D AND F-BLOCK ELEMENTS

CET: 7MARKS
JEE: 4-8MARKS
NEET: 12MARKS
INTRODUCTION
• The d block elements are in the middle of s and p
blocks, from groups 3 to 12.
• d-block elements are called transition elements
• The elements where last electron enters (n-1)d
orbital is called d-block elements.
• d-block elements are defined as
“incompletely or partially filled d-orbitals in
its ground state or in any one of its oxidation
states”.
• Their properties are intermediate and
transitional between s– (metals) and p–block
elements (non-metals) so they are called
transition elements.
PH7411979425
• The d block elements are in the middle of s and p
blocks, comprising the groups 3 to 12.
• 3d series: 21Scandium to 30Zinc (3d1-10 4s1-2) {First
transition series}
• 4d series: 39Yttrium to 48Cadmium (4d1-10 5s1-2)
{Second transition series}
• 5d series: 57Lanthanum, 72Hoffmium -
80Mercury(5d 6s1-2) {Third transition series}
1-10

• 6d series: 89Actinium, 104Rutherfordium-

112 Copernicium(6d 1-10
7s 1-2
) {Fourth transition
series}
PH7411979425
 What are d-block elements??
d-block elements are defined as “incompletely
or partially filled d-orbitals in its ground state”
So Zn is
called
Psuedo
Transition
element
 ELECTRONIC CONFIGURATION
• The general electronic configuration of d block
elements is [noble gas] (n-1)d1-10ns1-2
• The general electronic configuration of 3d series
is [Ar] 3d1-10 4s1-2
• The general electronic configuration of 4d series
is [Kr] 4d1-10 5s0-2
• The general electronic configuration of 5d series
is [Xe] 5d1-10 6s1-2
• The general electronic configuration of 6d series
is [Rn] 6d1-10 7s1-2
Pd: 4d10 5s0 Ag: 4d10 5s1
Pt: 5d9 6s1 Au: 5d10 6s1
 Uniqueness of Zn, Cd, Hg, Cn
• Fully filled d-orbital in ground state and common
oxidation state
• Zn2+ is 3d10, Cd2+ is 4d10 ,Hg2+ is 5d10
• Soft metals and Hg is liquid metal
• Low MP, BP, Enthalpy of atomization
• Colourless, Diamagnetic
• Pseudo transition elements
• Everything is lowest for these 4
 Uniqueness of Cr, Mo, W
• Highest unpaired electrons in ground state (6e)
• Hard metals
• Highest MP, BP, Enthalpy of atomization
• Tungsten is highest MP, BP, EOA
• Cr << Mo << W is most properties
Metallic property
ATOMIC SIZE
1. Reason: Why 4d and 5d elements have same size
A: Lanthanoid contraction
• Eg: Zr and Hf have same radii because of Lanthanoid
contraction
• Mo and W have same size due L.C
• Nb and Ta have same radii due L.C
• Atomic size and chemical properties of
• 4d and 5d elements are similar because of Lanthanoid
contraction
 2. IONISATION ENERGY

2. IE order: 5d>3d>4d (NCERT DATA)

TRICK: MaZaK (IE of Mercury > Zinc > Cadmium)
(NEET-2016)
NOTE: ALWAYS IE3>> IE2>> IE1
Note:
1. Second IE of Cu and Cr is high
2. Second IE of Zn is low
3. Third IE of Mn is high
DENSITY
4. MELTING POINT
• Cr, Mo, W – Highest MP.
• Zn, Cd, Hg have low
melting point and are
very soft in nature (fully
filled d-orbital)
• Zn, Cd, Hg are soft
metals (Low metallic
nature)
Low MP of
Manganese
5. ENTHALPHY OF ATOMISATION
Highest EOA:
Cr << Mo << W
Lowest EOA:
Zn >> Cd >> Hg
Hg has lowest EOA in d block and W has highest
EOA in d block
Mn has abnormally low EOA
 6. VARIABLE OXIDATION STATE
1. 3d element with highest OS in 3d= Mn (+7)
2. 3d element with lowest OS= Cu (+1)
3. 3d element without variable OS= Sc (+3)
4. d-block element with highest OS in P.T=
Osmium and Ruthenium (+8)
5. Common OS of d block elements is +2
6. Up to Mn, Higher O.S is stable
7. After Mn, Lower O.S is stable
Sc+2 is not viable on earth so doesn’t exist
INERT PAIR EFFECT:
• In p-block elements, Last elements loves lower state
(INERT PAIR EFFECT). Eg: Tl loves +1 instead of +3,
Pb loves +2 instead of +4 so Tl+1 and Pb+2 are
more stable.
CR FAMILY STABILITY:
• Mo+6 and W+6 are more stable than Cr+6.
(Cr+6<<Mo+6<<W+6)
COMPLEXES OF Ni and Fe
• Ni(CO)4, charge of Ni is ZERO (Due to synergic back
bonding)
• Fe(CO)5 charge of Fe is ZERO (Due to synergic back
bonding)
 7. MAGNETIC PROPERTY (MOST IMP FOR
JEE, KCET, NEET EVERY YEAR QUE)
• Magnetic properties is because of unpaired electrons
in d-orbtials.
• If it has unpaired electrons in d-orbital then it
paramagnetic (Weakly attracted in magnetic
field, if unpaired electrons is absent then
diamagnetic. (Weakly repelled in magnetic
field)
Magnetic property is measured by magnetic
moment. Spin only formula (VVVVVVVVVV IMP)

