Inorganic Chemistry 2: Alkali Metal Chemistry

Inorganic Chemistry 2: Chemistry of Metal Elements
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CHAPTER 1
ALKALI METAL CHEMISTRY
1.1 INTRODUCTION
Group 1A of the periodic table of elements consists of hydrogen, and
below it the six alkali metals ( the elements in Group 1A of the periodic table of
elements, with the exception of hydrogen) such as: lithium (Z = 3), sodium (Z =
11), potassium (Z = 19), rubidium (Z = 37), cesium (Z = 55), and francium (Z =
87). They almost follow directly after the inert gases and thus have one single
valence electron beyond a well-shielded nucleus.
All members of Group 1A on the periodic table of elements have a valence
electron configuration of s 1. This means that a single electron is involved in
chemical bonding, and that this single electron moves through an orbital, or range
of probabilities, roughly corresponding to a sphere.
Most elements bond according to what is known as the octet rule, meaning
that when two or more atoms are bonded, each has (or shares) eight valence
electrons. It is for this reason that the noble gases, at the opposite side of the
periodic table from the alkali metals, almost never bond with other elements (they
already have eight valence electrons).
The alkali metals are quite likely to find "willing partners," since they each
have just one valence electron. This brings up one of the reasons why hydrogen,
though it is also part of Group 1A, is not included as an alkali metal. First and
most obviously, it is not a metal. Additionally, it bonds according to what is called
the duet rule, such that it shares two electrons with another element.
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The term "alkali" (essentially the opposite of an acid) refers to a substance

that forms the negatively charged hydroxide ion (OH-) in contact with water.
Alkali metals almost always form positive ions (cations) with a charge of +1.
After reading this chapter, students should be able to explain the finding
history of alkali metals; the isolation manner of alkali metals from their
corresponding minerals; the natural abundance and distribution of the elements of
alkali metals in the earth crush; the uses of alkali metal elements; the properties of
alkali metal elements; the properties and reactions of the alkali compounds:
hydrides, oxides, hydroxides, and salts of oxyacids; the preparation methods of
the alkali compounds: hydrides, oxides, hydroxides, and salts of oxyacids; and the
uses of the alkali compounds: hydrides, oxides, hydroxides, and salts of oxyacids.
1.2 HISTORY
The discovery of lithium usually goes to Swedish chemist Johan August
Arfwedson (or Arfvedson; 1792-1841). Arfwedson found the new element in a
mineral that had first been identified about twenty years earlier by Brazilian
scientist Jozée Bonifácio de Andrada e Silva (1763-1838). He named it after the
Greek word for "stone." Four years later, another scientist named W. T. Brande
succeeded in isolating the highly reactive metal. Most of the lithium available on
Earth's crust is bound up with aluminum and silica in minerals.
In 1807, a few days after isolating potassium, Sir Humphry Davy isolated
sodium for the first time by electrolysis of dried sodium hydroxide, which had
been very slightly moistened. Davy noted that the metal which formed at the wire
electrode he placed in the sodium hydroxide was a liquid, but became solid on
cooling. Davy also noted that, when added to water, sodium decomposed the
water and releasing hydrogen. He named the new metal sodium, because he had
used caustic soda (more simply soda) as his source of the element. In Germany
caustic soda was known as natronlauge and L. W. Gilbert suggested the new
element should be called natronium. J. J. Berzelius preferred the shorter natrium,
from which we get the chemical symbol for sodium is Na.
In 1806 Sir Humphry Davy discovered that chemical bonding was
electrical in nature and that he could use electricity to split substances into their
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basic building blocks. In 1807 he isolated potassium as potassium hydroxide

(potash) for the first time. The name potassium is from the English word 'potash',
originally meaning an alkali extracted with water in a pot of ash of burned wood
or tree leaves. Potassium's symbol K comes from 'kalium' the name of the element
in Germany and Scandinavia.
Cesium was discovered by Robert Bunsen and Gustav Kirchhoff in 1860,
when they analyzed the spectrum of mineral water. Cesium was the first element
discovered using a spectroscope. Bunsen and Kirchhoff named the element
cesium, from the Latin word 'caesius' meaning “sky blue”, after the blue lines they
saw in the spectrum. The Latin spelling is still reflected in British English where
cesium is spelt 'caesium.'
Rubidium is one of four elements discovered by spectroscopy.
Spectroscopy is the process of analyzing the light produced when an element is
heated. Bunsen and Kirchhoff used a spectroscope to find rubidium in a mineral
called lepidolite. The mineral had been discovered in the 1790s by a Jesuit priest,
Abbé Nicolaus Poda of Neuhaus, Germany. When Bunsen and Kirchhoff heated a
sample of lepidolite, they found two new lines in the spectrum. The magnificent
dark red color of these new rays of the new alkali metal led us to give this element
the name rubidium and the symbol Rb from rubidus, which, with the ancients,
served to designate the deepest red.
Francium was discovered by Marguerite Perey in 1939 when examining
the radioactive decay of actinium-227. When actinium-227 emits an alpha-particle
the resulting nucleus is francium-223. Francium's discovery took place at the
Curie Institute in Paris, and the element's takes its name from France.
1.3 ISOLATION
Alkali elements can be obtained by electrolysis and reduction. Lithium

and sodium can be obtained by electrolysis of melted salt, such as CaCl 2 and NaCl
(Cotton, Wilkinson, & Gaus, 1995). K, Rb, and Cs have small melting point and
easy to evaporate, they cannot be made through electrolysis easily. They can be
obtained by processing of melted chloride with Na vapor. Then, the metals are
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purified by distillation. The metals Li, Na, K, and Rb are silvery-white, but Cs has
a golden-yellow cast (Housecroft & Sharpe, 2008). Francium is radioactive, so it
can be isolated.
Spodumene, LiAlSi2O6, is heated at temperature of 100oC, then added by
hot H2SO4 . After that, it is diluted in water to give Li2SO4. Li2SO4 react with
Na2CO3 to give insoluble Li2CO3
Li2SO4 + Na2CO3 → Li2CO3(s) + Na2SO4
After that, Li2CO3 is reacted with HCl to give LiCl.
Li2CO3 + 2HCl  2LiCl + H2O + O2
Melted LiCl is electrolyzed to obtain Li
Cathode: Li+(l) + e-  Li(l)
Anode: Cl-(l)  ½ Cl2(g) + e-
The high melting point of LiCl(> 600oC) can be decrease by adding KCl (55%
KCl and 45% LiCl). It will decrease the melting point until 430oC.
Sodium obtained by Down process namely electrolysis of NaCl fusion that
is added by CaCl2 58% and a little of KF to decrease the melting point (Sugiyarto,
2003). Old way is electrolysis NaOH fusion but now is not used again because of
the efficiency of current is very low. The electrolysis reactions is as follows
Cathode: Na+(l) + e-  Na(l)
Anode: Cl-(l)  ½ Cl2(g) + e-
Electrolysis of KCl to obtain potassium needs high temperature. Modern
way to obtain potassium is by flowing sodium vapor to the KCl fusion at 850oC.
Na + KCl⇌ NaCl + K
The reactions occur in equilibrium. The potassium resulted are easily to vaporize.
So, the potassium is released from the system and the equilibrium will shift into
the left.
Method used to extract rubidium by doing reduction. Rubidium can be
obtained by reducing the molten of RbCl , as the following reaction:
Na + RbCl → NaCl + Rb
The reactions occur in equilibrium. Since rubidium is easily to vaporize. So, the
rubidium can be produced continuously by same way with potassium reduction
process.
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The way to obtain cesium is through reduction method. Cesium can be

obtained by reducing the molten of CsCl as following reaction:
Na + CsCl ⇄ Cs + NaCl
The reactions occur in equilibrium. Since cesium is easily to vaporize. So, the
cesium can be produced continuously by same way with potassium reduction
process.
1.4 NATURAL ABUNDANCE

Earth shell contain about 0.006% of lithium mass. Main source of lithium
come from spodumen mineral, LiAlSi2O6. Sodium and potassium are abundant in
the Earth’s biosphere (2.6% and 2.4% respectively) but do not occur naturally in
the element state (Housecroft & Sharpe, 2008). The main sources of Na and K are
rock salt (almost pure NaCl), natural brines and sea water, solvate (KCl / NaCl)
and carnality (KCl.MgCl.6H2O). Potassium exist in the earth has little radioactive
40
properties because it contains about 0.02% of radioactive isotope K with half-
9
life 1.3 x 10 years. Significant proportions of radiation are resulted by human
body. In contrast to Na and K , natural abundances of Rb and Cs are small (%
abundance of Rb bigger than Cs). On the other hand, francium has very short half-
life that is formed in natural radioactive dating series or nuclear reactor.
Therefore, only few studies shown that the ions behave as expected from place of
francium in group I.
1.5 ELEMENTAL PROPERTIES

The influences of increasing in atomic and ionic size on physical and
chemical properties are more clearly shown by the alkali metals than the other
group of elements.
Physical Properties
All the alkali metals appear as shine metal, silver color, and high electric
conductivity. Some physical properties of the group 1 metals are given on Table
1.1.
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Table 1.1 Physical Properties of Alkali Metals

Properties Li Na K Rb Cs Fr
Atomic number, Z 3 11 19 37 55 87
1 1 1 1 1
Ground state electronic [He]2s [Ne]3s [Ar]4s [Kr]5s [Xe]6s [Rn]7s1
configuration
Enthalpy of atomization 161 108 90 82 78 -
Dissociation enthalpy 110 74 55 49 44 -

of M-M bond in M2
Melting point, K 453.5 371 336 312 301.5 -

Boiling point K 1615 1156 1032 959 942 -
-3
Dencity/ g cm (20C) 0.534 0.968 0.856 1.532 1.9 -
Enthalpy of atomization 162 110 90 88 79 -
Standard enthalpy of 3.0 2.6 2.3 2.2 2.1 -

fusion
Ionization energy 520.2 495.8 418.8 403.0 375.7 -375
Metallic radius, 152 186 227 248 265 -

Ionic radius, 76 102 138 149 170 180
Standard enthalpy of -519 -404 -321 -296 -271 -
hydration of M+
Standard entropy of -140 -110 -70 -70 -60 -

hydration of M+
Standard Gibbs energy -477 -371 -300 -275 -253 -

of hydration of M+
Standard reduction -3.04 -2.71 -2.93 -2.98 -3.03 -

potential
-
Flame color Dark red Yellow Violet Violet Blue
670.8
589.2 766.5 red 780 455.5
*
For 8-coordinate atom in body-centered cubic metal; compare values for 12-coordinate atoms
*
For 8-coordinate atom in body-centered cubic metal; compare values for 12-coordinate atoms
(Source: Housecroft and Sharpe, 2008)
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From the data we can see that:

1. With increasing atomic number, the atom become larger and the strength of
metallic bonding decrease.
2. The effect of increasing size evidently outweighs that of increasing nuclear
charge, since the ionization energies decrease from Li to Cs. The values of
IE2 for all alkali metals are so high that the formation of M2+ ions under
chemically reasonable conditions is not viable.
3. Except lithium, the is decrease from the top to bottom of alkali metals
group. Values of are related to energy changes accompanying the
processes
M(s) → M(g) atomization
M(g)→ M+(g) ionization
+ +
M (g) → M (aq) hydration
Chemical Properties
The general chemical properties of Alkali metals are as follows:
1. Alkali metal is the most reactive metals. Even in the air, the elements will
react with oxygen and water. Usually, the elements are saved in the kerosene
or inert hydrocarbon. The reactivity is increase from top to bottom. The
reactivity is caused by the weak ionization energy; the metals easy to release
electron. Most of alkali compound is ionic.
2. Have one valence electron. So, the atomization enthalpy of alkali metal is very
low. Generally, atomization enthalpies of metal are 400-600 kJ mol-1, but
alkali metals have lower atomization enthalpy (78-162 kJ mol-1). It is causing
the bonding energy in their metallic bonding is relatively weak. The low of
metallic bonding give occasion to the low of melting point and the softness of
alkali metal. The trend is following the increasing of number of atom. Lithium
can be cut by knife; potassium can be crumple like soft margarine. The
particularly low melting point of Cs means that it may be a liquid at ambient
temperatures in some hot climates (Housecroft & Sharpe, 2008). While, the
combination of high thermal conductivity and low melting point are causing
sodium useful in transferring heat in nuclear reactor.
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3. In the gas phase, alkali metals are diatomic molecules.

