CATALYTIC ACTIVITY

Some reactions catalysed by transition elements/their compounds.

process reaction Catalyst

Contact process 2SO2(g)+O2(g)2SO3 V2O5

Haber process N2(g)+3H2(g)2NH3(g) Fe(s)

Hydrogenation CH2=CH2(g)+H2(g)CH3CH3 Ni(s)

Thermal 2KCLO3(s)2KCL(s)+3O2(g) MnO2(S)

decomposition

Redox 2I-(aq)+S2O82-(aq)I2(aq) Fe3+(aq)

+2SO42-(aq)

Homogenous Catalysis
1. In homogenous catalysis, the catalyst and the reactants are in the same physical
states.
2. Homogenous catalysis is usually explained by the intermediate product theory.
3. Using the oxidation of iodide ions by peroxodisulphate ions as an example.
Fe3+
S2O8 (aq) + 2I (aq) ---------------------> 2SO42-(aq) + I2(aq)
2 -

a) The activation energy for an catalysed reaction is high because it involves

the direct collision of negative charge ions,which tends to repel each each
other.
b) However ,in the presence of Fe3+ (aq) as catalyst, the activation energy is
lower because it involves the collision of opposite charged particles.
4. Transition elements and their compounds are good homogenous catalysts
because they exhibit variable oxidation states.
Heterogeneous catalysis
1. In the heterogeneous catalysis, the physical state of the catalyst is different from
those of the reactants.
2. Examples of heterogeneous catalysis are:
Reaction Catalyst

N2(g) + 3H2  2NH3(g) Fe(s)

2SO2(g) + O2 (g)  2SO3(g) V2O5(s)

H2(g) + I2 (g)  2HI (g) Ni (s)

CH2 = CH2(g) + H2 (g)  CH3CH2(g) Ni (s)

CH3CH2OH(g)  CH2 = CH2 (g) + H2O(g) AL2O3(s)

3. Heterogeneous catalysis is usually explained by the adsorption theory.

4. the d-block metals have partly full d orbitals which can be used to form bonds
with adsorbed reactants. Thus they can be effective heterogeneous catalysts.
5. Consider the reaction
Ni (s) between hydrogen and iodine.
H2 (g) + I2 (g)  2HI (g)
The nickel atoms at the surface of nickel metal make use of their empty orbitals to
form temporary bonds with the H2 and I2 molecules .This is called adsorption.
This weakens the covalent bonds in H2 and I2 molecules, thus lowering the
activation energy for the reaction. Furthermore, the H2 and I2 molecules are
correctly orientated for new bonds to be formed.
After that, the HI molecules leave the surface of the catalyst, and other H2 and I2
molecules can be adsorbed.
6. Examples of d-block elements and compounds used as heterogeneous catalysts
are shown in table below:
process Product Catalyst

Haber Ammonia Iron

Contact Sulphuric acid Vanadium (v) oxide

Hydrogenation of oils Margarine Nickel

Ostwald Nitric acid Platinum

Oxidation of propan-2-ol propanone copper

MAGNETIC PROPERTIES
1. As electric current flows through a wire , magnetic moment is generated.
Similarly , the electrons spin on their axes and are regarded to generate magnetic
moment. The electrons occupying the same orbital have zero magnetic moment as
the opposite spins of the two electrons counter the magnetic moment
2. Substances which are weakly repelled by the strong magnetic field are termed as
diamagnetic while those which are weakly attracted by a strong magnetic field are
termed as paramagnetic.
3. On the basis of magnetic properties,substances are classified into the following 2
types:
a) Paramagnetic substances: substances which are weakly attracted by
the magnetic field are termed as paramagnetic. These substances lose
their magnetism on removing the magnetic field. Paramagnetism is
produced by the presence of unpaired electrons and most of the
transition metal atoms are having unpaired d-electrons, they are
paramagnetic in behavior.
b) Diamagnetic substances: substances which are repelled by magnetic
field are termed as diamagnetic. It is the property of the completely
filled electronic subshells. As all elements (except hydrogen atom) are
having filled electronic shells, some diamagnetism is shown by all
substances . a simple example of a diamagnetic substance is sodium
chloride.

