Classification

of Elements

Dr. Abdul jaleel

Lecturer
Department of Metallurgy and Materials Engineering
Classification of Elements
According to Periodic Table

• Metals
• Metals ( Transition)
• Metals ( Inner Transition)
• Non-metals
• Metalloids
 Properties of Elements

• Metals ( three shades of blue) (lower left corners in the periodic table).They
are • Conduct heat and
– Luster-Shiny solid at room temperature ( except Hg mercury is the only electricity well
liquid) • Malleable – hammered
– Metals form oxides (e.g., rust on iron = Fe₂O₃·xH₂O). into sheets
– Some metals react with water to produce hydrogen gas (e.g., Na, Ca). • Ductile – drawn into
wires.
– Metals react with acids (like HCl) to release hydrogen gas.
• Sonority
– Metals can be mixed with other metals or non-metals to make alloys
(e.g., steel, bronze, brass).
– Ferromagnetism – Iron, cobalt, and nickel can be magnetized.
– Paramagnetism & Diamagnetism -Other metals show weak attraction
or repulsion to magnets.
– Opacity -Metals do not allow light to pass through.
Reasons for Metallic Properties

• Luster (Shiny at room temperature, except Hg)

• Metals have free (delocalized) electrons in their
outer shells.
• These electrons reflect light, giving metals a shiny
appearance (metallic luster).
• Mercury (Hg) is liquid at room temperature because
of weak metallic bonding due to relativistic effects.
• Metals form oxides (e.g., rust Fe₂O₃·xH₂O)
• Metals are electropositive elements → they lose
electrons easily.
• Oxygen is highly electronegative → reacts with
metals to form metal oxides.
• Example: Iron rusting in moist air forms hydrated
ferric oxide.
• Reaction with water (Na, Ca release H₂ gas)
• Active metals displace hydrogen from water.
• Reaction:
2Na+2H2O→2NaOH+H2↑
• This happens because metals readily lose electrons to
hydrogen ions (reduction → H₂ gas).
• Reaction with acids (release hydrogen gas)
• Metals above hydrogen in the reactivity series
replace hydrogen from acids.
• Example:
Zn+2HCl→ZnCl2+H2↑
• Formation of alloys (e.g., steel, bronze, brass)
• Metals have non-directional metallic bonds, so their atoms
can be easily replaced by other metal/non-metal atoms.
• This allows solid solution formation → alloys with better
strength, corrosion resistance, etc.
• Ferromagnetism (Fe, Co, Ni)
• These metals have unpaired d-electrons that align parallel in
domains.
• Strong magnetic interactions cause permanent magnetism.
• Paramagnetism & Diamagnetism
• Paramagnetic metals: have unpaired electrons → weak
attraction to magnetic field.
• Diamagnetic metals: all electrons are paired → weak
repulsion from magnetic field.
• Opacity (do not allow light to pass)
• Free electrons in metals absorb and re-emit photons.
• This prevents transmission of visible light → making metals
opaque.
• Good conductors of heat & electricity
• Free-moving delocalized electrons carry charge (electricity)
and kinetic energy (heat).
• This is why metals are excellent conductors.
• Malleability (hammered into sheets)
• Metallic bonding is non-directional (electrons are shared in a
"sea").
• When hammered, layers of atoms slide without breaking
bonds.
• Ductility (drawn into wires)
• Same reason as malleability: metallic bonds hold atoms
together even when stretched → can be drawn into
wires.
• Sonority (produce ringing sound when struck)
• Strong metallic bonds allow vibrations to travel easily
through the lattice.
• This makes metals ring when struck.
• The nonmetals (yellow)
– Dull
– Bad conductor of heat and electricity
– Brittle solids at room temperature (bromine is the only liquid).
– Exist as solids (sulfur, phosphorus), liquids (bromine), or gases (oxygen, nitrogen, chlorine). Are
usually gases.
– Reactivity with Oxygen - Non-metals form acidic oxides (e.g., CO₂ → carbonic acid in water).
– Reactivity with Hydrogen –Form covalent hydrides (e.g., HCl, NH₃, CH₄).
– Reactivity with Acids –Non-metals usually do not react with acids.
– Reactivity with Metals – )Non-metals form ionic compounds with metals (e.g., NaCl).
– Electronegativity – )Non-metals have high electronegativity (tendency to gain electrons).
– Opacity ( –Some non-metals are transparent (like diamond, iodine crystals).
Reasons for the Properties of Non-Metals

• Dull appearance
– Non-metals lack free-moving delocalized electrons like metals.
– Without metallic bonding, they do not reflect light effectively,
hence appear dull.
• Bad conductors of heat and electricity
– In non-metals, electrons are tightly bound in covalent bonds or
localized.
– Since free electrons or ions are absent, they cannot carry charge
or heat → hence insulators.
• Brittle solids at room temperature
• Non-metallic solids (like sulfur, phosphorus) are held by
weak van der Waals forces or directional covalent
bonds.
• These bonds break easily under stress, making them
brittle (shatter instead of bending).
• Exception: Diamond is hard due to a 3D covalent
network.
• Existence in all three states of matter
• Non-metals have low melting and boiling points (due to weak intermolecular
forces).
• Some exist as gases (O₂, N₂, Cl₂), one as liquid (Br₂), and some as solids (S, P,
I₂).
• Reactivity with oxygen (acidic oxides)
• Non-metals are electron acceptors.
• When combined with oxygen, they form non-metal oxides that dissolve in
water to give acids.
• Example:𝐶𝑂2+𝐻2𝑂→𝐻2𝐶𝑂3
• Reactivity with hydrogen (covalent hydrides)
• Non-metals share electrons with hydrogen due to their high
electronegativity, forming covalent bonds.
• Example: HCl, NH₃, CH₄.
• Reactivity with acids
• Acids release H⁺ ions, and only metals can displace H₂ gas by
donating electrons.
• Non-metals cannot donate electrons easily → hence no
reaction with acids.
• Reactivity with metals (ionic compounds)
• Non-metals (high electronegativity) readily gain electrons
from metals (low electronegativity).
• This forms ionic compounds (e.g., Na⁺Cl⁻).
• High electronegativity
• Non-metals have a small atomic size and a large nuclear
charge relative to their size.
• This makes them strongly attract electrons.
• Opacity / Transparency
• Some non-metals (like diamond or iodine crystals)
have regular atomic structures that allow partial
transmission of light, making them transparent.
• Others have irregular bonding, scattering light →
appearing opaque or dull.
• The Metalloids
– Properties between metals and non-metals
Classification of Elements
into sub-categories
• Blocks
• Alkali metals
• Alkaline metals
• Halogen
• The Noble gases
• Representative elements
• Rare Earth elements.
• Noble Metals
• Semiconductors.
• Conductors
• Insulators
• Transition Elements
Blocks in Periodic Table
S-Block

