CLASS 12, CHEMISTRY, CHAPTER NO.

8
THE d and f- BLOCK ELEMENTS
• General introduction.
• electronic configuration.
• occurrence and characteristics of transition metals.
• General trends in properties of the first row transition metals –
- metallic character.
- ionization enthalpy.
- oxidation states.
- ionic radii.
- colour.
- catalytic property.
- magnetic properties.
- interstitial compounds.
- alloy formation.
• Lanthanoids - Electronic configuration
- oxidation states.
- lanthanoid contraction and its consequences.
Ionisation Enthalpies
 TRENDS IN STABILITY OF HIGHER OXIDATION STATES IN HALIDES

• The highest oxidation numbers are achieved in TiX4 (tetrahalides), VF5 and CrF6.

• +7 state for Mn is not represented in simple halides but MnO3F (Manganese

oxyfluoride)is known .(MnF7 will have too much steric effect and too much
repulsion among F atoms hence it does not exist but O forms multiple bonds
and that’s why no. of species becomes lesser in the molecule and is stabilised.)
• All the highest OS are found with fluorine because it stabilize the highest OS by
forming very strong bond due to being most electronegative. (high bond enthalpy in
covalent halides like VF5 and CrF6 and high lattice energy in ionic halides like CoF3.)

• Fluorides are unstable with lower OS and due to being most electronegative they
oxidise the transition metal to its higher OS

• Vanadium halides are generally hydrolysed to give oxohalide VOX3.

• Sc forms trihalides with all the four halogens, F, Cl, Br and I.

• Cu forms dihalide with F and Cl(higher OS with more electronegative atoms) and
mono halide with Cl, Br and I (less electronegative). Thus Cu2+ oxidises I– to I2:
2Cu 2+ + 4I − → Cu2I2 (s) + I2
However, many copper (I) compounds are unstable in aqueous solution and undergo
disproportionation: 2Cu+ → Cu2+ + Cu
The stability of Cu2+ (aq) rather than Cu+(aq) is due to the much more negative
hydration enthalpy of Cu2+(aq) than Cu+, which compensates for the 2nd IE of Cu.
 TRENDS IN STABILITY OF HIGHER OXIDATION STATES IN OXIDES

• 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.
• The ability of O to stabilise these high OS exceeds that of F due to The ability of
oxygen to form multiple bonds to metals which decreases steric hinderance (less O
atoms are needed than F for same OS) and form stronger bonds(multiple bonds are
stronger than single bonds.) Thus the highest Mn fluoride is MnF4(OS +4)whereas
the highest oxide is Mn2O7(OS +7).

• In the covalent oxide Mn2O7, each Mn is tetrahedrally surrounded by O’s including a

Mn–O–Mn bridge.

• The tetrahedral [MO4]n- ions are known for VV, CrVl, MnV, MnVl and MnVII. ( Examples:
[MnO4]–, [CrO4]2–, and [VO4]3–
• Besides the oxides, oxocations stabilise Vv as VO2+, VIV as VO2+ and TiIV as TiO2+
(These are derived from oxohalides).

• There are three mixed oxides: Fe3O4 = FeO.Fe2O3

Mn3O4 = MnO.Mn2O3
Co3O4 = CoO.Co2O3

• As usual oxides of highest OS (like Mn2O7, Cr2O6)are acidic in nature( tendency to

gain electrons due to greater +ve charge on metal ion), lowest OS are basic and
middle ones are amphoteric. V2O5 , in spite of having highest OS of V, have
amphoteric properties (Although it is little more acidic than basic)

• In a transition series the acidic nature of oxides for the same OS increases from left
to right due to decreasing size of metal which increases +ve charge density on it.

• As usual oxides of highest OS are covalent in nature due to more polarising power
 Let’s apply your knowledge
Q. How would you account for the increasing oxidising power in the series: 
VO2+< Cr2O72−< MnO4- ?
Ans: This is due to the increasing stability of the species with lower oxidation state
of metal atom to which they are reduced , e.g.,

Q. FeCl3 and FeCl2 are found as dimer in vapour phase. Explain the bonding in them.
Ans: FeCl3​ and FeCl2​ exist in dimer form in vapour phase. In dimer form, they
have (3C−4e−) bond. They contain chlorine bridges.

