D – AND F – BLOCK ELEMENTS

Biju-IISJ
MELTING POINT AND BOILING
POINT
• High M.P and B.P - Due to strong metallic
bond and the presence of half filled d-
orbitals
• Involvement of greater number of electrons
from (n-1)d in addition to the ns electrons in
the inter atomic metallic bonding.
• Because of stronger interatomic bonding,
transition elements have high M.P and B.P
• In moving along the period from left to right,
the M.P of these metals first INCREASES to
MAXIMUM and the DECREASES regularly
towards the end of the period.
• melting points of these metals rise to a maximum
at d5 except for anomalous values of Mn and Tc
and fall regularly as the atomic number increases.
TRENDS OF M.P OF 3- d , 4-d AND 5-d TRANSITION
METALS
• The strength of interatomic bonds in transition
elements is roughly related to the number of half
filled d- orbitals
• In the beginning the no. of half filled d- orbitals
increases till the middle of the period causing
increase in strength of interparticle bonds But
thereafter the pairing of electrons in d – orbitals
occurs and the no. of half filled orbitals decreases ,
which also cause deacrease in M.P
Trends in enthalpies of atomization of transition elements

1. greater the number of valence electrons, stronger the

inter atomic attraction, hence stronger bonding
between atoms resulting in higher enthalpies of
atomization.
2. metals of the second and third series have greater
enthalpies of atomization than the corresponding
elements of the first series
 ATOMIC AND IONIC RADII
• The Atomic/ionic radii first DECREASES till the
middle, becomes almost constant and then
INCREASES towards the end of the period.
• New electron enters a d orbital each time the
nuclear charge increases by unity, But the
shielding effect of a d electron is not that
effective, hence the net electrostatic attraction
between the nuclear charge and the outermost
electron increases and the ionic radius
decreases
• However the increased nuclear charge is partly
cancelled by the increased screening effect of
electrons in the d – orbitals of penultimate shell.
• When the increased nuclear charge and increased
Screening effect balance each other, the atomic
radii becomes almost constant.
• Increase in atomic radii towards the end may be
attributed to the electron – electron repulsion.
• In fact the pairing of electrons in d – orbitals
occurs after d5 configuration.
• The repulsive interaction between the paired
electron causes Increase in Atomic/ ionic radii
• There is increase from the first (3d) to the
second (4d) series of the elements.
• But the radii of the third (5d) series are
virtually the same as 4d
• This is due to the intervention of the 4f orbital
which must be filled before the 5d series of
elements begin.
• There is a steady decrease in atomic radii from
La due to the poor shielding of inner core
electrons (4f) is known lanthanoid contraction.
 IONISATION
ENTHALPIES
• Due to an increase in nuclear charge there is an
increase in ionisation enthalpy along each series
of the transition elements from left to right.
• Ionisation enthalpies give some guidance
concerning the relative stabilities of oxidation
states.
• Although the first ionisation enthalpy, in general,
increases, the magnitude of the increase in the
second and third ionisation enthalpies for the
successive elements, in general, is much higher.
• Mostly IE1<IE2 <IE3 in each group
• The increase in IE is primarily due to increase
in nuclear charge. As the transition elements
involve the gradual filling of (n-1)d orbitals,
the effect of increase in nuclear charge is
partly cancelled by the increase in screening
effect.
• Consequently, the increase in I.E along the
periods of d – block elements is very small.
RELATION BETWEEN I.E AND
STABILITY OF A METAL IN A
GIVEN OXDN STATE
• With the help of I.E, we can predict which of
the two metals in a given oxdn state is
thermodynamically more stable.
Eg
• When a metal M (0) is converted into M(11),
the energy required is equal to I1 + I2
Similerly M (IV) = I1 + I2+ I3 + I4
• Ni (0) Ni (II) I1 + I2 =2.49 x 103 kJ mol -1
• Pt (0) Pt (II) I1 + I2 =2.66 x 103 kJ mol -1
• Ni (0) Ni (IV)
I1 + I2+ I3 + I4 =11.299 x 103 kJ mol -1
• Pt (0) Pt (IV)
I1 + I2+ I3 + I4 =9.36 x 103 kJ mol -1
I1 + I2 for Ni (II) is less than I1 + I2 for Pt (II). So Ni
(II) is more stable
Similarly Pt (IV) is more stable
 OXIDATION STATES

