d and f block elements

• Position in the Periodic Table:

• d-Block: Groups 3-12, with d-orbitals progressively filled.
• f-Block: Separate panel at the bottom, where 4f and 5f orbitals are filled (lanthanoids and
actinoids).
• Types of Series:
• Transition Metals: 3d (Sc-Zn), 4d (Y-Cd), 5d (La/Hf-Hg), and 6d (Ac, Rf-Cn).
• Inner Transition Metals: 4f (Ce-Lu, lanthanoids) and 5f (Th-Lr, actinoids).
• Definition:
• Transition Metals: Metals with incomplete d-subshell in atoms/ions. Zinc, cadmium, and
mercury are exceptions due to fully filled d^10 configuration.
• General Characteristics:
• Properties vary due to partly filled d or f orbitals, leading to unique oxidation states,
reactivity, and stability.
• Important Compounds:
• Compounds like K₂Cr₂O₇ and KMnO₄ have industrial significance.
• Significance:
• Elements like Fe, Cu, Ag, Au (transition metals) and Th, Pa, U (inner transition metals) are
essential for civilization and nuclear energy.
Transition Elements (d-Block)
1. Position in Periodic Table:
• Located between s- and p-blocks, occupying the middle section of the periodic table.
2. d-Block Series:
• Comprises four rows based on d-orbitals: 3d, 4d, 5d, and 6d series.
3. Electronic Configuration:
• General form: (n-1)d^1–10 ns^1–2.
• Exception: Pd has a configuration of 4d^10 5s^0.
4. Stability of Half-Filled and Fully Filled Orbitals:
• Half-filled (e.g., Cr: 3d^5 4s^1) and fully filled configurations (e.g., Cu: 3d^10 4s^1)
are more stable, leading to exceptions in configuration.
Transition Elements’ Characteristics
1. Electronic Configuration:
• Zn, Cd, Hg, and Cn have (n−1)d10ns2 configuration; fully filled orbitals mean they
are not considered transition elements.
2. d-Orbitals’ Influence:
• d-Orbitals extend outward, interacting strongly with surrounding atoms, impacting
magnetic and electronic properties (for configurations d1–d9).
 3. Key Properties:
• Transition elements exhibit:
• Varied Oxidation States
• Colored Ions
• Complex Formation with ligands
• Catalytic Activity and Paramagnetism
4. Property Trends:
• Greater property similarities across horizontal rows, with notable trends in the 3d row;
some group similarities exist too.
Physical Properties of Transition Elements
1. Metallic Properties:
• Exhibit typical metallic traits: high tensile strength, ductility, malleability, high
thermal/electrical conductivity, and metallic luster.
• Common metallic structures except Zn, Cd, Hg, and Mn.
2. Melting and Boiling Points:
• High melting/boiling points due to strong metallic bonding from both (n-1)d and ns
electrons.
• Peaks in melting points occur at d5 configuration; exceptions are Mn and Tc.
3. Enthalpy of Atomisation:
• High enthalpy of atomisation correlates with strong interatomic bonding and
influences the metal's standard electrode potential.
• Metals in 4d and 5d series have higher atomisation enthalpy than 3d series, favoring
metal-metal bonding in heavier transition metals.
4. Lattice Structures:
• Structures vary: mainly hcp, bcc, and ccp arrangements, with notable trends across
series.
Variation in Atomic and Ionic Sizes of Transition Metals
1. Trend in Ionic/Atomic Sizes:
• Within a series, ionic and atomic radii decrease as atomic number increases due to
added nuclear charge and ineffective d-orbital shielding.
