Transition Elements-Ii: Structure
Transition Elements-Ii: Structure
UNIT 2
TRANSITION ELEMENTS-II
Structure
2.1 Introduction 2.5 Catalytic Properties
Expected Learning Outcomes 2.6 Alloys
2.2 Formation of Complexes 2.7 Interstitial Compounds
2.3 Colour of Transition Metal 2.8 Summary
Compounds
2.9 Terminal Questions
2.4 Magnetic Properties
2.10 Answers
2.1 INTRODUCTION
The transition metals have always held a special interest for inorganic
chemists. In the last unit you have learnt about the electronic configurations,
general characteristics of the transition elements and Latimer diagrams. In
this unit we are going to discuss other important aspects like complex
formation, colour, magnetic properties and catalytic properties of transition
metals and their compounds.
It is interesting to note at this point that the compounds of the main group
metals are almost always white, but those of the transition metals are
coloured. A lot of study of compounds of transition metals was done by the
Swiss chemist Alfred Werner who in 1893, proposed that the metal ion was
central and surrounded by other ions and molecules which acted as electron
pair donors. Werner and his students prepared many transition metal
compounds for the subsequent eight years to find proof to his theory which
has opened a new area in inorganic chemistry.
Polarization
NaCl, NaBr and NaI are all ionic, and colourless. AgCl is also colourless.
However, AgBr is pale yellow and AgI is yellow. The colour arises because the
Ag+ ion polarizes the halide ions. This means that it distorts the electron cloud,
and implies a greater covalent contribution. The polarizability of ions increases
with size: thus I is the most polarized and AgI is most coloured. So now can
you follow why the compounds Ag2CO3 and Ag3PO4 are yellow, and Ag2O and
Ag2S are black? Well the reasons are the same, that is polarization of the
electron cloud of anion by the Ag+ ion.
In the previous unit you have learnt that as per the latest IUPAC definition of
transition metals they have partially filled d orbitals, and these are key to the
formation of coloured compounds and complexes. As you know, substances
appear coloured when they absorb light of a particular wavelength in the
visible region of the spectrum and transmit light of other wavelengths. The
colour which we see is the colour of the transmitted wavelengths. In other
words, the colour of the compound observed by us is the complementary
colour of the colour absorbed by the compound.
Fig. 2.2:(a) An object is black if it absorbs all colours of light. If it reflects all
colours of light, it is white. An object has a colour if it absorbs all
colours except one, such as this yellow strip. The strip also appears
yellow if it absorbs the complementary colour from white light (in this
case, indigo). (b) Complementary colours are located directly across
from one another on the colour wheel.
EXAMPLE 2.1: Fig. 2.2 depicts a simple colour wheel.a) Copper(II) sulphate
solution looks pale blue because when light passes through it,
some frequencies of white light are absorbed. What colour
does copper(II) sulphate solution absorb? b)When you add an
excess of ammonia solution to copper(II) sulphate solution,
the colour changes to a very deep blue as the
tetraamminediaquacopper(II) ion is formed. What colour is the
solution now absorbing from white light? 37
Block 1 d and f Block Elements
SOLUTION: The blue colour of the [Cu(NH3)4]2+ ion results because this ion
absorbs orange and red light, leaving the complementary colours
of blue and green (Fig. 2.2). If white light (ordinary sunlight, for
example) passes through [Cu(NH3)4]SO4 solution, some
wavelengths in the light are absorbed by the solution. The
[Cu(NH3)4]2+ ions in solution absorb light in the red region of the
spectrum. The light which passes through the solution and comes
out the other side will have all the colours in it except for the red.
We see this mixture of wavelengths as dark blue. The diagram
gives an impression of what happens if you pass white light
through a [Cu(NH3)4]SO4 solution.
2+
Fig. 2.3: A solution of [Cu(NH3)4] ions absorbs red and orange light, so the
transmitted light appears as the complementary colour, blue.
Colour may arise from an entirely different cause in ions with incomplete d or f
shells. This source of colour is very important in most of the transition metal
compounds. In a free isolated gaseous ion the five d orbitals are degenerate,
that is they have the same energy. However the ion is not bare; when in
solution it is surrounded by solvent molecules, when in a complex it is
surrounded by other ligands and when in a crystal lattice, it is surrounded by
anions. The surrounding groups affect the energy of some d orbitals more than
others. Thus the d orbitals are no longer degenerate and at their simplest they
form two groups of orbitals of different energy, the difference in energy is
small. Thus in transition element ions with a partly filled d shell it is possible to
promote electrons from one d level to another d level of higher energy. This is
known as d –d transition and corresponds to a fairly small energy difference
and so light is absorbed in the visible region. The colour of a transition metal
complex is dependent on how large the energy difference is between the two d
levels. This in turn depends on the nature and number of the ligands, and on
the geometry of the complex formed. Thus the octahedral complex [Ni(NH3)6]2+
is blue, [Ni(H2O)6)2+ is green and [Ni(NO2)6]4is brown-red, that is the colour
changes with the ligand.