+3

• One of the notable features of a transition

element is the great variety of oxidation states it
may show in its compounds
• Stability of a particular oxdn state depends up
on nature of the element with which the
transition metals form the compound
• The elements which give the greatest number
of oxidation states occur in or near the middle
of the series. Manganese, for example, exhibits
all the oxidation states from +2 to +7.
• Elements in the beginning of the series exhibit
fewer oxidation state (have small no. of
electrons in which they lose or contribute for
sharing).
• Elements at the end of the series shows fewer
oxdn states because they have too many
electrons in d – orbitals. So they have few
vacant d – orbitals which can be invoved in
bonding.
• Lower oxdn state – Covalent character
• Higher oxdn state – ionic
• Higher oxdn states are more stable for heavier
members.
Eg : in group VI, Mo (VI) and W (VI) are more stable
than Cr (VI). So Cr (VI) act as strong oxidizing agent.
• The highest oxdn state - +8 (Ruthenium and
Osmium).
• Low oxidation states are found when a complex
compound has ligands capable of π-acceptor
character in addition to the σ-bonding. For example,
in Ni(CO)4 and Fe(CO)5, the oxidation state of nickel
and iron is zero.
TRENDS IN STABILITY OF HIGHER
OXIDATION STATES
• Stability – compounds with F and Oxygen
• The ability of Fluorine to stabilize the highest
oxidation state is due to either high lattice
energy as in case of CoF3 or high bond
enthalpy as in case of VF5 and CrF6.
• The ability of Oxygen to stabilize the highest
oxidation state is due to its ability to form
multiple bonds with metals.
STABLE HALIDES OF FIRST TRANSITION
ELEMENTS
Oxdn 4 5 6 7 8 9 10 11 12
no.
+6 Cr F6
+5 VF5 Cr F5
+4 TiX4 VX4 I Cr X4 MNf4
+3 TiX3 VX3 Cr X3 MnF3 Fe X3 Co F3
I II
+2 TiX2 III
VX2 Cr X2 MnX2 Fe X2 Co X2 Ni X2 Cu X2 ZnX2

+1 Cu XIII

X = F to I, XII = F,
XI = F to Br , X III = Cl to I
• The highest oxidation numbers are achieved in
TiX4 (tetrahalides), VF5 and CrF6. The +7 state
for Mn is not represented in simple halides but
MnO3F is known, and beyond Mn, no metal has
a trihalide except FeX3 and CoF3.
• Although V(V )is represented only by VF5, the
other halides, however, undergo hydrolysis to
give oxohalides, VOX3. Another feature of
fluorides is their instability in the low oxidation
states e.g., VX2 (X = CI, Br or I)
• All Cu(II) halides are known except the iodide.
In this case, Cu2+ oxidises I– to I2:
2Cu2+ + 4I- → Cu2I2 (s) + I 2
• However, many copper (I) compounds are
unstable in aqueous solution and undergo
disproportionation.
2Cu2+ → Cu2+ + Cu
• The stability of Cu2+ (aq) rather than Cu+(aq) is
due to the much more negative ΔhydH0 of Cu2+
(aq) than Cu+, which more than compensates
for the second ionisation enthalpy of Cu.
• Transition metals also exhibits the highest
Oxdn state in their Oxides.
• The ability of Oxygen to stabilize higher
oxidation states are much higher than
Fluorine..
• The highest Oxdn state with Fluorine by Mn is
+4 in MnF4 while it is + 7 in Mn2O7.
• Oxygen has the ability to form Multiple bonds
with Metal atom.

The oxides of 3 – d transition elements are

given below :
 Fluorine has the ability to stabilize higher oxidation state due
to: (i) high lattice energy (in case of CoF 3) and
(ii) higher bond enthalpy for higher covalent compounds
(VF5 and CrF6).
 The ability of oxygen to stabilize higher oxidation states is more
than fluorine. It is because oxygen has the ability to form
multiple bonds to metals.