Q. What happens if we dissolve anhydrous Mn2O7 in water?

Ans: It is acidic in nature hence it produces permanganic acid
Mn2O7 + H2O. -------> H2Mn2O8. ------>. 2HMnO4
Q. Write the anhydride of permanganic acid.
Ans: HMnO4​ is dehydrated by cold sulfuric acid to form its anhydride, Mn2O7 which is
highly explosive in nature.
 CHEMICAL REACTIVITY AND STANDARD ELECTRODE POTENTIAL
• The Chemical reactivity of transition metals can directly be explained by their
standard electrode potential (E)values.

• Higher the negative E, the metal will be more reactive.(M tends to be M 2+ by

forming compounds. Thus such metals are good reducing agents).

• Higher the positive E, the metal will be less reactive.(M 2+ tends to be M means its
ions are easily displaced from its compounds to form elemental M. Thus such
metals are good oxidizing agents.)

• In 3d series from left to right E for M 2+/ M becomes less negative so reactivity
also decreases. All of these except Cu can be oxidized by 1M H + ion
solution(acids). Cu having positive E becomes least reactive in 3d series.

• Evalues for Mn, Ni and Zn are more negative than expected from the general
trend. It is due to stabilities of half-filled d subshell (d5) in Mn2+, completely filled
d subshell (d10) in Zn2+ and highest negative enthalpy of hydration for Ni 2+. Thus
• The E values for the redox couple M3+/M2+ for Mn and Co are highly positive.
It means M2+ ions are more stable than M3+ ions in case of these two metals. It
is due to stability of half-filled d subshell (d5) in Mn2+ and stable complex
formation of Co2+ with water. Hence Mn3+ and Co3+ ions are the strongest
oxidising agents in aqueous solutions.

• The E values for the redox couple M3+/M2+ for Ti, V and Cr are negative. It
means M3+ ions are more stable than M2+ ions in case of these three metals. It
is due to t2g half filled d orbitals in Cr3+ and more hydration enthalpy as
compared to ionisation enthalpy in Ti3+ and V3+. Hence their M2+ ions are
strong reducing agents and will liberate hydrogen from a dilute acid and
convert themselves in M3+ ions.

2Cr2+(aq) + 2H+(aq) → 2Cr3+(aq) + H2(g)

 MAGNETIC PROPERTIES OF d-BLOCK ELEMENTS
• Many of the transition metal ions are paramagnetic.

• Para magnetism arises from the presence of unpaired electrons, each

such electron having a magnetic moment associated with its spin
angular momentum and orbital angular momentum.

• For the compounds of the first series of transition metals, the

contribution of the orbital angular momentum is effectively quenched
and hence is of no significance. (In order for an electron to contribute
to the orbital angular momentum the orbital in which it resides must
be able to transform into an exactly identical and degenerate orbital
by a simple rotation without any energy consumption. In transition
elements all the 5 d- orbitals are not same in shape and energy but
they are in the form of t2g and eg energy levels. Hence Orbital angular
moment is ignored.)
• For these, the magnetic moment is determined by the number of
unpaired electrons and is calculated by using the ‘spin-only’
formula, i.e.,

where n is the number of unpaired electrons and µ is the magnetic

moment in units of Bohr magneton (BM). A single unpaired
electron has a magnetic moment of 1.73 Bohr magnetons (BM).

• The magnetic moment increases with the increasing number of

unpaired electrons. Thus, the observed magnetic moment gives a
useful indication about the number of unpaired electrons present
in the atom, molecule or ion.
 Here, the observed values are somewhat different from calculated values. It depends on the
compound of which the metal ion is a part. The other part (ligand) may affect the no. of
unpaired electrons. They can cause pairing or unpairing of d- electrons of transition metals.
 NOW SOLVE THIS:

Q. Calculate the magnetic moment of a divalent ion in aqueous solution if its

atomic number is 25.
Solution: With atomic number 25, the divalent ion in aqueous solution will
have d5 configuration (five unpaired electrons). The magnetic moment,
µ is

Q.
 