ISOMERISM IN COMPLEXES
1. Three types of isomerism occur in transition element complexes :
✔ Geometrical isomerism
✔ Optical isomerism
✔ Structural isomerism
Geometrical isomerism
1. Geometrical isomerism ( or cis-trans isomerism ) is shown by
a) Square planar complexes with the formula Ma2b2
b) Octahedral complexes with the formula of Ma4b2 and Ma3b3
c) Octahedral complexes with the formula of M(x—x)2b2
[a and b are monodentate ligands , and (x—x) are bidentate ligands]
2.i) Complexes of Ma2b2
a a a b
M M
b b b
a
 cis isomer trans isomer
ii) Example: Diamminedichloroplatinum (II), [Pt(NH)3]2Cl2]
NH3 NH3 Cl NH3
Pt Pt
Cl NH3 Cl
Cl
cis isomer trans isomer

3.i) Complexes ofaMa2b b

b b a a
M M
a a a
a b a

Cis isomer trans isomer

ii) Example: tetraamminedichlrochromium (III),[Cr(NH3)4Cl2]

NH3 Cl
Cl Cl H3N NH3
Cr Cr
NH3 H 3N NH3
NH3
NH3 Cl
Cis isomer trans isomer
4.i) Complexes of M(x—x)2b2
x b
b x x
x
M M
b x x x
x b

Cis isomer trans isomer

ii) Example: Bis-ethane-1,2 diamminedichlorochromium (III),

CH2
[Cr(NH2CH2CH2NH2)2Cl2]+
NH2 Cl
+
CH + 2

NH2 H2N NH2

Cr CH2 Cr CH2
CH2
Cl NH2 NH2 NH2 CH2
NH2 Cl
 CH2
CH2

Cis isomer trans isomer

5.i) Complexes of Ma3b3

a a
b a
b a
M M

a b b
b
b a
fac-isomer mer-isomer
In the fac-isomer, the three identical groups ( a or b ) are in the same face of the
octahedron. In the mer-isomer, the three identical groups ( a or b ) are not found in
the same face of octahedron.
ii) Example: Triamminetrichlorochromium (III) , [CrCl3(NH3)3]
Cl Cl

H3N Cl H 3N Cl

Cr Cr

H 3N Cl H 3N NH3

NH3 Cl

Fac-isomer mer-isomer

Optical Isomerism
1. Optical isomerism occurs in octahedral complexes which do not have a plane of
symmetry. The complex cannot be divided into two equal halves through any plane.
2. Optical isomers occur in pairs. One is the mirror image of the other and they are
not superimposable.
3. Optical isomers are also called enantiomers. They are optically active. One
isomer will rotate plane polarized light in the clockwise direction ( the dextro or +
isomer ), while the other will rotate plane polarized light in the anti-clockwise
direction ( the laevo or – isomer )
4.i) Complexes with the formula of M (x—x )3

X X
X X
 X X
M
M
X X
X X
X
X

ii) Example : Tris-ethanedioatecobaltate (III)

o o
c o
o c c
o c o
o c o o o o o
c
o c Co Co c o
o o
o o
c o o c o
o
c c

o o

5.i) Complexes with the formula of M(x—x)2b2

b b
X b b X
M
M
X X
X X
X
X
 ii) Example: Bis-ethane-1,2-diamminedichlorochromium (III),
+
+
Cl Cl
H2C H 2N Cl Cl NH2
CH2
H 2C Cr Cr
H2N CH2
NH2 H 2N NH2
H2N CH2 NH2
CH2
CH2
CH2

6. EDTA complexes,
For example, [Ni(EDTA)]4-

O O
4- 4-
C C
O CH2 CH2 O
O O
C O O O C O
C O O C
CH2 Ni Ni
CH2 CH2 CH2
N N N N
CH2 CH2
O CH2 CH2
CH2 C O CH2
O
O
O

Structural isomerism
1. Structural isomerism occurs in complexes having the same molecular formula but
are different with respect to the type of ligands that are bonded to the central ion.
2. An interesting example is a compound of chromium having the molecular formula
of CrCl3 ●6H2O.
3. There are three compounds having the molecular formula of CrCl3 ●6H2O. One is
dark grenn, the other two are light green and purple respectively.
4. They can be differentiated by the number of moles of silver chloride precipitated
when excess aqueous silver nitrate is added separately to one mole of each of the
compounds.
The result of the experiment is shown in the table below.
Isomer Colour Number of moles of AgCl
precipitated

I Dark green 1

II Light green 2

III Purple 3

3+
5. Since chlorine atoms that are covalently bonded to the central Cr ion will not
be precipitated, the isomers are different in terms of the number of chlorine atoms
bonded to the chromium (III) ion. The structural formulae of the three isomers are
given in the table in the next page.
Isomer Formula Structure of complex ion

