CHEM 416: COMPARATIVE STUDY OF D AND F BLOCK

CF. 3.0
Purpose
To introduces students to metallurgy and general properties of transitional elements
Expected Learning Outcomes
By the end of the course the learner should be able to:
Discuss metallurgy and general properties of transitional elements
Explain the oxidation states of various transition ions
Perform several catalytic reactions experiment of the transitional ions
Work out the effective atomic number of transition elements in metal carbonyls
Discuss the spectral analysis and characterization of organometallic compounds.
Discuss the mechanism of formation of metal carbonyl
Describe the bonding, synthesis and reactions organometallic compounds.
Discuss the applications of organometallic compounds

Course Content
General trends in physical and chemical properties along the period and down the group;
organometallic compounds: organometallic compounds: Metal carbonyls and other related
compounds e.g. metal nitrosyls, cyanocomplexes (Bonding, structure, synthesis, properties and
reactions etc. valance electron count (the 16 and 18 electron rule); organometallic compounds of
pi-extended ligand systems; (e.g. metallocenes, polyenecomplexes etc); Bonding, synthesis and
reactions; organometallic catalytic reactions; (hydrogenation of alkenes, hydroformylation,
Wacker process; Ziegler –Natta polymerization catalysis); spectral analysis and characterization
of organometallic compounds; metal-metal bonding and introduction to metal clusters; cluster
valence electron count. (PREREQUISITE: CHEM 313)

Teaching / Learning Methodologies

Lectures; Tutorials; Class discussion, Practicals

Instructional Materials and Equipment

Handouts, practical manuals; Chalk board, laboratory

Course Assessment
Examination - 70%; Continuous Assessments (Exercises and Tests) - 30%; Total - 100%
Recommended Text Books
Geissman Ta; (2004). Principles Of Organic Chemistry, 4e.Cbs Publishers &DistributorsISBN:
8123910819
James E Huheey, Ellen A Keiter, Richard L Keiter; (2008). Inorganic Chemistry Principles Of
Structure & Reactivity. Dorling Kindersley (india) Pvt Ltd; BN: 8177581309
Abdul MannanSaifi; (2009). Textbook Of Inorganic Chemistry; ISBN: 8184111444
J D Lee ; A new Concise Inorganic Chemistry; Van Monstrand

Text Books For Further Reading

F. Lipot(2001); Inorganic Chemistry; Unwin Hyman
COMPARATIVE STUDY OF D AND F BLOCK ELEMENTS
A transition element is one which has a partially D or F orbitals either in elemental form or in
one of its common occurring oxidation states. The elements which meet this definition are
-the d-block,
-lanthanides and
-the actinides.
The specific elements in the D and F block elements with their respective atomic numbers are as
given in the table below and thereafter their electronic configurations:
gp3 gp4 gp5 gp6 gp7 gp8 gp9 gp10 gp11 gp12
st 21 22 23 24 25 26 27 28 29 30
1 D Sc Ti V Cr Mn Fe Co Ni Cu Zn
series
2nd D 39Y 40
Zr 41
Nb 42
Mo 43
Tc 44
Ru 45
Rh 46
Pd 47
Ag 48
Cd
series
3rd D 57La 72
Hf 73
Ta 74
W 75
Re 76
Os 77
Ir 78
Pt 79
Au 80
Hg
series
89 104 105
Ac Rf Ha

Lanthani 58C 59
P 60
N 61
P 62
S 63
Eu 64
G 65
T 66
D 67
H 68
Er 69
T 70
Yb 71
L
de e r d m m d b y o m u
actinide 90T 91
P 92
U 93
N 94
P 95
A 96
C 97
B 98
C 99
E 100
F 101
M 102
N 103
L
h a p u m m k f s m d o r

Electronic configuration of D block elements

The electronic on figuration 21Sc can be written as 1S22S22P63S23P63d14S2 eighteen electrons do
not participate in the reactions in which the element is involved in and they constitute argon
electronic configuration and hence the electronic configuration for Sc can best be written as
[Ar]3d14S2. The electronic configuration of other 1st row d series are:
22
Ti [Ar]3d24S2
23
V [Ar]3d34S2
24
Cr [Ar]3d54S1
25
Mn [Ar]3d54S2
26
Fe [Ar]3d64S2
27
Co [Ar]3d74S2
28
Ni [Ar]3d84S2
29
Cu [Ar]3d104S1
30
Zn [Ar]3d104S2
The electronic configuration of Cr and Cu are expected to be written as [Ar]3d 44S2
and[Ar]3d94S2 but they are normally written as [Ar]3d54S1 and [Ar]3d104S1. This gives Cr a half
filled configuration and Cu a fully filled d orbital electronic configuration. These configurations
are the most stable and the atoms prefer to exist in these configurations than the former ones. Mo
and Ag in the 2nd d series and W and Au in the 3 rd d series will have their configurations for
similar reasons.