Many copper(I) compounds are unstable in aqueous solution

2Cu2++4I− →Cu2I2(s )+ I2
Cu2+ undergo disproportionation. 2Cu+→ Cu2+ +Cu
Cu2+ is more stable than Cu+ due to more negative value of hydration
enthalpy of Cu2+ which more than compensates for the second
ionization enthalpy of copper.
Ox 3 4 5 6 7 8 9 10 11 12
dn
No

+7 Mn2O7
+6 CrO3
+5 V2O5 MnO2

+4 TiO2 V2O4 CrO2 Mn2O3 Fe2O3

+3 Sc2O3 Ti2O3 V2O3 Cr2O3 Mn3O4 Fe3O4 Co3O4
+2 TiO VO CrO MnO FeO CoO NiO CuO ZnO

+1 Cu2O
• The highest oxidation number in the oxides
coincides with the group number and is
attained in Sc2O3 to Mn2O7.
• Beyond Group 7, no higher oxides of Fe above
Fe2O3, are known, although ferrates (VI)
(FeO4)2–, are formed in alkaline media but they
readily decompose to Fe2O3 and O2.
• Besides the oxides, oxocations stabilise V(v) as
VO2+, V(IV) as VO2+ and Ti(IV) as TiO2+.
 STANDARD ELECTRODE POTENTIAL

• ELECTRODE POTENTIALS ARE THE

MEASURE OF THE VALUE OF TOTAL
ENTHALPY CHANGE.
• Electrode Potentials value depends
enthalpy of atomization ΔHa & hydration
ΔH hyd
• Lower the std E. P (Eo red), the more stable
is the oxdn state of the metal in aqueous
state.
The E0(M /M) value for copper is positive (+0.34V) : high ΔHa
2+

and low ΔH hyd). --- GREATER AMNT OF ENERGY REQUIRED TO

TRANSFORM Cu INTO Cu2+
• Due to +ve Eo, Cu does not liberate
hydrogen from acids.
• The general trend towards less negative Eo
values across the series is related to the
general increase in the sum of the first
and second ionisation enthalpies.
• It is interesting to note that the value of Eo
for Mn, Ni and Zn are more negative than
expected from the trend.
• The stability of the half-filled d sub-shell in Mn2+
and the completely filled d10 configuration in Zn2+
are related to their Eo values, whereas Eo for Ni is
related to the highest negative ΔhydHo.
• The low value for Sc reflects the stability of Sc3+
which has a noble gas configuration. The highest
value for Zn is due to the removal of an electron
from the stable d10 configuration of Zn2+. The
comparatively high value for Mn shows that
Mn2+(d5) is particularly stable, whereas
comparatively low value for Fe shows the extra
stability of Fe3+ (d5).
 CHEMICAL
REACTIVITY
• Transition metals vary widely in their chemical
reactivity. Many of them are sufficiently
electropositive to dissolve in mineral acids,
although a few are ‘noble’—that is, they are
unaffected by simple acids.
• The metals of the first series with the exception
of copper are relatively more reactive and are
oxidised by 1M H+, though the actual rate at
which these metals react with oxidising agents
like hydrogen ion (H+) is sometimes slow.
• The EO valuesfor M2+/M indicate a decreasing
tendency to form divalentcations across the
series.
• This general trend towards less negative EO
values is related to the increase in the sum of
the first and second ionisation enthalpies.
• It is interesting to note that the EO values for
Mn, Ni and Zn are more negative than
expected from the general trend.
• EO values for the redox couple M3+/M2+
shows that Mn3+ and Co3+ ions are the
strongest oxidising agents in aqueous
solutions. The ions Ti2+, V2+ and Cr2+ are strong
reducing agents and will liberate hydrogen
from a dilute acid,
e.g.,
• 2 Cr2+(aq) + 2 H+(aq) → 2 Cr3+(aq) + H2(g)
 MAGNETIC PROPERTIES
• Substances which contain species
(Atoms/ions/molecules) with unpared
electrons in their orbitals – PARAMAGNETIC.
• PARAMAGNETIC SUBSTANCES are weakly
attracted by the magnetic field.
• Strongly attracted called FERROMAGNETIC.
• Substances which do not contain any unpaired
electrons and are repelled my magnetic field _
DIAMAGNETIC.
• Transition metals usually contains unpaired
electrons – so it is paramagnetic.
• Paramagnetic behavior increases with
increase in unpaired electron.
• Paramagnetism expressed in terms of
Magnetic moment., it is related to no. of
unpaired electrons.
• The magnetic moments calculated from the
‘spin-only’ formula and those derived
experimentally.
Magnetic moment µ = √ n(n+2) BM
n- no. of unpaired electrons
BM – Bohr magnetone (unit of M.M)
BM = 9.27x10-21 erg/gauss
• Single unpaired electronhas a magnetic
moment of 1.73 Bohr magnetons (BM).
• magnetic moment of an electron is due to its
spin angular momentum and orbital angular
momentum
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.
• The frequency of the light absorbed is
determined by the nature of the ligand.
Dependence of d-Configuration in the
formation of colored ions:

• Zn 2+ / Cd 2+ - all d orbitals are fully filled

• Ti 4+ - all d orbitals are vacant
so, no d – d transition occurs. Therefor they
do not absorb radiations. So they are
colourless.
 Formationof Complex Compounds
•Metal ions bind a number of anions or neutral
molecules giving complex
[Fe(CN)6]3–, [Fe(CN)6]4–, [Cu(NH3)4]2+ and
[PtCl4]2–
.
This is due to the
•Comparatively smaller sizes of the metal ions,

• Their high ionic charges and

•The availability of d orbitals for bond formation.

 Formation of Interstitial Compounds

•When small atoms like H, C or N are trapped

inside the crystal lattices of metals

•They are usually non stoichiometric

•example, TiC, Mn4N, Fe3H, VH0.56 and TiH1.7

(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.
 ALLOY FORMATION

• Because of similar radii and other characteristics

of transition metals,
• The alloys so formed are hard and have often
high melting points.
• ferrous alloys: chromium, vanadium, tungsten,
molybdenum and manganese are used for the
production of a variety of steels and stainless
steel.
• Alloys of transition metals with non transition
metals such as brass (copper-zinc) and bronze
(copper-tin),
 CATALYTIC ACTIVITY
• The transition metals and their compounds
are known for their catalytic activity.
• This activity is ascribed to their ability to
adopt multiple oxidation states and to form
complexes.
 DISPROPORTIONATION
• When a particular oxidation state becomes less
stable relative to other oxidation states, one
lower, one higher, it is said to undergo
disproportionation. For example, manganese (VI)
becomes unstable relative to manganese(VII) and
manganese (IV) in acidic solution.
3 MnVIO4 2– + 4 H+ → 2 MnVIIO–4 + MnIVO2 + 2H2O
 OXIDES AND OXOANIONS OF METALS