2. Comparison Across Series:
• From 3d to 4d series, atomic sizes increase. However, 5d series radii are similar to 4d
due to Lanthanoid Contraction (the 4f orbital filling before 5d).
3. Lanthanoid Contraction:
• Caused by poor shielding within 4f orbitals, reducing atomic radii in the 5d series to
match the 4d series. Leads to similar physical and chemical properties between
second and third transition series (e.g., Zr and Hf).
4. Density Trend:
• Decreasing atomic radius with increasing atomic mass leads to higher density in
elements from titanium (Z=22) to copper (Z=29).
Ionisation Enthalpies of Transition Elements
1. General Trend:
• Ionisation enthalpy increases across each series from left to right due to increasing
nuclear charge.
• Increase is gradual in transition metals compared to non-transition elements.
2. 3d Series Irregularities:
• Irregular trend in first ionisation enthalpy of 3d series due to changes in relative
energies of 4s and 3d orbitals.
• Electrons are removed from ns before (n-1)d orbitals, leading to slight variations in
ionisation energies across the series.
3. Second and Third Ionisation Enthalpies:
• Second and third ionisation enthalpies generally increase due to increased nuclear
charge.
• Stability of d5 (e.g., Mn2+) and d10 (e.g., Zn2+) configurations cause high values,
making further ionisation difficult.
4. Exchange Energy and Stability:
• Exchange energy stabilizes electronic configurations with parallel spins (e.g., d5 and
d10).
• High exchange energy makes ionisation harder, explaining low enthalpy for certain
configurations (e.g., Mn+: 3d5).
5. Oxidation States and Ionisation Enthalpies:
• Transition elements typically show a +2 oxidation state, as the first and second
ionisation energies plus atomisation enthalpy favor this state.
• High third ionisation enthalpies limit oxidation states above +2 for metals like Cu, Ni,
and Zn.
Oxidation States of Transition Elements
1. Range of Oxidation States:
• Transition elements exhibit a wide range of oxidation states, peaking in the middle of
the series.
• Example: Manganese shows oxidation states from +2 to +7.
2. Factors Affecting Oxidation States:
• Early elements (e.g., Sc, Ti) show fewer oxidation states due to limited d electrons.
• Later elements (e.g., Cu, Zn) have fewer available orbitals for sharing due to filled d
orbitals, limiting higher oxidation states.
3. Stability of Higher Oxidation States:
• Stable high oxidation states up to Mn (+7) are common early in the series (e.g., TiIV,
VV, CrVI, MnVII).
• Stability of high oxidation states decreases after Mn, with typical oxidation states for
later elements (e.g., FeII/III, CoII/III, NiII).
4. Uniqueness of Transition Element Oxidation:
• Transition metals often vary in oxidation states by unity (e.g., VIV/V, MnVI/VII), unlike
non-transition elements, which commonly differ by two units.
 5. Group Trends:
• In d-block groups, heavier elements prefer higher oxidation states, unlike p-block
elements where lower states are favored due to the inert pair effect (e.g., MoVI and
WVI are more stable than CrVI).
6. Low Oxidation States in Complexes:
• Low oxidation states occur in complexes with π-acceptor ligands (e.g., Ni(CO)4,
Fe(CO)5), where transition metals can exhibit a zero oxidation state.