• Groups: 1 and 2 (Alkali metals & Alkaline earth

metals) + Hydrogen & Helium
• Last electron enters: s-orbital
• General properties: Highly reactive metals, soft, low
ionization energy, form ionic compounds.
P-Block

• Groups: 13 to 18
• Last electron enters: p-orbital
• ns2-np1 to ns2-np6
• General properties: Contains metals, metalloids, and
non-metals; wide variation in properties.
d-block

• Groups: 3 to 12 (OuterTransition metals)

• Last electron enters: d-orbital
• ns(n-1)d orbital
• General properties: Hard, dense metals, good
conductors, variable oxidation states, form colored
compounds.
F-Blocks

• Inner Transition
• (n-2)f orbital
• Placed separately (Lanthanides & Actinides)
• Last electron enters: f-orbital
• General properties: Mostly metals, many are radioactive,
and show complex chemical behavior.
• Examples: Ce, U, Th
 IA Alkali Metals
(Li, Na, K, Rb, Cs, Fr)
• ns¹ (only one electron in outermost shell).
• S-block
• Readily lose their outermost electron to form cations with charge +1.
• They are soft and can all be cut easily with a knife.
• Exposing a shiny surface that tarnishes rapidly in air due to oxidation by atmospheric moisture
and oxygen.
• Because of their high reactivity, they must be stored under oil to prevent reaction with air, And
are found naturally only in salts and never as the free elements.
• Cesium, the fifth alkali metal, is the most reactive of all the metals.
• All the alkali metals Highly reactive (especially with water), producing hydrogen gas and
strong alkalis, with the heavier alkali metals reacting more vigorously than the lighter ones.
• Form strongly basic oxides & hydroxides (e.g., NaOH, KOH – very soluble).
IIA Alkaline Metals
• Beryllium (Be), Magnesium (Mg), Calcium (Ca), Strontium (Sr), Barium (Ba),
and Radium (Ra).
• S-block
• ns² (two electrons in outermost shell).
• Readily lose to form cations with charge +2, and an oxidation state of +2
• Less reactive than alkali metals; reactivity increases down the group.
• Are slightly hard and High Melting point.
• All shiny, silvery-white
• Also not found free, but present in minerals (CaCO₃, MgCO₃, gypsum
CaSO₄·2H₂O).
• Oxides & hydroxides are less basic and less soluble (e.g., Mg(OH)₂ – sparingly
soluble).
Halogen (VIIA / 17A)

– (F, Cl, Br, I, At, Ts) = Astatine and Tennessine

– ns² np⁵
– Outer shell has 7 electrons, so they need 1 electron to
complete octet.
– Common valency = (-1) (by gaining one electron).
– Highly reactive non-metals.
– Ability to gain an electron from an anion, oxidation number (-
1).
– Highly reactive non-metals.Reactivity order: F > Cl > Br > I
> At(decreases down the group due to increasing atomic size).
• Melting/boiling point increases down the group.
• Electronegativity decreases down the group (F is most
electronegative element).
Chemical Properties
• Oxidizing nature: Strong oxidizing agents (F₂ strongest).
• Hydrides: Form hydrogen halides (HF, HCl, HBr, HI) – acidic in water.
• Salts (Halides): React with metals to form salts like NaCl, KBr, CaF₂.
• Displacement reactions: A more reactive halogen displaces a less
reactive one from its compound (e.g., Cl₂ displaces Br⁻ from NaBr).
Occurrence
• Not found free in nature (too reactive).
• Found as salts/minerals: NaCl (rock salt), KCl, CaF₂ (fluorspar), NaBr,
AgI, etc.
Uses
• Fluorine → Teflon, toothpaste (fluorides), nuclear fuel (UF₆).
• Chlorine → Disinfectant, PVC, bleaching powder.
• Bromine → Dyes, fire retardants, photography.
• Iodine → Antiseptic, nutrition (thyroid hormone).
 Noble gases group (VIIIA / 18A)
– He(2), Ne(10), Ar(18), Kr(36), Xe(54), Ra(86) radioactive, Og (oganesson 118) artificial, highly unstable.
• Properties
❑ Zero group.
❑ Colorless, odorless, tasteless gases.
❑ Very low chemical reactivity due to complete valence shell.
❑ Low boiling and melting points.
❑ Exist as monoatomic gases (single atoms).
❑ Non-flammable.
❑ Non-magnetic
❑ The Electronic arrangement of ns2, np6 is exceptionally stable. Discontinuities in the energy level
diagram occur after these configurations are attained. (means atoms with a full outer shell (ns², np⁶)
are highly stable, and this stability shows up as sudden jumps or breaks in the ionization energy
patterns of the periodic table. These discontinuities highlight the special stability of noble gas
configurations.)
Diamagnetism is considered as non magnetic materials.
Paramagnetism a very weak form of magnetism that is nonpermanent and persists only while an external field is being
applied.
Ferromagnetism Certain metallic materials possess a permanent magnetic moment in the absence of an external field
and manifest very large and permanent magnetizations. These are the characteristics of ferromagnetism,
Antiferromagnetism
Magnetic moment coupling between adjacent atoms or ions also occurs in materials other than those that are
ferromagnetic. In one such group, this coupling results in an antiparallel alignment; the alignment of the spin moments
of neighboring atoms or ions in exactly opposite directions is termed antiferromagnetism. Like ceramics materials.
Antiferromagnetic ≠ Diamagnetic
They are magnetic in nature internally, but with zero net magnetism externally.
Ferrimagnetism
Some ceramics also exhibit a permanent magnetization, termed ferrimagnetism. The macroscopic magnetic
characteristics of ferromagnets and ferrimagnets are similar; the distinction lies in the source of the net magnetic
moments.
Rare Earth Elements