Calculate the ‘spin only’ magnetic moment of M 2+(
aq) ion (Z = 27).
Solution:
 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.
• In aqueous solutions where water molecules are the ligands, the colours of
the ions observed are listed below:
Colours of some of the first row transition metal compounds
 FORMATION OF COMPLEX COPMOUNDS

• Complex compounds are those in which the metal ions bind a

number of anions or neutral molecules giving complex species
with characteristic properties.

• A few examples are: [Fe(CN)6]3–, [Fe(CN)6]4–, [Cu(NH3)4]2+ and

[PtCl4]2–. (The chemistry of complex compounds is dealt with in
detail in Unit 9).

• The transition metals form a large number of complex

compounds. 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.
 CATALYTIC PROPERTIES OF TRANSITION ELEMENTS

• The transition metals and their compounds are known for their catalytic
Properties activity. This activity is due to their ability to adopt multiple
oxidation states and to form complexes.

• Vanadium(V) oxide (in Contact Process), finely divided iron (in Haber’s
Process), and nickel (in Catalytic Hydrogenation) are some of the examples.

• Catalysts at a solid surface involve the formation of bonds between reactant

molecules and atoms of the surface of the catalyst (first row transition
metals utilise 3d and 4s electrons for bonding). This has the effect of
increasing the concentration of the reactants at the catalyst surface and also
weakening of the bonds in the reacting molecules (the activation energy is
   lowering).
 
• Also because the 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.

 
• An explanation of this catalytic
action can be given as:

 
 Formation of Interstitial Compound
• Interstitial compounds are those which 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. The formulas quoted do not, of course,
correspond to any normal oxidation state of the metal.
• Because of the nature of their composition, these
compounds are referred to as interstitial
compounds. The principal 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(like
TiB2)approach diamond in hardness.
(iii) They retain metallic conductivity.
Interstitial Compound of Fe and C
(iv) They are chemically inert.
 Alloy formation
• An alloy is a blend of metals prepared by mixing them

• Alloys may be homogeneous solid solutions in which

the atoms of one metal are distributed randomly
among the atoms of the other.

• Such alloys are formed by atoms with metallic radii

that are within about 15 percent of each other.

• Because of similar radii and other characteristics of transition metals, alloys are readily
formed by these metals. The alloys so formed are hard and have often high Mpt.

• The best known are 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), are also of considerable industrial importance.
Composition of some alloys
 Oxides and Oxoanions of Metals
• These oxides are generally formed by the reaction of metals with oxygen at high temp.

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

• The highest ON in the oxides coincides with the gr. No. and is seen in Sc2O3 to Mn2O7.
Beyond group 7, no higher oxides of iron above Fe2O3 are known.

• Besides the oxides, the oxo cations stabilise VV as VO2+, VIV as VO2+ and TiIV as TiO2+.

• As the ON of a metal increases, ionic character decreases. In the case of Mn, Mn2O7 is a
covalent green oil. Even CrO3 and V2O5 have low Mpt. In these higher oxides, the acidic
character is predominant. Thus, Mn2O7 gives HMnO4 and CrO3 gives H2CrO4 and H2Cr2O7.

• V2O5 is amphoteric though mainly acidic and it gives VO43– as well as VO2+ salts. In V, there is
gradual change from the basic V2O3 to less basic V2O4 and to amphoteric V2O5. V2O4
dissolves in acids to give VO2+ salts. Similarly, V2O5 reacts with alkalies as well as acids to
give VO43− and VO4+ respectively.
 f- BLOCK ELEMENTS
• The f-block consists of the two series:
(1) Lanthanoids or 4f series(the fourteen elements following lanthanum)
(2) Actinoids or 5f series(the fourteen elements following actinium).
• In 4f and 5f series elements, the last e- enters into 4f and 5f orbitals respectively
hence they are called so. Both series together are called inner transition elements
because they form transition series within the transition elements of d-block.
• if we keep lanthanides and actinides series in the main periodic table then the table
will be too wide. That’s why These two series are kept in the bottom of the table.
 