Trends in M3+/M2+ Standard Electrode Potentials

1. General Observations:
• The standard electrode potential (E∘) values for M3+/M2+ show significant variation
among transition metals.
2. Key Elements:
• Scandium (Sc): Exhibits a low E∘ value due to the stability of Sc3+, which has a
noble gas electron configuration.
• Zinc (Zn): The highest E∘ value among the series, as removing an electron from the
stable d10 configuration of Zn2+ destabilizes it.
• Manganese (Mn): Shows comparatively high E∘ due to the stability of Mn2+ with its
d5 configuration.
• Iron (Fe): Has a lower E∘ value, reflecting the extra stability of Fe3+, also having a
d5 configuration.
• Vanadium (V): Displays a comparatively low E∘ value, which is related to the
stability of V2+ with a half-filled t2g level.

Trends in Stability of Higher Oxidation States

1. Halides of Transition Metals:
• The highest oxidation states are represented in tetrahalides such as TiX4, VF5, and
CrF6.
• Manganese achieves a +7 oxidation state, not typically seen in simple halides but
present in MnO3F.
2. Oxidation State Limitations:
• Beyond manganese, no transition metals form stable trihalides, except for FeX3 and
CoF3.
• Fluorine is particularly effective at stabilizing higher oxidation states due to:
• Higher lattice energy (as in CoF3).
• Higher bond enthalpy in covalent compounds (e.g., VF5 and CrF6).
3. Hydrolysis and Oxohalides:
• Although V+5 is only represented by VF5, other halides often undergo hydrolysis,
forming oxohalides (VOX3).
• Fluorides tend to be unstable in low oxidation states (e.g., VX2 where X = Cl, Br, or I).
Chemical Reactivity and EV Values of Transition Metals
1. Reactivity Overview:
• Transition metals exhibit a wide range of chemical reactivity.
• Many are sufficiently electropositive to dissolve in mineral acids.
• Some, termed "noble" metals (e.g., gold, platinum), are unaffected by acids.
2. First Series Metals:
• Most first-row transition metals (except Cu) are relatively reactive and can be oxidized
by 1M H⁺.
• Reactivity rates with oxidizing agents like H⁺ can be slow; e.g., Ti and V are passive
to dilute non-oxidizing acids at room temperature.
3. EV Values for M²⁺/M:
• EV values show a decreasing trend for forming divalent cations across the series.
• This trend correlates with increasing first and second ionization enthalpies.
• Mn, Ni, and Zn have unexpectedly negative EV values:
• Mn²⁺: Stability due to half-filled d subshell (d⁵).
• Zn²⁺: Stability due to completely filled d subshell (d¹⁰).
• Ni: EV related to high negative enthalpy of hydration.
4. Redox Couples:
• EV values for the redox couple M³⁺/M²⁺ indicate that Mn³⁺ and Co³⁺ are strong
oxidizing agents in aqueous solutions.
• Transition metals like Ti²⁺, V²⁺, and Cr²⁺ act as strong reducing agents and can
liberate hydrogen from dilute acids:
• Example reaction:
2Cr2++2H+→2Cr3++H2(g)

Magnetic Properties of Transition Metals

1. Types of Magnetism:
• Diamagnetism: Substances are repelled by a magnetic field.
• Paramagnetism: Substances are attracted to a magnetic field due to unpaired
electrons.
• Ferromagnetism: An extreme form of paramagnetism, characterized by strong
attraction to a magnetic field.
2. Paramagnetism and Unpaired Electrons:
• Arises from unpaired electrons, each contributing a magnetic moment from their spin
and orbital angular momentum.
• In first-row transition metals, orbital angular momentum is effectively quenched,
making the spin contribution dominant.
3. Calculating Magnetic Moment:
• Magnetic moment (μ) is calculated using the spin-only formula: μ=n(n+2) where n is
the number of unpaired electrons.
• A single unpaired electron has a magnetic moment of 1.73 Bohr magnetons (BM).
4. Observations:
• The magnetic moment increases with the number of unpaired electrons.
 • The observed magnetic moment provides insight into the number of unpaired
electrons in ions, molecules, or atoms.
5. Experimental Data:
• Magnetic moments are often measured for hydrated ions in solution or in solid state,
with values compared to those calculated using the spin-only formula.

Formation of Colored Ions and Complex Compounds

1. Color Formation in Transition Metals:
• When an electron is excited from a lower energy d orbital to a higher one, it absorbs
energy that corresponds to a specific frequency of light, typically in the visible region.
• The color observed is the complementary color of the absorbed light.
• The specific frequency of light absorbed depends on the nature of the ligand
surrounding the metal ion.
2. Aqueous Solutions:
• In solutions where water acts as the ligand, various transition metal ions display
characteristic colors (e.g., V⁴⁺, V³⁺, Mn²⁺, Fe³⁺, Co²⁺, Ni²⁺, Cu²⁺).
3. Formation of Complex Compounds:
• Transition metals can form numerous complex compounds due to their smaller ionic
sizes, high charges, and availability of d orbitals for bonding.
• Examples of complex compounds include:
• [Fe(CN)6]3−
• [Fe(CN)6]4−
• [Cu(NH3)4]2+
• [PtCl4]2−
4. Color Examples:
• Some first-row transition metal ions and their colors in aqueous solutions:
• V⁴⁺: Blue
• V³⁺: Green
• Mn²⁺: Pale pink
• Fe³⁺: Yellow
• Co²⁺: Pink
• Ni²⁺: Green
• Cu²⁺: Blue
5. Magnetic Moment Calculation:
• For the calculation of the ‘spin-only’ magnetic moment of an M²⁺ ion with atomic
number Z=27 (which corresponds to Co²⁺):
• Co²⁺ has 3 unpaired electrons in its d⁷ configuration.
• The spin-only magnetic moment (μ) is calculated as: μ=n(n+2) where n is the
number of unpaired electrons. μ=3(3+2)=15≈3.87BM

