D- AND F-BLOCK ELEMENTS

A] General Introduction
 d-Block Elements: Located in Groups 3-12 of the periodic table. In these
elements, d orbitals are progressively filled across the four long periods.
 f-Block Elements: These consist of elements in which 4f and 5f orbitals are
progressively filled. These elements are placed separately at the bottom of the
periodic table.

A.a] Transition Metals & Inner Transition Metals

 The terms transition metals and inner transition metals refer to elements
of the d- and f-blocks respectively.
 Four series of transition metals:
o 3d series: Sc to Zn
o 4d series: Y to Cd
o 5d series: La and Hf to Hg
o 6d series: Ac, and elements from Rf to Cn
 Two series of inner transition metals:
o 4f series: Ce to Lu (Lanthanoids)
o 5f series: Th to Lr (Actinoids)

A.b] IUPAC Definition of Transition Metals

 Transition metals are defined as metals having incomplete d subshells either
in neutral atoms or in their ions.
 Exceptions: Zinc (Zn), Cadmium (Cd), and Mercury (Hg) from group 12
have a full d10 configuration in both their ground state and common oxidation
states, so they are not regarded as transition metals.
o Note: Despite this, their chemistry is still studied alongside transition
metals due to their position as end members of the 3d, 4d, and 5d
series.

A.c] Distinguishing Characteristics

 The partially filled d or f orbitals make transition metals different from non-
transition elements. This unique characteristic is why transition elements and
their compounds are studied separately.
 Valence Theory: The standard theory of valence, used for non-transition
elements, can also be applied to transition elements.

Examples of Transition Metals

 Precious Metals: Silver (Ag), Gold (Au), Platinum (Pt)
 Industrial Metals: Iron (Fe), Copper (Cu), Titanium (Ti)

A.d] Most Important Highlights:

 The d-block contains elements of Groups 3-12, and the f-block includes
elements filling 4f and 5f orbitals.
  Transition metals have incomplete d subshells, while inner transition
metals fill the f orbitals.
 Zn, Cd, Hg are not transition metals despite being in the d-block because they
have a full d10 configuration.

A.e] NEET Extra Points:

 Transition metals are crucial in understanding various industrial and chemical
processes.
 Be aware of the exceptions like Zn, Cd, Hg, as they may appear in specific
questions asking about transition metal properties.

A.f] Simplified Version (If Needed):

 d-Block: Groups 3-12, with progressively filled d orbitals.
 f-Block: Elements filling 4f and 5f orbitals (Lanthanoids and Actinoids).
 Transition Metals: Metals with incomplete d subshells (except Zn, Cd, Hg).

B] The Transition Elements (d-Block)

B.a] Position in the Periodic Table

 The d-block occupies the large middle section of the periodic table and is
flanked by the s-block and p-block.
 The transition elements are found in groups 3-12 of the periodic table, where
the d-orbitals of the penultimate energy level progressively receive electrons.
 There are four series of transition metals:
 1. 3d series (Scandium to Zinc)
2. 4d series (Yttrium to Cadmium)
3. 5d series (Lanthanum and Hafnium to Mercury)
4. 6d series (Actinium and elements from Rutherfordium to Copernicium)
 The f-block consists of the inner transition metals:

o 4f series (Lanthanoids: Cerium to Lutetium)

o 5f series (Actinoids: Thorium to Lawrencium)
 Transition metals: Elements whose d-subshells are partially filled.
 Inner transition metals: Elements whose f-subshells are progressively filled.

Note: Scandium (Z = 21) is considered a transition metal because it has an

incomplete 3d orbital in its ground state (3d¹). On the other hand, Zinc (Z =
30), with its completely filled 3d orbital (3d¹⁰) in both the ground and common
oxidation states, is not regarded as a transition metal.

B.b] Electronic Configurations of the d-Block Elements

 The general electronic configuration for the outer orbitals of transition metals
is:
(n-1)d¹–¹⁰ ns¹–²
Here, the (n-1)d orbitals may have between 1 and 10 electrons, and the
outermost ns orbital may contain 1 or 2 electrons.
 Exceptions:
o Chromium (Cr) and Copper (Cu) exhibit exceptions in their electronic
configurations. Due to the relatively small energy difference between the
(n-1)d and ns orbitals, these elements prefer configurations that offer
extra stability (half-filled or fully-filled d orbitals).
 Cr: The expected configuration would be 3d⁴ 4s², but it adopts 3d⁵
4s¹ for extra stability.
 Cu: The expected configuration would be 3d⁹ 4s², but it adopts 3d¹⁰
4s¹ to achieve a fully-filled d-subshell.
 Zinc (Zn), Cadmium (Cd), and Mercury (Hg) have completely filled d¹⁰
orbitals both in their ground state and common oxidation states, and hence they
are not classified as transition metals.

B.c] Properties of Transition Elements

1. Variety of Oxidation States:
Transition elements are known for having a wide range of oxidation states,
which arise due to the presence of partly filled d-orbitals. This allows
transition metals to lose different numbers of electrons, leading to different
oxidation states in their compounds.
2. Formation of Coloured Compounds:
Many transition metal ions, such as Cu²⁺ and Fe³⁺, are coloured. This is because
the electrons in the d-orbitals absorb visible light and get excited to higher
energy levels. The resulting transitions cause these compounds to have
characteristic colours.
3. Catalytic Properties:
Transition metals and their compounds are well-known catalysts in various
 industrial processes. For example, Platinum (Pt) and Iron (Fe) are widely
used as catalysts in processes like the Haber process for ammonia synthesis.
Their ability to exist in multiple oxidation states and form complex
compounds makes them effective catalysts.
4. Formation of Complexes:
Transition metals readily form coordination compounds with ligands due to
the availability of vacant d-orbitals that can accommodate electron pairs from
ligands. These complexes exhibit unique chemical and physical properties.
5. Magnetic Properties:
Transition metals can exhibit paramagnetism (due to unpaired electrons in the
d-orbitals) or ferromagnetism in some cases (e.g., Iron).

B.d] Key Concepts:

1. Electronic Configuration: The presence of partly filled d-orbitals is the key
characteristic of transition elements, which distinguishes them from other
metals and non-metals.
2. Exceptions to the General Rule: Some transition metals, like Cr and Cu,
show exceptions in their electron configurations, leading to unique chemical
behavior.
3. Catalysis: Transition metals play an essential role in catalysis due to their
ability to change oxidation states and form coordination complexes.
4. Color and Magnetism: The interaction of d-electrons with light gives rise to
the colourful appearance of transition metal compounds, and unpaired electrons
lead to their paramagnetic properties.