μ = √ n ( n +2 ) BM
• n = no of unpaired electrons
• Unit of magnetic moment is BM (Bohr Magneton)
• is directly proportional to unpaired electrons
 −
To find unpaired e ( n )
n =0 → Diamagnetic , Colourless
n = Z− O .S −18
n =0 → 5, n = Keep it same n ≠ 0 → Paramagnetic , Coloured
n =6 → 10, n =10− n

n=0 u=0BM
n can never cross5

n=1 u=1.7BM
n=2 u=2.8BM
n=3 u=3.8BM
n=4 u=4.9BM
n=5 u=5.9BM
CALCULATE MAGNETIC MOMENT, COMMENT ON
COLOUR AND ITS MAGNETIC PROPERTY
COLOUR OF TRANSITION ELEMENTS
(VVVVVV IMP)
The compounds of transition elements shows colour,
i) Due to the presence of unpaired electron in d-orbital
ii) Due to the ability to undergo d-d transition.
INTERSTITIAL COMPOUNDS (VVVV IMP)

• Non stoichiometric compounds are those which

are formed when small atoms like H, C or N are
trapped interstitial site the crystal lattices of
metals.
• They are usually non stoichiometric and are
neither typically ionic nor covalent,
• Eg: TiC, Mn4N, Fe3H, VH0.56 and TiH1.7, etc.
PROPERTIES OF INTERSTITIAL COMPOUNDS:
• They have high melting points, higher than those
of pure metals.
• They are very hard, some borides approach diamond
in hardness.
• Their malleability and ductility decreases
• They retain metallic conductivity
• They are chemically inert.
NOTE: INTERSTITIAL COMPOUNDS ARE NON
STOICHIOMETRIC AND NEITHER COVALENT OR
IONIC
 ALLOY FORMATION
• Homogenous solid solutions
• Both elements radius should differ more
than 15%
• Example: Brass (Cu+Zn), Bronze (Cu+Sn), Steel
(Fe+C) Stainless steel (Fe+Co+Ni+Small amount
of C).
• Properties: i) The alloys are hard
ii) They have high melting points.
• Fe, Co, Ni do not form amalgam with Hg
(Large difference of radius)
 Electrode potential of M2+/M
• E0Cu2+/Cu is +0.34V so it
shows inability of Cu to
react with dilute acids
like dil HCl but Cu can
react with conc HNO3
and conc H2SO4 and Cu
oxidises from Cu to Cu+2
• E0 of Mn, Ni, Zn is less than
expected values
 Electrode potential of M3+/M
• E0Sc3+/Sc is less so it Sc3+ does not want to
back to Sc because Sc3+ is more stable
due to NG configuration
• E0Zn3+/Zn is very high so it Zn3+ wants to
back to Zn because Zn3+ is less stable and
by becoming Zn it is becoming more
stable
 Stability of Halides and Oxides
• Highest known stable halides are TiX4, VF5, CrF6
• MnF7 is not known and Mn shows +7 as KMnO4
and MnO3F
• After Mn, Only Fe can make trihalide (FeX3)
• Flourine stabilizes higher oxidation state Eg:
CrF6, MnF4, VF5
STABILITY OF OXIDATION STATES (FAV TOPIC
FOR CET)
Elements in Higher O.S Acidic

Elements in Intermediate Amphoteric

O.S
Elements in Lower O.S Basic

V2O5 is exception and it is amphoteric

• Higher O.S is more stable in Fluorides than
Iodides
• Lower O.S is more stable in Iodides than
Fluorides
• Manganese is more stable in oxides in higher
COMPARE STABILITY OF HALIDES
COMPARE ACIDITY OF COMPOUNDS
 IMPORTANT POINTS OF D-BLOCK