4. The alkali metals can dissolve in ammonia. Dilute solution of alkali metals in
ammonia result blue solution.
Li(s) + NH3(l) → Li(NH3)4
5. The alkali metals react with oxygen to produce oxide M2O, peroxide M2O2
and superoxide MO2. The tendency to form superoxide is increase from top to
bottom. The fundamental difference is shown when the alkali metal react with
oxygen, caused by the difference of cation size. At 1 atm, alkali metals are
burned with oxygen. Lithium give Li2O. Usually sodium give peroxide Na2O2
continued by the existence of O2 at under pressure and heat, to produce
superoxide NaO2. Potassium, Rb, and Cs form superoxide MO2.
6. The alkali metals can react with non-metals and halogen
2M + Cl2 → 2MCl
6M + N2 → 2M3N
2M + S → M2S
3M + P → M3P
2M + M2 → 2MH
(only Lithium react directly with Nitrogen)
7. The alkali metals react with water. The heat resulted is very high, so the
hydrogen produce react directly with oxygen from air result light and blow.
2M + 2H2O → 2MOH + H2
Lithium reacts slowly with water at 25oC and not replaces weak hydrogen acid
in , but other can (Cotton, Wilkinson, & Gaus, 1995). Sodium
reacts marvelously with water, K aglow,Rb and Cs are exploding (Cotton,
Wilkinson, & Gaus, 1995). The exploding is the result of the burned of
hydrogen-oxygen by the hot metal. The hank of sodium also reacts with
explosion. Lithium, Sodium, and Potassium can be in hand (even being hot)
but the other must be use argon.
8. The alkali metals react with dilute acid to produce hydrogen gas
2M + 2H+ → 2M+ + H2
9. The alkali metals react with ammonia gas at 400oC
2M + 2NH3 → 2MHN2 + H2
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10. Sodium and the other metals dissolve vigorously in mercury. Amalgam
sodium (Na/Hg) is liquid if the sodium is a bit, and solid if have alot of
sodium. Amalgam is useful reduction substance and can be use as aqua
(Cotton, Wilkinson, & Gaus, 1995).
11. The metals react with alcohol to form oxide. Generally, Na or K in C2H5OH or
t-Butanol is use in organic chemistry as reduction substance and as source of
nucleofilic ions OR- (Cotton, Wilkinson, & Gaus, 1995).
12. Lithium is the only metals can react with nitrogen gas directly. It is slow at
25oC but fast at 400oC. Lithium needs energy as much as 945 kJ mol -1, to
break the triple bond of dinitrogen molecule.They will form red nitride crystal
Li3N. Like Mg3N, Li3N also use to absorb N2.
13. Lithium called ‘anomalous’ behavior and exhibits a diagonal relationship to
Mg (Housecroft & Sharpe, 2008). The resemblance of lithium and magnesium
properties can be explained from their charge density.
1.6 USES OF THE ELEMENTS

Lithium which has lowest density (0.53 gr cm -3) of all known metals, it is
used in the manufacture of alloy, and in certain glasses and ceramics (Cotton,
Wilkinson, & Gaus, 1995). The biggest industry of lithium is in lubricant oil-
lithium; more of 60% of some automotive contains lubricant oil. The compound is
Lithium stearat, C17H35COOLi. It is added to the oil to give lubricant that not
ossified at the low temperature, and also stable at high temperature. Lithium is
used in making ceramics and heat-resistant glass. Lithium compound is used as a
dye in fireworks pyrotechnic that produces a red light. Since these metals have a
high thermal specification, the metal is often used in heat transfer applications.
Lithium is used as a fuel deuerida fusion reaction in which if fired with neutrons
will produce tritium.
Alloys of lithium with other metals such as aluminum, cadmium, copper,
and manganese are used as materials for aircraft. It is caused by low density of
those metals. For example, alloy type of LA 141 that consist of 14% Li, 1% Al
and 85% Mg, the density only 1.35 gr cm-3, it only almost a half of density of pure
aluminum metal.
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Sodium metal is used in many synthesis of other metal compound, but

there are two main uses to extract another metals and in production of additive
substance for fuel. For extracting the other metals that have lower abundance such
as thorium, zirconium, tantalum, and titanium can be done by reducing their
compound with sodium. For example, titanium metal can be obtained by
reduction of titanium chloride based on the following reaction:
TiCl4(l) + 4Na(s) Ti(s) + 4NaCl(s)
In the production of additive substance for fuel, Tetra Ethyl Lead (TEL)
that is syntheses from Na-Pb alloy with ethyl chloride based on the following
reaction:
4NaPb(s) + 4C2H2(g) (C2H5)4(l) + 3Pb(s) + 4NaCl(s)
The molten sodium has a low melting point, so it can be used as a coolant
in nuclear reactors. In addition, sodium has good heat conductivity, so the molten
sodium taking fission heat generated and the heat is transferred by liquid sodium
to the outside of the reactor to vaporize the water. Resulting vapor is used to run
electric generators. Sodium lights are also used on the highway or on the vehicle
because the yellow light of the sodium has the ability to penetrate the fog. Last,
sodium is also used to photograph cells in electronic devices.
Potassium maintains blood pressure and levels of acidity in our bodies.
Potassium-40 can be taken into the body by drinking water, eating food, or
breathing air. Once taken in, potassium-40 behaves in the body in the same
manner as other potassium isotopes. Humans require potassium to sustain
biological processes, with most (including potassium-40) being almost completely
absorbed upon ingestion, moving quickly from the gastrointestinal tract to the
bloodstream. The potassium-40 that enters the bloodstream after ingestion or
inhalation is quickly distributed to all organs and tissues. Potassium-40 is
eliminated from the body with a biological half-life of 30 days. The potassium
content of the body is under strict homeostatic control (in which the amount
retained is actively regulated by the body to achieve the normal range required for
system functions), and it is not influenced by variations in environmental levels.
Hence, the potassium-40 content in the body is constant, with an adult male
having about 0.1 micro curie or 100,000 pCi. Each year, this isotope delivers
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doses of about 18 millirem (mrem) to soft tissues of the body and 14 mrem to
bone.
Potassium also helps to pump fluid in the heart and nerves. Potassium is
used in the manufacture of fertilizers. Potassium is used in the manufacture of
explosives and fireworks. Potassium in the form of potassium nitrate is used as a
food preservative. Potassium hydroxide is used to make detergents. Potassium is
also an essential plant nutrient, and K+ salts are widely used as fertilizer (Cotton,
Wilkinson, & Gaus, 1995).
Rubidium is used in the manufacture of atomic clocks. Rubidium is used
as a working fluid in steam turbines, in filaments photoelectric cell that converts
light energy into electrical energy. Besides, rubidium is used as a component in
the engine space and rubidium vapor is used for laser cooling.
Cesium-134 is used in the nuclear power industry. Cesium is used as a
catalyst for the hydrogenation of certain organic compounds, to remove air from
the vacuum tube. Cesium-137 used in brachy therapy to treat cancer. (Brachy
therapy is a method of cancer treatment using radioactive elements). Francium is
rare and not widely used. Francium is usually only used for scientific research in
the laboratory. Cesium is used as cathode at electronic lamp that its principle
works based on photoelectric effect.
Both Na and K are involved in various electrophysiological functions in
higher animals. The [Na+]: [K+] ratio is different in intra- and extra cellular fluids,
and the concentration gradients of these ions across cell membrane potential
difference that, in nerve and muscle cells, is responsible for the transmission of
nerve impulses. A balanced diet therefore includes both Na+ and K+ salts.
The uses of Li and Na also can be seen in batteries. The sodium/sulfur
battery operates around 570-620 K and consist of a molten sodium anode and a
liquid sulfur cathode separated by a solid -alumina electrolyte. The high
operating temperature of the sodium/ sulfur battery technologies has now
superseded these batteries for electric and hybrid electric vehicles. However, the
use of stationary sodium/ sulfur batteries for energy storage systems is currently
being exploited, notably in Japan. This application follows from the fact that self-
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discharges from sodium/sulfur batteries occurs only at very low level (Cotton,
Wilkinson, & Gaus, 1995).
Several properties of lithium, including its highly negative reduction
potential, make it suitable for battery use. For example, the lithium/iron sulfide
battery contains a lithium anode and an FeS2 cathode and find use in camera. An
important advancement in battery technology has been the development of
rechargeable, high energy density lithium-ion batteries, first introduced to the
commercial market in 1991. The lithium –ion battery has a cell potential of 3.6 V
and consist of positive LiCoO2 electrode separated from graphite electrode by
solid electrolyte across which Li+ ion migrate when the cell is charging. In
commercial lithium-ion batteries, the electrolyte is usually LiPF6 in an alkyl
carbonate material. Lithium –ion batteries are manufactured in a discharged state
(Cotton, Wilkinson, & Gaus, 1995). Lithium has high potential reduction standard
and the density only 1/12 of lead density, so the battery is lighter and dense.
In order to avoid the reaction with water, lithium atom is placed in lattice
spaces of metal oxide. The process entering atom (guest) to the solid house is
called intercalation and the result is called intercalation compound. In this process,
it only little of change of reversible structure occur. In fact, potential reduction
turn dramatically from normal value E0 = -3.05 V. Reduction potential of lithium
in compound in intercalation compound depends on the identity of metal oxide or
its house. For example, reduction potential of lithium in manganese dioxide is
positive but vanadium dioxide is negative.
Li+(aq) + e → Li (Mn2O4) (s) E0 = + 1.0 V
Li+(aq) + e → Li (VO2)(s) E0 = -0.5 V
The difference of potential as much as 1.5, between of both lithium
environments cause battery cell reaction.
In process of use battery cell, redox reaction of cell emptying is occurred.
Li+(aq) + e → Li (Mn2O4) (s) E0 = + 1.0 V
Li (VO2)(s) → Li+(aq) + e E0 = +0.5 V
Filling back the battery cell causes reverse reaction occurs.
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1.7 PROPERTIES OF ALKALI METAL COMPOUNDS