I [Cr(H2O)4Cl2]+ ● Cl -
● 2H2O b
a

M
Cl
a
H 2O Cl

Cr

H2O OH2
OH2

II [Cr(H2O)5Cl]2+●2Cl -
● H2O

Cl
H 2O OH2

Cr

H 2O OH2
OH2
 b

III [Cr(H2O)6]3+● 3Cl -]

OH2

H 2O OH2

Cr

H2O OH2
OH2

STABILITY OF COMPLEXES
1. Complexes ions have different stabilities depending on the types of ligands.
2. If the ligands are easily displace, the complex is not stable. On the other hand,
ligands that are stubborn and hard to be displace give rise to strong and stable
complexes.
3. When concentrated hydrochloric acid is added to aqueous copper(II), the
solution changes from blue to yellow. From the colour change, it is due that the
chloride ions is a stronger ligand than water and an exchange of ligands has
occurred.
[Cu(H2O)6]2+ (aq) + 4Cl- (aq) [CuCl4]2- (aq) + 6H2O (l)
4. The equilibrium constant of the complex ion in solution is called the stability
constant. All complexes dissociate partially in solution according to the equation:
 M(aq) + nL(aq) MLn(aq) where M = Transition metal ion
L = Ligand
n = Number of ligands
The equilibrium constant, K, of the reaction at constant temperature is given as:

K is the stability constant used to measure the stability of the complex ion with
respect to its constituent species. The larger the value of K, the higher the
concentration of MLn in solution and thus the more stable the complex.
5. Stability constant have a wide range of values. As such, thet are better expressed
as their logarithm, log10 K or simply lg K.
6. The table below shows the stability constant of some complex ions.

Complex ion Stability constant (K) lg K

[Fe(Cn)6]3- 1 x 1042 42

[Fe(Cn)6]4- 1 x 1037 37

[Co(NH3)6]3+ 4.5 x 1033 33.7

[AlF6]3- 6.7 x 1019 19.8

[Cu(NH3)4]2+ 1.4 x 1013 13.0

[CuCl4]2- 3.98 x 105 5.6

7. The stability of a complex depends on the following factors.

a) the oxidation state of the central metal ion
The higher the charge density of the central ion, the more stable is the
complex.
eg : Iron (II) in [Fe(Cn)6]4- lg K = 24

Iron (II) in [Fe(Cn)6]3- lg K = 31

b) the size of the halide ion
 The strength of the halide ion ligands increase in the order Cl- < Br- < I-.
Eg : [CdCl4]2- < [CdBr4]2- < [CdI4]2-
lg K = 2.3 lg K = 3.7 lg K = 6.1
c) the presence of polydentate ligands
The stability of complex increase significantly with the presence of
polydentate ligands. As such, hexadentate ligand like EDTA will produce a far
more stable complex than monodentate and bidentate ligsnds.
eg : [Co(NH3)6]2+ < [Co(H2NCH2CH2NH2)]2+ < [Co(EDTA)]2- g
lg K = 4.9 lg K = 10.6 lg K = 19.0

Even though four of lone pairs in EDTA are from nitrogen atoms as in ammonia, the
binding effect is much stronger than ammonia ligands. EDTA liberates six water
molecules during bonding, resulting in a strong ‘clawing’ effect on the complex and
thus it is stable entropically.

USES OF TRANSITION METAL AND THEIR COMPOUNDS

Titanium
1. Titanium has the same mechanical strength of steel but it is lighter and does not
corrode.
2. The main titanium ores are rutile, TiO2, and ilmenite which is a combination of
rutile and iron(II) oxide, FeTio3.
3. Extraction of titanium can be tedious because it combines strongly with non-
metals like nitrogen, oxygen and carbon. Titanium can be extracted by Kroll process
which consists of four stages:
(a) Purification of oxide
The first stage involves the removal of impurities like clay and granite that come
with the ore. Pure titanium(IV) oxide, being amphoteric is obtained from rutile by
dissolving it in concentrated sulphuric acid. Titanyl sulphate, [TiO][SO4], is first
formed.
However, upon dilution Ti(OH)4 is precipitated. It is then filtered off, washed and
heated strongly to obtain the oxide.
Ti(OH)4 (s)  TiO2 (s) + 2H2O (l)
(b) Formation of titanium(IV) chloride
The second stage is to produce titanium(IV) chloride by heating the oxide with
chlorine and carbon to about 900°C.
TiO2 (s) + 2C (s) + 2Cl2 (g)  TiCl4 (l) + 2CO2 (g)
Titanium(IV) chloride produced is a colourless, covalent liquid (boiling point 136°C)
which fumes strongly in moist air. It is then separated and purified through
fractional distillation. It is kept in a bronze container containing argon to prevent
hydrolysis by moist air.
TiCl4 (l) + 2H2O (g)  TiO2 (s) + 4HCl (aq)
(c) Reduction of titanium(IV) chloride
The titanium(IV) chloride stored under inert condition is then reduced by molten
magnesium at 1000°C to produce the titanium metal.