C] GROUND STATE ELECTRONIC CONFIGURATIONS OF

TRANSITION ELEMENTS

C.a] 1st Series (3d Transition Elements)

Electronic Configuration (Outer

Element Z
Orbitals)
Scandium
21 4s² 3d¹
(Sc)
Titanium (Ti) 22 4s² 3d²
Vanadium (V) 23 4s² 3d³
Chromium
24 4s¹ 3d⁵ (Exception)
(Cr)
Manganese
25 4s² 3d⁵
(Mn)
Iron (Fe) 26 4s² 3d⁶
Cobalt (Co) 27 4s² 3d⁷
Nickel (Ni) 28 4s² 3d⁸
Copper (Cu) 29 4s¹ 3d¹⁰ (Exception)
 Zinc (Zn) 30 4s² 3d¹⁰

C.b] 2nd Series (4d Transition Elements)

Electronic Configuration (Outer

Element Z
Orbitals)
Yttrium (Y) 39 5s² 4d¹
Zirconium (Zr) 40 5s² 4d²
Niobium (Nb) 41 5s² 4d³
Molybdenum
42 5s¹ 4d⁵
(Mo)
Technetium
43 5s² 4d⁵
(Tc)
Ruthenium
44 5s¹ 4d⁷
(Ru)
Rhodium (Rh) 45 5s¹ 4d⁸
Palladium (Pd) 46 5s⁰ 4d¹⁰ (Exception)
Silver (Ag) 47 5s¹ 4d¹⁰
Cadmium (Cd) 48 5s² 4d¹⁰

C.c] 3rd Series (5d Transition Elements)

Electronic Configuration (Outer

Element Z
Orbitals)
Lanthanum (La) 57 6s² 5d¹
Hafnium (Hf) 72 6s² 5d²
Tantalum (Ta) 73 6s² 5d³
Tungsten (W) 74 6s² 5d⁴
Rhenium (Re) 75 6s² 5d⁵
Osmium (Os) 76 6s² 5d⁶
Iridium (Ir) 77 6s² 5d⁷
Platinum (Pt) 78 6s¹ 5d⁹
Gold (Au) 79 6s¹ 5d¹⁰

Note: The exceptions are for Chromium (Cr) and Copper (Cu), where their
electronic configurations are unusual due to extra stability provided by half-
filled or fully-filled d orbitals.
D] General Properties of the Transition Elements (d-Block)

D.a] Physical Properties

 Typical Metallic Properties:
Almost all transition elements show typical metallic characteristics like:
o High tensile strength
o Ductility
o Malleability
o High thermal and electrical conductivity
o Metallic lustre
 Exceptions:
Zn, Cd, Hg, and Mn do not exhibit these typical metallic properties.
 Lattice Structures:
The transition elements can have various lattice structures at normal
temperatures, such as:
o hcp (hexagonal close packed)
o bcc (body-centered cubic)
o ccp (cubic close packed)

Transition Metal Lattice Structures:

D.b] Melting Points and Enthalpy of Atomisation
 High Melting Points:
Transition metals (except Zn, Cd, and Hg) generally have high melting
points. This is due to the involvement of additional electrons from (n-1)d
orbitals in addition to the ns electrons in metallic bonding.
 Trend:
Melting points rise to a maximum at d⁵ (except Mn and Tc), and then fall as
atomic number increases. This trend is depicted in Fig. 4.1.
 High Enthalpies of Atomisation:
Transition metals exhibit high enthalpies of atomisation, which can be seen
in Fig. 4.2. This trend shows that metals with more unpaired electrons per d-
orbital have stronger metal-metal bonding and, therefore, higher enthalpies.

Trends in melting points of transition elements

D.c] Why Do Transition Elements Have Higher Enthalpies of
Atomisation?
 Stronger Bonding:
The high enthalpies of atomisation are due to the strong interatomic
bonding resulting from a large number of unpaired electrons in the d-
orbitals, which lead to stronger interatomic interactions.

Trends in enthalpies of atomisation of transition elements

D.d] Variation in Atomic and Ionic Sizes of Transition Metals

 Trend in Ionic Radius:
In a given series of transition metals, ions of the same charge generally show a
progressive decrease in ionic radius as atomic number increases. This is
due to the increasing nuclear charge, which is not fully shielded by the d-
electrons, resulting in a stronger attraction between the nucleus and the
outermost electrons.
 Atomic Radii:
Similarly, atomic radii decrease across a period but the variation is relatively
small.
Trends in atomic radii of transition elements

E] Lanthanoid Contraction
 Effect on Size:
When comparing the atomic radii of elements in different series (e.g., 3d, 4d,
and 5d), the 5d series has nearly the same radii as the 4d series. This is due
to the lanthanoid contraction — a phenomenon where the filling of the 4f
orbitals before the 5d orbitals leads to a decrease in size.
 Impact:
As the 4f orbitals fill, the atomic size of the elements in the 5d series
decreases, compensating for the expected increase in size with increasing
atomic number. This makes the 2nd and 3rd series of transition metals
have similar properties and sizes.
 Lanthanoid Contraction Causes:
The contraction is due to the incomplete shielding of the electrons in the 4f
orbitals. The 4f electrons are less effective in shielding compared to d
electrons, leading to a more regular decrease in atomic size.

F] Density Trend in Transition Metals

 Increasing Density:
From Ti (Z=22) to Cu (Z=29), the density of transition metals increases
significantly due to the decrease in size (due to lanthanoid contraction) and the
corresponding increase in atomic mass.

In-Text Question Answers

1. Why do the transition elements exhibit higher enthalpies of
atomisation?
 o Answer: The transition elements have higher enthalpies of atomisation
because they have a large number of unpaired electrons in their d-
orbitals, which results in stronger interatomic interactions and bonding.
2. Why is the enthalpy of atomisation of Zinc (Zn) (126 kJ/mol) the lowest
among the transition metals?
o Answer: Zinc (Zn) has completely filled d-orbitals (3d¹⁰), resulting in
weak bonding between its atoms. This is why its enthalpy of atomisation
is lower than other transition metals, which have partially filled d-orbitals
and thus stronger metallic bonding.

Summary of Key Points

 Transition elements display typical metallic properties such as high
conductivity, strength, and ductility.
 Enthalpy of atomisation is higher due to stronger metallic bonding, caused
by a large number of unpaired electrons in the d-orbitals.
 The atomic radius decreases across the series due to the increase in nuclear
charge, with a notable lanthanoid contraction in the 4d and 5d series.
 Density increases due to the decrease in atomic size and increase in atomic
mass.

G] Ionisation Enthalpies

 Ionisation Enthalpy Trend:

o General Trend: There is a general increase in ionisation enthalpy from
left to right across a series of transition elements. This is due to an
increase in nuclear charge as electrons are added to the inner d orbitals.
o Comparison with Non-Transition Elements:
 The increase in ionisation enthalpy for transition elements is not as
steep as it is for non-transition elements. This shows a smaller
variation in ionisation enthalpy across a transition series compared
to a period of non-transition elements.
 Transition elements exhibit less variation in ionisation enthalpy
due to the additional shielding from electrons in the inner d-orbitals.
 Ionisation Enthalpy of 3d Series:
 o First Ionisation Enthalpy: In general, the first ionisation enthalpy
increases as we move across the 3d series. However, the increase is not
as steep as it would be in non-transition elements.
o Second and Third Ionisation Enthalpy: The increase in the second and
third ionisation enthalpies is more pronounced. This is because as the
nuclear charge increases, the electrons are held more tightly, requiring
more energy to remove them.
 Irregular Trend Explanation:
o The trend in ionisation enthalpies is not uniform across the 3d series.
 Reason: As we move from left to right, the 4s orbital fills first,
followed by the 3d orbitals. However, d-electrons have less
shielding compared to s-electrons, causing a smaller decrease in
atomic size.
 The removal of one electron from an atom can alter the relative
energies of the 4s and 3d orbitals. The ionisation enthalpy increase
is not as sharp due to this overlapping orbital energy.

G.a] Important Factors Affecting Ionisation Enthalpy:

1. Shielding Effect:
o The 3d electrons provide more shielding for the 4s electrons as
compared to the outer electrons in the same shell. This results in a less
rapid decrease in atomic size and, consequently, a smaller increase in
ionisation enthalpy.
2. Electrostatic Attraction:
o The increased nuclear charge means that the attraction between the
nucleus and the electrons increases, raising the ionisation enthalpy.
However, the shielding from the d-electrons means that this effect is less
pronounced than expected.