• There is a set of 17 nearly indistinguishable lustrous silvery-white soft heavy metals

• Scandium and yttrium are considered rare-earth elements because they tend to occur in the
same ore deposits as the lanthanides and exhibit similar chemical properties, but have
different electronic and magnetic properties
• The term 'rare-earth' is a misnomer because they are not actually scarce,
• Though rare-earth elements are technically relatively plentiful in the entire Earth's
crust (cerium being the 25th-most-abundant element at 68 parts per million, more abundant
than copper), in practice this is spread thin across trace impurities, so to obtain rare earths
at usable purity requires processing enormous amounts of raw ore at great expense, thus
the name "rare" earths.
 Rare Earth Elements
S.No Atomic No: Symbol Name
• Because of 1 21 Sc Scandium
their geochemical properties 2 39 Y Yttirium
3 57 La Lanthanum
, rare-earth elements are 4 58 Ce Cerium
typically dispersed and not 5 59 Pr Praseodymium
6 60 Nd Neodymium
often found concentrated 7 61 Pm Promethum
in rare-earth minerals. 8 62 Sm Samarium
Consequently, economically 9
10
63
64
Eu
Gd
Europium
Gadolinium
exploitable ore deposits are 11 65 Tb Terbium
sparse. 12 66 Dy Dysprosium
13 67 Ho Holmium
14 68 Er Erbium
15 69 Th Tholium
16 70 Yb Ytterbium
17 71 Lu Lutetium
Noble Metals

Dr. Abdul Jaleel

 Noble metals:

1. Gold (Au)
2. Iridium (Ir),
3. Osmium (Os)
4. Palladium (Pd),
5. Platinum (Pt),
6. Rhodium (Rh),
7. Ruthenium (Ru),
8. Silver (Ag),
Except Ag and Au, the others are collectively called platinum metals
Properties

• Geochemical
• The noble metals are siderophiles (iron-lovers).
• Most siderophile elements have practically no affinity whatsoever for oxygen:
indeed, oxides of gold are thermodynamically unstable with respect to the
elements.
• Electrochemical
• Nobles metals have high +ve electrode potential and are disinclined to react
with oxygen and, for that reason (as well as their scarcity) have been valued
for millennia, and used in jewelry and coins.[14]
• Corrosion resistance
Due to the following reasons:
1. Formation of Stable Oxide Layer (Passive Film):
• very quickly react with oxygen in air or water to form a thin, adherent, and stable
oxide layer (e.g., CeO₂, La₂O₃).
• This oxide film is dense and protective, preventing further attack of oxygen, water,
or acids on the underlying metal.
• Similar to how aluminum forms Al₂O₃ and becomes corrosion-resistant.
• High Thermodynamic Stability of Oxides
• REE oxides have very negative Gibbs free energies of formation (ΔG°).
• This means once the oxide forms, it is very stable and does not easily decompose back to
metal + oxygen.
• Low Reactivity in Mild Environments: due to the oxide layer.
• Addition in Alloys for Corrosion Resistance
• Rare earth elements are often added in small amounts to steels, aluminum alloys, and
magnesium alloys.
• They improve corrosion resistance by refining grain size, removing impurities (like sulfur
and oxygen), and forming protective rare-earth oxides/sulfides.
 Electrochemical

▪ Electronegativity is included since it is reckoned to be "a major driver of metal

nobleness and reactivity".
▪ On account of their high electron affinity values, the incorporation of a noble
metal in the electrochemical photolysis process, such as platinum and gold,
among others, can increase photoactivity.
▪ Noble metals act as a cathode in water splitting applications to produce H2 and O2 in
100% pure form. By matching the electrode potential with water.
▪ ...The...metal with...a potential less than 0.4 V acts as an anode...loses
electrons...and dissolves in the aqueous medium. The noble metal (with a
higher electrochemical potential) acts as a cathode.
 Catalytic properties

▪ Platinum is used in catalytic

converters, devices which Hydrogenation is a chemical reaction between
convert toxic gases molecular hydrogen (H2) and another compound or element, usually
produced in car engines, in the presence of a catalyst such as nickel, palladium or platinum.
1. Hydrogenation of Unsaturated Hydrocarbons (alkenes/alkynes):
such as the oxides of Double or triple bonds are converted into single bonds.
nitrogen, into non-polluting Example: (Ethene → Ethane)
substances. And in the 2. Hydrogenation in Food Industry:
water splitting application Used to convert vegetable oils (liquid) into margarine or ghee
(solid/semi-solid) by adding hydrogen across C=C bonds.
▪ Gold has many industrial
applications; it is used as a The water–gas shift reaction (WGSR) describes the reaction
catalyst of carbon monoxide and water vapor to form carbon
in hydrogenation and dioxide and hydrogen:
the water gas shift reaction. CO + H2O ⇌ CO2 + H2
How is platinum used in catalytic converters, devices that convert toxic
gases produced in car engines, such as oxides of nitrogen, into non-
polluting substances?