There some compound of alkali metals, such as hydrides, halides, oxides,
hydroxides, and salts of oxyacids. The general properties of the compound of
alkali metals are as follows
a. Ionic characteristic
Alkali metal ions always have oxidation number +1 and most of its compound
are in the form of ionic solid and stable. The compounds are colorless, except
with colored anion such as chromate and permanganate.
b. Ion hydration
The higher density of ion charge will cause the stronger hydration of ion.
Alkali metals have low density than other metal, so the hydration energy of
alkali compound is also low. Li+ have hydration energy as much as 519 kJ
mol-1, while Mg+2 have hydration energy as much as 1920 kJ mol-1.
c. Solubility
Most of alkali metal is soluble in water, although the solubility is different.
For example, supersaturated lithium chloride (LiCl) have concentration 14
mol L-1, bul supersaturated lithium carbonate (Li2CO3) only have
concentration 0.18 mol L-1.
1.8 ALKALI METAL COMPOUNDS

1.8.1 Halides
Alkali metals are easy to release one electron. So, it is easy to react with
non-metal element such as halogen and oxygen. The reaction is as follows:
2M(s) + X2→ 2MX(s)
For examples:
2Li + Cl2→ 2LiCl
2K + Cl2→ 2KCl
2Rb + Cl2 → 2RbCl
2Cs + Cl2 → 2CsCl
The solubility of the alkali metal halides in water are determined by a
delicate balance between lattice energies and Gibbs energies of hydration
(Housecroft & Sharpe, 2008). LiF has the highest lattice energy of the group 1
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metal halides. The salt LiCl, LiBr and NaI are soluble in some oxygen-containing
organic solvent for example LiCl dissolve in THF and MeOH. Complexation of
the Li+ and Na+ ion by the O- donor solvents is likely in all cases. Both Lil and
NaI are very soluble in liquid NH3 , forming complexes; the unstable complex
[Na(NH3)4]I has been isolated and contains a tetrahedrally coordinated Na+ ion. In
vapor state, alkali metal halides are present mainly as ion-pairs, but measurements
of M-X bond distances and electric dipole moments suggest that covalent
contributions to the bonding, particularly in the lithium halides, are important.
1.8.2 Oxides
Generally metal is react with dioxygen gas to form oxide with consist of
“oxide ion” O-2. But for alkali metal, just lithium form oxide “normal” if it is
reacted with oxygen, based on reaction as follow:
4Li(s) + O2(g) → 2Li2O(s)
Sodium reacts with dioxygen to produce sodium dioxide(2-), Na2O2, called
as sodium peroxide.
2Na(s) + O2(g) → Na2O2(s)
Sodium peroxide consist of ion dioxide(2-), O2-2, that usually called ion
peroxide. Notation “2-“ just for show the charge at ion that related; process of
writing of Arab number in this namenclature follow the reacomendation the
American Chemical Society that is applaide if there is possibility more than one
ionic charge.
Sodium dioxide(2-) has diamagnetic properties, and the length of bond O-O,
about 149 pm, more length than the bond at dioxygen molecule (O=O) namely
121 pm. Diamagnetic properties dan the weak bond of this compound can be
describe based on orbital model of dioxide(2-) ion molucule. All of electron is
paired and place four bonding orbital and three antibonding orbital, produce bond
order 1; so this compound has diamagnetic properties and the length is more long
than the length of O2 molecule that has 2 bond order.
Three other alkali metal react with excess of dioxygen form dioxide(1-) or
usually called superoxide that has paramagnetic properties therefore it consist of
dioxide(1-) ion, O2-; example, potassium metal react like equation below:
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K(s) + O2(g) → KO2(s)

Bond length of O-O in dioxide(1-) ions namely 133 pm, shorter than bond
length in dioxide(2-) ion, but a little longer than bond length in dioxygen
molecule. The oxides compound of alkali metal is as follows:
4Li + O2→ 2Li2O
Na + O2 → Na2O
2Na + O2→ Na2O2
K + O2 → KO2
2K + O2 → K2O2
Rb + O2 → RbO2
2Rb + O2 → Rb2O2
Cs + O2 → CsO2
2Cs + O2 → Cs2O2
O22- is easier to polarize than O2- and the force to polarize Na+ is stronger
than K+. So, the oxides of sodium are stable as dioxide (2-) or peroxide and oxides
of potassium are stable as dioxide (1-) or superoxide.
All of alkali oxide reacts vigorously with water to produce alkali hydroxide
solution. In addition, the reaction of water with dioxide (2-) produce hydrogen
peroxide and with dioxide (1-) produce hydrogen peroxide and hydrogen gas, as
the equation below:
2 Li2O (s) + H2O (l) → 2 LiOH(aq)
Na2O2 (s) + 2H2O (l) → 2 NaOH(aq)+ 2H2O2(aq)
2KO2 (s) + 2H2O (l) → 2 KOH(aq)+ H2O2(aq) + O2(g)
Potassium dioxide (1-) KO2 is used in outer space capsule, submarine, and
some breath tools. dioxide (1-) can absorb carbon dioxide and release oxygen.
2KO2 (s) + 2CO2 (g) → 2 K 2CO3 (s)+ 3O2(g)
K2CO3 (s) + CO2 (g) + H2O (g) → 2KHCO3 (s)
1.8.3 Hydroxide
Hydroxides of alkali are commonly solid form and white colored. They
can absorb water therefore it can be dissolve in excess of water. The reaction will
result hydroxide compound and hydrogen gas.
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2M(s)+ H2O(l) → 2MOH(aq)+ H2(g)

All hydroxide alkali is dangerous because it can react with protein of skin
therefore can break the skin surface. NaOH is used throughout organic and
inorganic chemistry whenever a cheap alkali is needed. Solid NaOH with melting
point 591 K is often handled as flakes or pellets, and dissolves in water with
considerable evolution of heat. As solid or solution, hydroxide alkali adsorbs
carbon dioxide from the atmosphere to form carbonate, based on the following
reaction(Cotton, Wilkinson, & Gaus, 1995):
2NaOH(aq) + CO2(g) Na2CO3(aq) + H2O(l)
Sodium hydroxide is prepared from solution of table salt by hydrolysis in
diaphragm cell, membrane cell and cathode cell of mercury. Sodium hydroxide is
used as reactant in various synthetic factory of organic, inorganic and it is
consumed in as well as paper factory. Sodium hydroxide is also used as cleaner of
housing tool for example oven. This cleaner is usually in the form of powder from
mixture between sodium hydroxide with aluminum.
Figure 1.1 Uses of NaOH
Potassium hydroxide with melting point 633 K closely resembles NaOH in

preparation and properties. It is more soluble than NaOH in EtOH , in which it
produces a low concentration of ethoxide ions, this gives rise to the use of
ethanolic KOH in organic synthesis(Cotton, Wilkinson, & Gaus, 1995).
C2H5OH + [OH-] ⇌ [C2H5O]- + H2O
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The crystal structures of alkali metal hydroxides are usually complicated,

but the high temperature form of KOH has the NaCl structure, with the [OH-] ions
undergoing rotation rendering them pseudo-spherical (Cotton, Wilkinson, &
Gaus, 1995). The other hydroxides of alkali metal are:
2Li + 2H2O → 2LiOH + H2
2Na + 2H2O → 2NaOH + H2
2K + 2H2O → 2KOH + H2
Rb + 2H2O → 2RbOH + H2
Cs + 2H2O → 2CsOH + H2
1.8.4 Salts of Oxoacids

The properties of alkali metal salts of most oxoacids depend on the
oxoanion present and not on the cation. So, it tends to discuss salts of oxoacids
under the appropriate acid. Whereas Li2CO3 is sparingly soluble in water, the
remaining carbonates of the group I metals are very soluble (Cotton, Wilkinson, &
Gaus, 1995).
In many countries, sodium carbonate (soda ash) and sodium
hydrogencarbonate (commonly called sodium bicarbonate) are manufactured by
Solvay process, but this is being superseded where natural sources of mineral
trona ,Na2CO3.NaHCO3.2H2O, are available. From the Solvay process, it can be
seen that NH3 can be recycled, but most CaCl2 is dumped for example into sea
water or used in winter road clearance (Cotton, Wilkinson, & Gaus, 1995).
Sodium hydrogencarbonate , although a direct product in the Solvay
process, is also manufactured by passing CO2 through aqueous Na2CO3 or by
dissolving trona in H2O saturated with CO2. It uses includes those as a foaming
agent, a food addictive for example baking powder and an effervescent in
pharmaceutical products. The Solvay Company has now developed a process for
using NaHCO3 in pollution control for example by neutralizing SO2 or HCl in
industrial and other waste emission (Cotton, Wilkinson, & Gaus, 1995).
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Figure 1.2 Schematic representation of the Solvay process for the manufacture of
Na2CO3, and NaHCO3 from CaCO3, NH3 and NaCl.
Deposits of sodium nitrate (saltpeter) in great amount exist in Chile. This

compound is composed by oxygen evolution in 5000 C based in this equation:
2NaNO3(s) ∆ 2NaNO2(s) + O2(g)
Potassium nitrate is prepared from its chloride with sodium nitrate based
on the following equation:
KCl(aq) + NaNO3(aq) → KNO3(aq) + NaCl(aq)
This process occurs in temperature below 1000C, because the lowest
solubility is in room temperature, KNO3 can be separated by doing fractional
crystallization.
About 50% of sodium carbonate in America is used in glass factory. In
this process, sodium carbonate is reacted with silicone dioxide (sand) and the
other components in 15000 C.
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Na2CO3(l) + xSiO2(s) → Na2O.x SiO2(l) + CO2(g)

Sodium carbonate is also used in removing ions of earth alkali metal in
water that is changed become solid carbonate, a process that is known as softening
of hard water, metal ions that most general is Ca2+ from limestone (Sugiyarto,
2003).
CO32-(aq) + Ca2+ → CaCO3(s)
In food industry, sodium bicarbonate is used for mixture of bread dough in
order to make bread expand. It is used mixture of calcium dehydrogenate
phosphate and some starch as filler. Calcium dehydrogenates phosphate have acid
properties and when in wet condition, it will react with bicarbonate to form carbon
dioxide gas that has function to make the bread expand when combusting. The
reaction can be seen as follows:
2NaHCO3 + Ca(O2PO4)2(s) → Na2HPO4(s) + CaHPO4(s) + 2CO2(g) + 2H2O(l)
1.8.5 Hidrides
Alkali metals that react with hydrogen can form hydrides compound
through heating process. Hydrides compound is compound of alkali metals that its
hydrogen atoms has oxidation number -1.
2M(s) + H2(g) → 2MH(s)
The example for reaction of alkali metals can be seen as follows:
2Li + H2→ 2LiH
As white crystal solid with density about 0.8 g/cm3 , it can be decomposed in
water and soluble in acid.
2Na + H2→ 2NaH
It has density about 0.92 g/cm3 and insoluble in ammonia.
2K + H2→ 2KH
It has density 1.47 1,47 g/cm3 react marvelously in water but insoluble in benzene
and ether.
1.8.6 Reaction with Ammonia