3. Exchange Energy:
o Exchange energy refers to the stabilization that occurs when parallel
spins are maximized in degenerate orbitals. The more parallel spins
there are, the more stable the electron configuration is, making the
ionisation process harder.
 o When electrons are in a d⁵ configuration (like in Mn²⁺ or Fe³⁺), they
have a particularly stable configuration due to exchange energy, making
them harder to ionise.

G.b] Notable Irregular Trends:

 For Mn²⁺ (3d⁵) and Fe³⁺ (d⁵), the ionisation enthalpies show breaks in the
trend. These ions have half-filled d-orbitals, which are more stable due to
exchange energy, resulting in a lower ionisation enthalpy compared to
other elements.
 For Cu²⁺ (d¹⁰):
o Copper has a stable d¹⁰ configuration when it forms Cu²⁺. This stable
configuration leads to a lower ionisation enthalpy compared to what is
expected for other elements in its group.
 Zinc’s Ionisation Enthalpy:
o Zinc has a d¹⁰ configuration in its Zn²⁺ ion, which makes its ionisation
enthalpy lower than expected because the d-orbitals are fully
occupied, creating extra stability.

G.c] Key Points on Ionisation Enthalpy Trends:

 The first ionisation enthalpy increases from left to right across the 3d series,
but the increase is moderate due to the filling of inner d orbitals.
 The second and third ionisation enthalpies increase more dramatically
because of the higher effective nuclear charge.
 Irregularities in ionisation enthalpy are seen in Mn²⁺ and Fe³⁺ ions due to their
stable d⁵ configuration.
 Exchange energy plays a significant role in the stability of these elements'
ions and influences their ionisation enthalpies.
 Copper and Zinc exhibit unique trends due to their stable d⁵ and d¹⁰
configurations, which make them more stable and thus easier to ionise than
expected.

G.d] Why Does Ionisation Enthalpy Increase Across a Period?

 Nuclear Charge: As protons are added to the nucleus, the effective nuclear
charge increases, making it harder to remove electrons.
 Electron Configuration: The filling of the d-orbitals provides some shielding,
but the effect of increasing nuclear charge still makes the ionisation enthalpy
increase gradually.
 G.e] Summary of Ionisation Trends and Their Implications:
 The ionisation enthalpies of transition metals show a moderate increase
across the 3d series due to the filling of 3d orbitals and the increased nuclear
charge.
 The second and third ionisation enthalpies exhibit a more pronounced
increase because the electrons become more tightly bound as the nuclear
charge increases.
 Irregularities in trends occur at Mn²⁺, Fe³⁺, Cu²⁺, and Zn²⁺ due to the stable d⁵
and d¹⁰ configurations of these ions.
 Exchange energy contributes to the stability of certain ions, making them
more difficult to ionize.

H] Oxidation States
Transition elements are known for exhibiting a wide variety of oxidation states in their
compounds. The ability to adopt different oxidation states is a characteristic feature of
these elements, and this variability is observed most notably in the middle of the
transition series.

Common Oxidation States of the First Row Transition Elements

Element +2 +3 +4 +5 +6 +
7
Sc +2 +3
Ti +2 +3 +4
V +2 +3 +4 +5
Cr +2 +3 +4 +5 +6
Mn +2 +3 +4 +5 +6 +
7
Fe +2 +3 +4
Co +2 +3 +4
Ni +2 +3 +4
Cu +1 +2
Zn +2

H.a] Key Points about Oxidation States:

1. Middle of the Series:

 o The elements in the middle of the transition series tend to show a greater
variety of oxidation states. For example, Manganese (Mn) can exhibit
oxidation states ranging from +2 to +7.
2. Oxidation States at the Extremes:
o At the extremes of the series (e.g., Scandium (Sc) and Zinc (Zn)), the
number of oxidation states is limited:
 Scandium (Sc) typically shows only +3 because it has few
electrons to lose.
 Titanium (Ti) can show a stable +4 oxidation state, but lower
oxidation states (Ti³⁺ and Ti²⁺) are less stable.
 Zinc (Zn) only shows +2, as it has a fully filled d¹⁰ configuration, so
it does not readily form higher oxidation states.

3. Maximal Oxidation States:

o The maximum oxidation states that can be formed by transition
elements generally correspond to the sum of their s and d electrons (up
to Manganese).
o For example, Manganese (Mn) can achieve a +7 oxidation state (as in
MnO₄⁻), while elements such as Chromium (Cr) and Vanadium (V) can
show oxidation states of +6 and +5, respectively.
o After Manganese, higher oxidation states are less stable, and we
typically see Fe²⁺, Fe³⁺, Co²⁺, Co³⁺, Ni²⁺, Cu²⁺, and Zn²⁺ as the more
common oxidation states.
4. Stability of Higher Oxidation States:
o The stability of higher oxidation states decreases as we move across the
series. This is due to the electronic configuration and the energy
levels of the d orbitals.
o The higher oxidation states are more stable for the elements toward
the middle of the series (e.g., Cr and Mn), but less stable for the
elements at the ends, like Zn and Cu.
5. Reasons for Oxidation State Variability:
o The variability in oxidation states arises due to the incomplete filling of
the d orbitals. The transition metals can lose electrons from both the s
and d orbitals, which allows them to exhibit multiple oxidation states that
differ by one unit (e.g., +2, +3, +4, etc.).
o This contrasts with non-transition elements, where the oxidation states
usually differ by two units (e.g., +2, +4, +6).
6. Low vs. High Oxidation States:
o Low oxidation states are often found in transition metal complexes with
ligands that have p-acceptor character (like CO, CN⁻, etc.), which
allows for back-bonding in addition to s-bonding, stabilizing the metal
in the zero oxidation state.
o For example, in complexes like Ni(CO)₄ and Fe(CO)₅, both Nickel (Ni)
and Iron (Fe) are in the zero oxidation state.
H.b] Why does Manganese exhibit such a wide range of
oxidation states?
 Manganese (Mn) exhibits oxidation states from +2 to +7 because it has a
relatively large number of d-electrons (5 electrons in its d-orbitals). This
allows it to form multiple stable oxidation states as it can lose electrons from
both the 4s and 3d orbitals.
 This wide variability is due to the partial filling of its 3d orbitals and the
ability to oxidize and reduce without the loss of stability.

H.c] Trends in Stability of Higher Oxidation States

 Highest oxidation states occur in TiX₄, VF₅, CrF₆.
 Mn's +7 state is not found in simple halides, but MnO₃F exists.
 Fluorine stabilizes the highest oxidation states via:
o Higher lattice energy (CoF₃).
o Higher bond enthalpy in covalent compounds (VF₅, CrF₆).
 Fluorides of lower oxidation states like VX₂ are unstable.
 Cu:
o Cu²⁺ oxidizes I⁻ to I₂:
2Cu⁺ + 2I⁻ → Cu₂I₂ + I₂
o Cu²⁺ is more stable in solution than Cu⁺ due to negative ΔH hydration.
o Higher oxidation states of Cu stabilize in oxygen (like CuO).
o Cu⁺ is unstable in aqueous solutions, undergoes disproportionation:
2Cu⁺ → Cu²⁺ + Cu

Intext Question 4.3:

Which of the 3d series of transition metals exhibits the largest number of
oxidation states and why?

