SCH 400

LECTURE 2
Physical and chemical properties

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 Did you know that we use
Transition metals every day?
Lithium Ion Batteries
• Most lithium batteries (Li-ion) used in 3C (computer,
communication, consumer electronics) products use
cathodes of lithium materials, such as lithium cobalt
oxide (LiCoO2), lithium manganese oxide (LiMn2O4),
lithium nickel oxide (LiNiO2), or lithium iron
phosphate (LiFePO4).
• The anodes are generally made of carbon.
• Look out for the electrode half-reactions
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General
• Most d-block metals should, on thermodynamic
grounds, liberate H2 from acids but, in practice,
many do not since
• they are passivated by a thin surface coating of
oxide or
• by having a high dihydrogen overpotential, or
both.
• Hydrogen overvoltage may be defined as the
difference of potential that exists between a
reversible hydrogen electrode, and an electrode, in
the same solution, at which hydrogen, H2, is being
formed from hydrogen ions. 3
a) Atomic (covalent) radii
• Atoms of the transition elements are smaller than those of
Group 1 or 2 in the same period
Reason:
• Partly because of the usual contraction in size across a
horizontal period discussed, and
• Partly because the orbital electrons are added to the
penultimate d subshell instead of the outer shell of the atom

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20_435

Variations in Atomic radii

0.2
La
1st series (3d)
Y 2nd series (4d)
Hf 3rd series (5d)
Atomic radii (nm)

Zr
Sc Ta
Au
0.15 Nb W Ag
Mo Re Os
Ti Tc Ir Pt
Ru
V Rh Pd
Cr Fe Cu
Mn Co Ni

0.1
Atomic number 5
 Atomic Radii Trends in pm
Sc Ti V Cr Mn Fe Co Ni Cu Zn
144 132 122 118 117 117 116 115 117 125
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
162 145 134 130 127 125 125 128 134 148
La ** Hf Ta W Re Os Ir Pt Au Hg
169 144 134 130 128 126 127 130 134 149
• Across the series the radii generally decrease then increase
towards the end
• The observed increase in atomic radii at the end of each
series is attributed to increased electron-electron repulsion
between the electrons being paired in the d orbitals. 6
 Atomic Radii Trends
• Down the groups the atomic radii generally increase due to the
increase in the number of electron sub-shells. The increase is not
regular.
Examples:
• The elements in the first group show the expected increase in size
Sc → Y → La.
• Groups 4 – 12 there is an increase in radius of 10 to 20 pm between
the first and second member, but hardly any increase between the
second and third elements. This is attributed to
Lanthanide/lanthanoid contraction.

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 Lanthanide contraction
• The steady decrease in atomic radii
of the f-block lanthanide elements
between La and Hf (Z = 58 - 71).
• Caused by poor shielding of the
nucleus by 4f subshell electrons
• Wipes out expected increase in size
in third transition series
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 Effects of the Lanthanide contraction

1. The radii of the elements following the

lanthanides are smaller than would be
expected if there were no f-transition
metals.
2. Elements in 2nd and 3rd series have
similar sizes
• lattice energies, and solvation energies due to similar atomic and
ionic sizes.
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(b) Atomic volumes and Densities

• The atomic volumes of transition

elements are generally lower than those
of the elements of the s-block.
• Density and atomic volumes are inversely
proportional to each other. Thus, transition
metals have high densities (> 5 gcm-3 except
Sc 3.0 gcm-3 and Y and Ti 4.5 g cm-3).
• The densities increase across the periods. 11
 Trends in Densities
• The densities increase down the Groups.
• The densities of third transition series
elements are almost double those of the 2nd
series elements.
• This is because the atomic weights of the
elements of the 3rd series are also almost
double those of the 2nd transition series.
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Trends in Densities

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 c) Trends in Electronegativity
• Generally increase across the periods and down the
groups. Why?