The mixture of alkali metal and ammonia in dilute solution result dark
blue solution. It can conduct electricity because the solvation electron as the result
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of metal ionization. For sodium, the ionization equation in ammonia solution is as

follows:
Na(s) + NH3 ⇌ NA+(NH3) + e (NH3)
At concentrated through evaporation, the solution turns into bronze color
and behave as liquid metal. If we let in in long time or acceleration by addition of
catalysis of transition metal, the solution will decomposed and produce amide salt
and hydrogen gas.
2Na+ (NH3) +2 NH3(l) + 2e → 2NaNH2(NH3) +H2(g)
The other examples are:
2Li + 2NH3→ 2LiNH2 + H2
2Na + 2NH3→ 2NaNH2 + H2
2K + 2NH3→ KNH2 + H2
2Rb + 2NH3→ RbO2 + H2
2Cs + 2NH3→ CsO2 H2
1.9 SUMMARY
In the beginning of 19 century, Sir Humphry Davy found elements of
sodium, potassium, barium, strontium, boron, calcium, and magnesium. While,
francium (Fr) was found by Marguerite Perey (French) at 1939. Except the
radioactive Francium, all of alkali metals can be isolated by electrolysis or
reduction. Earth shell contain about 0.006% of lithium mass. Main source of
lithium is spodumen mineral, LiAlSi2O6 . Sodium and potassium metals are
abundant in the Earth’s biosphere (2.6% and 2.4% respectively). The main
sources of Na and K are rock salt (almost pure NaCl), natural brines and sea
water, minerals of solvate (KCl/NaCl) and carnalite (KCl.MgCl.6H2O).
Potassium exist in the earth has little radioactive properties because it contains
about 0.02% of radioactive isotope 40K with half-life 1.3 x 109 years. Significant
proportions of radiation are resulted by human body. Natural abundances of Rb
and Cs are small (% abundance of Rb is bigger than that of Cs). Francium has
very short half-life that is formed in natural radioactive dating series or nuclear
reactor.
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The influences of increasing in atomic and ionic size on physical and

chemical properties are more clearly shown by the alkali metals than the other
groups of elements. Both elements and compounds of alkali metals are largely
used in our daily life. There some compounds of alkali metals, such as hydrides,
halides, oxides, hydroxides, and salts of oxyacids. Further, the reaction of alkali
metal and ammonia is also the interest one. Generally, the reactions of alkali
compounds are influenced by ionic characteristic, ion hydration, and solubility.
STUDY QUESTIONS
1.1 Explain the finding histories of alkali metal elements!
1.2 Compare the natural abundances of alkali metal elements!
1.3 Explain how to isolate sodium as well as lithium metals from their minerals!
1.4 Explain how to get pure NaCl from see water!
1.5 Explain why the oxides of sodium are stable as dioxide (2-) or peroxide, but
the oxides of potassium are stable as dioxide (1-) or superoxide!
1.6 Expain how to synthesize Na2CO3 using Solvay Process!
1.7 Compare the reactions if sodium metal is put into water and if the metal is put
into ammonia!
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CHAPTER 2
EARTH ALKALI METAL CHEMISTRY
2.1 INTRODUCTION
Group IIA elements in periodic table are known as the alkaline earth
metal. The alkaline earth metals are somewhat less electropositive and less
reactive than the alkali metals (Chang, 2010: 901). Except for the first member of
the family, beryllium, which resembles aluminum (a Group 3A metal) in some
respects, the alkaline earth metals have similar chemical properties. The
relationships among the elements in group IIA (beryllium, magnesium, calcium,
strontium, barium and radium) are very like those among the alkali metals.
Because their M2+ ions attain the stable electron configuration of the preceding
noble gas, the oxidation number of alkaline earth metals in the combined form is
almost always +2. Radium was little to say in this essay because it is radioactive
226 238
and is formed as Ra88 α-emitter in the U92 decay series. This is to explain
briefly the history, abundance, isolation, uses and properties of alkaline earth
metal elements, as well as the properties of alkaline earth metal compounds such
as the hydrides, halides, oxides, hydroxides, and salt of oxyacids.
2.2 HISTORY
The earliest known alkaline earth was lime (Latin: calx), which is now
known to be calcium oxide; it was used in ancient times in the composition of
mortar. Magnesia (the name derives probably from the ancient district of
Magnesia in Asia Minor), the oxide of magnesium, was shown to be an alkaline
earth different from lime by the Scottish chemist Joseph Black in 1755; he
observed that magnesia gave rise to a soluble sulfate, whereas that derived from
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lime was known to be insoluble. In 1774 Carl Wilhelm Scheele, the Swedish
chemist who discovered oxygen, found that the mineral called heavy spar or barys
(Greek: heavy) contained a new earth, which became known as baryta (barium
oxide). A further earth, strontia (strontium oxide), was identified by the London
chemists Adair Crawford and William Cruickshank in 1790 on examining a
mineral (strontium carbonate) found in a lead mine at Strontian in Argyllshire,
Scotland. Beryllia (beryllium oxide) was extracted from the mineral beryl and
recognized as an earth by the French analytical chemist Nicolas-Louis Vauquelin
in 1798 (Britannica Encyclopedia, 2012).
Magnesium, calcium, strontium, and barium that is elements derived from
alkaline earths were isolated as impure metals by Sir Humphry Davy in 1808 by
means of the electrolytic method he had previously used for isolating the alkali
metals potassium and sodium. The alkaline-earth metals were later produced by
reduction of their salts with free alkali metals, and it was in this way (the action of
potassium on beryllium chloride) that beryllium was first isolated by the German
chemist Friedrich Wöhler and the French chemist Antoine Bussy independently in
1828. Radium was discovered in 1898 by means of its radioactivity by Pierre and
Marie Curie, who separated it from barium (Britannica Encyclopedia, 2012).
2.3 PROPERTIES
The group 2 elements are good conductor and electricity. The alkaline
earth metals are less electropositive and less reactive than the alkali metals. In all
compounds, group 2 have an oxidation number +2. The observed result of this
decrease in size is that the Group 2 elements are denser and have higher ionization
energies than the Group 1 elements. Group 2 also have higher melting and boiling
points and higher enthalpies of fusion and vaporization (Miessler & Tarr, -: 255).
Selected physical properties of the alkaline earths are given in the following table.
Table 2.1 Physical Properties of Alkaline Earth Metals
Be Mg Ca Sr Ba
2
Valence electron configuration 2s 3s2 4s2 5s2 6s2
Density (g/cm3) 1.86 1.74 1.55 2.6 3.5
Melting point (oC) 1280 650 838 770 714
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Boiling point (oC) 2770 1170 1484 1380 1640

Atomic radius (pm) 112 160 197 215 222
Ionic radius (pm*) 34 78 106 127 143
First and second ionization 899 738 590 548 502
energies (kJ/mol) 1757 1450 1145 1058 958
Electronegativity 1.5 1.2 1.0 1.0 0.9
Standard reduction potential (V) -1.85 -2.37 -2.87 -2.89 -2.90
Source: Chang, 2010: 901
Beryllium and magnesium are grayish metals, while the remaining group 2
metals are soft and silver-colored. The metals are malleable, ductile and quite
brittle; in air, the shiny surface of each metal quickly tarnishes (Housecroft &
Sharpe, 2008: 305-306).
The elements in Group 2 (IIA), with the exception of beryllium, have very
similar chemical properties, with much of their chemistry governed by their
tendency to lose two electrons to achieve a noble gas electron configuration. In
general, elements in this group are good reducing agents. Although not as
violently reactive toward water as the alkali metals, the alkaline earths react
readily with acids to generate hydrogen:
Mg + 2H+ → Mg2+ + H2
The reducing ability of these elements increases with atomic number. As a
consequence, calcium and the heavier alkaline earths react directly with water in a
reaction that can conveniently generate small quantities of hydrogen (Miessler
&Tarr, 2004:255):
Ca + H2O → Ca(OH)2 + H2
When heated, all the group 2 metals combine with O2, N2, sulfur or halogens as
shown in the following equation.
2M + O2 → 2MO M = Ca, Sr, Ba
3M + N2 → M3N2
8M + S8 → 8MS
M + X2 → MX2 X = F, Cl, Br, I
When heated with H2, Ca, Sr and Ba form saline hydrides, MH2, but Mg
reacts only under high pressure. In contrast, BeH2 is prepared from beryllium
alkyl. Beryllium combines with carbon at high temperature to form Be2C. The
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other elements of group 2 metals form carbides MC2. Whereas Be2C reacts with
water, the carbides of the later metals hydrolyze to yield C2H2 according the
following equation.
Be2C + 4H2O → 2Be(OH)2 + CH4
MC2 + 2H2O → M(OH)2 + C2H2 M = Mg, Ca, Sr, Ba
Beryllium is distinctly different from the other alkaline earths in its
chemical properties. The smallest of the alkaline earths, it participates primarily in
covalent rather than ionic bonding. Although the ion [Be(H2O)4]2+ is known, free
Be2+ ions are rarely, if ever, encountered. Beryllium and its compounds are
extremely toxic, and special precautions are required in their handling. (Miessler
&Tarr, 2004:255)
Besides, emission spectra for the group 2 metals are readily observed and
flame test can be used to distinguish between Ca, Sr and Ba containing
compounds: Ca (orange-red, but pale green when viewed through blue gas), Sr
(crimson, but violet through blue gas), Ba (apple-green) (Housecroft & Sharpe,
2008: 305-306).

Beryllium occur as the silicate mineral beryl, Be3Al2[Si6O18]. It is also
found in many natural minerals, and precious forms including emerald and
aquamarine. Magnesium and calcium are the eighth and fifth most abundant
elements in the Earth’s crust, and Mg is third most abundant in the sea. The
elements Mg, Ca, Sr and Ba are widely distributed in mineral and as dissolved
salts in seawater. The minerals are dolomite (CaCO3.MgCO3), magnesite
(MgCO3), olivine ((Mg,Fe)2SiO4), carnallite (KCl.MgCl2.6H2O), CaCO3 (chalk,
limestone, and marble), gypsum (CaSO4.2H2O), calastite (SrSO4), strontianite
226
(SrCO3) and barites (BaSO4). Radium is radioactive and is formed as Ra88 in
238
the U92 decay series. (Housecroft & Sharpe, 2008: 305-306)
2.5 ISOLATION
Magnesium is produced in several ways. Two important sources are
dolomite rock and seawater. Magnesium is manufactured on a large scale. The
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mixed metals carbonate dolomite as thermally decomposed to a mixture of CaO