• The elements of first transition series form

variety of oxides of different oxidation states
having general formula MO, M2O3, M3O6,
MO2, MO3.
• Theses oxides are generally formed by heating
the metal with oxygen at high temperature.
Sc – Sc2O3 Basic
Ti – TiO Basic, Ti2O2 Basic, TiO2 Amphoteric
V – VO Basic, V2O3 Basic, VO2 Ampho, V2O5 Acidic
Cr – CrO Basic, Cr2O3 Ampho, CrO2 Ampho,
CrO3Acidic
Mn – MnO basic, Mn2O3 Basic, Mn3O4 Ampho,
MnO2 Ampho, Mn2O7 Acidic
Fe – FeO Basic, Fe2O3 Amph, Fe3O4 Basic
Co – CoO Basic
Ni – NiO Basic
Cu – Cu2O Basic, CuO Ampho
Zn – ZnO Ampho
• In general
lower oxidation state metal – BASIC
Higher oxidation state metal – ACIDIC
Intermediate oxidation state - AMPHOTERIC
• Example
MnO (+2)basic, Mn2O3 (+3)Basic, Mn3O4 (+
8/3)Ampho,
MnO2 (+4) Ampho, Mn2O7 (+7)Acidic
• The highest oxidation number in the oxides
coincides with the group number and is
attained in Sc2O3 to Mn2O7.
• Beyond Group 7, no higher oxides of Fe
above Fe2O3, are known, although ferrates
(VI) (FeO4)2–, are formed in alkaline media
but they readily decompose to Fe2O3 and
O2.
• Besides the oxides, oxocations stabilise
V(v) as VO2+, V(IV) as VO2+ and Ti(IV) as
TiO2+.
• As the oxidation number of a metal increases,
ionic character decreases. In the case of Mn,
Mn2O7 is a covalent green oil. Even CrO3 and
V2O5 have low melting points. In these higher
oxides, the acidic character is predominant.
 POTASSIUM DICHROMATE K2CR2O7
STEP 1
• Dichromates are generally prepared from
chromate which in turn are obtained by the
fusion of chromite ore (FeCr2O4) with
sodium or potassium carbonate in free
access of air. The reaction with sodium
carbonate occurs as follows:
4 FeCr2O4 + 8 Na2CO3 + 7 O2 → 8 Na2CrO4+2
Fe2O3 + 8 CO2
STEP 2
• The yellow solution of sodium chromate is
filtered and acidified with sulphuric acid to give a
solution from which orange sodium dichromate,
Na2Cr2O7. 2H2O can be crystallised.
2Na2CrO4 + H2SO4 → Na2Cr2O7 + Na2SO4 + H2O
STEP 3
Conversion of Sodium dichromate in to Potassium
dichromate
Na2Cr2O7 + 2 KCl → K2Cr2O7 + 2 NaCl
• The oxidation state of chromium in
chromate and dichromate is the same.
2– + 2–
2 CrO4 + 2H → Cr2O7 + H2O
2– - 2–
Cr2O7 + 2 OH → 2 CrO4 + H2O
• The chromate ion is tetrahedral whereas the
dichromate ion consists of two tetrahedra
sharing one corner with Cr–O–Cr bond angle
of 126°.
•Sodium and potassium dichromates are strong oxidising
agents
Potassium dichromate is used as a primary standard in
volumetric analysis. In acidic solution, its oxidising action
can be represented as follows:
Cr2O 2– + 14H+ + 6e– → 2Cr3+ + 7H O (EV = 1.33V)
7 2
• acidified potassium dichromate will oxidise
iodides to iodine, sulphides to sulphur, tin(II)
to tin(IV) and iron(II) salts to iron(III). The half-
reactions are noted below:
• 6 I– → 3I2 + 6 e– ;
• 3 H2S → 6H+ + 3S + 6e–
• 3 Sn2+ → 3Sn4+ + 6 e–
• 6 Fe2+ → 6Fe3+ + 6 e–
2– + 2+ 3+ 3+
Cr2O7 + 14 H + 6 Fe → 2 Cr + 6 Fe + 7 H2O
POTASSIUM PERMANGANATE KMNO4
• Potassium permanganate is prepared by fusion
of MnO2 with an alkali metal hydroxide and an
oxidising agent like KNO3. This produces the
dark green K2MnO4 which disproportionates in
a neutral or acidic solution to give
permanganate.
2MnO2 + 4KOH + O2 → 2K2MnO4 + 2H2O