Catalytic Properties of Transition Metals

1. Catalytic Activity:
• Transition metals and their compounds are renowned for their catalytic abilities.
 • This is due to their capability to adopt multiple oxidation states and form complexes.
2. Examples of Catalysts:
• Vanadium(V) Oxide: Used in the Contact Process for sulfuric acid production.
• Finely Divided Iron: Acts as a catalyst in the Haber Process for ammonia synthesis.
• Nickel: Utilized in catalytic hydrogenation reactions.
3. Mechanism of Catalysis:
• Catalysts provide a solid surface where reactant molecules form bonds with the
catalyst atoms.
• Transition metals utilize their 3d and 4s electrons for bonding.
• This interaction increases the concentration of reactants at the catalyst surface and
weakens the bonds in the reactants, lowering the activation energy required for the
reaction.
4. Oxidation State Changes:
• Transition metal ions can readily change oxidation states, enhancing their
effectiveness as catalysts.
• For example, in the reaction between iodide and persulfate ions: 2I−+S2O82−→I2
+2SO42−
• The catalytic cycle involving iron:
• 2Fe3++2I−→2Fe2++I2
• 2Fe2++S2O82−→2Fe3++2SO42−

Formation of Interstitial Compounds and Alloys

1. Interstitial Compounds:
• Definition: Formed when small atoms (like H, C, or N) are trapped within the crystal lattices
of metals.
• Characteristics:
• Typically non-stoichiometric; do not correspond to normal oxidation states of the
metal.
• Examples include TiC, Mn₄N, Fe₃H, VH₀.₅₆, and TiH₁.₇.
• Physical and Chemical Properties:
• High Melting Points: Generally higher than those of pure metals.
• Hardness: Very hard, with some compounds (like certain borides) approaching the
hardness of diamond.
• Metallic Conductivity: Retain the metallic conductivity characteristic of the parent
metal.
• Chemical Inertness: Typically chemically inert.

2. Alloy Formation:
• Definition: Alloys are mixtures of metals created by blending their components.
• Types:
• Homogeneous Solid Solutions: Atoms of one metal are distributed randomly
among the atoms of another, typically when atomic radii are within 15% of each
other.
• Transition Metals and Alloys:
 • Due to similar radii and properties, transition metals readily form alloys.
• Alloys formed are usually hard and often have high melting points.
• Common Alloys:
• Ferrous Alloys: Include metals like chromium, vanadium, tungsten, molybdenum,
and manganese; used to produce various steels and stainless steel.
• Alloys with Non-Transition Metals: Such as brass (copper-zinc) and bronze
(copper-tin), which are also significant in industrial applications.

mportant Compounds of Transition Elements

Oxides and Oxoanions
Formation of Oxides:
• Transition metals typically form oxides (MO) through high-temperature reactions with
oxygen.
• Most metals except scandium form ionic oxides. The highest oxidation states range from
Sc₂O₃ to Mn₂O₇.
• Beyond group 7, iron's highest oxide known is Fe₂O₃.
• As oxidation states increase, ionic character generally decreases, leading to covalent
behavior in some oxides (e.g., Mn₂O₇ is a covalent green oil).
Acidic and Basic Properties:
• Higher oxidation states of transition metals often exhibit acidic character.
• For example:
• Mn₂O₇ yields HMnO₄ (permanganic acid).
• CrO₃ gives H₂CrO₄ and H₂Cr₂O₇.
• V₂O₅ is mainly acidic and amphoteric, forming VO₄³⁻ and VO₂⁺ salts.

Potassium Dichromate (K₂Cr₂O₇)

• Significance: Widely used in the leather industry and as an oxidant for various reactions.
• Preparation: Obtained by fusing chromite (FeCr₂O₄) with sodium or potassium carbonate,
followed by acidification to yield sodium chromate, which can be converted to potassium
dichromate:
• FeCr4 FeCr2O4+8Na2CO3+7O2→8Na2CrO4+2Fe2O3+8CO2
• Sodium chromate is converted to potassium dichromate via:
• Na2Cr2O7+2KCl→K2Cr2O7+2NaCl
• Properties:
• Orange crystals; soluble in water.
• Strong oxidizing agent, useful in volumetric analysis.
• Oxidizing reactions in acidic conditions can be represented as:
• Cr2O72−+14H++6e−→2Cr3++7H2O

Potassium Permanganate (KMnO₄)

• Preparation: Made by fusing MnO₂ with an alkali metal hydroxide and an oxidizing agent
(KNO₃) or through electrolytic oxidation of manganate.
• 2MnO2+4KOH+O2→2K2MnO4+2H2O
 • Properties:
• Dark purple (almost black) crystals; low solubility in water.
• Intense color and unique magnetic properties (diamagnetic with weak
paramagnetism).
• Oxidizing agent in acidic solutions:
• Can oxidize iodides to iodine, Fe²⁺ to Fe³⁺, and oxalates to CO₂.