and MgO, MgO is reduced by ferrosilicon in Ni vessels; Mg is removed by
distillation in vacuo. (Housecroft & Sharpe, 2008: 306)
2MgO + 2CaO + FeSi → 2Mg + Ca2SiO4 + Fe T = 1450 K
Magnesium is also isolated from MgCl2 by electrolysis and is applied to the
extraction of the metal from seawater. The first step is precipitation of Mg(OH)2
by addition of Ca(OH)2 (slake lime), produced from CaCO3. Neutralization with
hydrochloric acid and evaporation of water gives MgCl2. xH2O, which, after
heating at 990 K, yields the anhydrous chloride. Electrolysis of molten MgCl2 and
solidification of Mg completes the process is shown in the following equation.
(Housecroft & Sharpe, 2008: 306)
2HCl + Mg(OH)2 → MgCl2 + H2O
cathode: Mg2+(l) + 2e- → Mg(l)
anode: 2Cl-(l) → Cl2(g) + 2e-
Beryllium is obtained from beryl by heating with Na2SiF6 and extracting
the water, and then soluble BeF2 and precipitate of Be(OH)2 are formed. Then
beryllium is produced by reduction of BeF2 or by electrolysis of BeCl2 which is
fused with NaCl. (Housecroft & Sharpe, 2008: 306)
BeF2 + Mg → Be + MgF2 T = 1550 K
The production of Ca is by electrolysis of fused CaCl2 and CaF2.
Strontium and barium are extracted by reduction of corresponding oxides by Al,
or by electrolysis of MCl2 (M = Sr, Ba).
The metal of strontium can be prepared by electrolysis of melted strontium
chloride mixed with potassium chloride:
cathode: Sr2+ + 2e- → Sr
anode: 2Cl- → Cl2(g) + 2e-
Alternatively it is made by reducing strontium oxide with aluminium in a vacuum
at a temperature at which strontium distills off.
Barium metal is difficult to obtain in its pure form, because it quickly
becomes oxidized in air. It is primarily found and extracted from the mineral
barite which is crystallized barium sulfate. Barium is commercially produced
through the electrolysis of molten barium chloride (BaCl2) Isolation;
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cathode: Ba2+ + 2e- → Ba

anode: Cl- → 0.5Cl2(g) + e-
Radium as radioactive was first isolated by Pierre and Marie Curie from
the uranium ore, pitchblende. It was collected from solutions by coprecipitation
with BaSO4 and the nitrates subsequently fractionally crystallized.
2.6 USES
Beryllium is used in the manufacture of body part in high-speed aircraft
and missiles, and in communication satellites because it is very light. Because of
its low electron density, Be is poor absorber of electromagnetic radiation and, as a
result, is used in X-ray tube windows. It has high melting point and cross-section
for neutron capture make Be useful in the nuclear energy industry.
The presence of Mg having a strong reducing power in Mg/Al alloys gives
greater mechanical strength and resistance to corrosion, and also improves
fabrication properties. Alloys of Mg/Al are used in aircraft and automobile body
parts and lightweight tools. Its strong reducing power also means that it can be
used to extract less electropositive metals such as titanium in the Kroll process,
which take place at 1250 K under an argon atmosphere(Ratcliff et. al, 2004: 217):
2Mg(s) + TiCl4(g) → Ti(s) + 2MgCl2(l)
Magnesium is still used in the manufacture of fireworks, flares, and photographic
flashlights and medical applications such as indigestion powder (milk of
magnesia, Mg(OH)2) and a purgative (Epsom salts, MgSO4.7H2O) (Housecroft &
Sharpe, 2008: 307). Magnesium is also used for the preparation of Grignard
reagents. Magnesium plays several important biological roles. It is present in
intracellular and extracellular fluids. Magnesium ions are essential for the proper
functioning of a number of enzymes. Magnesium is also present in the green plant
pigment chlorophyll, which plays an important part in photosynthesis.
Uses of calcium compounds far outnumber those of the metal, with the
world production of CaO, Ca(OH)2, CaO.MgO, Ca(OH)2.MgO and
Ca(OH)2.Mg(OH)2. Calcium oxide (quicklime or lime) is produced by calcining
limestone and it is used as a component in building mortar. Calcium oxide is the
origin of the theatrical term ‘limelight’, because it glows with a bright white light
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when strongly heated and was originally used in stage lightening (Ratcliff et. al,
2004: 218). Dry sand and CaO mixtures can be stored and transported. On adding
water, and as CO2 is absorbed, the mortar sets as solid CaCO3. The sand in the
mortar is a binding agent (Housecroft & Sharpe, 2008: 307).
CaO(s) + H2O(l) → Ca(OH)2(s) ΔHr0 = -65 kJ mol-1
Quicklime Slaked lime
Ca(OH)2(s) + CO2(g) → CaCO3(s) + H2O(l)
Lime is also used in the steel industry, pulp, and paper manufacturing, and
extraction of Mg. For example, calcium carbonate is in manufacturing of steel,
glass, cement and concrete. Large quantities of Ca(OH)2 are used to manufacture
bleaching powder, Ca(OCl)2.Ca(OH)2.CaCl2.2H2O and in water treatment.
Calcium fluoride that occurs in nature as the fluorspar is important as the raw
material for the manufacture of HF and F2 as the following reaction equation.
CaF2 +H2SO4 → 2HF + Ca(HSO4)2
In small amount, CaF2 is also used as a flux in the steel industry, for welding
electrode coatings, and manufacture of glass.
There are two mineral source of strontium, namely the sulfate (celestite)
and carbonate (strontianite). The main use of strontium is as a component in color
television faceplate glass where it has function to stop X-ray emissions from the
cathode ray tube (CRT). Other uses of strontium are in ferrite ceramic magnets
and pyrotechnics.
Barite (BaSO4) which is known as the mineral of barium is used as
weighting material in oil and gas. On small scale of application, the ability of
BaSO4 to stop the passage of X-rays leads to its use as a barium meal in radiology
for imaging the alimentary tract. Uses of Ba as a getter in vacuum tubes arise
from its high reactivity with gases including O2 and N2. Radium has been used in
the treatment of cancerous tumors, but its use has largely been superseded by
other radioisotopes.
2.7 HYDRIDES
All Group II elements, except beryllium, form hydrides by direct
combination with hydrogen. Beryllium hydride (BeH2) was first prepared in 1951
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by reduction of BeCl2 in ether and by reaction of BeMe2 with LiAlH4. The purer
one can be obtained by pryolysis of Be(t-Bu)2 at 210oC. (Greenwood &
Earnshaw; 1997: 115)
The hydrides of the metals except magnesium and beryllium are white and
ionic solids. The hydrides are stable in dry air but react with water, the vigor of
the reaction increasing with the molecular weight of the hydride.
MH2 + 2H2O → M(OH)2 + H2 ↑
This reaction is due to the very strong basic property of the hydride ion H- which
behaves as a powerful proton acceptor and is therefore strongly basic, i.e.
H- + H2O → H2 + OH-
When the molten ionic hydrides are electrolyzed, all yield hydrogen at the anode
and the metal at the cathode.
The hydrides of beryllium and magnesium are covalent. Magnesium hydride
has a “rutile” structure while beryllium hydride forms an electron-deficient chain
structure. (Chambers and Holliday, 1975: 126)
2.8 HALIDES
Group II metals also form halides but the properties of beryllium halides are
slightly different with the rests in group. As a consequence of the high ionization
energy, beryllium halides are essentially covalent, with comparatively low melting
points. Its melts is non-conducting and dissolving in many organic solvents. BeF2
is obtained as a glass (sublimation point 1073 K) from thermal decomposition of
[NH4]2[BeF4]. In the other hand, BeCl2 can be prepared from its oxide as
following reaction
2 BeO + C + Cl2 → 2 BeCl2 + CO2
Polymerization may occur in beryllium halides trough bridging, such as in F and
Cl giving chain polymers of type [BeF2]n and [BeCl2]n. For instance, the internal
Cl-Be-Cl angles in [BeCl2]n are 98o which means that Be(μ2-Cl)2Be units are
somewhat elongated in the direction of the chain exist. In this case, each Be atom
can be considered to be sp3 hybridized and a localized σ-bonding scheme is
appropriate in which each Cl donates a lone pair electrons into an empty hybrid
orbital on an adjacent Be atom. These distortions from ideal tetrahedral angle for a
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four coordinate Be atom are dependents on the nature of the bridging group and
are related to the presence of lone pairs on the bridging atoms.
Cl
Cl
Cl
Be Be
Be
Be
Cl Cl
Cl
Figure 2.1 The Chain Structure of BeCl2

In the gas phase at high temperature, the halides forms are linear molecules, X-
Be-X. At low temperature, however, the halides exist in appreciable amounts as
dimer.
Cl
Be Be
Cl
Figure 2.2 The Dimer Structure of BeCl2
The lower members in Group II form essentially ionic halides, with

magnesium having intermediate properties. Since they are ionic; therefore have
relatively high melting point, the melts acting as conductors. The bromide,
chloride, iodide readily absorb water. The ability to form hydrates as well as
solubility in water decrease with increasing atomic size. This is because the
hydration energies decrease more rapidly than the lattice energy with increasing
M2+.
The fluoride vary in solubility, that is Mg<Ca<Sr<Ba because of the small
size of the F- relative to the M2+ ion. The lattice energy decreases unusually
rapidly because the large cations make contact with one another at the same time
making contact with F- ions. (Cotton, 1995: 313)
The most important fluoride of the alkaline earth metals is CaF2 since the
mineral (fluorite) is the only large-scale sources of fluorine. Magnesium chloride
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(MgCl2) is one of the most important salts of Mg industrially and its concentration
in sea water exceed only by NaCl. Calcium chloride (CaCl2) also has great
importance. Its traditional use include: (1) brine for refrigeration plants; (2)
control snow and ice on highways and pavements; (3) dust control on secondary
roads, unpaved streets. (Greenwood & Earnshaw; 1997: 119)
2.9 OXIDES
The oxides (MO) are white, high melting crystalline solids, with NaCl-type
lattice. They are best obtained by calcining the carbonates. Beryllium oxide (BeO)
has good chemical stability and a very high conductivity. Calcium oxide (CaO),
which is also referred to as quicklime, is one of the oldest materials known to
mankind. Quicklime is produced by the thermal decomposition of calcium
carbonate:
CaCO3(s) + CaO(s) → CO2(g)
Calcium oxide is used in cement, mortar and plaster manufacture. It still has a
very important role in purifying iron, as it reacts with impurities in the ore to from
a molten slag:
CaO + SiO2 → CaSiO3
The chemistry of magnesium is intermediate between that of beryllium
and the heavier Group 2A elements. Magnesium does not react with cold water
but does react slowly with steam:
Mg(s) + H2O(g) → MgO(s) + H2(g)
Magnesium oxide reacts very slowly with water to form magnesium hydroxide, a
white solid suspension called milk of magnesia, which is used to treat acid
indigestion:
MgO(s) + H2O(l) → Mg(OH)2(s)
2.10 HYDROXIDES
The hydroxides M"(OH)2 of alkaline earth metal are generally less soluble
and are of lower base strength than alkaline metal (Chambers & Holliday, 1975:
130). Beryllium hydroxide is obtained as a white gelatinous precipitate when OH-
ions are added to a solution of a beryllium salt. Beryllium hydroxide is amphoteric
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and this sets it apart from the hydroxide of the other group 2 metals which are
basic. This amphoteric is also shown by aluminium hydroxide in Group III where
it has characteristic of small ions of high charge, i.e. Be2+ and A13+ (Housecroft &
Sharpe, 2008: 317). It is only sparingly soluble in water, dissolving in strong acids
to give the hydrated beryllium ion [Be(H2O)4]2+ , but also dissolving in solutions
containing the hydroxide ion to give the tetrahedral complex ion of
tetrahydroxoberyllate(II) ion [Be(OH)4]2+; addition of acid first reprecipitates the
hydroxide Be(OH)2 (as a white gelatinous hydrated precipitate) and then re-
dissolves it to give the hydrated ion; hence the following is sequence of the
reaction (Chambers & Holliday, 1975: 131):
OH Be(OH)2 OH
2+ 2-
[Be(H2O)4] + [Be(H2O)4]
+ (H 2O)2 H
H
2-
OH
Be OH
HO
OH
Figure 2.3 Tetrahedral complex ion of [Be(OH)4]2-