TiCl4 (g) + 2Mg (l)  Ti (s) + 2MgCl2 (s)

(d) Purification
Titanium produced by the Kroll process needs to be processed further to remove
impurities like unreacted magnesium and side-product magnesium chloride.
Magnesium chloride cam be recycled through electrolysis, producing chlorine gas
which can in turn be used to produce titanium(IV) chloride.
4.Titanium is used in the making of aircraft body, space capsules and nuclear
reactors. It is added to steel in the form of alloy with iron to remove combined
oxygen and nitrogen. Titanium(IV) oxide is used as white pigments in paints. It is
also used as ‘filters’ for plastic and rubber.

Chromium

1. Chromium is a bright, shiny metal which forms a transparent yet stable oxide
layer on its surface.

2. The only commercial important chromium ore is chromite, FeCr2O4.

3. If pure chromium is needed, the ore is first concentrated and converted to
chromium(III) oxide. The oxide is then reduced by Thermite process, in which a
powdered mixture of chromium(III) oxide and aluminium is ignited.

Cr2O3 (s) + 2Al (s)  2Cr (l) + Al2O3 (s)

The reaction is highly exothermic and the molten chromium metal produced settles
at the bottom of the refractory container and collected through a pipe.

4. If it is used to produce ferrochrome alloy, then the concentrated chromite ore is

reduced by carbon in an electric arc furnace.

FeCr2O4 (s) + 4C (s)  Fe (l) + 2Cr (l) + 4CO (g)

Molten chromium is then mixed with nickel to produce heat-resistant alloys or with
iron and nickel to produce stainless steels.

5. Chromium is used to harden steel and increase its resistance to corrosion. It is

used in electroplating. Alloy of chromium with vanadium and tungsten is used in
high speed cutting tools.

6. Dichromate such as K2Cr2O7 are oxidizing agents and are used in quantitative
analysis and also in tanning leather.

7. Chromium is used by the aircraft and other industries for anodizing aluminium.
The refractory industry uses chromite for forming bricks and shapes, as it has a
high melting point, moderate thermal expansion, and stable crystalline structure.

Cobalt

1. Cobalt is a hard silvery-white metal. Cobalt is harder than iron, but melts at a
lower temperature and is somewhat heavier.

2. Most cobalt is obtained as a by-product in smelting nickel or copper ores.

3. Cobalt is used in magnet steels and stainless steels. It is used in alloys used in jet
turbines and gas turbine generators and electroplating because of its appearance,
hardness, and resistance to oxidation.

4. Cobalt-60, an artificial isotope, is an important γ ray source, and is extensively

used as a tracer and a radio therapeutic agent. Single compact sources of 60Co are
readily available.

5. Different kinds of compounds cobalt are used as pigment in pottery, glass

enamels and paints. Some compounds of cobalt are used as driers, substances that
promote drying in paints, varnishes and printing inks.
Manganese

1. Manganese is a pinkish-gray, chemically active element. It is a hard metal and is

very brittle. It is hard to melt, but easily oxidized. Manganese is reactive when pure,
and as a powder it will burn in oxygen, it reacts with water (it rusts like iron) and
dissolves in dilute acids.

2. Manganese shows a variety of oxidation states (+2 to +7). The most stable
oxidation state is +2 which is always ionic. While +4 may be ionic or covalent, +6
and +7 are always covalent.

3. Steel becomes harder when it is alloyed with manganese. Manganese dioxide is

used to manufacture ferroalloys and dry cell batteries. It is used to "decolorize"
glass and to dry black paints. Manganese sulfate (MnSO4) is used as a chemical
intermediate and as a micronutrient in animal feeds and plant fertilizers.