Wide form of the periodic table

• The lanthanides resemble one another more closely than do the members of
ordinary transition elements in any series. It is because they have only one
stable oxidation state(M+3) and there are small changes in size and nuclear
charge along a series as compared to other transition series.

• The chemistry of the actinides is, on the other hand, much more
complicated. The complication arises partly owing to the occurrence of a
wide range of oxidation states in these elements and partly because their
radioactivity creates special problems in their study.

• La and Ac are considered d-block elements on the basis of their position in

the periodic table but actually they belong to Lanthanoid and Actinoid family
respectively on the basis of their chemical and physical properties. Thus we
can say that 4f series contain 14 elements from Ce to Lu but Lanthanide
family( denoted as Ln) consists of 15 elements from La to Lu. Same is true
for 5f series also.
The general ele. config. of these elements can be written as [Xe] 4f 1-14 ,5d0-1, 6s2.
 LANTHANOIDS
GENERAL CHARACTERISTICS:
• They are called rare earth metals since the
occurrence of these elements is very small
(3×10-4 % of Earth’s crust).
• All the lanthanoids are silvery white soft
metals and tarnish rapidly in air.
• The hardness increases with increasing
atomic number, samarium being steel hard.
• Their melting points range between 1000 to
1200 K but samarium melts at 1623 K.
• They have typical metallic structure and are
good conductors of heat and electricity.
• Density and other properties change
smoothly except for Eu and Yb and
occasionally for Sm and Tm.
Lanthanoinds
ATOMIC AND IONIC RADII: THE LANTHANIDES CONTRACTION
• The more than expected
regular decrease in the
atomic and ionic radii of
lanthanide series from La to
Lu due to least shielding
effect of 4f electrons is called
lanthanide contraction.

• This decrease is even more

regular for trivalent ions(M3+).
 CONSEQUENCES OF LANTHANIDES CONTRACTION
(A) EFFECTS ON d- BLOCK ELEMENTS:
1. Silmilar atomic sizes of 3d and 4d transition series: As we go down from 3d to 4d
in a group, the size should increase due to increasing no. of shells. But due to
lanthanoid contraction, the effective nuclear charge is much more in 4d series as
compared to the effect of increasing shell. Therefore, size of the atom of third
transition series is nearly the same as that of the atom of the second transition
series. For example:
radius of Zr = radius of Hf
radius of Nb = radius of Ta
2. Difficulty in the separation of 3d and 4d elements: As there is negligible change in
the ionic radii of 3d and 4d series, these elements occur together in the nature and
their chemical properties are similar. This makes the separation of elements in the
pure state difficult.
3. High Ionization energy of 5d series:  Attraction of electrons by the nuclear charge
is much higher and hence Ionization energy of 5d elements are much larger than
4d and 3d. In 5d series, all elements except Pt and Au have filled s-shell. Iridium
and Gold have the maximum Ionization Energy.
(B) EFFECTS OF LANTHANIDE CONTRACTION ON LANTHENIDES:
1. DIFFICULTY IN SEPARATION OF LANTHANIDE ELEMENTS: However, there is a
regular unexpected decrease in the size from La to Lu but the difference in the sizes
of two consecutive lanthanide elements is still very small, which makes them
difficult to separate from each other.

2. EFFECT ON THE BASIC STRENGTH OF HYDROXIDES: As the size of lanthanides

decreases from La to Lu, the covalent character of the hydroxides increases and
hence their basic strength decreases. Thus, La(OH)3 is more basic and Lu(OH)3 is
the least basic.

3. COMPLEX FORMATION: Because of the smaller size but higher nuclear charge,
tendency to form coordinate. Complexes increases from La3+ to Lu3+.

4. INCREASE IN ELECTRONEGATIVITY FROM LA TO LU: Due to decrease in size, the

hold of nucleus on 3.outer most electrons increase and hence ionisation enthalpy and
electronegativity  increase from La to Lu.
 IONISATION ENTHALPIES OF LANTHANOIDS
• The first ionisation enthalpies of the
lanthanoids are around 600 kJ mol–1.