1.CuI2 does not exist and all other halides are

known
2.All Cu2+ Halides are stable except Iodides
2+ −
Cu +I Cu2 I 2 + I 2
→

3. Cu+ compounds are unstable so undergo

disproportionation to Cu and Cu2+
+ 2+
Cu → Cu + Cu
2+ +
Because Stability Cu >> Cu
+2
Due to − ve Hydration energy of Cu which is greater than2 nd IE
4. Cu does not react with dil HCl and dil H2SO4
5. Mn+3 and Co3+ are strong OA and Ti+2, V+2, Cr2+ are
strong RA and react with dilute acids
6. CuCl2 is more stable Cu2Cl2 in aqueous medium
IONIC CHARACTER AND COVALENT
CHARECTER
f-BLOCK ELEMENTS (1Q CET)
 INTRODUCTION
• The f-block elements have 2series of 14 elements
called Lanthanoids and Actinoids.
• f-block elements are called inner transition
elements because they are derived from transition
elements.
• The electronic configuration is
[noble gas] (n-2)f 1 – 14 (n-1)d0- 1 ns2
 LANTHANOIDS (4f SERIES)
• 14 elements after lanthanum (57) from atomic
number 58-71
• The last electron enters 4f subshell so they are called
4f series
• 6th period in the periodic table
• Lanthanum is d block element and after La(57),
lanthanoids starts
• Lanthanoid starts from Cerium(58) and
Lutetium(71)
• The general electronic configuration of
Lanthanoids is [Xe] 4f 1 – 14 5d0- 1 6s2
 ELECTRONIC CONFIGURATION

Atomic Element Symbol E.C M3+

no
58 Cerium Ce 4f1 5d1 4f1
6s2
63 Europium Eu 4f7 5d0 4f6
6s2
64 Gadoliniu Gd 4f7 5d1 4f7
m 6s2
70 Ytterbiu Yb 4f14 6s2 4f13
m
71 Lutetium Lu 4f14 5d1 4f14
 LANTHANOID CONTRACTION

“Gradual decrease in the atomic and ionic size of

lanthanoid series with increase in atomic number is
known as lanthanoid contraction.”
 Reason: Due to imperfect shielding effect of 4f
electrons.
CONSEQUENCES OF L.C
 The size of 4d and 5d series is similar
Eg: Zr and Hf have similar radii
Nb and Ta have similar radii
Mo and W have similar radii
 Difficulty in separation of lanthanoids due to
similarity in chemical properties. (Chem properties
is same)
 Basic nature of Lanthanoid hydroxides (La(OH)3 to
Lu(OH)3) gradually decreases
 4d and 5d elements will have same size, same
chemical and physical properties
 OXIDATION STATE
• Lanthanoid shows most common oxidation state
of +3
• Except Ce(Cerium), Tb(Terbium),
Nd(Neodynium), Dy(Dysprosium), Pr
(Promethium) shows +4
Trick: Seeta Narada Took Dinosaur to Park at 4pm
• Sm (Samarium), Europium (Eu), Thulium (Tm),
Yb (Ytterbium) shows +2 state
Trick: Some England use 2 thick Yachts
• Compounds in +4 are oxidising agents (Eg:
Ce+4 is Oxidizing agent)
• Compounds in +2 are reducing agents (Eg:
Eu+2 is a reducing agent)
• Ce(IV) oxidises water (E0Ce4+/Ce3+ = 1.74V)
• Promethium is the only synthetic radio active
lanthanide (Kcet-2022)
 CHEMICAL PROPERTIES OF LANTHANOIDS
• Lanthanides are highly reactive and beginning members
behave as calcium and last members behave as
Aluminium
 USES OF LANTHANOIDS

• The composition of mischmetall is lanthanoid

metal (~ 95%) and iron (~ 5%) and traces of S,
C, Ca and Al.
• USE: Mischmetall is used in Mg-based alloy to produce
bullets, shell and lighter flint
NOTE:
• Lanthanides are silvery white soft metal and Samarium
is the hardest lanthanide
• Gd3+, La3+ and Lu3+ are colourless because of unpaired
electrons
 ACTINIDES (5f SERIES)
• 14 elements after Actinum from atomic number
90-103
• The last electron enters 5f subshell so they are called
5f series
• 7th period in the periodic table
• Actinium is d block element and after (89), Actinides
starts
• Actinides starts from Thorium(90) and
Lawrencium(103)
• The general electronic configuration of Actinides
is
[Rn] 5f 1 – 14 6d0- 1 7s2
 ACTINOID CONTRACTION