The electronic configurations of the 2nd d series elements are:

39
Y [Kr]4d15S2
40
Zr [Kr]4d25S2
41
Nb [Kr]4d35S2
42
Mo [Kr]4d55S1
43
Te [Kr]4d55S2
44
Ru [Kr]4d65S2
45
Rh [Kr]4d75S2
46
Pd [Kr]4d85S2
47
Ag [Kr]4d105S1
48
Cd [Kr]4d105S2

The electronic configuration of the 3rd d series elements are;

57
La [Xe]5d16S2
72
Hf [Xe]4f145d26S2
73
Ta [Xe]4f145d36S2
74
W [Xe]4f145d56S1
75
Re [Xe]4f145d56S2
76
Os [Xe]4f145d66S2
77
Ir [Xe]4f145d76S2
78
Pt [Xe]4f145d86S2
79
Au [Xe]4f145d106S1
80
Hg [Xe]4f145d106S2

The electronic configuration of the 4th d series elements are:

89
Ac [Rn]6d15f07S2
104
Rf [Rn] 5f146d27S2
105
Ha [Rn] 5f146d37S2
Between the 2nd and 3rd d series are the lanthanides which constitute the filling of the 4f
orbitals. The 4f orbitals are lower in energy than the 5d and hence more stable. Therefore the
incoming electrons will enter into 4f instead of the 5d orbitals. For the next 14 elements the
electrons are added into 4f orbitals which normally take a maximum of 14 electrons.

Electronic configuration of the lanthanide elements are:

58
Ce [Xe]5d04f26S2
59
Pr [Xe]5d04f36S2
60
Nd [Xe]5d04f46S2
61
Pm [Xe]5d04f56S2
62
Sm [Xe]5d04f66S2
63
Eu [Xe]5d04f76S2
64
Gd [Xe]5d04f86S2
65
Tb [Xe]5d04f96S2
66
Dy [Xe]5d04f106S2
67
Ho [Xe]5d04f116S2
68
Er [Xe]5d04f126S2
69
Tm [Xe]5d04f136S2
70
Yb [Xe]5d04f146S2
71
Lu [Xe]5d14f146S2
The electronic configuration of actinide elements are:
90
Th [Rn]6d25f07S2
91
Pa [Rn]6d25f17S2
92
U [Rn]6d15f37S2
93
Np [Rn]6d15f47S2
94
Pu [Rn]6d05f67S2
95
Am [Rn]6d05f77S2
96
Cm [Rn]6d15f77S2
97
Bk [Rn]6d05f97S2
98
Cf [Rn]6d05f107S2
99
Es [Rn]6d05f117S2
100
Fm [Rn]6d05f127S2
101
Md [Rn]6d05f137S2
102
No [Rn]6d05f147S2
103
Lr [Rn]6d15f147S2

In the actinides the electrons enter into the 5f or 6d or both orbitals (this happens because 5f and
6d orbitals do not have big energy difference until after 4 electrons are added) but after 4 or 5
electrons have been added to the actinide, the 5f becomes more stable and hence the electrons
enter the 5f orbitals.
-For transition elements partially filled 3d, 4d, 5d are utilized. It is found that the d orbitals
project well out to the periphery of the atoms and ions so that the electrons occupying them are
strongly influenced by the surrounding of the ions and in turn are able to influence the
environment. Thus many of the properties of the ions of partly filled d orbitals are quite sensitive
to the arrangement of the d electrons present.
-The 4f orbitals of the lanthanides are deeply buried in the atom or ions such that all those
electrons occupying them are largely screened off from the surrounding by the overlying 6S and
5d orbitals. This explains why the chemistry of the lanthanides is so homologous while that of
transition elements has variations. The chemical behavior of the actinides lie between that of the
transition elements and the lanthanides because the 5d orbitals are not so well shielded like the 4f
orbitals
-From the electronic configuration of elements the electronic configuration of the ions can be
worked and used to explain the chemistry of the elements. It must be recalled that a species with
either half filled or fully filled obtains is accorded stability and the ions of various elements
prefer to attain these electronic configurations.
Trends in physical and chemical properties of D block elements (along the periods and down the
groups)
The physical properties of d block elements include:

1. Atomic radii (nm)

The atomic radii of the first d series and group 4 elements are as follows:
0.17 0.16 0.155 0.150 0.145 0.140 0.135 0.130 0.125 0.120
0.155
0.154
The atomic radii of the transition elements decrease as a period is transversed from the left to the
right. As a period is moved from one group to the next there is increase in the number of protons
in the nucleus as the incoming electrons are added to the same energy level. This increases
effective nuclear charge of the atoms of the elements along the period. The nucleus is positively
charged while the electrons in the energy levels have a negative charge. There is usually an
attraction among oppositely charged particles. This attraction between the positively charged
nucleus and the negatively charged electrons in the outermost energy level is called nuclear
attraction. The increase in the number of protons a cross the period increases the nuclear
attraction in the same trend. There is the pulling effect of the outermost energy level electrons
towards the nucleus with increasing vigor as the period is transversed from the left to the right.
This results in the atomic size reduction across the period. The decrease in the size of atoms of
the elements across the period is called the lanthanide contraction.
The size of the atoms of the elements increases as one move from the 1 st d series element to the
2nd d series element but as one moves from the 2 nd d series to the 3rd d series element there is no
change in the size of the atoms of the elements within a given group. The increase in size as one
moves from the 1st to the 2nd d series element within a give group is due to increase in the
shielding effect and increase in the number of energy levels. The 3 rd and 2nd d series elements in a
given period have the same size as the second and third orbitals in the 3 rd d series element are the
4f and 5d orbitals which have very poor screening effect for the 6s electrons. This make the 6s
electrons in the element to be attracted strongly towards the nucleus resulting in the reduction of
the elemental atomic size than expected, making it to have a similar size to that of the 2 nd d series
element. The change in the size of the elements is as a consequence of the lanthanide contraction.

2. Melting Point (OC)

1540 1680 1900 1890 1240 1540 1500 1450 1080 420
1855 2468 2610 3180 2310 1960 1552 961 321
2222 2996 3410 3400 3050 2443 1769 1063 138.87
o
The melting points of the elements are over 1000 c in contrast to the s-block elements. The molar
enthalpies of fusion are high. These properties suggest strong metallic bonding .metallic bonding
involves delocalization of electrons and the availability for this purpose of 3d and 4s electrons
which are easily realized offers a feasible explanation of the strong metallic bonds. We notice
some irregularities in the melting points which are found in manganese (3d 5) and zinc (3d10).
These two have low melting point due to the fact that they have half and fully filled orbitals
(respectively). Half and fully filled orbitals are very stable and this lowers the availability of the
d electrons for use in delocalization. The same situation is observed in the corresponding 2 nd and
3rd d series elements. The change in the melting points in elements across a given period is
irregular. This is because the factors which determine the melting points of metals such as
packing and the metallic crystal structures of the elements change irregularly among the
elements. The melting points increase down the groups due to the increase in the strength of the
metallic bonds as the group is descended.

3. Boiling point (OC)

2730 3260 3400 2480 2100 3000 2900 2730 2600 910
767
357
The change in the boiling points of the elements across the period and down a given period is in
the same trend as for the melting points and for similar reasons.
4. Enthalpies of atomization (KJ /Mole)
469 515 398 279 418 427 431 339
611 724 651 648 640 556 390 289
669 774 844 791 782 665 565 369