 Answer: Manganese (Mn) exhibits the largest number of oxidation states in

the 3d series. This is due to its five d-electrons which allow it to achieve
oxidation states from +2 to +7. The ability to lose electrons from both the 4s
and 3d orbitals gives it a wide range of oxidation states.

Conclusion:
 Transition elements are capable of adopting a variety of oxidation states,
especially in the middle of the series (like Mn), because of their ability to lose
electrons from both the s and d orbitals.
 Elements at the ends of the transition series (like Sc and Zn) tend to exhibit
fewer oxidation states due to either too few electrons to lose (Sc) or fully
filled d-orbitals that limit electron loss (Zn).
I] Trends in the M²⁺/M Standard Electrode Potentials
 Table 4.4 shows thermochemical parameters and standard electrode potentials
(E°) for the transformation of solid metal atoms to M²⁺ ions in solution.
 Trend across the series: E° values generally become less negative as you
move across the transition series.
 Copper (Cu) has a positive E° (+0.34 V), meaning it can't liberate H₂ from
acids, only from oxidising acids like nitric acid and hot concentrated sulfuric
acid.
 Reason for Cu's unique behaviour: The high energy needed to transform
Cu(s) to Cu²⁺(aq) isn’t compensated by its hydration enthalpy.
 Mn²⁺, Ni²⁺, and Zn²⁺: Their E° values are more negative than expected due to
ionisation enthalpy and hydration enthalpy.
 Cr²⁺ is reducing because it goes from d⁴ to d³, which is stable.
 Mn³⁺ is oxidising because it goes from d⁴ to d², forming a half-filled stable d⁵
configuration.

I.a] Trends in the M³⁺/M²⁺ Standard Electrode Potentials

 Sc: Low value due to stability of Sc³⁺ (noble gas configuration).
 Zn: Highest value due to the removal of an electron from Zn²⁺ (stable d¹⁰
configuration).
 Mn²⁺: Stable due to d⁵ configuration, hence higher value for Mn³⁺.
 Fe³⁺: Extra stability due to d⁵ configuration.
 V²⁺: Low value due to stability of half-filled t₂g level.

Observed and calculated values for the standard electrode potentials

 (M2+ → M°) of the elements Ti to Zn

Thermochemical data (kJ mol1) for the first row Transition Elements and the Standard
Electrode Potentials for the Reduction of MII to M.

Halides of 3d Metals

Table 4.6: Oxides of 3d Metals

Example 4.5: Oxidising Power Series (VO₂⁺ < Cr₂O₇²⁻ < MnO₄⁻)

 Increasing oxidizing power is due to increasing stability of the reduced species.

Intext Question 4.5
How would you account for the irregular variation of ionisation enthalpies
(first and second) in the first series of the transition elements?

 Ionization enthalpies vary irregularly due to:

o Electron configuration: Half-filled and fully-filled d orbitals provide extra
stability.
o Atomic size: Affects the ease of ionization.
o Shielding effect: Varies across the transition series.

I] Chemical Reactivity and E⁰ Values

 Transition Metals Reactivity:

o Transition metals vary widely in their chemical reactivity.
o Many are electropositive and dissolve in mineral acids. However, a few are
"noble," meaning they are unaffected by acids.
o Metals in the first transition series (except copper) are more reactive and
can be oxidized by 1M H⁺. However, their reactions with oxidizing agents
like hydrogen ions (H⁺) can sometimes be slow.
o Titanium and Vanadium are passive to dilute non-oxidizing acids at
room temperature.
 Trends in E⁰ Values for M²⁺/M:
o E⁰ values indicate a decreasing tendency to form divalent cations across
the series.
o This trend toward less negative E⁰ values is linked to the increase in the
sum of the first and second ionization enthalpies.
o Interestingly, the E⁰ values for Mn, Ni, and Zn are more negative than
expected:
 Mn²⁺'s stability is due to the half-filled d⁵ subshell.
 Zn²⁺'s stability arises from the completely filled d¹⁰ subshell.
 Ni's E⁰ value is influenced by its highly negative enthalpy of
hydration.
 Redox Couples and Oxidizing/Reducing Agents:
o The Mn³⁺ and Co³⁺ ions are among the strongest oxidizing agents in
aqueous solutions.
o Ti²⁺, V²⁺, and Cr²⁺ are strong reducing agents and can liberate hydrogen
from dilute acid:
2Cr²⁺ (aq) + 2H⁺ (aq) → 2Cr³⁺ (aq) + H₂ (g).

Example 4.6

For the first-row transition metals, the E⁰ values are:

Meta E⁰ (M²⁺/M)
 l
V –1.18
Cr –0.91
Mn –1.18
Fe –0.44
Co –0.28
Ni –0.25
Cu +0.34

Explanation for the Irregularity in the Above Values:

 The irregularity in the E⁰ (M²⁺/M) values can be explained by:

o Ionization enthalpies: The variation in first and second ionization
energies.
o Sublimation enthalpies: These are relatively much lower for Mn and V
than for other metals.

Why is the E⁰ value for the Mn³⁺/Mn²⁺ couple much more positive
than that for Cr³⁺/Cr²⁺ or Fe³⁺/Fe²⁺?

 The larger third ionization energy of Mn (from d⁵ to d⁴) is the primary reason for
this.
 This large change makes the +3 state of Mn less stable and of little importance
in comparison to Cr³⁺ and Fe³⁺.

Intext Questions:
4.6 Why is the highest oxidation state of a metal exhibited in its oxide or fluoride
only?

 The highest oxidation states of metals are usually stabilized by the strong ionic
bonds formed with highly electronegative elements like oxygen or fluorine.
This stability is not easily achieved with other compounds due to weaker bonds
or larger ions that cannot effectively stabilize high oxidation states.

4.7 Which is a stronger reducing agent: Cr²⁺ or Fe²⁺, and why?

 Cr²⁺ is a stronger reducing agent than Fe²⁺. This is because the Cr²⁺ ion has a
higher tendency to lose electrons and be oxidized to Cr³⁺. The more negative E⁰
value for Cr²⁺ compared to Fe²⁺ indicates that Cr²⁺ is more easily oxidized,
making it a stronger reducing agent.

K] Magnetic Properties
When a magnetic field is applied to substances, two main types of magnetic behavior
are observed: diamagnetism and paramagnetism.

 Diamagnetic Substances: These are repelled by the applied magnetic field.

  Paramagnetic Substances: These are attracted by the applied magnetic field.
 Ferromagnetic Substances: Substances that are strongly attracted to a
magnetic field. Ferromagnetism is an extreme form of paramagnetism.

Many transition metal ions exhibit paramagnetism, which arises from the presence
of unpaired electrons. Each unpaired electron has a magnetic moment associated
with its spin angular momentum and orbital angular momentum. However, for
the compounds of the first series of transition metals, the contribution of orbital
angular momentum is effectively quenched and has no significance. As a result, the
magnetic moment is determined solely by the number of unpaired electrons.

The magnetic moment (µ) can be calculated using the 'spin-only' formula:

μ=n(n+2)BM

 nn is the number of unpaired electrons.

 μ\mu is the magnetic moment in units of Bohr magnetons (BM).

For a single unpaired electron, the magnetic moment is 1.73 BM.

The magnetic moment increases as the number of unpaired electrons increases.

Thus, the observed magnetic moment can provide useful information about the
number of unpaired electrons present in the atom, molecule, or ion.