Key Oxidizing Reactions of KMnO₄

1. In Acidic Solutions:
• 10I−+2MnO4−+16H+→2Mn2++8H2O+5I2
• 5Fe2++MnO4−+8H+→Mn2++4H2O+5Fe3+
• Oxidation of oxalic acid:
• 5C2O42−+2MnO4−+16H+→2Mn2++8H2O+10CO2
2. In Neutral or Alkaline Solutions:
• Iodide to iodate:
• 2MnO4−+H2O+I−→2MnO2+2OH−+IO3−

The Inner Transition Elements (f-Block)

The f-block of the periodic table consists of two series of elements: the lanthanoids and the
actinoids.

Lanthanoids
• Definition: The lanthanoids are the fourteen elements that follow lanthanum (La), typically
ranging from cerium (Ce, atomic number 58) to lutetium (Lu, atomic number 71).
• Properties:
• Lanthanoids are known for their similar chemical and physical properties, largely due
to the filling of the 4f orbitals.
• They predominantly exhibit a +3 oxidation state, which is their most stable state.
• The elements show a gradual change in size and nuclear charge, allowing for a clear
examination of periodic trends.
• Reactivity: These elements react with water and acids, forming hydroxides and salts.

Actinoids
• Definition: The actinoids consist of the fourteen elements following actinium (Ac),
extending from thorium (Th, atomic number 90) to lawrencium (Lr, atomic number 103).
• Properties:
• The actinoids are more complex than the lanthanoids due to a wider range of
oxidation states, from +3 to +6, and even higher for some elements.
• They exhibit significant radioactivity, making them challenging to study and handle.
• Reactivity: Like lanthanoids, actinoids also react with water and acids, but their chemistry is
more varied due to differing oxidation states and the presence of radioactivity.
The Actinoids
Radioactivity and Study Challenges
The actinoids are a series of radioactive elements that include atomic numbers from 89 (actinium)
to 103 (lawrencium). The earlier actinoids have relatively long half-lives, making them somewhat
easier to study. In contrast, the later members have very short half-lives, ranging from a day down
to just a few minutes for lawrencium (Z = 103). This instability and the fact that these elements can
only be produced in very small quantities (often in nanogram amounts) present significant
challenges for researchers.

Electronic Configurations
The electronic configurations of actinoids are characterized by:
• General Configuration: All actinoids are believed to have the configuration of 7s2 with
variable occupancy of the 5f and 6d subshells.
• 5f Orbitals: The addition of electrons to the 5f subshell occurs as follows:
• Thorium (Z = 90) is an exception, primarily filling the 6d subshell.
• Starting from protactinium (Pa, Z = 91), electrons begin filling the 5f subshell.
• By the time we reach element 103, the 5f orbitals are effectively complete.

Stability and Irregularities

Similar to the lanthanoids, the actinoids exhibit irregularities in their electronic configurations, often
due to the stability associated with specific electron arrangements. Notably, configurations like f0,
f7, and f14 confer particular stability.
For example:
• Americium (Am) has the configuration [Rn]5f77s2.
• Curium (Cm) has the configuration [Rn]5f76d17s2.

Bonding Characteristics
The 5f orbitals of actinoids, while similar in angular properties to the 4f orbitals of lanthanoids, are
less shielded from the nucleus. This lesser shielding allows 5f electrons to participate more
actively in chemical bonding, enhancing the variety of chemical behavior observed in actinoids
compared to lanthanoids.