1. Reduction of Nitrogen Oxides (NO and NO₂):

• Platinum, along with rhodium (Rh), facilitates the
breakdown of nitrogen oxides into nitrogen (N₂) and
oxygen (O₂).
• Reaction:
2. Oxidation of Carbon Monoxide (CO):
• Platinum helps oxidize poisonous carbon monoxide
into non-toxic carbon dioxide.
• Reaction:
3. Oxidation of Unburnt Hydrocarbons (HCs):
• Platinum (often with palladium, Pd) converts unburnt
hydrocarbons from fuel into carbon dioxide and
water.
• Reaction:
 Properties vary from left to right and top to
bottom.

• Periods
• Vertical columns are called periods. There are 7 periods.
• Elements in a period have different chemical properties.
• Groups
• In general, elements in a group have similar chemical properties.
• All the metals in the periodic table are classified into different
groups, namely, alkali metals, alkaline earth metals, noble gases,
and transition metals
Elements Properties vary from
left to right and top to bottom.

Group Trends in the Periodic Table

When you move down a group (top → bottom) in the
periodic table, elements show systematic changes in their
physical and chemical properties due to:
• Increase in atomic number
• Addition of new electron shells
• Changes in shielding effect and nuclear attraction
1. Atomic Radius
• Trend: Increases down a group.
• Reason: New electron shells are added, increasing the
distance between nucleus and valence electrons, despite
increased nuclear charge.
2. Ionization Energy (energy required to remove an electron)
• Trend: Decreases down a group.
• Reason: Outer electrons are farther from the nucleus and
more shielded, so they are easier to remove.
3. Electronegativity (ability to attract electrons in a bond)
Trend: Decreases down a group.
Reason: Larger atomic size reduces nucleus’ pull on bonding electrons.
4. Electron Affinity (energy released when atom gains an electron)
Trend: Generally becomes less negative down a group.
Reason: Larger atoms have less effective attraction for an added
electron.
(Exception: Halogens still have high negative values due to their strong
tendency to complete octet.)
5. Metallic Character
• Trend: Increases down a group.
• Reason: Easier loss of electrons (low ionization energy).
• Example: In Group 1, Li → Na → K → Rb → Cs → Fr becomes more metallic.
6. Melting and Boiling Points
• Trend: Depends on group.
– Alkali metals (Group 1): Decrease down the group.
– Halogens (Group 17): Increase down the group (due to stronger van der
Waals forces with larger size).
7. Density
• Trend: Generally increases down a group (due to increase in
mass being greater than increase in volume).
• (Exceptions exist, e.g., K is less dense than Na.)
8. Oxidizing and Reducing Power
Alkali Metals (Group 1): Reducing power increases down the
group.
Halogens (Group 17): Oxidizing power decreases down the
group.
Z effective
( Effective Nuclear Charge, Zeff)

Dr. Abdul jaleel

• Z effective (also called effective nuclear charge, 𝑍eff )
Refers to the net positive charge experienced by an electron in a multi-electron atom.
It is a measure of how strongly the nucleus attracts a particular electron, considering the
repulsive effects of other electrons in the atom.
• Concept:
• In an atom with multiple electrons, each electron experiences two main forces:
1. Attraction to the positively charged nucleus (due to protons).
2. Repulsion from other electrons, which are negatively charged.
• The repulsive force from other electrons reduces the overall attraction felt by any single
electron toward the nucleus. This reduced attraction is quantified by the effective nuclear
charge.
Calculation:

The effective nuclear charge 𝑍eff​ can be approximated using the formula:
𝑍eff=𝑍−𝜎 :
Z= The actual nuclear charge, which is the number of protons in the
nucleus (equal to the atomic number).
σ: The shielding constant, which represents the degree to which inner
electrons shield the outer electrons from the full nuclear charge.
• Inner electrons reduce the full nuclear charge felt by outer electrons.
The closer an electron is to the nucleus, the less it is shielded by other
electrons, meaning it experiences a higher effective nuclear charge.
Example

• For a simple atom like sodium (Na), with an atomic number of 11:The
full nuclear charge 𝑍 is 11 (since there are 11 protons in the
nucleus).If an electron in the outer shell (3s electron) is being
considered, the inner electrons (from the 1s and 2s/2p shells) will
shield some of the nuclear charge. Suppose the shielding constant σ
is around 10 for this electron. Then:𝑍eff≈11−10=1
• Z eff​ ≈11−10=1
• This means that the outer electron in sodium "feels" an effective
nuclear charge of +1 rather than the full +11 charge.
Factors Affecting 𝑍eff​ :

1. Shielding (or Screening):

• Inner electrons shield outer electrons from the nucleus, reducing the
effective charge felt by the outer electrons.
• Electrons in the same shell contribute less to shielding compared to
electrons in inner shells.
•Penetration:
•Electrons in orbitals closer to the nucleus (like s-orbitals) experience less shielding
and feel a higher effective nuclear charge than electrons in outer orbitals (like p- or d-
orbitals).
•Orbital Type:
•s-orbitals penetrate the electron cloud more deeply than p, d, or f orbitals, meaning
electrons in s-orbitals experience a higher effective nuclear charge.
Periodic Trends:

• Across a period (left to right in the periodic table), Zeff

increases because more protons are added to the nucleus
without a significant increase in shielding (as electrons are
added to the same shell).
• Down a group (top to bottom), 𝑍eff increases slightly, but
the shielding effect becomes more significant due to the
increasing number of electron shells, so outer electrons
experience less attraction to the nucleus.
Importance of 𝑍eff:

1. Atomic Size: As 𝑍eff​ increases, electrons are pulled closer to the nucleus, reducing the
atomic radius.
2. Ionization Energy: Higher 𝑍eff​ means electrons are held more tightly, leading to
higher ionization energy (the energy required to remove an electron).
3. Electronegativity: Elements with higher 𝑍eff​ tend to attract electrons more strongly,
increasing electronegativity.
4. Electron Affinity: A higher 𝑍eff​ means the atom can more easily attract and add an
electron.
In summary, Z effective reflects the reduced nuclear charge felt by an electron due to the
presence of other electrons. It helps explain trends in atomic properties like size, ionization
energy, and electronegativity.
Conductor,
Semiconductor
and
Insulator
Dr. Abdul Jaleel Laghari
Semiconductors

• When a solid conducts electricity > 107 (Ώm)-1 , called conductor such
as, Ag and Cu etc.
• Low conductivity range between 10-10 to 10-20 (Ώm)-1 are called
insulators, such as wood, diamond, plastic etc.
• Intermediate range between 10-8 to 104 (Ώm)-1 are called
semiconductors such as Si (Z=14) and Ge (Z=32).
 Energy Band Theory

• Between two atoms that are bonded to make a solid, a discrete energy
band is called the forbidden energy gap.
• Every atom has electrons and contains a valence shell called the valence
band energy. It may be filled or partially filled, but will never be empty.
• The band above the valence band is the conduction band.
(In the conduction band, electrons can move freely and conduct electricity in a
solid).
• An electron leaving the valence band then occupies the conduction band. It
may be partially filled with electrons or may be empty.
 Energy Band Theory

Insulator

Conductor Semi conductor

Intrinsic and Extrinsic semiconductor

• A semi conductor is in pure form is known as intrinsic.

• The doped semiconductor is called extrinsic semiconductor.
• Pure elements of silicon and germanium, are intrinsic semiconductors.
• These Si, and Ge have four valence electrons.
• In solid crystalline form, the atoms of these elements arrange themselves in
a such pattern that each atom has four equidistant neighbors.
• This effectively allocates eight electrons in the outermost shell of each atom
which is a stable state.
• This sharing of electrons between atoms create covalent bond.
 n and P semiconductors

• When a pentavalent element (15A group) such as Phosphorous

(P), Arsenic (As), Antimony (Sb), etc., is doped in a Silicon crystal,
then an n-type free electron semiconductor is generated.
• These pentavalent atoms are donor atoms because they donate
electrons and create free electrons.
• When a Si crystal is doped with trivalent elements (Group IIIA)
such as: aluminum, boron, gallium, or indium, etc., it creates a
hole; it is called P-type semiconductor.
• Three valence electrons of the impurity atom form a covalent
bond with the three neighboring Si atoms, while one missing
electron in a covalent bond with the fourth neighboring Si atom
is called a hole. So trivalent are called acceptors of electrons.
• Best dopants for n-type semiconductors:
Phosphorus (P), Arsenic (As), and Antimony (Sb).
• Not used:
Nitrogen → too small, too electronegative, deep donor
level.
Bismuth → too large, low solubility, causes lattice defects.
1. Nitrogen (N)
• Too small atomic size:
Nitrogen is much smaller than silicon (Si) or germanium (Ge). Substituting nitrogen into the
crystal lattice causes severe lattice distortion and strain, making it unstable.
• Very high electronegativity:
Nitrogen strongly attracts electrons, so instead of donating a free electron, it tends to hold
onto its valence electrons tightly.
• Deep energy level:
If nitrogen is added, the extra electron lies too deep in the band gap (far from the
conduction band). It cannot be easily excited into the conduction band at room
temperature → hence, not an effective donor impurity.
2. Bismuth (Bi)
• Too large atomic size:
Bismuth is much bigger than Si or Ge atoms. If it replaces a silicon atom, it
causes severe lattice distortion and defects, reducing crystal quality.
• Poor solubility:
Bi does not easily dissolve or substitute uniformly into the Si/Ge lattice. It tends
to segregate instead of forming substitutional dopant atoms.
• Shallow donor inefficiency:
Although Bi has 5 valence electrons, its extra electron is not efficiently donated
because the mismatch in orbital energy levels prevents effective band alignment
with the semiconductor conduction band.
Nitrogen’s deep energy level problem in
semiconductors:
1. What is a donor level?
• When we dope a semiconductor (like Si or Ge) with a
pentavalent atom (P, As, Sb), the 5th electron is only loosely
bound.
• This creates an energy level (donor level) very close to the
conduction band (only ~0.01 eV below it).
• At room temperature, thermal energy (~0.025 eV) is enough
to excite that electron into the conduction band → free
electron conduction.
2. What happens with Nitrogen (N)?
•Nitrogen has very high electronegativity (3.04 on Pauling scale,
much higher than Si = 1.9).
•When nitrogen substitutes into the silicon lattice, it strongly
binds its extra electron instead of leaving it loosely bound.
•The donor energy level formed by nitrogen lies deep inside the
band gap, much farther from the conduction band (often >0.1
eV).
3. Meaning of "Deep Level"
•Shallow donor: P, As, Sb → donor level very close (few meV) below
conduction band → electrons easily thermally excited at room
temperature.
•Deep donor: N → donor level far below conduction band (hundreds of
meV) → requires much higher energy (UV light or high temperature) to
excite electrons.
At room temperature, thermal energy (~0.025 eV) is not sufficient to
excite nitrogen’s electron into the conduction band.
→ That’s why nitrogen does not contribute free electrons effectively,
making it a poor n-type dopant.
4. Analogy
Think of the conduction band as the roof of a building and donor levels as
steps that help electrons climb onto the roof:
•P, As, Sb = shallow step (almost touching the roof). Electrons easily hop
onto the roof (conduction band).
•N = deep step far below the roof. Electrons are stuck far down and
cannot jump up with normal room-temperature energy.
Electrical conduction by Electrons and Holes in
Semiconductor
Superconductor

• Some materials their resistivity

becomes zero at certain temperature Tc
called critical temperature. Below this
temperature materials becomes
superconductor.
P-n junction
• Due to charge on these ions a
potential difference develop
across the depletion region.