Certain ligands cause a large split in the energies of d orbitals of the central
metal atom. Compounds with these ligands are yellow, orange, or red
because they absorb higher-energy violet or blue light. On the other hand,
compounds of transition metals with ligands that cause small split in energies
of d orbitals are often blue-green, blue, or indigo because they absorb
38 lower-energy yellow, orange, or red light.
Unit 2 Transition Elements-II
Fig. 2.4: Both (a) hexaaqua iron(II) sulphate and (b) potassium
6
hexacyanoferrate(II) contain d iron(II) octahedral metal centres, but
they absorb photons in different ranges of the visible spectrum.
The source of colour in the lanthanoids and the actinoids is very similar,
arising from ff transitions. With the lanthanoids the 4f orbitals are deeply
embedded inside the atom, and are well shielded by the 5s and 5p electrons.
The f electrons are practically unaffected by complex formation: hence the
colour remains almost constant for a particular ion regardless of the ligand.
The absorption bands are also very narrow.
Some compounds of the transition metals are white, for example CuCl and
TiO2. In these compounds it is not possible to promote electrons within the d
level. Cu+ has a d10 configuration and the d level is full. Ti4+ has a d0
configuration and the d level is empty. For this reason zinc sulphate is also
white. In the series Sc(+3), Ti(+4), V(+5), Cr(+6) and Mn(+7), these ions may
all be considered to have an empty d shell: hence d – d transitions are
impossible and they should be colourless. However, as the oxidation number
increases these states become increasingly covalent and rather than forming
highly charged simple ions, oxoions are formed TiO2+; VO2+, VO43, CrO42 and
MnO4. VO2+ is pale yellow, but CrO42 is strongly yellow coloured, and MnO4
has an intense purple colour in solution though the solid is almost black. The
colour arises by charge transfer where an electron is momentarily transferred
from oxygen to the metal thereby causing temporary reduction of the metal.
Since transfer of electron is transfer of charge these spectra are called charge
transfer spectra. Charge transfer requires that the energy levels on the two
different atoms are fairly close. Charge transfer always produces intense
colours.
The s- and p-block elements do not have a partially filled d shell so there
cannot be any dd transitions. The energy to promote an s or p electron to a
higher energy level is much greater and corresponds to ultraviolet light being
absorbed. Thus compounds of s-and p-block elements typically are not
coloured. Compounds of transition elements are usually markedly coloured, in
contrast to compounds of s-and p-block elements which are mostly white or
colourless unless the anion is coloured. For example, the aqua ion Ti(H 2 O) 36 ,
which has one electron in the 3d orbital absorbs light of wavelength in the
yellow-green region of spectrum and therefore, appears reddish violet in
colour. Table 2.1 gives the relationship between the colour and the wavelength
of light. 39
Block 1 d and f Block Elements
Table 2.2: Oxidation States and observed colours for some aqua species
of the Transition Metal Ions
Element +2 +3 +6 +7
Sc Colourless
3+
[Sc(H2O)6]
Ti Violet
3+
[Ti(H2O)6]
V Violet Green
2+ 2+
[V(H2O)6] [V(H2O)6]
Cr Blue Violet/green Orange/yellow
2+ 3+
[Cr(H2O)6] [Cr(H2O)6] Cr 2 O 72 , CrO 24
Many transition metal compounds have bright colours and thereby they are
useful as pigments in paints and dyes.
3+ 3+
Ruby Al2O3 Red Cr replacing Al in octahedral sites
3+ 3+
Emerald Be3Al2(SiO3)6 Green Cr replacing Al in octahedral sites
2+
Sapphire Al2O3 Blue Intervalence transition between Fe and
4+ 3+
Ti replacing Al in adjacent octahedral
sites
Conclusion:
SAQ 1
Explain briefly why CuSO4 is blue while ZnSO4 is white.
In the above expression, S is the sum of the spin quantum numbers and L is
the sum of orbital angular momentum quantum number of all the electrons. In
many compounds including those of the first row transition elements, the
orbital contribution is quenched out by the electric fields of the surrounding
atoms and as an approximation, the observed magnetic moment may be
considered to arise only from unpaired spins. Putting L = 0 in the above
expression, you can get the spin-only magnetic moment µs.
Hence, μS 4S(S 1) 4n / 2 (n / 2 1)
n (n 2) …(2.3)
The above expression gives the value of magnetic moment in Bohr magnetons
which can be converted into SI unit of Ampere square meter (Am2) by the
following relationship:
In some case (e.g. Mn2+, or Fe3+, in which all the d orbitals are occupied singly
by electron for which ml = 2, 1, 0, -1 and -2, giving l = 0) the observed
magnetic moment values agree very well with the spin-only value as given in
Table 2.4. But generally, experimental values differ from the spin-only values.