Ionic Sizes
Actinoid Contraction
Similar to the lanthanoid series, the actinoid elements exhibit a trend known as actinoid
contraction. This refers to the gradual decrease in the size of the atoms or M3+ ions across the
series. However, the actinoid contraction is more pronounced than that of the lanthanoids. This
greater contraction is primarily due to the poor shielding effect of the 5f electrons, which leads to
a stronger effective nuclear charge felt by the outer electrons.
Oxidation States
Range of Oxidation States
The actinoids are characterized by a wide range of oxidation states, a feature attributed to the
comparable energies of the 5f, 6d, and 7s orbitals. The known oxidation states of actinoids include:
• The most common oxidation state for actinoids is +3.
• In the first half of the series, higher oxidation states are more frequently observed. For
instance:
• Thorium (Th) has a maximum oxidation state of +4.
• Protactinium (Pa) can exhibit +5.
• Uranium (U) and Neptunium (Np) can reach +6 and +7, respectively.
• In later actinoids, the tendency to achieve these higher oxidation states decreases.

General Characteristics of Actinoids

1. Appearance: Actinoid metals generally have a silvery luster, similar to many transition
metals. However, their appearance can vary due to oxidation and the presence of different
compounds.
2. Structural Variability: The actinoids exhibit a wide range of structural forms. This variability
is attributed to:
• Irregularities in Metallic Radii: The metallic radii of actinoids are less consistent
compared to those of lanthanoids. As a result, different actinoids can adopt various
crystalline structures, leading to more diverse physical properties.
3. Metallic Characteristics: Actinoids are typically metallic in nature, exhibiting good electrical
conductivity and malleability. However, their metallic properties can be influenced by factors
like oxidation state and the presence of impurities.

Comparison with Lanthanoids

• Metallic Radii: The irregularities in metallic radii are more pronounced in actinoids than in
lanthanoids. While lanthanoids show a smoother trend in size due to their more stable
electron configurations, actinoids have more variability due to the involvement of the 5f
electrons.
• Oxidation States: Actinoids have a wider range of oxidation states compared to
lanthanoids. While lanthanoids predominantly exhibit the +3 oxidation state, actinoids can
display states ranging from +3 to +7.
• Radioactivity: All actinoids are radioactive, which distinguishes them from lanthanoids. The
presence of radioactivity introduces additional complexities in their chemistry and handling.
• Chemical Behavior: The chemistry of actinoids is generally more complicated due to their
varying oxidation states and the effects of radioactivity. In contrast, lanthanoids exhibit more
consistent chemical behavior primarily in the +3 state.

Applications of d- and f-Block Elements

1. Construction Materials:
 • Iron and Steels: Iron is a foundational material in construction. Its production
involves the reduction of iron oxides, impurity removal, and the addition of carbon
and alloying elements like chromium (Cr), manganese (Mn), and nickel (Ni) to
enhance strength and corrosion resistance.
2. Pigments and Batteries:
• Titanium Dioxide (TiO₂): Widely used in the pigment industry for its brightness and
high refractive index.
• Manganese Dioxide (MnO₂): Utilized in dry batteries for its role as an oxidizing
agent. Additionally, zinc (Zn) and nickel/cadmium (Ni/Cd) are important for battery
applications.
3. Coinage Metals:
• Copper (Cu), Silver (Ag), and Gold (Au): Known as coinage metals, though modern
coins may include alloys (e.g., UK coins are copper-coated steel and "silver" coins
are Cu/Ni alloys). Silver and gold are often collected as investment items.
4. Catalysts in Chemical Industry:
• Vanadium Pentoxide (V₂O₅): Used as a catalyst in the production of sulfuric acid by
oxidizing sulfur dioxide (SO₂).
• Titanium Tetrachloride (TiCl₄): Combined with aluminum alkyls to form Ziegler
catalysts for polyethylene (polythene) production.
• Iron Catalysts: Employed in the Haber process for synthesizing ammonia from
nitrogen (N₂) and hydrogen (H₂) gases.
• Nickel Catalysts: Facilitate the hydrogenation of fats, making them essential in the
food industry.
• Palladium Chloride (PdCl₂): Catalyzes the oxidation of ethyne (acetylene) to
ethanal (acetaldehyde) in the Wacker process.
5. Polymerization and Organic Chemistry:
• Nickel Complexes: Useful in the polymerization of alkynes and other organic
compounds like benzene, contributing to the production of various plastics and
synthetic materials.
6. Photographic Industry:
• Silver Bromide (AgBr): Noted for its light-sensitive properties, making it a key
component in photographic films and papers.