• the second IE is about 1200 kJ mol–1

comparable with those of calcium.

• A detailed discussion of the variation of the

third ionisation enthalpies indicates that the
exchange enthalpy considerations (as in 3d
orbitals of the first transition series), appear to
impart a certain degree of stability to empty,
half-filled and completely filled orbitals f level.

• This is indicated from the abnormally low value

of the third ionisation enthalpy of lanthanum,
gadolinium and lutetium.
 OXIDATION STATES OF LANTHANOIDS
• General trend:The most common oxidation state is M+3. It is because the
hydration enthalpy of M+3 compensates for the three ionisation enthalpies. But
in case of M+2 , the hydration enthalpy is too less due to less +ve charge and it
can not to compensate for the two ionisation enthalpies. Similarly M +4 is also
very rre because the 4th ionisation enthalpy is too large.(Almost equal to the
sum of first three ionisation enthalpies)

• However, 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 VARIOUS OXIDATION STATES AND THEIR COLOURS IN AQUEOUS SOLUTIONS

• Thus, the formation of CeIV is favoured by its noble gas configuration, but it
is a strong oxidant reverting to the common +3 state. The Eo value for Ce4+/
Ce3+ is + 1.74 V which suggests that it can oxidise water. However, the
reaction rate is very slow and hence Ce(IV) is a good analytical reagent.

• Pr, Nd, Tb and Dy also exhibit +4 state but only in oxides, MO 2.

• Eu2+ is formed by losing the two s electrons and its f 7 configuration

accounts for the formation of this ion. However, Eu2+ is a strong reducing
agent changing to the common +3 state.

• Similarly Yb2+ which has f 14 configuration is a reductant.

• TbIV has half-filled f-orbitals and is an oxidant.

• The behaviour of samarium is very much like europium, exhibiting both +2

and +3 oxidation state.
 FORMATION OF COLOURED IONS BY LANTHANOIDS
• Many trivalent Ln ions are coloured both in the solid
state and in aqueous solutions. Colour of these ions may
be attributed to the presence of unpaired f electrons.
Neither La3+ nor Lu3+ ion shows any colour but the rest do
so. However, absorption bands are narrow, probably
because of the excitation within f level.(f-f transition)

• Elements with (n)f electrons

often have a similar colour to
those with (14 - n)f electrons.
However, the elements in other
valency states do not all have
colours similar to their
isoelectronic 3+ counterparts.
 Magnetic properties
• La+3, Ce+4, Lu+3 and Yb+2 have either empty or fully filled
4f, 5d and 6s orbitals so they are diamagnetic in nature.
• Other trivalent ions which have unpaired electrons in
these orbitals, show para magnetism, which is
calculated by the following formula:

Where g and J have again complicated formulae based

on both spin and orbital magnetic moment. In
Lanthanoids, the splitting of f orbital due to ligand is
very small as f orbitals are well covered by 5s, 5p, 5d
and 6s orbitals.(see figure) Therefore, the electrons
can almost freely rotate from one to another f orbitals
causing orbital magnetic moment. Hence both spin
and orbital magnetic moment are considered.
• The para magnetism rises to maximum in
neodymium. Then it decreases. From Eu
it again starts increasing and reaches to
maximum in Dysprosium and then again
decreases up to Lu
• Nd is used as powerful magnet which
has versatile use in industry. Due to
magnetic properties of Gadolinium, it
is used in MRI (Magnetic resonance
imaging) Samarium- cobalt magnets
are used in motors and in military
weapons.

neodymium.
Neodymium Gadolinium Sm + Co
 CHEMICAL REACTIVITY OF LANTHANOIDS
In their chemical behaviour, in general, the earlier members of the series are
quite reactive similar to calcium but, with increasing atomic number, they
behave more like aluminium. Values for EV for the half-reaction:

Ln3+(aq) + 3e– → Ln(s)

are in the range of –2.2 to –2.4 V except for Eu for which the value is –2.0 V.
This is, of course, a small variation.
Some reactions of lanthanoids are as follows:

1. Reaction with hydrogen gas: The metals combine with hydrogen when
gently heated in the gas to form dihydrides and trihydrides.