Calculated and Observed Magnetic Moments (BM)

Ion Configuratio Unpaired Magnetic Moment Magnetic Moment
n Electron(s) (Calculated) (Observed)
Sc³⁺ 3d⁰ 0 0 0
Ti³⁺ 3d¹ 1 1.73 1.75
Ti²⁺ 3d² 2 2.84 2.76
V²⁺ 3d³ 3 3.87 3.86
Cr²⁺ 3d⁴ 4 4.90 4.80
Mn² 3d⁵ 5 5.92 5.96
⁺
Fe²⁺ 3d⁶ 4 4.90 5.3 – 5.5
Co²⁺ 3d⁷ 3 3.87 4.4 – 5.2
Ni²⁺ 3d⁸ 2 2.84 2.9 – 3.4
Cu²⁺ 3d⁹ 1 1.73 1.8 – 2.2
Zn²⁺ 3d¹⁰ 0 0 0

Magnetic Moment Calculation

Question:
Calculate the magnetic moment of a divalent ion in aqueous solution if its atomic
number is 25.

 Step 1: Atomic number 25 means the ion is Mn²⁺, which has a d⁵ configuration.
 Step 2: There are 5 unpaired electrons in the Mn²⁺ ion.

Using the formula:

μ=n(n+2)=5(5+2)=35≈5.92BM
Thus, the magnetic moment is 5.92 BM.

Intext Question:
4.8 Calculate the ‘spin-only’ magnetic moment of M²⁺ (aq) ion where Z=27Z = 27.

 Step 1: For Z=27Z = 27, the ion is Co²⁺ with a d⁷ configuration.

 Step 2: There are 3 unpaired electrons in Co²⁺.

μ= n(n+2)= 3(3+2)= 15 ≈3.87BM

Thus, the magnetic moment of Co²⁺ (aq) is approximately 3.87 BM.

L] Formation of Coloured Ions

When an electron from a lower energy d orbital is excited to a higher energy d
orbital, the energy required for this excitation corresponds to the frequency of light
absorbed (as discussed in Unit 5). This absorbed light generally falls in the visible
region of the electromagnetic spectrum. The colour observed corresponds to the
complementary colour of the light absorbed.

The frequency of the light absorbed depends on the nature of the ligand. In
aqueous solutions, where water molecules act as ligands, the colours of various d-
block metal ions are observed. These colours are influenced by the electronic
transitions in the metal ion.

L.a] Colours of Transition Metal Ions in Aqueous Solutions

Configuratio Exampl Colour
n e
3d⁰ Sc³⁺ Colourles
s
3d⁰ Ti⁴⁺ Colourles
s
3d¹ Ti³⁺ Purple
3d¹ V⁴⁺ Blue
3d² V³⁺ Green
3d³ V²⁺ Violet
3d³ Cr³⁺ Violet
3d⁴ Mn³⁺ Violet
3d⁴ Cr²⁺ Blue
3d⁵ Mn²⁺ Pink
3d⁵ Fe³⁺ Yellow
 3d⁶ Fe²⁺ Green
3d⁶ Co³⁺ Blue
3d⁷ Co²⁺ Pink
3d⁸ Ni²⁺ Green
3d⁹ Cu²⁺ Blue
3d¹⁰ Zn²⁺ Colourles
s

Colours of some of the first row transition metal ions in aqueous solutions. From left to right: V4+,V3+,Mn2+,Fe3+,Co2+,Ni2+and Cu2+ .

M] Formation of Complex Compounds

Complex compounds are formed when metal ions bind to several anions or neutral
molecules, resulting in complex species with distinctive properties. Some examples of
complex compounds are:

 [Fe(CN)₆]³⁻, [Fe(CN)₆]⁴⁻
 [Cu(NH₃)₄]²⁺, [PtCl₄]²⁻

The transition metals form a wide variety of complex compounds due to the
relatively smaller sizes of their metal ions, their high ionic charges, and the availability
of d orbitals for bonding.

N] Catalytic Properties
Transition metals and their compounds exhibit significant catalytic activity. This is
due to their ability to:

 Adopt multiple oxidation states.

 Form complexes.

Examples of catalysts include:

 Vanadium(V) oxide (used in the Contact Process)

 Finely divided iron (used in Haber’s Process)
 Nickel (used in Catalytic Hydrogenation)

Catalysts, especially at solid surfaces, interact with reactant molecules, forming bonds
with atoms on the surface of the catalyst. This process increases the concentration
of reactants at the catalyst surface and weakens the bonds in the reacting
molecules, which lowers the activation energy.

Transition metal ions, which can change oxidation states, become more effective
catalysts. An example is:

Catalysis of the reaction between iodide and persulphate ions by iron(III):

 2 I⁻ + S₂O₈²⁻ → I₂ + 2 SO₄²⁻

Catalytic mechanism:

1. 2 Fe³⁺ + 2 I⁻ → 2 Fe²⁺ + I₂
2. 2 Fe²⁺ + S₂O₈²⁻ → 2 Fe³⁺ + 2 SO₄²⁻

O] Formation of Interstitial Compounds

Interstitial compounds are formed when small atoms, such as H, C, or N, are
trapped inside the crystal lattices of metals. These compounds are often non-
stoichiometric and are neither typically ionic nor covalent. Examples include:

 TiC
 Mn₄N
 Fe₃H
 VH₀.₅₆
 TiH₁.₇

These formulas do not correspond to the normal oxidation states of the metal. Due to
their unique composition, these compounds are referred to as interstitial
compounds. Key characteristics include:

1. High melting points — higher than those of pure metals.

2. High hardness — some borides approach diamond in hardness.
3. Retained metallic conductivity.
4. Chemical inertness.
P] Alloy Formation
An alloy is a blend of metals, prepared by mixing their components. Alloys may be
homogeneous solid solutions, where atoms of one metal are distributed randomly
among the atoms of another metal. These alloys are typically formed by metals with
metallic radii within about 15% of each other.

Because of the similar radii and other characteristics of transition metals, alloys are
easily formed by these metals. The alloys created tend to be hard and often have
high melting points.

Some well-known examples of alloys include:

 Ferrous alloys: Alloys of chromium, vanadium, tungsten, molybdenum,

and manganese are used to produce a variety of steels and stainless steel.
 Brass (copper-zinc) and bronze (copper-tin) are important alloys in industrial
applications.
 Example 4.0: Disproportionation
 Definition: When a particular oxidation state becomes unstable and
simultaneously converts into a higher and a lower oxidation state, it undergoes
disproportionation.
 Example: Manganese(VI) disproportionates in acidic solution:

3MnO2 + 4H + ⟶ MnO4− + MnO2 + 2H2O

In-text Question 4.9

Why is the Cu⁺ ion not stable in aqueous solutions?

