APPLICATIONS OF LANTHANOID CONTRACTION (e) Important reactions of Lanthanoids
• Atomic size: The ionic radius of Hf*4, instead of increasing
(because of inclusion of one more electronic shell), decreases
(or is virtually equal to Zr+4) as a consequence of the
lanthanoid contraction.
This explains the close similarities between the members of
the second and third transition series than between the
elements of the first and second series.

➢ Basic nature of hydroxide: The effect of lanthanoid

contraction basic nature of hydroxide regularly decreases.

➢ Similarity in properties lanthanoids: Due to small difference

in size the chemical properties of lanthanoids are similar and
their separation is difficult.
Chemical reactions of the lanthanoids
Mish metal is an alloy of lanthaoids (mainly cerium) and iron.
Actioids or (i) The elements in which the extra electron enters 5f-orbitals of (n – 2)th main shell are known as
actinoids.
(5f-series) (ii) The man-made eleven elements Np93 – Lr103 are placed beyond uranium in the periodic table and are
collectively called trans-uranium elements.
(iii) Th, Pa and U first three actinoids are natural elements.

(a) Electronic Configuration

The general configuration of actinoids may be given as IRn] 5f1-14 6d0,1,2 ,7s2.

Outer Electronic Configuration

Atomic No. Elements Symbol
Atomic +3 ion
90 Thorium Th 6d27s2 Sf1
91 Proactenium Pa 5f26d17S2 5f2
92 Uranium U 5f36d17S2 st3
93 Neptunium Np 5f46d17s2 st4
94 Plutonium Pu 5f66d07s2 st5
95 Americium Am 5f66d17S2 Sf6
96 Curium Cm 5f 76d17S2 5f 7
97 Berkellium Bk 5f96d07s2 5f8
98 Californium Cf 5f106d07s2 5f9
99 Einstenium Es 5f116d07s2 5f10
100 Fermium Fm 5f126d07s2 5f11
101 Mandelevium Md 5f136d07s2 5f12
102 Nobellium No 5f146d07s2 5f13
103 Lowrencium Lr 5f146d17s2 5f14
 (d) Oxidation states:
(i) In lanthanoids and actinoids +3 oxidation is the most common for both of the series of Elements.

(ii) This oxidation state becomes increasingly more stable as the atomic number increase in the actinide series.

(iii) Highest oxidation states in the actinoids is +7 exhibited by Np93 and Pu94. it is unstable.

(iv) Highest stable oxidation state is +6 shown by U92.

Other Properties • Melting Boiling properties: They have high melting and
• Physical appearance: Acitinides are silvery white metals. boiling points. They do not follow regular gradation of
They get tarnished when exposed to the attack of alkalies. melting or boiling points with increase in atomic number.
• Density: All the actinoids except thorium and americium • Magnetic properties: The actinide elements are
have high densities. paramagnetic due to the presence of unpaired electrons.
• Colour: Actinide ions are generally coloured. The colour of • Radioactive nature: All the actinoids are radioactive in nature.
actinide ions depends upon the number or 5f-electrons. The
• Actinide contraction: The size of atom/cation decrease
ions containing no unpaired 5f-electrons (exactly full filled f-
regularly along the actinoids series. The steady decrease in
subshell) are colourless, as expected.
ionic radii with increase in atomic number is referred to as
• Ionisation energies: Ionisation energies values of actinoids actinide contraction. This is to poor shielding of 5f-electrons.
are low.
• Electropositivie character: All the known actinide metals are
highly electropositive. They resemble lanthanoid series in
this respect.
 Comparison of Lanthanides and Actinoids
Points of Resemblance :
(i) Both lanthanoids and actinoids show a dominant oxidation state of +3.
(ii) Both are electropositive and act as strong reducing agents.
(iii) Cations with unpaired electrons in both of them are paramagnetic.
(iv) Most of the cations of lanthanoids and actinoids are coloured.
(v) Both of them show a steady decrease in their ionic radii along the series. Thus, lanthanords show lanthanoid
contraction and actinoids show actinide contraction.

Points or
distinction
Lathanoids Actinoids Some important uses of actinoids are as follows -
1. Besides the most common Besides the most common Thorium: Thorium is used in atomic reactors as fuel rods
oxidation state of +3 Lantha- oxidation state of +3, and in the treatment of cancer.
noids show +2 and +4 actinoids show +4, +5 and Uranium: Uranium is used as nuclear fuel. Its salts are
oxidation states in case of +6 oxidation states in case of used in glass industry (for imparting green colour),
certain elements. certain elements.
textile industry and also in medicines.
2. Lanthanoids have less tend- Actinoids have a stronger
Plutonium: Plutonium is used as fuel for atomic reactors
ency towards complex tendency towards complex
as well as in atomic bombs.
formation. formation.
3. Except promethium, they are All the actinoids are
non radioactive. radioactive.
4. Oxides and hydroxide of Oxides and hydroxides of
lanthanoids are less basic actinoids are more basic
Thank
You