4. Manganese metal is used as a brick and ceramic colorant, in copper and

aluminum alloys, and as a chemical oxidizer and catalyst. Potassium permanganate
(KMnO4) is used as a bactericide and algicide in water and wastewater treatment,
and as an oxidant in organic chemical synthesis.

GEOMETRY OF COMPLEX IONS

These shapes are for complex ions formed using monodentate ligands - ligands
which only form one bond to the central metal ion.

You will probably be familiar with working out the shapes of simple compounds
using the electron pair repulsion theory. Unfortunately that doesn't work for most
complex metal ions involving transition metals. The answer is just to learn the
shapes you need to know about. As you will see, it isn't difficult.

6-co-ordinated complex ions

These are complex ions in which the central metal ion is forming six bonds. In the
simple cases we are talking about, that means that it will be attached to six ligands.

These ions have an octahedral shape. Four of the ligands are in one plane, with the
fifth one above the plane, and the sixth one below the plane.

The diagram shows four fairly random examples of octahedral ions.

4-co-ordinated complex ions

These are far less common, and they can take up one of two different shapes.

Tetrahedral ions

These are the ones you are most likely to need for A' level purposes in the UK.
There are two very similar ions which crop up commonly at this level: [CuCl4]2- and
[CoCl4]2-.
The copper(II) and cobalt(II) ions have four chloride ions bonded to them rather than
six, because the chloride ions are too big to fit any more around the central metal
ion.

A square planar complex

Occasionally a 4-co-ordinated complex turns out to be square planar. There's no

easy way of predicting that this is going to happen. The only one you might possibly
come across at this level is cisplatin which is used as an anti-cancer drug.

Cisplatin is a neutral complex, Pt(NH3)2Cl2. It is neutral because the 2+ charge of the

original platinum(II) ion is exactly cancelled by the two negative charges supplied
by the chloride ions. The platinum, the two chlorines, and the two nitrogens are all
in the same plane.

Bonding In Complex Ions

1.In complex compounds, transition metals ions use empty orbitals (3s, 4s and 4p)
to
form coordinate bonds with ligands. Ligands like chloride ion donates their lone pair
of electrons and occupy the available empty orbitals. For example, in complex ion
[CuCl4]2- the copper(II) ion has four empty 4s and 4p orbitals to accommodate the
four lone pair of electrons from the chloride ions.
With four equivalent bonds, [CuCl4]2- ion has a tetrahedron shape.
 2-

-
Cl Cl

Cu 2+ Cu Cl
Cl - Cl

-
Cl Cl

Bonding in tetrahedral complex,[CuCl4]2-

2. For complex ions to form an octahedral, the single electron in the 3d orbitals
paired up leaving six empty orbitals. Initially, the iron(II) ion is paramagnetic (can
be attracted by a magnetic field) caused by unpaired electrons in the d suborbitals.
After all the electrons in the d suborbitals are paired up, the six empty orbitals are
filled up by the lone electrons from the water or cyanide ligands. The complex ion is
no longer influenced by magnetic fields and is now called diamagnetic. For
example, in hexacyanoferrate(II) ion, [Fe(CN)6]4- ,

Types Of Ligands
1. The molecules or ions that surround the centre metal ions through dative bonds
are called ligands. Ligands play the role of Lewis bases as they act as electron
donors. On the other hand, the centre metal ions are Lewis acids, acting as
electron recipients.
2. Depending on the number of electron pairs donated, lagands are classified as
monodentate, bidentate or polydentate.
3. H2O, CN-, Cl- and NH3 are monodentate ligands donating only one donor pair of
electron for coordinate bonds.

4. Two known bidentate ligands are ethylenediamine (in short, en) and oxalate
ion (in short, ox), whereby there are two pairs of donor electrons in each ligand.

Figure below shows complexes with these two bidentate ligands.

5. One popular example of polydentate ligand is

ethyenediamminetetraacetate ion(EDTA), a hexadentate. There are six donor
pairs forming a very stable complex ion.
The stability of the complex formed with polydentate ligands is due to chelating
effect. Unlike cyanide ion, EDTA is non-toxic. As such, it is useful madically as it
can be used to treat metal poisoning such as lead and cadmium. EDTA acts as
sequestering agent, forming complex with the toxic lead ions and thus dissolving
it. It can be then removed from the blood and tissues by excreting from the body.