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 15
Structures (at 298K), melting points(K) and values of standard enthalpies of atomization of metallic
elements
(d) Ionization energy /Potential
• The energy required to remove one mole of
electrons from one mole of isolated gaseous
atoms or ions, i.e. energy for the process;
Mn+ → M(n+1)+ + e- n = 0,1,…
n = 0 we have first ionization energy,
n = 1, 2nd ionization energy, etc.
Importance
It is an indicator of the reactivity of an element.
Elements with low ionization energy tend to be
reducing agents and vice versa.
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 Trends in First Ionization energy /Potential
• Across any series the values of the first ionization energies
increase gradually but the increase is not very regular.
• Reason: Zeff

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 First ionization energy trends

Sc Ti V Cr Mn Fe Co Ni Cu Zn
633.1 658.8 650.9 652.9 717.3 762.5 760.4 737.1 745.5 906.4
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
600 640.1 652.1 684.3 702 710.2 719.7 804.4 731.0 867.8
La Hf Ta W Re Os Ir Pt Au Hg
538.1 658.5 761 770 760 840 880 870 890.1 1007

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Q. Explain the variation in I.E across the series
• Across each series effective nuclear charge
increases. However, as the electron is added to
the (n-1)d subshell at each next element, the ns2
electrons are shielded more and more. The effect
of the increasing nuclear charge is opposed to
the additional screening effect of the nucleus and
consequently, the I.E. increase but quite slowly.
• Zn, Cd and Hg have the highest I.E in their respective
periods.
– Reason: extra stability associated with their completely
filled orbitals
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Q. Explain the variation in I.E. down the Groups

• Down the groups the trend is not regular.

• Between the first and the second series elements
the expected decrease in 1st I.E is observed. This is
attributed the increase in atomic sizes and
increased screening with increase in electron
shells.
• In the elements following La the I.E increase
instead of decreasing. These elements have smaller
than expected atomic radii due to lanthanide
contraction. 20
 (e) Melting and boiling points
• are both high in comparison to main group elements.
• This arises from strong metallic bonding in
transition metals which occurs due to
delocalization of electrons facilitated by the
availability of both d and s electrons.
• Zn, Cd and Hg have exceptionally low melting
points because the d shell is full and the d
electrons do not participate in metallic bonding.

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 Melting and boiling points of transition elements/oC
Sc Ti V Cr Mn Fe Co Ni Cu Zn
M.P 1539 1667 1915 1900 1244 1535 1495 1455 1083 419.5
B.P 2748 3285 3350 2690 2060 2750 3100 2920 2570 907
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
M.P 1530 1857 2468 1620 2200 2282 1960 1552 961 320.8
B.P 3264 4200 4758 4650 4567 (4050) 3760 2940 2155 765
La Hf Ta W Re Os Ir Pt Au Hg
M.P 920 2267 2980 3422 3180 3045 2443 1749 1064 -38.9
B.P 3240 4450 5534 5500 (5650) (5025) (4550) 4170 2808 357
• Along a given series the melting points increase with the
number of unpaired electrons in the valence shells.

• Down the groups MP are irregular due to the differences in 22

metallic structures the metals adopt. BP increase
 (f) Magnetic properties
• Compounds of TM with unpaired electrons
may be paramagnetic, ferromagnetic, or
antiferromagnetic.
• Those with paired electrons are classified as
diamagnetic.
• Paramagnetism originates from electron spins
and orbital motion, spin-spin, orbital-orbital
and spin-orbital interactions.
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 Paramagnetism
• Generally a property associated with individual
atoms/ions in compounds or complexes.
• Arises from unpaired electrons.
• The paramagnetism of a substance is expressed in
terms of its magnetic moment, m, and is measured in
Bohr magnetons (B.M).
Importance
It helps in distinguishing between low-spin and high-
spin octahedral complexes.
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Ferromagnetism
• a property of an aggregate of atoms or ions.
• a special case of paramagnetism in which the
moments on individual atoms become aligned and all
point in the same direction resulting in increased
magnetic susceptibility.
• Alignment occurs when materials are magnetized.
Example: Fe, Co and Ni can form permanent magnets
upon magnetization.

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Ferromagnetism

• CrO2 - it is used in data tape applications for

enterprise-class storage systems

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 Antiferromagnetism

• is also a property of an aggregate of atoms or

ions.
• arises by pairing the moments in adjacent
atoms which point in opposite directions. This
gives a magnetic moment less than would be
expected for an array of independent ions.

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 Antiferromagnetism

• occurs in several salts of Fe2+, Mn2+ and Gd3+.

Since ferromagnetism and antiferromagnetism

depend on orientation, they disappear on solution of
the material.

