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Q. Compare Cu, Ag, Au with respect to stability of their oxidation states.

The Group 11 metals all show binary compounds in oxidation states +1 and +2 with gold and
silver also showing compounds in the +3 state. Au also shows oxidation state of +5 and
perhaps +7 even gold can form Au-. The +2 oxidation state is the most stable oxidation state
of Cu while for Ag and Au the most stable oxidation states are + 1 and +3 respectively. Cu
forms all the halides except iodide in their +2 oxidation state together with the oxide and
sulphide. Cu(l) compounds are normally unstable with respect to disproportionation in
solution transforming readily into Cu(II) and Cu(0). This is because the sum of ionization energies
(I1+ I2) is easily overcome by the gain in hydration energy of the smaller Cu2+ ion Over the larger Cu+
ion in water. Cu does not form any binary compounds in the + 3 state though some complex fluorides
and oxides are known in this state. The increased nuclear charge and consequent higher value of the
sum of ion ionization energies (I1 + I2 + I3) supports the instability of + 3 oxidation state for Cu.

In contrast, +2 oxidation state is not common for silver Ag(II) is strongly oxidizing but is known in
the compound AgF2. The most stable oxidation state of Ag is + 1 . For Ag, the ionic radii are
themselves much larger and supposed to gain of hydration energy cannot stabilized Ag (II) over Ag(I)
in water. That's why the only stable aqua ion of silver is Ag+(aq). Ag2+(aq) is strongly oxidizing in
nature.

Au with its stable oxidation states is in the + 3, which is shown in the stability of the their halides.eg.
AuF3, AuCl3, and AuBr3. Au(II) belongs to 5d series and corresponding 10Dq value is nearly 80%
greater than that of Cu(II) keeping other conditions identical. Thus the last d electron of Au (II) would
be highly destabilized favoring a square planer Au(lIII). Cu(II) on the other hand, owing to Jahn-
Teller effect, experiences a z-out distortion and hence never its 10Dq value becomes so much high as
Au(II) and hence relatively stable in +2 state. Au+(aq) disproportionates readily to Au(III) and Au(0).

Q. Compare the patterns of electronic absorption bands of Lanthanides with those of transition
metals with explanation.

Electronic absorption bands in lanthanides arise mainly due to f-f transitions. Compared to d-
d transitions in transition metal complexes, lanthanides ions display weak but sharper
absorption spectra as the f-orbitals are deep seated and are not influenced by crystal field
distortions. Moreover due to spin-orbit coupling being more important in lanthanides than
crystal field effects, the states with different J values are sufficiently apart in energy giving
rise to distinct and more narrower bands than those of d-metal complexes.

In contrast to the pale colours of Ln(III) complexes, many complexes of Ln(II) and Ln(IV)
are intensely coloured as a result of charge transfer transitions in the visible region of the
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spectrum. Due to presence of larger number of theoretically possible transitions due to large
number of microstates for each electronic configuration even after applying selection rules,
the electronic spectrum of lanthanides consist of a large number of sharp bands. Sometimes
fine structure is observed in some bands owing to weak crystal field effects.

In contrast to the d-metal ions which show one or two bands of moderate intensity due to
vibronic coupling, lanthanides consist of low-intensity peaks as there is little coupling
between electronic transitions with molecular vibrations in lanthanides. Sometimes more
intense broad bands can be seen due to transitions between 4f and 5d as they are not orbitally
forbidden ego in Ce3+ and Tb3+

Q. Comment on the statement - 'Nb' and 'Ta' are difficult to separate.

Considering the atomic radii of the elements in 3d, 4d and 5d series, one could see that the 3d
metals are significantly smaller than their 4d and 5d congeners. The similarity in sizes of the
4d and 5d metals is due to the effect of Lanthanide contraction. For the elements La to Lu due
to the first filling of the poorly screening and penetrating 4f orbital electrons there is a steady
increase in effective nuclear charge which results in a steady decrease in size of the
lanthanides elements known as Lanthanide contraction. This factor influences the element Ta
(5d36s2) by increase in its nuclear charge which was incompletely shielded by fl4 electrons
thereby effective nuclear charge increases with a concominant decrease in its atomic radii,
inspite of the introduction of a new quantum shell with higher principal quantum number i.e.
5d from 4d which increases its radii. Thus the resultant of two opposing factors decreases the
size of Ta and it becomes nearly equal to that of Nb (4d46s1). Due to this similarity in size the
chemical properties and physical properties are similar which makes Nb and Ta difficult to
distinguish and separate.