This is because the orbital motion of the electron also makes some
contribution to the moment. More detail on the magnetic properties of the
transition elements can be studied in higher courses on the subject. 43
Block 1 d and f Block Elements
[V(H 2O) 6 ]3 3d 2 ↑ ↑
2 2.84 2.75
[V(H 2O) 6 ] 2 3d 3 ↑ ↑ ↑
3 3.87 3.86
[Cr(H2O)6 ] 2 3d 4 ↑ ↑ ↑ ↑
4 4.90 4.80
[Mn(H 2O) 6 ]2 3d 5 ↑ ↑ ↑ ↑ ↑
5 5.92 5.96
[Fe(H 2 O) 6 ] 2 3d 6 ⇅ ↑ ↑ ↑ ↑
4 4.90 5.00
[Co(H 2 O) 6 ] 2 3d 7 ⇅ ⇅ ↑ ↑ ↑
3 3.87 4.40
[Ni(H 2 O) 6 ] 2 3d 8 ⇅ ⇅ ⇅ ↑ ↑
2 2.84 2.90
[Cu(H 2 O) 6 ] 2 3d 9 ⇅ ⇅ ⇅ ⇅ ↑
1 1.73 1.80
SAQ 2
In [Co(H2O)6]2+ the observed magnetic moment is higher than the spin-only
value. Explain the reason for this in the space provided below.
An enzyme is a
biological catalyst 2.5 CATALYTIC PROPERTIES
which can bring about
specific chemical
reactions. It is known
Many transition metals and their compounds have catalytic properties. These
that several transition metals can function as catalysts because they can utilize both d and s
metal ions e.g., iron, electrons for the formation of bonds between reactant molecules and the
manganese, cobalt, surface catalyst atoms. This increases the concentration of the reactants at
zinc and molybdenum
ions are involved in
the catalyst surface and weakens the bonds in the reactant molecules with
various processes. the result that the activation energy is lowered. Compounds of transition
metals are able to act as catalysts because of the ease with which the metal
can adopt different oxidation states and also because of their ability to form
complexes, thus they readily form intermediates. Some of the common
catalysts used for important reactions are:
44
Unit 2 Transition Elements-II
Apart from their role as catalysts transition metals are important in the
biological system. Iron is present in hemoglobin of blood which acts as oxygen
carrier. It is also present in myoglobin which acts as oxygen reservoir and in
ferredoxins of photosynthetic process.
2.6 ALLOYS
Alloys are a combination of two or more solid metals. Transition elements,
(e.g. gold and copper) have similar metallic radii and so they both easily form
alloys. Some common alloys, their compositions and their uses are given
below in Table 2.5.
2.8 SUMMARY
Let us now summarise what we have learnt in this unit. This unit focuses on
the colour and magnetic properties of the transition metals. We have also
learnt about the formation of complexes and catalytic properties of transition
element and their compounds.
2.10 ANSWERS
Self-Assessment Questions
1. Cu2+ in CuSO4 has [Ar]3d94s0 configuration and its electrons can be
promoted to the half filled d orbital. Thus it can undergo d-d transition
which absorbs mainly in the red region of the visible light and CuSO4
appears blue in colour (blue is complementary colour of red). Because
Zn2+ in ZnSO4 has the configuration [Ar]3d104s0, the transition of electron
from one d orbital to another is not possible and no light is absorbed in
the visible region of spectrum by ZnSO4 and therefore, it appears white.
momentum and thus the observed magnetic moment is higher than the
calculated spin-only magnetic moment.
Terminal Questions
1. Transition elements have partially filled d orbitals, and these are key to
the coloured compounds and complexes they form.
The transition metal ions with partially filled d-orbitals exhibit colours in
aqueous solutions and also in crystals due to d- d transitions. However,
these transitions are not possible with empty or full-filled i.e. d0 and d10
configurations and metal ions with these configurations usually does not
show any colour(said to be white). So we can infer:
Sources of Figures
Fig. 2.2:
https://chem.libretexts.org/Bookshelves/General_Chemistry/Map%3A_
General_Chemistry_(Petrucci_et_al.)/24%3A_Complex_Ions_and_Coordinatio
n_Compounds/24.07%3A_Colour_and_the_Colours_of_Complexes,
LibreTexts content is licensed by CC BY-NC-SA 3.0.)
Fig. 2.4:
https://chem.libretexts.org/Bookshelves/General_Chemistry/Map%
3A_General_Chemistry_(Petrucci_et_al.)/24%3A_Complex_Ions_and_Coordi
nation_Compounds/24.07%3A_Colour_and_the_Colours_of_Complexes,
LibreTexts content is licensed by CC BY-NC-SA 3.0.)
Fig. 2.5:
https://en.wikipedia.org/wiki/Prussian_blue_(medical_use)#/media/File:Pigmen
t Berliner_Blau.JPG,CC0).
Fig. 2.6:
https://commons.wikimedia.org/wiki/File:Titanium(IV)_oxide.jpg, Wikimedia
Commons, the free media repository)
Fig. 2.7:
https://en.wikipedia.org/wiki/Ruby_(color)#/media/File:Ruby_gem.JPG,
https://en.wikipedia.org/wiki/Emerald#/media/File:5_Emeralds_
from_Colombia.JPG,
https://en.wikipedia.org/wiki/Sapphire#/media/File:Geschliffener_
blauer_Saphir.jpg,
48