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 Ferrimagnetism
• Arises when the magnetic moments of the
atoms on different sublattices are opposed, as
in antiferromagnetism.
• In ferrimagnetic materials, the opposing
moments are unequal and a spontaneous
magnetization remains.
• This happens when the sublattices consist of
different materials or ions (such as Fe2+ and
Fe3+). 29
Examples of ferrimagnetic materials
• Ferrites (ceramic materials with Fe2O3 as their
principal component.)
• magnetic garnets (e.g. yttrium iron garnet),
• magnetite (iron(II,III) oxide; Fe3O4) and
• ferrites composed of iron oxides and other
elements such as aluminum, cobalt, nickel,
manganese and zinc.
• Ferrimagnetic materials are like ferromagnets in that
they hold a spontaneous magnetization below the
Curie temperature, and show no magnetic order (are
paramagnetic) above this temperature. 30
 Measurement of magnetic
susceptibilities
• Two methods are used:
1. the Faraday method using a small single crystal
and
2. the Gouy method using Gouy balance for larger
sample volumes.
• The volume susceptibility κ, is determined by
weighing a sample in and out of a magnetic field.
This is then used to calculate the molar susceptibility
M, the magnetic moment m, the total spin S, and
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eventually n the number of unpaired electrons
responsible for the paramagnetism.
 Gouy Balance

• Schematic diagram of the Gouy Balance

Magnetic susceptibility
• In the Gouy’s method of susceptibility measurement, the solid
sample in the form of a long cylinder (area of cross section A)
is hung from the pan of a balance and is placed such that one
end of the sample is between the pole-pieces of the magnet
(field H ) and the other one is outside the field. The force
exerted on the sample by the inhomogeneous magnetic field
is obtained by measuring the apparent change (Dm) in the
mass of the sample.

• The susceptibility  is given by  = 2Dm g/AH2

• If the sample is in the form of powder, it is filled in a long

nonmagnetic tube which is then suspended from the pan of
the balance.
Schematic Diagram of Gouy’s Balance
• Indicates the degree of
magnetization of a
material in response to
an applied magnetic field.
• Paramagnetic materials will weigh more in a
magnetic field being attracted by the same but
diamagnetic materials will be repelled by the
magnetic field and hence weigh less in the field.

• The information obtained from the magnetic

moment of a transition metal compound
a) Number of unpaired electrons in an atoms/ions
b) The orbitals occupied
c) Sometimes the structure of the complex or
molecule.
Calculation of magnetic moments

• If the magnetic moment is entirely due to the spin of

unpaired electron ms, then it is given in Bohr
magnetons by the equation:

μ s  2 S(S  1) B.M
where S is the total spin quantum number.
It is also related to the number of unpaired electrons,
n, by
μ s  n(n  2) B.M 36
 • When magnetism arises from both electron
spin as well as orbital angular momentum,
them the magnetic moment is given by:

μ S L  4 S(S  1)  L( L  1) .μ B

where S is the total of the spin quantum numbers, and L

is the resultant of the orbital angular momentum
quantum numbers of all the electrons in the molecule 37
• In many compounds of the first transition
series elements, the orbital contribution is
quenched by the electric fields of the
surrounding atoms.
• Thus, the orbital contribution can be ignored
so that the observed magnetic moment may
be considered to arise only from unpaired
spins.
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• In the 2nd and 3rd series transition elements,
and particularly in the lanthanide elements,
the orbital motion is not quenched.
• In some cases there is coupling between the
spin contribution S and the orbital
contribution L (spin orbit coupling or Russel-
Saunders coupling) to give a new quantum
number J. Thus, the magnetic moment is
given by
μ  g J(J  1) M.B
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S ( S  1)  L( L  1)  J ( J  1)
g  1
2 J ( J  1)
Alloy Formation
An alloy is an intimate mixture or, in some
cases, a compound of two or more metals, or
metals and non-metals.
• Alloying changes the physical properties
such as strength, malleability, ductility,
hardness and resistance to corrosion, heat
etc. of the material.

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Alloy Manufacture
• by combining the component elements in the
molten state followed by cooling.
• When the melt is quenched (cooled rapidly), the
distribution of the two types of metal atoms in the
solid solution will be random;
• the element in excess is termed the solvent, and
the minor component is the solute.
• Slow cooling may result in a more ordered
distribution of the solute atoms.
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Substitutional alloys
• Atoms of the solute occupy sites in the lattice of the solvent
metal.
• To maintain the original structure of the host metal, atoms
of both components should be of a similar size. The solute
atoms must also tolerate the same coordination
environment as atoms in the host lattice.
Example of a substitutional alloy
• sterling silver (92.5% Ag and 7.5% Cu)
• elemental Ag and Cu both adopt ccp lattices and rmetal
(Ag) ≈ rmetal(Cu)
• used for silver cutlery and jewelry 42
 Substitutional alloy

• Some of the atom sites in the host lattice (shown in

grey) are occupied by solute atoms (shown in red). 43