3MnO42– + 4H+ → 2MnO4- + MnO2 + 2H2O

The manganate and permanganate ions are
tetrahedral; the green manganate is
paramagnetic with one unpaired electron but the
permanganate is diamagnetic.
THE INNER TRANSITION ELEMENTS
(F-BLOCK)
• The elements in which the additional
electrons enters (n-2)f orbitals are called inner
transition elements. The valence shell
electronic configuration of these elements can
be represented as (n – 2)f0-14(n – 1)d0-1ns2.
• 4f inner transition metals are known as
lanthanides because they come immediately
after lanthanum and 5f inner transition metals
are known as actinoids because they come
immediately after actinium.
 ELECTRONIC
CONFIGURATION
Element name Symbol Z Ln Ln3+ Radius
Ln3+/ pm
Lanthanum La 57 [Xe]6s25d1 [Xe]4f0 116
Cerium Ce 58 [Xe]4f16s25d1 [Xe]4f1 114
Praesodymium Pr 59 [Xe]4f36s2 [Xe]4f2 113
Neodymium Nd 60 [Xe]4f46s2 [Xe]4f3 111
Promethium Pm 61 [Xe]4f56s2 [Xe]4f4 109
Samarium Sm 62 [Xe]4f66s2 [Xe]4f5 108
Europium Eu 63 [Xe]4f76s2 [Xe]4f6 107
Gadolinium Eu 64 [Xe]4f76s25d1 [Xe]4f7 105
Terbium Tb 65 [Xe] 4f96s2 [Xe]4f8 104
Dysprosium Dy 66 [Xe] 4f106s2 [Xe]4f9 103
Holmium Ho 67 [Xe] 4f116s2 [Xe]4f10 102
Erbium Er 68 [Xe] 4f126s2 [Xe]4f11 100
Thulium Tm 69 [Xe] 4f136s2 [Xe]4f12 99
Ytterbium Yb 70 [Xe] 4f146s2 [Xe]4f13 99
Lutetium Lu 71 [Xe] 4f146s25d1 [Xe]4f14 98
 Atomic and ionic sizes: The Lanthanoid
Contraction
• As the atomic number increases in right, each
succeeding element contains one more
electron in the 4f orbital and one proton in
the nucleus. The 4f electrons are ineffective in
screening the outer electrons from the
nucleus causing imperfect shielding. As a
result, there is a gradual increase in the
nucleus attraction for the outer electrons.
Consequently gradual decrease in size occur.
This is called lanthanoid contraction.
Consequences of Lanthanoid Contraction
• There is a very close resemblance between
4d and 5d transition series.
• Ionization energy of 5d transition series is
higher than 3d and 4d transition series.
• Difficulty in separation of lanthanides.
 IONIZATION ENTHALPIES

• Fairly low I. E
• First ionization enthalpy is around 600 kJ mol-1,
the second about 1200 kJ mol-1 comparable
with those of calcium.
• Due to low I. E, lanthanides have high
electropositive character
 COLOURED IONS
• Many of the lanthanoid ions are coloured in
both solid and in solution due to f – f
transition since they have partially filled f –
orbitals.
• Absorption bands are narrow, probably
because of the excitation within f level.
• La3+ and Lu3+ ions do not show any colour
due to vacant and fully filled f- orbitals.
COLOURED IONS
Unpaired Unpaired
Color Ion Color
Electrons Electrons

0 Colorless Tb3+ 6 Pale Pink

1 Colorless Dy3+ 5 Yellow

2 Green Ho3+ 4 Pink; yellow

3 Reddish Er3+ 3 Reddish

4 Pink; yellow Tm3+ 2 Green

5 Yellow Yb3+ 1 Colorless

6 Pale Pink Lu3+ 0 Colorless

7 Colorless
 MAGNETIC PROPERTIES

• The lanthanoid ions other then the f 0 type

(La3+ and Ce4+) and the f14 type (Yb2+ and Lu3+)
are all paramagnetic. The paramagnetism rises
to the maximum in neodymium.
• Lanthanides have very high magnetic
susceptibilities due to their large numbers of
unpaired f-electrons.
 OXIDATION STATES
• Predominantly +3 oxidation state.
• +3 oxidation state in La, Gd, Lu are especially
stable ( Empty half filled and Completely filled f –
subshell respectively)
• Ce and Tb shows +4 oxdn state ( Ce 4+ - 4fo & Tb 4+
4f7)
• Occasionally +2 and +4 ions in solution or in solid
compounds are also obtained.
• This irregularity arises mainly from the extra
stability of empty, half filled or filled f subshell.
• The most stable oxidation state of lanthanoids
is +3. Hence the ions in +2 oxidation state tend
to change +3 state by loss of electron acting as
reducing agents whereas those in +4 oxidation
state tend to change to +3 oxidation state by
gain of electron acting as a good oxidising
agent in aqueous solution.