The other Group II hydroxides M"(OH)2 (M"=Mg, Ca, Sr, Ba) are
sparingly soluble in water, the solubility increasing down the group; as do their
thermal stabilities with respect to decomposition into MO and H2O (Housecroft &
Sharpe, 2008: 317). Magnesium hydroxide acts as weak base, whereas Ca(OH)2,
Sr(OH)2 and Ba(OH)2, are strong base. Magnesium hydroxide is precipitated only
by an appreciable concentration of hydroxide ion (not by ammonium hydroxide in
presence of ammonium chloride) and the others are not precipitated. Magnesium
hydroxide is a weak alkali and is also used in toothpastes; where it helps to
neutralize acids in mouth with encourage tooth decay. Representing acid as
H+(aq), the following reaction occurs:
Mg(OH)2(s) + 2H+(aq) → Mg2+(aq) +2H2O(l)
Soda lime is a mixture of NaOH and Ca(OH)2 and is manufactured from CaO and
aqueous NaOH. Soda lime is easier to handle than NaOH and is commercially
available, being used, for example, as an absorbent for CO2, and in qualitative test
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for [NH4]+ salts, amides, imides and related compounds which evolve NH3 when
heated with soda lime.
Table 2.2 Summary Properties of Earth Alkali Hydroxides
Element Be Mg Ca Sr Ba
Insoluble Solubility increase
M(OH)2 Amphoteric Base strength increase
Source: Chambers & Holliday, 1975: 131
2.11 SALTS OF OXYACIDS

There are some salts of oxyacids of group two metal such as the
carbonates and sulfates. Most beryllium salts of strong oxyacids crystallize as
soluble hydrates. Beryllium carbonate tends to hydrolyze, giving a salt containing
[Be(OH2)4]2+. Beryllium carbonate can be isolated only by precipitation under an
atmosphere of CO2. Beryllium is unique in forming a series of stable volatile,
molecular oxide-carboxylates of general formula [OBe4(RCO2)6], where R= H,
Me, Et, Pr, Ph, etc (Greenwood & Earnshaw, 1997: 122). These white crystalline
compounds, of which “basic beryllium acetate” (R=Me) is a typical, are readily
soluble in organic solvents, including alkanes, but are insoluble in water or the
lower alcohols. The carbonate of Mg and the later metals are sparingly soluble in
water (Housecroft & Sharpe, 2008: 317). Their thermal stabilities increase with
cation size, and this trend can be rationalized in terms of lattice energies. The
metal carbonates are much more soluble in a solution of CO2 than in water due to
the formation of [HCO3]-. However, salts of the type ‘M(HCO3)2’ have not been
isolated.
Hard water contains Mg2+ and Ca2+ ions which complex with the stearate
ions in soaps, producing insoluble “scum” in household baths and basins
(Housecroft & Sharpe, 2008: 318). Temporary hardness is due to the presence of
hydrogencarbonate salts and can be overcome by boiling which produce
precipitate of CaCO3 and/or MgCO3, or by adding an appropriate amount of
Ca(OH)2 as the following reaction.
Ca(HCO3)2 (aq) ⇌ CaCO3(s) + CO2(g) + H2O(l)
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Ca(HCO3)2 (aq) + Ca(OH)2(aq) → 2CaCO3(s) + H2O(l)

Permanent hardness is caused by other Mg2+ and Ca2+ salts (e.g. sulfates). The
process of water softening involves passing the hard water through a cation-
exchange resin. Washing-machine detergents contain ‘builders’ that remove Mg2+
and Ca2+ ions from washing water; polyphosphate have been used for this
purpose, but because phosphates are damaging to the environment, zeolite are
used in preference.
Calcium carbonate occurs naturally in two crystalline forms, calcite and
the metastable aragonite (Housecroft & Sharpe, 2008: 318). In calcite, the Ca2+
and CO32- ions are arranged in such as way that each Ca2+ ion is 6-coordinate with
respect to the carbonate O atoms, whereas in aragonite, each Ca2+ ion is
surrounded by nine O atoms. The energy difference between them is <5 kJ/mol
with calcite being thermodynamically favored form. However, aragonite is
kinetically stable with respect to conversion to calcite. Aragonite can be prepared
in the laboratory by precipitation of CaCO3 from hot aqueous solution.
Sulfates of Mg and Ca have important applications. Hydrated calcium
sulfate (CaSO4.2H2O, gypsum) occurs naturally and is also a product of
desulfurization processes involving Ca(OH)2 or CaCO3 (Housecroft & Sharpe,
2008: 318). Gypsum crystals cleave easily owing to the presence of layers which
are held together by hydrogen bonding. When gypsum is heated at ≈400K, it form
the hemihydrate CaSO4. ½ H2O, and if this is mixed with water, the material
expands slightly as the dihydrate is regenerated. Barium sulfate is a sparingly
soluble salt (Ksp= 1.07 x 10-10) and the formation of white precipitate of BaSO4 is
used as a qualitative test for the presence of sulfate ions in aqueous solution.
BaCl2(aq) + SO42-(aq) → BaSO4(s) + 2Cl-(aq)
2.12 SUMMARY
Based on the explanation above, it can be concluded that the alkaline earth
metals are less electropositive and less reactive than the alkali metals. The
elements are good conductor and electricity; and in all compounds, groups 2 have
an oxidation number +2. The elements are widely founded in the form of mineral
and the isolation of the elements can be done by several ways e.g. electrolysis.
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Alkaline earth metal elements have many uses namely beryllium is used in the
manufacture of body part in high-speed aircraft and missiles, and in
communication satellites; magnesium is still used in the manufacture of fireworks,
flares, and photographic flashlights and medical applications such as indigestion
powder (milk of magnesia, Mg(OH)2) and a purgative (Epsom salts,
MgSO4.7H2O); uses of calcium compounds far outnumber those of the metal,
with the world production of CaO, Ca(OH)2, CaO.MgO, Ca(OH)2.MgO and
Ca(OH)2.Mg(OH)2.; strontium is used as a component in color television faceplate
glass; radium has been used in the treatment of cancerous tumors. Alkaline earth
metals are forming compounds with other elements in the form of hydrides,
halides, oxides, hydroxides, and salt of oxyacids which have different
characteristics.
STUDY QUESTIONS
2.1 Explain the finding history of earth alkali metals!
2.2 Explain the isolation manner of earth alkali metals from their corresponding
minerals!
2.3 Explain the natural abundance and distribution of the elements of earth alkali
metals in the earth crush!
2.4 Explain the uses of earth alkali metal elements!
2.5 Explain the properties of earth alkali metal elements!
2.6 Explain the properties and reactions of the earth alkali compounds: hydrides,
halides; carbides, oxides, hydroxides, and salts of oxyacids!
2.7 Explain the preparation methods of the earth alkali compounds: halides,
carbides, oxides, hydroxides, and salts of oxyacids!
2.8 Explain the uses of the alkali compounds: halides, carbides, oxides,
hydroxides, and salts of oxyacids!
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CHAPTER 3
ALUMINIUM CHEMISTRY
3.1 INTRODUCTION
Aluminium is the commonest metallic element in the earth crust and
occurs in rocks such as feldspar and micas Cotton, 1995: 357). Aluminium has
excellent resistance to corrosion due to the thin layer of aluminium oxide that
forms on the surface of aluminium when it is exposed to air. Aluminium is a
popular choice of material for complex sectioned hollow extrusions. Aluminium is
much more metallic than boron and forms a greater number and variety of ionic
substances. Aluminium can be easily fabricated into various forms such as foil,
sheets, geometric shapes, rod, tube and wire. This is to explain briefly the history,
abundance, isolation, uses, properties of aluminium, hydrides and their complexes,
carbides and nitrides, halides and their complexes, oxide and chalconides, hydroxides,
spinnel and aluminates, salts of oxyacid.
3.2 HISTORY OF ALUMINIUM

Aluminium derives its name from alum, the double sulfate KAl(SO4)2 .
12H2O, which was used medicinally as an astringent in ancient Greece and Rome
(latin alumen, bitter salt). Humphry Davy was unable to isolate the metal
proposed the name “aluminum” and then “aluminium”, this was soon modified to
aluminium and this form is used throughout the world except in North America
where the ACS decided in 1925 to adopt “aluminium” in its publication. The
impure metal was first isolated by the Danish scientist H.C Oersted using the
reaction of potassium amalgam on AlCl3. This method was improve in 1827 by H.
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Wohler who used metallic potassium, but the first commercially successful
process was devised by H. St.C Deville in 1854 using sodium. In the same year
both he and R. W Bunsen independently obtained metallic aluminium by
electrolysis of fused NaAlCl4. 1n 1855, Emperor Louis Napoleon III used Al
cutlery on state occasions. By W. Siements in 1870, aluminium it is used as
cheap electric power the development of dynamo and secondly to the independent
development in 1886 electrolysis of alumina dissolved in cryolite by P.L.T
Heroult in France and C.M Hall the USA. World production rose quickly and
1879 exceeded 1000 tones pa for the first time (Greenwood, 199: 216)

Aluminium is the most abundant metal in the earth crust (8.3% by weight),
it is exceeded in abundance only by O (45.5%) and Si (25.7%) and is approached
only by Fe (6.2%) and Ca (4.6%) (Enhag:2004). Aluminium is a major constituent
of many common igneous minerals including feldspars and mics. The most
important of aluminum production is bauxite, which is hydrated aluminum oxide
containing 50 to 60% Al2O3, 1 to 20% Fe2O3, 1 to 10% silicate little titanium,
zirconium, vanadium, and other transition metal oxides, and the rest 20 to 30%
water.
3.4 ISOLATION
In 1825, Oersted was obtained pure aluminium by reduction of aluminium
chloride with amalgana potassium-mercurium. By destilation mercury can
separate and get aluminium metal.
AlCl3(s) + 3K(Hg)x(l) 3KCl(s) + Al(Hg)3x(l)
The isolation of aluminium can get from bauxite by two processes namely
Bayer and Hall-Heroult process. In the Bayer process, the bauxite is purifying to get
the aluminium oxide. Second step is Hall-Heroult process by molten of aluminium
dioxide to get the pure aluminium.
Hall-Heroult
Bayer Process Process
BAUXITE ALUMINA ALUMINIUM
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Bayer process consist of three steps, namely extraction, precipitation, and

calcinations (Anonymous, 2009). In extraction process, the bauxite is broke by
mechanic and then dissolve in aluminium oxide become aluminium hydroxide ,
Al(OH)3. Remaining of more OH- will produce [Al(OH)4]-
Al2O3 + 2OH- +3H2O ]-(aq)
SiO2 that contain in bauxite is react with NaOH. The reaction as follows:
SiO2 + 2OH- SiO32-(aq) +H2O(l)
Al(OH)4-(aq) + CO2 Al(OH)3(s) + CO32-(aq) + H+
The other component except aluminium oxide is not dissolve. So the aluminium
oxide will be separated from interference of Fe. This separation can be done by
filtration. After the separation, it interferences which not dissolve will enter to the
precipitation process. The filtrate that contain of aluminium hydroxide is cooling,
the produce solid white precipitate. Next step is calcinations, solid white
precipitate of aluminium hydroxide is heat in the temperature 10500C. In this
step, the heating of aluminium hydroxide will decomposition become alumina and
produce vapour in its process.
Al(OH)3(s) Al2O3(s) + 3H2O
Aluminium was obtained by Hall-Heroult process. In the second steps ,
electrolysis of Al2O3. Electrolysis cell is made from steel that coated with
graphite. This graphite has function as anode and cathode that formed from
carbon. Al2O3 is dissolve in kryolite (Na3AlF6). The reaction in electrode can write
as follow:
Cathode: AlF4-(aq) + 3e Al(s) + 4F-(aq) or
2Al3+ + 6e 2Al(s)
4-
Anode : 2AlOF5 (aq) + C CO2(g) + AlF63-(aq) + AlF4- + 4e or
3O2-(aq) + 3/2 C 3/2 CO2(g) + 6e
Based on the reaction above, all of reaction can write by simpler reaction
became:
2Al2O3(s) + 3C(s) 4Al(s) + 3 CO2(g)
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3.5 PROPERTIES AND USES