 Answer: Cu⁺ undergoes disproportionation because its hydration enthalpy

(ΔHₕyd) is much less negative than that of Cu²⁺. As a result, Cu⁺ is both oxidized
to Cu²⁺ and reduced to Cu metal:

2Cu+⟶Cu2++Cu(disproportionation)
Q] Some Important Compounds of Transition Elements

Oxides and Oxoanions of Metals

 Formation: Most transition metals react with O₂ at high T to give MO (ionic)
oxides—Sc₂O₃ through Mn₂O₇ cover oxidation states equal to group number.
Beyond group 7, Fe₂O₃ is the highest simple oxide.
 Oxocations:
o V⁵⁺ → VO₂⁺
o V⁴⁺ → VO²⁺
o Ti⁴⁺ → TiO₂⁺
 Trend: As oxidation number ↑, ionic character ↓ → higher oxides become
more covalent and acidic.
o Mn₂O₇: covalent green oil → HMnO₄
o CrO₃: low mp, yields H₂CrO₄ & H₂Cr₂O₇
o V₂O₅: amphoteric → VO₄³⁻ and VO₂⁺ salts
o V₂O₃ basic → V₂O₄ less basic → V₂O₅ amphoteric
o CrO basic; Cr₂O₃ amphoteric

Q.a] Potassium Dichromate (K₂Cr₂O₇)

• Uses: Leather industry, oxidant for azo syntheses, primary standard in volumetric
analysis.
• Preparation:

1. Fusion of chromite:
4 FeCr₂O₄ + 8 Na₂CO₃ + 7 O₂ → 8 Na₂CrO₄ + 2 Fe₂O₃ + 8 CO₂
 2. Acidify and crystallize:
2 Na₂CrO₄ + 2 H⁺ → Na₂Cr₂O₇ + 2 Na⁺ + H₂O

3. Exchange with KCl:

Na₂Cr₂O₇ + 2 KCl → K₂Cr₂O₇ + 2 NaCl

2 CrO₄²⁻ + 2 H⁺ ⇌ Cr₂O₇²⁻ + H₂O

• Chromate–Dichromate Equilibrium:

• Structure:
o CrO₄²⁻: tetrahedral
o Cr₂O₇²⁻: two tetrahedra sharing one corner (Cr–O–Cr angle ≈ 126°)

• Oxidizing Reaction (acidified):

Cr₂O₇²⁻ + 14 H⁺ + 6 e⁻ → 2 Cr³⁺ + 7 H₂O (E° = +1.33 V)
• Typical Redox Examples:
o 6 I⁻ → 3 I₂ + 6 e⁻
o 3 Sn²⁺ → 3 Sn⁴⁺ + 6 e⁻
o 3 H₂S → 6 H⁺ + 3 S + 6 e⁻
o 6 Fe²⁺ → 6 Fe³⁺ + 6 e⁻

• Overall (with Fe²⁺):

Cr₂O₇²⁻ + 14 H⁺ + 6 Fe²⁺ → 2 Cr³⁺ + 6 Fe³⁺ + 7 H₂O

Q.b] Potassium Permanganate (KMnO₄)

• Preparation (Contact or lab):

1. Alkaline fusion:
2 MnO₂ + 4 KOH + ½ O₂ → 2 K₂MnO₄ + 2 H₂O

2. Disproportionation in acid/neutral:
3 MnO₄²⁻ + 4 H⁺ → 2 MnO₄⁻ + MnO₂ + 2 H₂O

3. Lab oxidation via persulphate:

2 Mn²⁺ + 5 S₂O₈²⁻ + 8 H₂O → 2 MnO₄⁻ + 10 SO₄²⁻ + 16 H⁺
• Properties:
o Dark purple crystals (KClO₄ structure), weakly soluble (6.4 g/100 g H₂O at 293 K).
o On heating (513 K): 2 KMnO₄ → K₂MnO₄ + MnO₂ + O₂
o Magnetic: diamagnetic (Mn⁷⁺, d⁰), manganate (Mn⁶⁺, d¹) is paramagnetic.

• Key Half Reactions:

0. MnO₄⁻ + e⁻ → MnO₄²⁻ (E° = +0.56 V)

1. MnO₄⁻ + 4 H⁺ + 3 e⁻ → MnO₂ + 2 H₂O (E° = +1.69 V)

2. MnO₄⁻ + 8 H⁺ + 5 e⁻ → Mn²⁺ + 4 H₂O (E° = +1.52 V)

• pH Dependent Oxidations:
o Acidic (e.g., I⁻ → I₂):
10 I⁻ + 2 MnO₄⁻ + 16 H⁺ → 5 I₂ + 2 Mn²⁺ + 8 H₂O

o Neutral/Alkaline (I⁻ → IO₃⁻):

2 MnO₄⁻ + H₂O + I⁻ → 2 MnO₂ + IO₃⁻ + 2 OH⁻

o S₂O₃²⁻ → SO₄²⁻:
8 MnO₄⁻ + 3 S₂O₃²⁻ + H₂O → 8 MnO₂ + 6 SO₄²⁻ + 2 OH⁻

o Mn²⁺ → MnO₂ (catalyzed by Zn²⁺):

2 MnO₄⁻ + 3 Mn²⁺ + 2 H₂O → 5 MnO₂ + 4 H⁺

• Note: Permanganate titrations in HCl are unsuitable (Cl⁻ oxidized to Cl₂).

• Applications: Analytical titrations, organic oxidations, bleaching textiles,

decolorizing oils.
A] The Inner Transition Elements (f-Block)
The f-block elements consist of two series: Lanthanoids and Actinoids.

 Lanthanoids: These are the fourteen elements following lanthanum (La), and
they closely resemble each other. Lanthanum itself is often included in
discussions about the lanthanoids, and the general symbol Ln is used to refer to
this series.
 Actinoids: These are the fourteen elements following actinium (Ac), and like
lanthanoids, actinium is included in discussions of the actinoid series.

Lanthanoids Overview
Lanthanoids are particularly similar to one another in terms of their chemical
properties. They exhibit:

 One stable oxidation state: This makes their chemistry easier to study in
comparison to other transition elements.
 Small changes in size and nuclear charge across the series: This provides
an opportunity to analyze how slight variations impact their chemical properties.

Actinoids Overview
The chemistry of actinoids is more complex due to:

 Wide range of oxidation states: Actinoids can exhibit a variety of oxidation

states, unlike the lanthanoids, which predominantly show a +3 oxidation state.
 Radioactivity: The radioactivity of actinoid elements creates unique challenges
in their study, making their chemistry more intricate.

Electronic Configurations of Lanthanoids

 General Configuration: All lanthanoids have a common 6s² configuration but
show variable occupancy in the 4f orbital.
 Stable Oxidation State: The tripositive ion (Ln³⁺) is the most stable
oxidation state across all lanthanoids. The electronic configuration of these ions
is 4fⁿ (where n = 1 to 14, depending on the atomic number).

The electronic configuration and the ionic radii of lanthanum and the lanthanoids
are listed in Table 4.9 (not included here).

4.5.2 Atomic and Ionic Sizes: The Lanthanoid Contraction

One of the most important features in the chemistry of the lanthanoids is the
lanthanoid contraction—the gradual decrease in atomic and ionic radii as we move
from lanthanum (La) to lutetium (Lu).
 Trends in ionic radii of lan
thanoids

Key Characteristics:

[Link] Contraction:
o The atomic and ionic radii decrease steadily across the lanthanoid series,
from La to Lu.
o This decrease is not perfectly regular for atomic radii (measured in metal
structures), but it is regular for M³⁺ ions.

[Link]:
o The contraction is similar to the behavior seen in ordinary transition series
elements and is primarily caused by the imperfect shielding of one
electron by another in the same sub-shell.
o In the case of the lanthanoids, the 4f electrons provide less shielding
than the d electrons in the transition elements, meaning the increase in
nuclear charge (number of protons) across the series leads to a greater
pull on the electrons and thus a decrease in size.
Consequences of Lanthanoid Contraction:
 The radii of the third transition series elements (e.g., Zr and Hf) are very
similar to those of the corresponding second transition series elements due to
the lanthanoid contraction.
o Example: The atomic radii of Zr (160 pm) and Hf (159 pm) are nearly
identical. This similarity is a direct result of the lanthanoid contraction,
which causes the radii of the lanthanoids and these transition elements to
align closely.
 Impact: This near-identical radii of Zr and Hf leads to their occurrence together
in nature and presents difficulties in their separation due to their similar
physical properties.