• Why Sm2+, Eu2+, and Yb2+ ions in solutions are

good reducing agents but an aqueous solution
of Ce4+ is a good oxidizing agent?
PROPERTIES
• Silvery white soft metals, tarnish in air rapidly
• Hardness increases with increasing atomic
number, samarium being steel hard.
• Good conductor of heat and electricity.
• Promethium - Radioactive
CHEMICAL PROPERTIES
• Metal combines with hydrogen when gently
heated in the gas.
• The carbides, Ln3C, Ln2C3 and LnC2 are formed
when the metals are heated with carbon.
• They liberate hydrogen from dilute acids and
burn in halogens to form halides.
• They form oxides and hydroxides, M2O3 and
M(OH)3, basic like alkaline earth metal oxides
and hydroxides.
 Ln2O3 H2

Ln2S3 Heated with S Ln With helogens LnX3

C 2773 K

LnN LnC2 Ln(OH)3 +H2

 THE ACTINOIDS

• All isotopes are radioactive, with only 232Th,

235U, 238U and 244Pu having long half-lives.

• Only Th and U occur naturally-both are more

abundant in the earth’s crust than tin.
• The others must be made by nuclear
processes.
• The dominant oxidation state of actinoids is
+3. Actinoids also exhibit an oxidation state of
+4. Some actinides such as uranium,
neptunium and plutonium also exhibit an
oxidation state of +6.
• The actinoids show actinide contraction (like
lanthanide contraction) due to poor shielding
of the nuclear charge by 5f electrons.
• All the actinides are radioactive. Actinoids are
radioactive in nature.
ACTINOID CONTRACTION
• The size of atoms / M3+ ions decreases
 regularly along actinoid series. The steady
decrease in ionic/ atomic radii with increase in
atomic number is called Actinoid
Contraction.
• The contraction is greater from element to
element in this series – due to poor shielding
effect by 5 f electron.
 ELECTRONIC
CONFIGURATION
Element name Symbol Z Ln Ln3+ Radius
Ln3+/ pm
Actinium Ac 89 [Rn] 6d17s2 [Rn]4f0 111
Thorium Th 90 [Rn ]5d27s2 [Rn]4f1
Protactinium Pa 91 [Rn]5f26d17s2 [Rn]4f2
Uranium U 92 [Rn]5f36d17s2 [Rn]4f3 103
Neptunium Np 93 [Rn]5f46d17s2 [Rn]4f4 101
Plutonium Pu 94 [Rn]5f67s2 [Rn]4f5 100
Americium Am 95 [Rn]5f77s2 [Rn]4f6 99
Curium Cm 96 [Rn]5f76d17s2 [Rn]4f7 99
Berkelium Bk 97 [Rn]5f97s2 [Rn]4f8 98
Californium Cf 98 [Rn]5f107s2 [Rn]4f9 98
Einsteinium Es 99 [Rn]5f117s2 [Rn]4f10
Fermium Fm 100 [Rn]5f127s2 [Rn]4f11
Mendelevium Md 101 [Rn]5f137s2 [Rn]4f12
Nobelium No 102 [Rn]5f147s2 [Rn]4f13
Lawrencium Lr 103 [Rn]5f146d17s2 [Rn]4f14
MAGNETIC PROPERTIES
• Paramagnetic behaviour
• Magnetic properties are more complex than
those of lanthanoids.
M.P and B.P
High M.P and B.P
Do not follow regular gradation of M.P or B.P
with increase in atomic number
IONISATION
ENTHALPY
• Low I.E. so electropositiity is High
COLOUR
• Generally coloured
• Colour depends up on the number of 5 f
electrons
• The ions containing 5 f o and 5 f 7 are
colouress
Eg –
U 3+ (5 f 3 ) – Red
NP 3+ (5 f 4 ) – Bluish
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