Aluminium is a silvery white metal with many desirable properties. It is
one of the two common metals having electrical conductivity high enough for use as
an electrical conductor. The conductivity of electrical conductor grade (alloy 1350) is
about 62% that of the International Annealed Copper Standard. Aluminium has non-
magnetic properties which make it useful for electrical shielding such as busbar or
magnetic compass housings. The fact that aluminium is essentially nontoxic was
discovered in the early days of the industry. It is this characteristic which enables the
metal to be used in cooking utensils without any harmful effect on the body (Mathers,
2002). Aluminium with its smooth surface is easily cleaned, promoting a hygienic
environment for food processing. Selected atomic properties of aluminium are given
in the following table.
Table 3.1 The atomic properties of aluminium
Atomic number 13
Period in periodic table 3
Group in periodic table III A
Color Silver
Classification Metallic
Atomic weight 26.981538
Electron configuration 1s22s22p63s23p1
Ionization energy/ kJ mol-1 I. 577.5
II. 1816.7
III. 2744.8
Table 3.2 Physical Properties of Aluminium

Melting Point/ 0C 660.45
Boiling Point/ 0C 2520
Density (200C)/gcm-3 2.699
Hardness (Mohs) 2.75
Hfus/kJ mot-1 10.71
Hvap/kJ mot-1 294
Hf (monoatomic gas)/kJ mol -1 329.7
Electrical resistivity/  ohm cm 2.655
E0(M3+ + 3e- = M(s))/V -1.676
E0(M+ + 3e- = M(s))/V 0.55
Electronegativity 1.5
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Aluminium is easily to burn and produce high of reaction heat. The

reaction as follows:
2 Al + 3/2 O2 Al2O3
This properties is used as the basic to reduction of sulphide and oxide. Example:
2Al + Fe2O3 2Fe + Al2O3 + 199 k.cal
Aluminium is react with acid to produce hydrogen gas. The reaction as follows:
2Al(s) + 6 H+ (aq) 2Al3+(aq) + 3H2
It has properties to produce hydrogen gas when react with strong base. The
reaction as follow
2Al(s) + 2OH- (aq) + 2H2O 2AlO-2 + 3H2
Aluminium foils are able to withstand the heat, because it has power
reflectivity of 95%-98% that receivedsolar heat will be reflected back.
Installationof aluminium foil placed under the battens, so the heat received by a
layer of roofing directly returned from getting into the room. Aluminium foil is
heat resistant of roof coating, roof insulation serves as a building material made of
strong, elasticand waterproofasa weelas freonresistant. So,it is safe for
environment.
Because of aluminium is very light, so it can be used in the transportations
industry such as airplane. Aluminium has a weight1/3 if compare with iron or
steel.
3.6 ALUMINIUM COMPOUNDS

3.6.1 Hydrides and Related Complexes
AlH3 is a colorless in volatile solid which is extensively polymerized via
Al-H-Al bonds, it is thermally unstable above 150-200 , is a strong reducing agent
and reacts violently with water other protic reagents to liberate H2. Several
crystalline and amorphous modifications have been described and the structure of
-AlH3 has been determined by X-ray and neutron diffraction. AlH3 is prepared
by the reaction of ethereal solutions of LiAlH4 and AlCl3 under very carefully
controlled condition (Greenwood:1997).
3LiAlH4 + AlCl3 4[AlH3(Et2O)6] + 3LiCl
Et2O
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AlH3 readily forms adducts with strong Lewis bases (L) but these are more
conveniently prepared by reactions of the type
Et2O
LiAlH4 + NMe3HCl [AlH3(NMe3)] + LiCl + H2
[AlH3(NMe3)] has a tetrahedral structure and can take up a further mole of ligand
to give [AlH3(NMe3)2] this was the first compound in which Al was shown to
adopt a 5-coordinate trigonal bipyramidal structure. LiAlH4 is a white crystalline
solid, stable is dry air but highly reactive towards moisture, protic solvents, and
many organic functional groups. It is readily soluble in ether and is normally used
in this solvent. LiAlH4 has proved to be an outstandingly versatile reducing agent
since its discovery some 50 years ago. It can be prepared on the laboratory (and
industrial) scale by the reaction
4LiH + AlCl3 LiAlH4 + 3LiCl
On the industrial (multitonne) scale it can also be prepared by direct high-pressure
reaction of the elements or preferably via the intermediate formation of the Na
analogue.
Na + Al + 2H2 NaAlH4
3.6.2 Halides and Their Complexes

AlF3 is made by treating AL2O3 with HF gas at 700o and the other
trihalides are made by the direct exothermic combination of element. AlF3 is
important in the industrial production. AlF3 is also prepared by the reaction :
Al2O3 + 6HF 2AlF3 + 3H2O
AlF3 find extensive use as a Friedel-Crafts catalyst (p.236). AlF3 is differs
from the other trihalides of Al in being involatile and insoluble, and in having a
much greater heat of formation. In AlF3 each Al is surrounded by a distorted
octahedron of 6 F atoms and the 1:3 stoichiometry is achieved by the corner
sharing of each F between 2 octahedral.
Table 3.3 Properties of Crystalline AlX3
Properties AlF3 AlCl3 AlBr3 AlI3
MP/0C 1290 192.4 97.8 189.4
Sublimation 1272 180 256 382
H0f 1498 707 527 310
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Aluminium chloride is one of compound of aluminium and chlorine.

Aluminium chloride have chemical formula of AlCl3 or AlCl3.(6H2O). The
molecular weight of AlCl3 is 133.34 (anhydrous) and 241.43 (hexahydrate). It is
white, but samples are often contaminated with iron trichloride, giving it a yellow
colour. The solid has a low melting and boiling point. It is mainly produced and
consumed in the production of aluminium metal, but large amounts are also used
in other areas of chemical industry. The compound is often cited as a Lewis
acid.Aluminium chloride can be prepared by the reaction as follows:
2Al(s) + 6HCl(aq) 2AlCl3(aq) + 3H2(g)
In Al2Cl6 dimmer, Al atom in AlCl3 is follow the octet rule with use one pair
electron together. The structure dimmer of Al2Cl6
Cl
Cl Cl
Al Al
Cl Cl
Cl
Figure 3.2 The Structure of Al2Cl6
Al2Cl6 can dissociate became AlCl3, the reaction as follow:

Al2Cl6 2AlCl3
Aluminium chloride in water will hydrolyze as the reaction:
Al3-(aq) + 3 H2O(l) Al(OH)3 + 3H-(aq)
Aluminium chloride is used as an acid catalyst, as a chemical intermediate for
other aluminium compounds, in the cracking of petroleum in the manufacturing of
rubbers and lubricants, and as an antiperspirant. The hexahydrate form is used in
preserving wood, in disinfecting stables and slaughterhouses, in deodorants and
antiperspirants, in cosmetics as a topical astringent, in refining crude oil, in dyeing
fabrics, and in manufacturing paper (Knottnerus:2009)
By contrast, Al2Br6 and Al2I6 form dimeric molecular units in the
crystalline phase as well as in the liquid and gaseous states and fusion is not
attended by such extensive changes in properties . In the gas phase Hdissoc is
59KJ mol-1 for AlBr3 and 50 kJ mol-1 for AlI3. The preparation to get Al2Br6 and
Al2I6, by the reaction:
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2Al(s) + 3Br2(l) Al2Br6(s)

2Al(s) + 3I2(l) Al2I6(s)
Br I
Br Br I I
Al Al Al Al
Br Br I I
Br I
The structure of Al2Br6 The structure of Al2I6

Aluminum chloride is a Lewis acid is most commonly used. The
application is used in the chemical industry, as catalysts of Friedel-Crafts
reactions, both as akilasy and alkylation, for example for the preparation of
antraquinone (dye industry) from benzene and phosgene. The product that
produce include detergents and etilbenzen. This substance is also used in
polymerization and isomerization reactions of hydrocarbons (Knottnerus:2009)
3.6.3 Carbides
The chemical formula of aluminium carbide is Al4C3. It has the
appearance of pale yellow to brown crystals. It is stable up to 1400 °C and
decomposes in water with the production of methane. Aluminium carbide has an
unusual crystal structure that consists of two types of layers. It is based on AlC 4
tetrahedral of two types and thus two types of carbon atoms. One is surrounded by
a deformed octahedron of 6 Al atoms at a distance of 217 pm. The other is
surrounded by 4 Al atoms at 190–194 pm and a fifth Al atom at 221 pm.
Aluminium carbide hydrolyses with evolution of methane. The reaction
proceeds at room temperature but is rapidly accelerated by heating.
Al4C3 + 12 H2O 4 Al(OH)3 + 3 CH4
Similar reactions occur with other protic reagents:
Al4C3 + 12 HCl 4 AlCl3 + 3 CH4
Aluminium carbide is prepared by direct reaction of aluminium and carbon in an

electric arc furnace
4 Al + 3 C Al4C3
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An alternative reaction begins with alumina, but it is less favorable because of