Q. Explain the general trends in complex formation of 3d, 4d and 5d elements.

The general trends in complex formation show the following characteristics with respect to
3d, 4d and 5d elements:

i. 4d and 5d elements form fewer complexes in common geometries than 3d

elements and the geometry is restricted with respect to each metals. 4d and 5d
elements show higher coordination number (>6) due to larger size and availability
of orbitals leading to several other geometries with higher symmetry.
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ii. Higher oxidation states are much more stable for 4d and 5d than for 3d
compounds; some oxidation states have no analogues in the 3d series. The +3
oxidation state is of relatively little importance in 4d, 5d series (except for Ru),
but is of major importance in the 3d series. The +III oxidation state is dominant in
the 3d series, but relatively unimportant in 4d, 5d (exceptions are for Rh, Ir, Ru
and Re). Rather, +IV, +V and +VI are more often met with 4d and 5d metals. The
4d, 5d rows are much more prone to metal-metal bonding than the 3d row, and
multiple metal-metal bonds are common. For 3d, M- M bonds are only common
in metal carbonyls. Polynuclear (and cluster) compounds are more common for
4d, 5d than for 3d species.
iii. Lighter elements of the d block tend to prefer O-, N- or halide ion donor groups,
whereas heavier elements lean towards coordination by ligands featuring heavier
p-block elements such as S- and P-donors.
iv. 4d and 5d metals elements predominantly tend to form low spin complexes
compared to 3d elements which forms both low and high spin complexes
depending upon the ligand environment and oxidation state.

Q. La3+ is diamagnetic but Eu3+ is not. Explain.

The magnetic properties of Lanthanoids arise due to the presence of incompletely filled 4f
orbitals and the magnetic effects of the different electrons do not cancel out each other. But
due to the deep seated nature of the 4f orbitals it is not under the crystal field effect of
surrounding ions and thus the orbital moment is not quenched. Thus in this case the spins of
the unpaired electrons strongly couple with the orbital angular momentum ( LS coupling) and
the magnetic moment for a given fn configuration is close to the value calculated for the free
ion and is given by the expression µj= gj ={J(J+ I)}1/2 µB where the Lande g-factor is

gj = I + J(1+ 1) + S(S+ 1) - L(L+ 1)/ 2J(J+ 1)

In most of the cases the J levels are widely separated and it is assumed that only one
2S+1
{L}J , level is occupied at the temperature of the experiment. Calculated in this manner
La3+ is diamagnetic. But in case of Eu3+, the first excited state lies close to the ground state
(multiplet width small comparable to kT) and is partly populated even at room temperature.
Although the value of µ based on occupation of only the ground state is zero(J=O), the
experimentally observed value is nonzero and varies with temperature according to
Boltzmann population of the higher state.
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Q.

Magnetic properties:

Lanthanoids- f0 and fl4 configurations are diamagnetic and the other fn configurations are
paramagnetic. However, paramagnetism does not obey spin only formula, since the 4f
orbitals are deep seated core like and not influenced by the outer 5s, 5p orbitals. Both spin
and orbital contributions determine µS+L in lanthanoids.

Actinoids- The µ values of the actinoids are appreciably lower and much more temperature
dependent than those of the lanthanoids. 5f orbitals are more diffuse and exposed to ligand
field effects, which considerably lower µ values. RS coupling involving J values on µ is less
operative. (µ.= g[J(J+ I)]½.

Spectral properties:

Lanthanoids- f-f transitions are narrow, sharp, weakly coloured and their positions are little
affected by the ligand environment due to the core like 4f orbitals. Hence the visible spectra
usually consist of a large number of sharp, low-intensity peaks that are barely affected by
changing the coordination environment of the ion. Molar absorption coefficients € are
typically 1-10 dm3mol-1

Actinoids- the 5f orbitals of the early actinoids are more diffuse, f-f transitions are weak,
broader and more intense than those of the 4f elements. Their spectra are more strongly
affected by ligands. All sorts of 5f→5f, 5f→6d and LMCT transitions are possible, because
5f orbitals interact mere with the ligand, and € values typically lie between 10-100dm3mol-1.