• Its value is 0.7V for Si and 0.3 V in

case of Ge.
Forward biased p-n junction diode
• When a P-N junction is in forward bias, an external voltage is applied in
such a way that it allows current to flow through the junction. Here’s how
forward bias works and some of its applications:
• Threshold Voltage
• For current to flow, the external voltage must exceed the threshold voltage
(also called cut-in voltage). This is the minimum voltage required to
overcome the potential barrier of the depletion region.
• For silicon diodes, this threshold voltage is typically around 0.7 V, and for
germanium diodes, it's about 0.3 V.
Applications of Forward Bias in Devices:

1. Diodes
• In forward bias, diodes conduct electricity, allowing current to pass
through. This is used in applications like:
• Rectifiers: (AC into DC)
• LEDs (Light Emitting Diodes):
2. Transistors
3. Solar Cells
4. Zener Diodes (at lower voltages)
5. Photodiodes (in photoconductive mode)
Reverse Biased P-n junction diode
•This causes the depletion region to become wider, making it more difficult for charge
carriers to move across the junction.
•As a result, very little current flows—only a small leakage current called reverse
saturation current (due to minority charge carriers.
• Summary of Reverse Bias Applications:
• Zener diodes for voltage regulation.
• Photodiodes for light detection.
• Varactor diodes for variable capacitance.
• Transistor operation in the reverse-biased base-collector junction.
• Avalanche diodes for high-voltage applications.
• PIN diodes for RF signal switching and attenuation.
 Semiconductor diode uses

• Conversion of alternating current

into direct current and vice versa.
• Light emitting diode (LED).
• Photo diode Optical transmitters are devices that generate and
– Detection of visible and invisible radiation.modulate light signals, often using lasers or light-
emitting diodes (LEDs). They convert the electrical
– Automatic switching signals into optical signals that can be transmitted
– Logic circuit through fiber optic cables. Optical receivers, on
the other hand, receive the optical signals and
– Optical communication equipment. convert them back into electrical signals for
further processing.
Transistor

• Transistor as an amplifier
• Transistor as a switch
MATERIAL
CHEMISTRY
Transition Elements

Dr. Abdul jaleel

Lecturer
Department of Metallurgy and Materials
Transition Elements / Metals

❖That have valence electrons—i.e., electrons that

can participate in the formation of chemical
bonds—in two shells instead of only one.
❖They occupy the middle portions of the long
periods of the periodic table, Groups 3 (IIIb)
through 12 (IIb).
✓all metals and that most of them are hard, strong, and
lustrous, have high melting and boiling points, and are
good conductors of heat and electricity.
 Importance
❖Many of the elements are technologically important:
1. Titanium, Iron, Nickel, and Copper, and Cobalt for
example, are used structurally and in electrical
technology.
2. Second, the transition metals form many useful alloys,
with one another and with other metallic elements.
3. Third, most of these elements dissolve in mineral acids,
although a few, such as platinum, silver, and gold, are
called “noble”—that is, are unaffected by simple
(nonoxidizing) acids.
Classification
❖ The transition metals may be subdivided according to the electronic
structures of their atoms into three main transition series, called the first,
second, and third transition series, and two inner transition series, called
the lanthanoids and the actinoids.
1. The first main transition series begins with either scandium (symbol
Sc, atomic number 21) or titanium (symbol Ti, atomic number 22) and
ends with zinc (symbol Zn, atomic number 30).
2. The second series includes the elements yttrium (symbol Y, atomic
number 39) to cadmium (symbol Cd, atomic number 48).
3. The third series extends from lanthanum (symbol La, atomic number
57) to mercury (symbol Hg, atomic number 80).
❖The transition elements (transition
metals) make up the d block (B groups) and f
block (inner transition elements) (Figure
22.1) and have crucial uses in industry and
biology.
 Examples and Uses

• Some indispensable transition elements

are iron (steel), copper (wiring),
chromium (plumbing fixtures), gold
and silver (jewelry and electronics), Steel Copper Chromium Plumbing
platinum (catalytic converters),
titanium (bicycle and aircraft parts),
nickel (coins and catalysts), and zinc
(batteries), to mention a few of the
Gold
better known ones.
• There are also the lesser known
zirconium (nuclear-reactor liners),
vanadium (axles and crankshafts), Axle

molybdenum (boiler plates), tantalum

(organ-replacement parts), palladium
(telephone-relay contacts)—the list Crankshafts
goes on and on. As ions, quite a few of
these elements also play vital roles in
organisms.
Properties of t he Transition Elements