Ln(s) + H2(g) ----------------------> LnH2

At high pressure
2Ln(s) + 3H2(g) ------------------> 2LnH3
2. Reaction with carbon: The carbides, Ln3C, Ln2C3 and LnC2 are formed when
the metals are heated with carbon.

3. Reaction with dil acids: They liberate hydrogen from dilute acids
Ln(s) + HCl(aq) ---------------> LnCl3 (aq) + H2(g)

4. Reaction with halogens: They burn in halogens to form halides.

2Ln(s) + 3X2(g) ---------------> 2LnX
heat 3 (aq)

5. Reaction with oxygen: They form oxides M2O3

4M(s) + 3O2(g) -------------> 2M2O3
6. Reaction with water : With water they∆form hydroxides M(OH)3. The
hydroxides are definite compounds, not just hydrated oxides. They are basic
like alkaline earth metal oxides and hydroxides.
2Ln + 3H2O -------- Ln2O3 + 3H2
Ln2O3 + 3H2O---------- 2Ln(OH)3
Summary of chemical reactions:
 USES OF LANTHANOIDS
• The best single use of the lanthanoids is for the production of alloy steels for
plates and pipes.
• A well known alloy is mischmetall which consists of a lanthanoid metal (~
95%) and iron (~ 5%) and traces of S, C, Ca and Al. A good deal of mischmetall
is used in Mg-based alloy to produce bullets, shell and lighter flint.

mischmetall

• Mixed oxides of lanthanoids are employed as catalysts in petroleum cracking.

• Some individual Ln oxides are used as phosphors in television screens and

similar fluorescing surfaces.
 
 THE ACTINOIDS
• The actinoids include the fourteen elements from Th to Lr.

• The actinoids are radioactive elements and the earlier

members have relatively long half-lives.

• the latter ones have half-life values ranging from a day to 3

minutes for lawrencium (Z =103).

• The latter members could be prepared only in nanogram

quantities. These facts render their study more difficult.
 ACTINOIDS: ELECTRONIC CONFIGURATION
• All the actinoids are believed to have the electronic configuration
of 7s2 Configurations and variable occupancy of the 5f and 6d
subshells.
• The fourteen electrons are formally added to 5f, though not in
thorium (Z = 90) but from Pa onwards the 5f orbitals are complete
at element 103.
• The irregularities in the electronic configurations of the actinoids,
like those in the lanthanoids are related to the stabilities of the f 0,
f 7 and f 14 occupancies of the 5f orbitals.
• Thus, the configurations of Am and Cm are [Rn] 5f 77s2 and [Rn]
5f 76d17s2. Although the 5f orbitals resemble the 4f orbitals in
their angular part of the wave-function, they are not as buried as
4f orbitals and hence 5f electrons can participate in bonding to a
 IONIC SIZES
• The general trend in lanthanoids
is observable in the actinoids as
well.

• There is a gradual decrease in the

size of atoms or M3+ ions across
the series.

• This may be referred to as the

actinoid contraction (like
lanthanoid contraction). The
contraction is, however, greater
from element to element in this
series resulting from poor
shielding by 5f electrons.
 OXIDATION STATES OF ACTINOIDS

• There is a greater range of oxidation states, which is in part attributed to the fact
that the 5f, 6d and 7s levels are of comparable energies.

• The actinoids show in general +3 oxidation state. (same reason as in

lanthanides)

• The elements, in the first half of the series frequently exhibit higher oxidation
states. For example, the maximum oxidation state increases from +4 in Th to +5,
+6 and +7 respectively in Pa, U and Np but decreases in succeeding elements.

• The actinoids resemble the lanthanoids in having more compounds in +3 state

than in the +4 state. However, +3 and +4 ions tend to hydrolyse. Because the
distribution of oxidation states among the actinoids is so uneven and so
different for the earlier and latter elements, it is unsatisfactory to review their
chemistry in terms of O.N.
Oxidation states of actinoids
• The oxidation states
in bold are most
stable.