Summary:
 The lanthanoid contraction causes a steady decrease in size from La to Lu,
and this contraction affects the chemistry of elements in the third transition
series.
 The result is that Zr and Hf have almost identical atomic sizes, which
contributes to challenges in their natural occurrence and separation.

4.5.3 Oxidation States of Lanthanoids

 Predominant Oxidation States: The most common oxidation states of
lanthanoids are +2 and +3, with Ln³⁺ being the most stable and widespread.
However, certain lanthanoids also form +4 ions, especially in oxides.
 Stability Factors: The irregularity in oxidation states arises mainly from the
extra stability associated with having empty, half-filled, or fully filled f
subshells. This contributes to the formation of certain oxidation states being
more favored under specific conditions.

Examples of Lanthanoid Oxidation States:

[Link] (Ce):
o Ce⁴⁺ has a noble gas configuration, making it relatively stable. The
standard electrode potential E° (Ce⁴⁺/Ce³⁺) is +1.74 V, suggesting that
Ce⁴⁺ can act as a strong oxidizing agent. Despite this, Ce⁴⁺ is slow to
oxidize, making it a useful analytical reagent.
[Link] (Eu):
o Eu²⁺ is formed by losing the two s electrons, and its f⁷ configuration
accounts for the stability of this ion. However, Eu²⁺ is a strong reducing
agent, easily reverting to the +3 state.
[Link] (Yb):
o Similar to Eu, Yb²⁺ has an f¹⁴ configuration, making it a reductant.
 [Link] (Pr), Neodymium (Nd), Terbium (Tb),
Dysprosium (Dy):
o These lanthanoids occasionally form the +4 oxidation state, but only in
specific compounds like oxides (e.g., Pr⁴⁺ and Nd⁴⁺).
[Link] (Sm):
o Sm behaves similarly to Europium, existing in both +2 and +3 oxidation
states.

Oxidation States in Lanthanoid Compounds:

 Ln²⁺ and Ln³⁺ compounds are the most common.
 For example:
o Ce⁴⁺ (a strong oxidizer)
o Eu²⁺ (a strong reducer)
o Yb²⁺ (reductant)
o Tb⁴⁺ (an oxidant due to half-filled f-orbitals)

Summary Table:
Electronic Ln²⁺ Ln³⁺ Ln⁴⁺ Atomic Ionic
Atomi
Element Configurati Configura Configur Configura Radius Radius
c No.
on tion ation tion (pm) (pm)
Lanthanum [Xe] 5d¹ [Xe] 5d¹ [Xe] 4f¹ [Xe] 4f¹
57 187 106
(La) 6s² 4f⁰ 6s² 5d¹ 6s²
Cerium [Xe] 4f¹ [Xe] 4f² [Xe] 4f¹ [Xe] 4f⁰
58 183 103
(Ce) 5d¹ 6s² 6s² 6s² 6s²
Praseodymi [Xe] 4f³ [Xe] 4f² [Xe] 4f¹
59 [Xe] 4f³ 6s² 182 101
um (Pr) 6s² 6s² 6s²
Neodymiu [Xe] 4f⁴ [Xe] 4f³ [Xe] 4f²
60 [Xe] 4f⁴ 6s² 181 99
m (Nd) 6s² 6s² 6s²
Promethiu [Xe] 4f⁵ [Xe] 4f⁴ [Xe] 4f³
61 [Xe] 4f⁵ 6s² 181 98
m (Pm) 6s² 6s² 6s²
Samarium [Xe] 4f⁶ [Xe] 4f⁵ [Xe] 4f⁴
62 [Xe] 4f⁶ 6s² 180 96
(Sm) 6s² 6s² 6s²
Europium [Xe] 4f⁷ [Xe] 4f⁶
63 [Xe] 4f⁷ 6s² - 199 95
(Eu) 6s² 6s²
 Gadolinium [Xe] 4f⁷ [Xe] 4f⁷ [Xe] 4f⁷ [Xe] 4f⁷
64 180 94
(Gd) 5d¹ 6s² 6s² 5d¹ 6s² 6s²
Terbium [Xe] 4f⁹ [Xe] 4f⁸ [Xe] 4f⁷
65 [Xe] 4f⁹ 6s² 178 92
(Tb) 6s² 6s² 6s²
Dysprosiu [Xe] 4f¹⁰ [Xe] 4f¹⁰ [Xe] 4f⁹ [Xe] 4f⁸
66 177 91
m (Dy) 6s² 6s² 6s² 6s²
Holmium [Xe] 4f¹¹ [Xe] 4f¹¹ [Xe] 4f¹⁰ [Xe] 4f⁹
67 176 89
(Ho) 6s² 6s² 6s² 6s²
[Xe] 4f¹² [Xe] 4f¹² [Xe] 4f¹¹ [Xe] 4f¹⁰
68 Erbium (Er) 175 88
6s² 6s² 6s² 6s²
Thulium [Xe] 4f¹³ [Xe] 4f¹³ [Xe] 4f¹² [Xe] 4f¹¹
69 174 87
(Tm) 6s² 6s² 6s² 6s²
Ytterbium [Xe] 4f¹⁴ [Xe] 4f¹⁴ [Xe] 4f¹³ [Xe] 4f¹²
70 173 86
(Yb) 6s² 6s² 6s² 6s²
Lutetium [Xe] 4f¹⁴ [Xe] 4f¹⁴ [Xe] 4f¹⁴ [Xe] 4f¹⁴
71 - -
(Lu) 5d¹ 6s² 6s² 5d¹ 6s² 6s²

4.5.4 General Characteristics of Lanthanoids

 Physical Properties:
o Lanthanoids are silvery-white soft metals that tarnish quickly in air.
o Hardness increases with atomic number, with samarium being steel-
hard.
o Melting points range from 1000 to 1200 K, except for samarium, which
melts at 1623 K.
o They have a typical metallic structure and are good conductors of
heat and electricity.
o Density and other properties vary smoothly, except for Europium (Eu)
and Ytterbium (Yb), and occasionally Samarium (Sm) and Thulium
(Tm).

 Color:
o Many trivalent lanthanoid ions are colored both in the solid state and
in aqueous solutions, which can be attributed to the presence of f-
electrons.
o La³⁺ and Lu³⁺ ions are colorless, while others display color.
o The absorption bands of these ions are narrow, likely due to excitation
within the f-level.

 Magnetic Properties:
o All lanthanoids except f⁰ (La³⁺ and Ce⁴⁺) and f¹⁴ (Yb²⁺ and Lu³⁺) ions
are paramagnetic.
 Ionization Enthalpy:
o First ionization enthalpy of lanthanoids is around 600 kJ/mol and the
second ionization enthalpy is about 1200 kJ/mol, similar to calcium.
o The third ionization enthalpy exhibits irregularities due to exchange
enthalpy considerations that impart stability to empty, half-filled,
and completely filled f-orbitals. This is evident from the abnormally
low third ionization enthalpy of La, Gd, and Lu.