•The transition elements differ considerably in physical and

chemical behavior from the main-group elements:
• All transition elements are metals, whereas main-group elements
in each period change from metal to nonmetal.
• Many transition metal compounds are colored and
paramagnetic, whereas most main group ionic compounds are
colorless and diamagnetic
Electronic Configuration
 Electron Configurations
of the Transition Metals
and Their Ions
• As Figure 22.1 shows (slide-5), d-block (B-group) elements occur in four series that lie within Periods 4
through 7.
• Each series represents the filling of five d orbitals.
• Lying between the first and second members of the series in Periods 6 and 7 are the inner transition elements,
in which f orbitals are filled.
• Two points are important to review:
1. Electron configurations of the atoms.
• Despite several exceptions, in general, the condensed ground-state electron configuration for the atoms in each
d-block series is
– [noble gas] ns2 (n-1) dx, with n=4 to 7 and x=1 to 10
• In Periods 6 and 7, the condensed configuration includes the f sublevel:
– [noble gas] ns2(n-2)f14 (n-1)dx, with n= 6 or 7
• The partial (valence-level) electron configuration for the d-block elements excludes the noble gas core and the
filled inner f sublevel:
– ns2(n-1)dx
2. Electron configurations of the ions.
• Transition metal ions form through the loss of ns electrons before (n-1)d electrons.
Thus, the electron configuration of Ti2+ is [Ar] 3d2, not [Ar] 4s2, and Ti2+ is referred
to as a d2 ion.
• Ions of different metals with the same configuration often have similar properties:
for example, both Mn2+ and Fe3+ (d5 ions) have pale colors in solution and form
complex ions with similar magnetic properties.
• As we would expect, it is the electron configuration of the transition metal atom that
correlates with the properties of the element, such as density and magnetic behavior,
whereas it is the electron configuration of the ion that correlates with the color and
magnetic properties of the compounds.
Atomic and Physical Properties
of the Transition Elements

• Properties of the transition elements contrast in several ways with properties of the main-group elements
 Chemical Properties
of the Transition Elements

• Multiple Oxidation States One of the most characteristic chemical

properties of the transition metals is the occurrence of multiple
oxidation states; main-group metals, display one or, at most, two
states. For example, vanadium has two common oxidation states,
chromium and manganese have three (Figure 22.5A).

• Since the ns and (n-1)d electrons are so close in energy and energy difference between them
is small, as a result electrons of 3d as well as 4s take part in the bond formation.
• The +2 oxidation state is common because ns2 electrons are readily lost.
• The elements exhibit less metallic behavior in their higher states of oxidation states.
• Metallic Behavior and Oxide Acidity. Atomic size and oxidation state have a
major effect on the nature of bonding in transition metal compounds. ionic
bonding is more prevalent for the lower oxidation states, and covalent bonding is
more prevalent for the higher states. For example, at room temperature, TiCl2
(O.N. of Ti =+2) is an IONIC SOLID, whereas TiCl4 (O.N. of T=+4) is a
molecular liquid COVALENT BOND.
• In the higher oxidation states, the atoms have higher charge densities, so they
polarize the electron clouds of the nonmetal ions more strongly and the bonding
becomes more covalent. For the same reason, the oxides become less basic as the
oxidation state increases: TiO is weakly basic in water, whereas TiO2 is
amphoteric (reacts with both acid and base).
Why ionic bonding is more prevalent for the
lower oxidation states
• This is because on increasing oxidation state of a cation it's size
decreases and hence its polarizing power increases. According to
Fajan's rule smaller is the size of cation greater will be its polarizing
power and hence greater will be its covalent character.
• To form an ionic bond, the neutral atoms need to lose or gain
electrons - this change in the electronic state is not notional but real;
this is where ionization enthalpy or electron gain enthalpy come into
the picture; losing more than two electrons is very difficult (needs
lots of energy) and similarly gaining more than two electrons is also
very difficult; which is why ionic bonds are formed at lower oxidation
states (between -2 to +2);
Why ionic bonding is more prevalent for the
lower oxidation states
• higher oxidation state means more positive charge density over the atom
and hence smaller size.
• the combined effect-high charge and smaller size tends to exert more electric
field in its vicinity hence bringing more closer the electron cloud of the
surrounding atom and hence resulting into increased covalent character in
the bond since covalent bond is all about sharing of bonding electrons
• the said so is commonly stated as principles of Fajan wherein the central
atom is said to as become a more polarizing atom in its higher oxidation state
and hence increasing the covalent character in the bond.
• Reducing Strength, Table 22.3 shows the standard
electrode potentials of the Period 4 transition metals in
their +2 oxidation state in acid solution. Note that, in
general, reducing strength decreases across the series. All
the Period 4 transition metals, except copper, are active
enough to reduce H+ from aqueous acid to form hydrogen
gas. In contrast to the rapid reaction at room temperature
of the Group 1A(1) and 2A(2) metals with water, however,
most transition metals have an oxide coating that allows
rapid reaction only with hot water or steam.
• Color and Magnetism of Compounds: Most main-group
ionic compounds are Colorless because the metal ion has a
filled outer level (ns2 or ns2np6: noble gas electron
configuration). With only much higher energy orbitals
available to receive an excited electron, the ion does not
absorb visible light. In contrast, electrons in a partially filled
d sublevel can absorb visible wavelengths and move to
slightly higher energy orbitals. As a result, many transition
metal compounds have striking colors. Exceptions are the
compounds of scandium, titanium(IV), and zinc, which are
colorless because their metal ions have either an empty d
sublevel (Sc3+ or Ti4+: [Ar] 3d0 ) or a filled one (Zn2+: [Ar]
3d10) (Figure 22.6). Looking unpaired electron effect on
color.
Crystal field theory

• Crystal Field Theory (CFT) is a model that explains the

behavior of transition metal complexes, particularly how
the metal's d-orbitals are affected by the surrounding
ligands (ions or molecules that coordinate to the metal).
It is used to understand the color, magnetism, and
stability of these complexes by considering the
interaction between the metal's d-electrons and the
electric field created by the ligands.
CFT

• Key Concepts of Crystal Field Theory:

1. Metal-Ligand Interaction: In transition metal complexes, ligands (negatively
charged ions or neutral molecules) surround the central metal ion. These
ligands are treated as point charges, and they create an electric field (or
crystal field) around the metal ion. This field influences the energies of the d-
orbitals of the metal ion.
2. Splitting of d-Orbitals: In a free metal ion, the five d-orbitals (degenerate,
meaning they have the same energy) are symmetrically distributed. However,
when ligands approach the metal ion, they interact with the d-orbitals,
causing these orbitals to split into different energy levels. The way the d-
orbitals split depends on the geometry of the complex (e.g., octahedral,
tetrahedral, square planar).
CFT