• +5 ON of Uranium is
stable only in solid
state. In solutions, it
disproportionates to
give +4 and +6 O.N.
UO2+  U+4 + UO2+2

• The divalent ions of

actinides behave
like Ba+2 ion in
chemical behaviour.
(In lanthanides, they
behave like Ca+2)
 IMPORTANT QUESTIONS ON OXIDATION STATE OF ACTINOIDS

Q1. Why No+2 is more stable?

Ans 1. Due to 5f14 configuration in divalent state

Q2. The most stable oxidation state up to uranium is the one involving all the
valence electrons. Why?
Ans 2. Because they get 5f0 electronic configuration after losing all their
valence electrons.

Q3. How the higher oxidation states like +6 of lower actinides are stabilized ?
Ans 3. +6 oxidation state is possible only with most electronegative
fluorine or in oxocations MO2+2
 COLOUR OF THE ACTINIDE IONS

(Electronic transfers between neighbouring atoms)

 REACTIVITY OF ACTINOIDS

• The actinoids are highly reactive metals, especially when finely

divided.

• The action of boiling water on them, for example, gives a mixture

of oxide and hydride.

• Combination with most non metals takes place at moderate temp.

• HCl attacks all metals but most are slightly affected by nitric acid
owing to the formation of protective oxide layers.

• alkalies have no action.

 
 MAGNETIC PROPERTIES OF THE ACTINIDES
• The magnetic properties of
the actinoids are more
complex than those of the
lanthanoids.

• Although the variation in

the magnetic susceptibility
of the actinoids with the
number of unpaired 5f
electrons is roughly parallel
to the corresponding
results for the lanthanoids,
the latter have higher
values.
 
 IONISATION ENTHALPIES OF ACTINOIDS

• It is evident from the behaviour of the actinoids that the

ionisation enthalpies of the early actinoids, though not accurately
known, but are lower than for the early lanthanoids.

• This is quite reasonable since it is to be expected that when 5f

orbitals are beginning to be occupied, they will penetrate less
into the inner core of electrons. The 5f electrons, will therefore,
be more effectively shielded from the nuclear charge than the 4f
electrons of the corresponding lanthanoids. Because the outer
electrons are less firmly held, they are available for bonding in
the actinoids.
 
 SOME APPLICATIONS OF d- AND f-BLOCK ELEMENTS
• In construction: Iron and steels are the most important construction
materials. Their production is based on the reduction of iron oxides, the
removal of impurities and the addition of carbon and alloying metals such
as Cr, Mn and Ni.

• In pigment industry: Some compounds are manufactured for special

purposes such as TiO for the pigment industry.

• In battery industry: MnO2 is manufactured to use it in dry battery cells. The

battery industry also requires Zn and Ni/Cd.  
• Precious metals: The elements of Group 11 are still
worthy of being called the coinage metals, although
Ag and Au are restricted to collection items and the
contemporary UK ‘copper’ coins are copper-coated
steel. The ‘silver’ UK coins are a Cu/Ni alloy. UK ‘copper’ and ‘silver' coins
• In catalysis: Many of the metals and/or their compounds are essential
catalysts in the chemical industry. For example:
1. V2O5 catalyses the oxidation of SO2 in the manufacture of sulphuric acid.
2. TiCl4 with Al(CH3)3 forms the basis of the Ziegler catalysts used to
manufacture polyethylene (polythene).
3. Iron catalysts are used in the Haber process for the production of
ammonia from N2/H2 mixtures.
4. Nickel catalysts enable the hydrogenation of fats to proceed.
5. In the Wacker process the oxidation of ethyne to ethanal is catalysed by
PdCl2.
• In polymerisation processes: Nickel complexes are
useful in the polymerisation of alkynes and other
organic compounds such as benzene.

• In photographic industry: The photographic industry

relies on the special light-sensitive properties of AgBr.
Text Book questions