“Steady decrease in the atomic and ionic size of

Actinoid series with increase in atomic number is
known as actinoid contraction.”
 Reason: Due to imperfect shielding effect of 5f
electrons.
 Actinoid contraction is greater than lanthanoid
contraction because poor shielding of 5f electrons
is greater than 4f (VVV IMP)
 OXIDATION STATE

 Most common O.S of actinoid is +3

 It shows O.S from +3 to +7
 Np and Pu shows highest charge +7
 Stable O.S of Uranium is +6
 All elements after Uranium(92) are called Trans
Uranic elements
 In actinides 5f, 6d and 7s levels are of
comparable energies, hence they show VARIABLE
OXIDATION STATE (Most important point)
 All actinides are silvery metals and radioactive.
• Actinides are slightly affected by conc
HNO3 as they form a protective layer of
oxide but gets highly affected by conc HCl
 USES OF ACTINOIDS

• Thorium is used in atomic reactors as fuel rods and in

treatment of cancer
• Uranium is used as nuclear fuel and used in glass
industry for imparting green colour
• Plutonium is used as fuel for atomic reactors and
atomic bombs

NOTE: Study of actinide is very difficult because

they are radioactive and have variable oxidation
state and can be prepared in nano grams only
 APPLICATION OF D AND F BLOCK ELEMENTS

• TiCl4 and Et3Al is called Ziegler natta catalyst and it

used in manufacture of polyethene
• AgBr is used special light sensitive photography
• PdCl2 is used catalyst to convert ethyne to ethanol by
Wacker process
• Nickel complex is used in polymerisation of alkynes to
benzene
• MnO2 is used in dry batteries
• Cu/Ni alloy in making coins
PH7411979425
POTASSIUM DICHROMATE
(K2Cr2O7)
 INTRODUCTION
Potassium Dichromate is prepared from Chromite
ore (FeO.Cr2O3)
PREPARATION OF K2Cr2O7
IMPORTANT COLOURS OF Cr SALTS
STRUCTURES OF DICHROMATE AND CHROMATE
CHROMYL CHLORIDE TEST
 CONVERSION OF DICHROMATE AND
CHROMATES
Dichromates (Orange) and Chromates (Yellow)
are interconvertible by altering pH.
PROPERTIES OF POT. DICHROMATE
POT. DICHROMATE IN ACIDIC MEDIUM AS
STRONG O.A (IMP FOR CET)
2− + − +3
Cr 2 O +14 H +6 e →2 Cr +7 H2 O
7
All these reactions happens only in acidic medium
and nf= 6 (6e reactions)
1. Reaction of K2Cr2O7 with (Iodide) I-

¿¿
2. Reaction of K2Cr2O7 with H2S (Hydrogen sulphide)

¿ PH7411979425
3. Reaction of K2Cr2O7 with Fe2+ (ferrous)

¿
4. Reaction of K2Cr2O7 with Sn2+ (Stannous)

¿ PH7411979425
LIGAND METAL CHARGE TRANSFER
POTASSIUM PERMANGANATE
(KMnO4)
 INTRODUCTION
Potassium Permangante is prepared from
Pyrolusite ore (MnO2)
PREPARATION OF KMnO4
 IMPORTANT POINTS OF KMnO4
1. KMnO4 is purple colour and not very soluble in water
2. KMnO4 is isostructural with KClO4 (Potassium
perchlorate)
3. KMnO4 decomposes when heated at 513K to give K2MnO4
and MnO2 and O2 (Paramagnetic colourless gas)

4. Strong O.A (Stronger than Potassium dichromate)

POT. PERMANGANTE AS STRONG O.A (IMP
FOR CET)
POT. PERMANGANATE IN ACIDIC
MEDIUM
OXIDISING PROPERTY IN ACIDIC MEDIUM:
Reaction of KMnO4 with I-

¿
(Iodide)
Reaction of KMnO4 with Fe2+ (Ferrous)

¿
Reaction of KMnO4 with C2O4(2-) (Oxalato)

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 ¿
Reaction of KMnO4 with H2S(Hydrogen Sulphide)

Reaction of KMnO4 with NO2-(Nitrite)

¿ PH7411979425
Reaction of KMnO4 with SO3-2(Sulphite)

¿
PH7411979425
POT. PERMANGANATE IN FAINTLY
ALKALINE/NEUTRAL MEDIUM
NOTE: In titration or during oxidation,
KMnO4+ H2SO4 is used instead of HCl,
why?