 Chemical Behavior:
o The earlier members of the lanthanoid series are quite reactive, similar
to calcium. As the atomic number increases, they behave more like
aluminum.
o Electrode potentials (E₀) for the half-reaction:
 Ln³⁺(aq) + 3e⁻ → Ln(s) range from -2.2 to -2.4 V, except for Eu
(Europium), which is -2.0 V.
o Lanthanoid metals combine with hydrogen when gently heated in the
gas phase.
o Lanthanoids form carbides (Ln₃C, Ln₂C₃, and LnC₂) when heated with
carbon.
o They liberate hydrogen from dilute acids and react with halogens to
form halides.
o They form oxides (M₂O₃) and hydroxides (M(OH)₃) that are basic,
much like alkaline earth metals.

Chemical reactions of the lanthanoids

 Uses of Lanthanoids:
o Mischmetall, an alloy of lanthanoid metal (~95%) and iron (~5%), along
with small amounts of sulfur (S), carbon (C), calcium (Ca), and aluminum
(Al), is used extensively.
 Mischmetall is used in Mg-based alloys for producing bullets,
shells, and lighter flints.
 o Lanthanoid mixed oxides are employed as catalysts in petroleum
cracking.
o Individual lanthanoid oxides are used as phosphors in television
screens and other fluorescent surfaces.

4.6 The Actinoids

The actinoids consist of fourteen elements from Thorium (Th) to Lawrencium
(Lr). These elements are all radioactive, and their study is complicated due to their
short half-lives, especially for the latter members.

Properties Table of Actinoids

Key Characteristics:
 Radioactivity: All actinoids are radioactive.
 Half-Lives: The earlier actinoid elements have relatively long half-lives, while
the later elements have half-lives that can range from a day to just 3 minutes
(for Lawrencium, Z = 103).
 Preparation: The later members can only be prepared in nanogram
quantities, making their study particularly challenging.

These radioactive properties and the difficulty in handling these elements due to their
instability and short half-lives are some of the main reasons the study of actinoids is
complex and specialized.

4.6.1 Electronic Configurations

All actinoids have the 7s² configuration with variable occupancy of the 5f and 6d
subshells. The five 5f orbitals are filled starting from Protactinium (Pa) onward,
but not in Thorium (Th). From Protactinium (Pa) to Lawrencium (Lr), the 5f
orbitals fill up, with element 103 having a complete set of 5f orbitals.

The irregularities in electronic configurations of actinoids, like in lanthanoids, arise

from the stabilities of the f⁰, f⁷, and f¹⁴ electron configurations. For example,
Americium (Am) and Curium (Cm) have the following configurations:

 Americium (Am): [Rn] 5f⁷ 7s²

 Curium (Cm): [Rn] 5f⁷ 6d¹ 7s²

Though 5f orbitals resemble the 4f orbitals in their angular wave-function, they are
not as "buried," meaning 5f electrons can participate more significantly in bonding
than 4f electrons.

4.6.2 Ionic Sizes

The actinoid series follows a similar trend to the lanthanoids with a gradual
decrease in the size of M³⁺ ions across the series, known as the actinoid
contraction. However, the contraction is greater from element to element in the
actinoids due to poor shielding by the 5f electrons.

4.6.3 Oxidation States

Actinoids exhibit a wider range of oxidation states, largely due to the comparable
energies of the 5f, 6d, and 7s levels. The +3 oxidation state is the most common,
similar to the lanthanoids. The range of oxidation states among actinoids is as follows:

 Thorium (Th): Maximum oxidation state of +4

 Protactinium (Pa): +5
  Uranium (U): +6
 Neptunium (Np): +7
 Plutonium (Pu): +3 and +4 states
 Higher oxidation states are more frequent in the early elements, but they
decrease as we move down the series.

Oxidation States of Actinoids (Table 4.11):

Note: The distribution of oxidation states in actinoids is uneven, with earlier

elements displaying higher oxidation states, which tend to decrease in the later
elements. The complex oxidation state behavior makes it challenging to review their
chemistry based on oxidation states alone.

4.6.4 General Characteristics and Comparison with

Lanthanoids
The actinoid metals exhibit the following general characteristics:

 Appearance: They are silvery in appearance but show structural variability

due to irregularities in their metallic radii, which are much larger than those of
the lanthanoids.
 Reactivity: Actinoid metals are highly reactive, especially in finely divided
form. For example:
o When they react with boiling water, they form a mixture of oxide and
hydride.
o They combine with most non-metals at moderate temperatures.
o Hydrochloric acid attacks all actinoid metals, but nitric acid has only a
slight effect due to the formation of protective oxide layers.
o Alkalies do not affect them significantly.
 Magnetic Properties: The magnetic properties of the actinoids are more
complex compared to lanthanoids. Although the variation in magnetic
susceptibility with the number of unpaired 5f electrons follows a similar
pattern to the lanthanoids, the magnetic susceptibility values for the actinoids
are generally lower than those of lanthanoids.
 Ionization Enthalpies: The ionization enthalpies of early actinoids are
believed to be lower than those of the early lanthanoids. This is because, as the
5f orbitals begin to fill, they penetrate less into the inner core of electrons.
Therefore, 5f electrons are more effectively shielded from the nuclear charge
than 4f electrons in lanthanoids, making them more available for bonding.
Comparison of Actinoids with Lanthanoids
 Early actinoids show similarities with lanthanoids, especially in terms of
gradual changes in properties without significant changes in oxidation state.
 The lanthanoid and actinoid contractions have extended effects on the
sizes of subsequent elements, impacting their properties. The lanthanoid
contraction is more significant because the chemistry of the elements
succeeding the actinoids is less understood.
 The actinoid contraction is greater from element to element than the
lanthanoid contraction due to the poorer shielding of the 5f electrons in the
actinoids.

Context Question
Why is the actinoid contraction greater from element to element than the
lanthanoid contraction?

 The actinoid contraction is greater because 5f electrons are poorly shielded,

leading to a greater effective nuclear charge and resulting in a more
noticeable shrinkage in size as you move across the actinoid series.

Lanthanoid Member Exhibiting +4 Oxidation State

 Cerium (Z = 58) is well-known for exhibiting the +4 oxidation state. This is a
significant feature of cerium, distinguishing it from many other lanthanoids,
which predominantly exhibit the +3 oxidation state.

4.7 Some Applications of d- and f-Block Elements

The d-block and f-block elements have a wide range of industrial and
technological applications:

 Iron and Steels: These are critical in the construction industry. The production
process involves:
o Reduction of iron oxides.
o Removal of impurities.
o Addition of carbon and alloying metals like Cr, Mn, and Ni.
 Pigment Industry: TiO₂ is used in the pigment industry, and MnO₂ is essential
in dry battery cells.
 Battery Industry: Metals like Zn and Ni (e.g., Ni/Cd batteries) are vital for
battery production.
 Coinage Metals: Ag and Au are traditionally used in coins, but modern coins
(like the UK copper coins) are made from copper-coated steel or Cu/Ni
alloys.
 Catalysts in Chemical Industry:
o V₂O₅ is a catalyst in the oxidation of SO₂ to SO₃ for the production of
sulfuric acid.
o TiCl₄ and Al(CH₃)₃ form the basis of the Ziegler catalysts for
manufacturing polyethylene.
o Iron catalysts are used in the Haber process for ammonia production.
o Nickel catalysts help in the hydrogenation of fats.
o The Wacker process uses PdCl₂ to catalyze the oxidation of ethyne
(acetylene) to ethanal (acetaldehyde).
o Nickel complexes are used in the polymerization of alkynes and other
organic compounds like benzene.
 Photographic Industry: AgBr is used for its light-sensitive properties in
photographic processes.

These elements are integral to a variety of industries due to their unique properties,
particularly in catalysis, alloys, and electronics.