5. Ionization energies
The ionization energies for most d block elements lies between those of s and p block elements.
In moving across the series of metals from scandium to zinc there are small changes in the first
and second ionization energies. This is due to the build-up of electrons in the immediately
underlying d sub shells which efficiently shields the 4s electrons from the nucleus; thus
minimizing the increase in effective nuclear charge from element to element. The increase in the
third and fourth ionization energy values are due to the fact that the electro ns are removed from
d orbitals which are closer to the nucleus. However the trends in values show the usual
discontinuity half way along the series. The reason is that the five d electrons are unpaired and
occupy the orbitals singly. Addition of the sixth and subsequent electrons to the d orbitals, the
electrons have to share the already occupied orbitals resulting in inter-electron repulsion which
would require less energy to remove an electron resulting in lower ionization energy.
Why are the ionization energies of Mn and Zn higher than that of Cr and Cu respectively?
Mn (3d5 4s2) has half filled while Zn (3d 10 4s2) is fully filled orbitals with electrons. Half and
fully filled orbital elements are very stable. Cr (3d 5 4s1) and Cu (3d10 4s1) each have one electron
in the 4s orbital which will require less energy to be removed unlike the paired 4s electrons in
Mn and Zn.

Chemical properties
Transition elements exhibit a number of chemical properties; we shall consider only those ones
mainly shown by the transition elements. These properties include;

1. Transition elements have variable oxidation states

The elements have loosely held electrons by the nucleus and on supplying different amounts of
energy they loss different number of electrons making them to exhibit different oxidation states.
The transition metals show a formidable number of oxidation states. The reason for exhibiting
such a variety of oxidation states is the fact that apart from losing the outermost electrons (ns 2)
they also lose a number of (n-1) d electrons. This due to the closeness of the 3d and 4s energy
states and on supplying enough energy electrons can be lost from both the orbitals. The 1 st d
series elements can show the following oxidation states:
Sc Ti V Cr Mn Fe Co Ni Cu Zn
1 √ √ √ √ √ √ √ √√
2 √ √√ √ √√ √√ √√ √√ √√ √√
3 √√ √√ √√ √√ √ √√ √√ √√ √
4 √ √√ √ √ √ √ √
5 √√ √ √ √ √
6 √√ √ √
7 √√
√√- oxidation state of great importance.
2. Transition elements form non classical compounds
Transition metals combine with ligands with one centre electron rich and the other electron
deficient to form non classical compound. The transition element has vacant d orbitals and non
bonding electrons in its structure. The transition element transfers its non bonding electrons to
the vacant orbital in the ligand and the ligand transfers the electrons unused in bonding onto the
vacant orbital in the transition metal. This results in the formation of synergic or back donation
type of bonding. This is a strong bond and is responsible for formation of compounds such as
metal carbonyls.

3. Transition elements form at least paramagnetic compounds

Transition metal ions have unpaired d and f orbitals with electrons. The unpaired electrons rotate
on their axis generating an electric field which is opposite to that of a magnet brought close to
ion/compound attracting it. Simple interpretations of magnetic susceptibilities of the compounds
of the first d series elements usually give the number of unpaired electrons, the oxidation state
and the d orbital configuration. More complex behavior is encountered for compounds in the 2 nd
and 3rd d series. One important characteristic of the heavier metals is that they tend to give low-
spin compounds, which means that in oxidation states where there is an odd number of d-orbital
electrons there is frequently only one unpaired electron and the ions with even number of
unpaired d electrons are often diamagnetic. There are two main reasons for this intrinsically
greater tendency to spin pairing. First, the 4d and 5d orbitals are spatially larger than the 3d
orbitals, so that the double occupations of the orbital produces significantly less inter electronic
repulsion.
Second, a given set of ligand atoms produces larger splitting of 5d than that of the 4d and in both
cases larger splitting than for the 3d orbitals.

4. Transition elements form colored compounds

Transition metal ions have unpaired electrons in their d and f orbitals. When the ions are placed
in a ligand field the d and f orbitals are split into different levels and in the process the orbitals
move with the electrons they possess. For example the d orbitals are spilt into e g and t2g levels
with different amounts of energies. The e g (dx2-y2 and dz2) orbitals have their energy raised while
t2g (dxy, dxz and dyz) orbitals have their energy lowered as compared to the energy of the
hypothetical degenerate d state. When the solution of the ion is exposed to light spectrum
different wavelengths are absorbed to excite an electron to move from the lower energy t 2g level
to the higher energy eg level. The wavelengths of light not absorbed in the process are reflected
and is what is seen as the color of the solution.

5. Transition elements form alloys with each other and with other elements
Transition elements have unpaired d and f orbital electrons. When the elements are heated
together the electrons are orientated such that they the right approach to each other leading to
them pairing. This leads to formation of compound called alloys.