• Octahedral Complex: In an octahedral field (where six ligands surround the

metal ion), the d-orbitals split into two sets:
• e𝑔​ (higher energy): 𝑑𝑧2 ​ and 𝑑𝑥2−𝑦2 ​ orbitals.
• t2𝑔 (lower energy): 𝑑𝑥𝑦, 𝑑𝑥𝑧​ , and 𝑑𝑦𝑧​ orbitals.
• The splitting energy is called Δ₀ (octahedral crystal field splitting energy).
• Tetrahedral Complex: In a tetrahedral field (where four ligands surround the
metal ion), the splitting is reversed compared to octahedral complexes, with
the e𝑔​ orbitals at lower energy and the t2𝑔 orbitals at higher energy.
• The splitting energy in tetrahedral fields is smaller and is denoted as Δₜ.
CFT

• High-Spin and Low-Spin Complexes:

• High-Spin Complex: In cases where the crystal field splitting energy
(Δ) is small, electrons tend to occupy higher energy orbitals to
minimize electron pairing. This leads to a complex with more
unpaired electrons and higher magnetic moment.
• Low-Spin Complex: If Δ is large, electrons prefer to pair up in the
lower energy orbitals, resulting in fewer unpaired electrons and a
lower magnetic moment.
• Whether a complex is high-spin or low-spin depends on both the
metal ion and the nature of the ligand.
CFT

• Color of Complexes: The color of transition metal complexes arises from the
absorption of light, which promotes an electron from a lower energy d-orbital to a
higher energy d-orbital. The energy difference (Δ) between these orbitals corresponds
to the wavelength of light absorbed, and the complementary color is observed. Strong
field ligands, which cause larger Δ values, typically lead to the absorption of shorter
wavelengths (higher energy light), whereas weak field ligands lead to the absorption of
longer wavelengths (lower energy light).
• Magnetic Properties: The number of unpaired electrons in a complex determines its
magnetic behavior. Complexes with unpaired electrons exhibit paramagnetism, while
those without unpaired electrons are diamagnetic. Crystal field splitting affects
whether electrons are paired or unpaired, influencing the complex's magnetic
properties.
CFT

• Applications of Crystal Field Theory:

• Explains Color: CFT helps explain why many transition metal complexes are colored
and how the color changes depending on the ligand and geometry.
• Predicts Magnetism: It allows for the prediction of the magnetic properties
(paramagnetic vs. diamagnetic) based on the electron configuration in the split d-
orbitals.
• Stability of Complexes: The magnitude of the crystal field splitting can also give insight
into the stability of complexes, especially when considering factors like the ligand's
field strength.
• In summary, Crystal Field Theory provides a model to explain the electronic structure
of transition metal complexes, focusing on how the arrangement of ligands influences
the energy levels of d-orbitals, and in turn, affects the complex’s color, magnetism, and
stability.
• Magnetic properties are also related to sublevel occupancy
(Section 8.5). Most main-group metal ions are diamagnetic for
the same reason they are colorless: all their electrons are paired.
• In contrast, many transition metal compounds are paramagnetic
because of their unpaired d-electrons.
• Offcourse, transition metal ions with a d0 or d10 configuration are
colorless and diamagnetic because all the electrons are paired.
• Fe, Co and Ni are ferromagnetic.
Catalytic Properties:-

• Catalysts accelerate the rate of reaction.

• These provides suitable surface area where gases are
absorbed.
• For example for water splitting Pt is used for hydrogen
evolution reaction, fast and at low voltage.
Interstitial (Non-Stoichiometric Compounds:-

• This non-stoichiometric / interstitial compound due

to variable oxidation state of d-block and also
presence of defects in solid structure.
• Examples are brass (Cu-Zn), bronze (Cu-Zn-Sn) etc.
Complex Formation/ C-ordinate compounds

• Due to small highly charged and vacant d-

orbitals of suitable energy.
• These vacant d-orbitals accept lone electron
pairs from atoms, ions or molecules called
ligands.
• example: ferrocyanide containing six cyanide
(CN-) ions donating their lone electron pair to
the central ferrous (Fe2+) ion.
Isomerisim in coordinate compounds
Theoretical Basis for t he Bonding
and Properties of Complexes

• On book and youtube

Transition Metal Complexes in Biological Systems
• Outer ns electrons are close in energy to the inner (n-1)d electrons, which allows transition elements to use several
different numbers of electrons in bonding. For this reason, transition elements have multiple oxidation states, in
which the lower states display more metallic behavior (ionic bonding and basic oxides). The compounds of ions with a
partially filled d sublevel are colored and paramagnetic. (Section 22.1)
• Many transition elements form coordination compounds, which consist of a complex ion and counter ions. A complex ion
has a central metal ion and surrounding molecular or anionic ligands. The number of ligands bonded to the metal ion
determines the shape of the complex ion. Different positions and bonding arrangements of ligands lead to various types of
isomerism. (Section 22.2)
• According to valence bond theory, the shapes of complex ions arise from hybridization of different combinations of (n-
1)d, ns, and np orbitals. (Section 22.3)
• According to crystal field theory, ligands approaching a metal ion split the energies of its d orbitals, creating two sets of
orbitals. Each type of ligand causes a characteristic difference (crystal field splitting energy, D) between the energies of the
two sets, which allows us to rank ligands in a spectrochemical series. The energy difference between the two sets of d
orbitals is related to the color of the compound. It also determines the electron occupancy of the two sets, which
influences the magnetic behavior of the compound. (Section 22.3)
THE END