Q.

Separation of lanthanides by ion-exchange process:

The size of Ln3+ ions decreases gradually from Ce3+ to Lu3+ ( lanthanide contraction), and
binding of the Ln3+ ions to a complexing agent like EDTA, triammonium-EDTA, gradually
and regularly increases with increasing atomic number of the lanthanide ion. When a mixture
of lanthanide ions bound on an ion exchange bed (Dowex-50) is eluted with a dilute solution
of EDTA under adjusted conditions, the ions will be eluted in a sequence from higher atomic
number to lower atomic number. (Lu3+, then Yb3+, and so on). The ions are absorbed on the
resin (R) bed replacing the hydrogen in- SO3H groups.
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Ln3+(aq) + 3H-R(s) = LnR3(s) + 3H+(aq)

Affinity of the lanthanide ions for the resin increases slightly with increase in atomic number,
but this is not sufficient to effect a good separation. Elution is effected at pH 8 or citric acid-
ammonium acetate buffer, when the following equilibrium is established:

Ln3+R3(s) + 3NH4+ + HEDTA+ + xH2O == [Ln(H2O),HEDTA](aq) + 3NH4+-R(s)

The equilibrium is gradually pushed to the right as fresh eluent is added and the Ln-EDTA
complex removed to lower layers of the column. The heavier congeners are gradually
enriched in the solution phase and are eluted in the reverse order of their atomic number. The
different ions concentrate in bands in different regions of the column and their downward
movement may be followed by fluorescence spectroscopy. From the solutions obtained from
the column, the lanthanides may be precipitated as fluorides, hydroxides or oxalates,
converted to oxides on heating, and reconverted to chlorides by NH4Cl or CCl4.

Q.

Lanthanide contraction in general accounts for the greater similarity between the chemistry of
Mo and W than between Mo and Cr. This may be illustrated by-
*Cr forms highly oxidising compounds in the +6 state, whereas the equivalent compounds of
Mo and Ware not appreciably oxidising. CrO3 [Cr2O72- and CrO42-] is strongly oxidising,
but MoO3, WO3) are not.
*Mo and W form electrically conducting complex oxides with other metals (bronzes)
*CrO3 chains of vertex sharing tetrahedral, MoO3, WO3 linked octahedral.
*With X=F MX6 known for all three, but X=Cl,Br, only Mo and W compounds known.
Moving vertically down in the d-block there is a very little increase in size from 4d to 5d
where the size remains practically unchanged. Metallic radii: Cr=129pm, Mo= 140pm, W=
141 pm.

Q.

Sc exhibits only +3 oxidation state, coccesponding to ionization of both 4s2and 3d1 which are
of similar energy. After this, the most common state for the 3d elements is +2, corresponding
to ionization of 4s2 only. The 3d electrons become more stabilized after Sc and in line with
this, the oxidizing power increases in the series Sc(III)< Ti(IV)< V(V)< Ce(VI)< Mn(VII) the
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+2 state is thus strongly reducing for Ti,V,Cr, but becomes fairly stable in the elements Mn
onward. Compounds formed in +2 state are likely to show pronounced ionic character. With
increase in oxidation state, covalence should develop and acidity increase. Oxides of the
metals in their +2 state are basic and dissolve in acids to form aquo ions. Redox potential data
for the 3d elements (plots of nE0 Vs oxidation state) suggest that from Ti to CO, there is a
sharp downward slope at the beginning, reaching a minima at the + 2 and + 3 oxidation
states. Hence higher and lower oxidation states are expected to revert to these states on
reaction, and the higher oxidation states become increasingly unfavourable. Most stable
oxidations states for all the 3d elements may thus be listed as: Sc( + 3), Ti ( + 3, +4), V (+4),
Cr(+3), Mn(+2,+4), Fe(+2,+3), Co(+3), Ni(+2), Cu(+2)