generation of carbon monoxide. The reaction as follow:
2 Al2O3 + 9 C Al4C3 + 6 CO
Silicon carbide also reacts with aluminium to yield Al4C3. This conversion limits
the mechanical applications of SiC, because Al4C3 is more brittle than SiC
4 Al + 3 SiC Al4C3 + 3 Si
Aluminium carbide particles finely dispersed in aluminium matrix lower the
tendency of the material to creep, especially in combination with silicon carbide
particles. Aluminium carbide can be used as an abrasive in high-speed cutting
tools.
3.6.4 Nitrides
Aluminium nitride is the only stable compound in the binary system Al -
N and exists in only one crystal structure (wurtzite, hexagonal). Pure AlN has a
density of 3.26 g/cm3 and dissociates under atmospheric pressure above 2500 °C.
Pure AlN is colorless and translucent but is easily colored by dopants or
impurities. Thus, carbon impurities cause the typical light gray color of AlN
powder. AlN powder is susceptible to hydrolysis by water and humidity. This is
the reason for its characteristic ammonia smell. Because AlN is a covalent
compound, limited atomic mobility prevents complete densification of pure AlN.
Thus, relatively high pressures or sintering aids are required to assist
densification. Typical sintering additives are rare-earth or alkaline-earth oxides.
To achieve high thermal conductivities mostly yttrium compounds are used. The
formation and microstructural distribution of yttrium aluminium garnet controls
both densification and thermal properties. The sintering temperatures highly
depend on the additives and range from 1600 to 1900 °C.
Aluminium nitride components and substrates are used momentarily for
various applications: (1) Power electronics (electrical engines). Aluminium metal
act as capacitate polar in power electronic , because the surface of aluminium
metal can form layer oxide metal. This layer can form by electrolysis. this
electrode is dye in electrolyte solution and the give negative voltage. Oxygen in
electrolyte solution is remove and oxidize the surface metal. So, it will for the
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oxide layer of Al2O3 in it surface; (2) Microelectronics (LSI circuits, sensor

carriers, high frequency modules specially in radio system). In radio system there
are the process of digital signal to change the characteristic of wave carrier
properties so the modulated carrier have characteristic from 0 or 1 that it contains.
By observe of modulated carrier, can know the sequence of bit. By this process,
the signal in each level can be received, to make good received it use of metal
aluminum as physic transmission media.
AlN is synthesized by the carbothermal reduction of aluminium oxide or
by direct nitridation of aluminium. The use of sintering aids and hot pressing is
required to produce a dense technical grade material. (Davydson,2009)
3.6.5 Oxides
Alumina (Al2O3) or Aluminum Oxide is the only oxide formed by the
metal aluminum and occurs in nature as the minerals corundum (Al2O3); diaspore,
gibbsite and most commonly as bauxite, which is an impure form of gibbsite. The
precious stones ruby and sapphire are composed of corundum (and thus also
natural forms of alumina) getting their colors by small amounts of impurities.
Some of these are Corundum (discovered in 1799), Diaspore (1801), Gibbsite
(1820), Boehmite (1924), Bayerite (1925), Nordstrandite (1956).
Alumina is main materials in process of aluminium electrolyze, aluminium
have morphology as white powder with melt point 2050 C and gravity
specification is 3,5-4,0. Alumina is usually in the form of ionic crystals, but the
oxide ion (O2-) polarized by aluminum ions so that most bonds are covalent, melts
at a temperature of 2053°C, insoluble in water is very hard and stable. Aluminum
oxide is found in nature as corundum as an extremely hard crystal that is used as
an abrasive and sharpening. Corundum containing impurities (a little mix of other
metal oxides) are widely used as precious stones such as: (1) white sapphire (no
mixing), (2) blue sapphire (containing Fe, Ti), (3) green sapphire (containing
Co), yellow sapphire (containing Ni, Mg), star sapphire (containing Ti), and ruby
(containing Cr).
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Figure 3.3 The type of Corundum
Aluminium oxide is occurs in two form such as -Al2O3 (corundum) and

-Al2O3 (activated alumina). -Al2O3 is stable at high temperatures and also
indefinitely met stable at low temperatures. It occurs in nature as the mineral and
may be prepared by heating -Al2O3 or any hydrous oxide above 1000 C.
Gamma-Al2O3 is obtained by dehydration of hydrous oxide at low temperatures (
450 C). Alpha-Al2O3 is hard and is resistant to hydration and to attack to acids.
Gamma-Al2O3 readily absorbs water and dissolves in acids; the alumina used for
chromatography and conditioned to different reactivities are -Al2O3. Large
quantities of -Al2O3 are used in industry as a support material for heterogeneous
catalysts.
There are several hydrated forms of alumina of stoichiometries from
AlO.OH to Al(OH)3. Addition of an aluminium salt produces a form of AlO.OH
known as boehmite. A second form of AlO.OH occurs in nature as the mineral
diaspore. The true hydroxide, Al(OH)3, is obtained as a crystalline white
precipitate when CO2 is passed into alkaline “aluminate” solutions.
Aluminium oxide is amphoteric anhydrous is react with acids and with
strong bases (alkalys) according to the reaction.
Reaction with acids:
Al2O3(s) + 6 H+(aq) 2 Al3+ (aq) + 3 H2O (l)
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Reaction with strong base:

Al2O3 (s) + 2 OH- (aq) + 3 H2O (l) → 2Al(OH)4- (aq)
Aluminium oxide is different from aluminum oxide trihydrate anhydrous. Its
density is small and is usually called aluminum hydroxide.
Al2O3.3H2O ↔ 2Al(OH)3
Release of water from the trihydrate reaction is endothermic. Therefore,
aluminum oxide trihydrate is both fire resistant. Many plastics, rubber
compounds, textiles, and some other building materials made by using these
properties. In case of fire the heat energy is absorbed by the aluminum oxide
trihydrate this.
The preparation alumina from bauxite by bayer process:
(1) Hulling process of bauxite until certain size
(2) The dissolve process of alumina with NaOH by concentration of 35-45%.
Al2O3.2H2O + 2 NaOH 2 Na2AlO2 + 3H2O
(3) Separation of soiled that precipitate by filter and get the colorless sodium
aluminate solution
(4) Sodium aluminate dissolve in water and then the precipitate of sodium
aluminate by adding seed (smooth powder of alumina) which spread in
alumina solution and precipitation of alumina, so that obtained precipitation
of alumina with big size as result of production of alumina and the smooth of
precipitation of alumina used as seed to precipitation.
2NaAlO2 + 4H2O 2 NaOH + Al2O3.3H2O
(5) Then, alumina precipitation toasted to vapor the water
(6) Dry of aluminium to fusion aluminium materials.
There are some uses of alumina such as:
(1) Mechanical Cheramics:
Due to their excellent mechanical properties, alumina based ceramics are
being increasingly used as a substitute material for several applications. These
include the use of ceramic for abrasive and cutting tools. Alumina-based
ceramics are also used for making extrusion and sanding nozzles and for parts
of machinery (particularly in the mining industry) where wear resistant
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qualities are critical. They are also used for making ice skate blades and some
friction parts such as wear-resistant seals in piston engines.
(2) Military Uses
The shock-resisting quality of alumina-ceramics makes them useful as armor
plating for protection of tanks and helicopters as well as for bullet-proof
jackets and in aeronautics for protection of hydraulic parts.
(3) Biomedical
Alumina is also an inert substance, and at room temperature, it is insoluble in
all ordinary chemical reagents. It also has excellent wear resistance and can
be polished to high surface finish. These qualities make it useful as a
biomaterial. For example, alumina is used for artificial joint replacements;
porous alumina is used as a ‘bone spacer’ and for teeth implants. In the
biomedical field, alumina is also used for cochlear implants (hearing aids for
the deaf). In the more general field of medical instruments, ceramics are also
used to manufacture medical tubes and other scientific, medical products
(4) Electronics
Alumina is widely used in the electronics industry for passive components
such as interconnection, resistances, and capacitors and is specifically
employed in applications such as substrates for hybrid circuits, multi-layer
interconnection circuits, materials for type II condensers, and hyper frequency
resonators (mobile phones).
3.6.6 Chalcogenides
The chalcogens are the chemical elements in group VIA of the periodic
table. This group is also known as the oxygen family. It consists of the elements
oxygen (O), sulfur (S), selenium (Se), tellurium (Te), the radioactive element
polonium (Po). The synthetic element livermorium (Lv) is predicted to be a
chalcogen as well. The word chalcogen comes from the Greek word chalkos,
meaning "bronze" or "ore", and the word genēs, meaning "born". While sulfur has
been known since antiquity, oxygen was only recognized as an element in the
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18th century. Selenium, tellurium and polonium were discovered in the 19th
century, while livermorium was discovered in 2000.
At normal temperatures the only stable chalconides of Al are Al2S3
(white), Al2Se3 (grey) and Al2Te3 (dark grey). It can be prepared by direct reaction
of the elements at 1000 and all hydrolyze rapidly and completely in aqueous
solution to give Al(OH)3 and H2X (X=S, Se, Te). The small size of Al relative to
the chalcogens dictates tetrahedral coordination and the various polymorphs are
related to wurtzite (hexagonal ZnS), two-thirds of the available metal sites being
occupied in either an ordered ( ) or a random ( ) fashion. Al2S3 also has a -form
related to -Al2O3, and very recently a novel high-temperature hexagonal
modification of Al2S3 containing 5-coordinate Al has been obtained by annealing
-Al2O3 at 550 C; in this new formhalf the Al atoms are tetrahedrally coodinated
(Al-S 223-227 pm) whereas the other half are in trigonal bipyramidal coodination
with Al-Seq 227-232 pm and Al-Sax 250-252 pm. Aluminium sulfide is readily
prepared by ignition of the elements.
2 Al + 3 S → Al2S3
This reaction is extremely exothermic and it is not necessary or desirable to heat
the whole mass of the sulfur-aluminium mixture; (except possibly for very small
amounts of reactants). The product will be created in a fused form it reaches a
temperature greater than 1100 °C and may melt its way through steel. The cooled
product is very hard.
3.6.7 Hydroxides
Aluminium hydroxide is called hydrate of alumina. It is found in nature as
the mineral. Closely related of aluminium oxide hydroxide, AlO(OH), and
aluminium oxide. These compounds together are the major components of the
aluminium ore bauxite. Freshly precipitated aluminium hydroxide forms gels,
which is the basis for application of aluminium salts as flocculants in water
purification. This gel crystallizes with time. Aluminium hydroxide gels can be to
form an amorphous aluminium hydroxide powder, which is readily soluble in
acids.
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Diaspore, -AlO(OH) occurs in some types of clay and bauxite; it is stable

in the range 280-450C and can be mde by hydrothermal treatment of bochmite,
-AlO(OH), in 0.4% aqueous NaOH at 380 and 500 atm. Crystalline boechmite
is readily prepared by warming the amorphous, gelatinous white precipitate which
first forms when aqueous NH3 is added to cold solutions of Al salts. In -
AlO(OH) the O atoms are arranged in hcp; continous chains of edge-shared
octahedral are stacked in layers and are further interconnected by H bonds. The
underlying hcp structure ensures that diaspore dehydrates directly to -Al2O3
(corundum) which has the same basic hcp arrangement of o atoms. The structure
is also adopted by several other -MO(OH) (M=Ba, V, Mn, and Fe); this contrast
with the structure of boechmite, -AlO(OH), which as a whole is not close-
packed, though within each layer the O atoms are arranged in cubic close packing.
dehydration at temperatures up to 450C proceeds via a succession of phases to
the cubic -Al2O3 and the (hexagonal) strucutre cannot be attained without
much more reconstruction of the lattice at 1100-1200C (Greenwood & Earshaw,
1997).
Aluminium hydroxide is used in stomach antacids, as a desiccant powder
in antiperspirants and dentifrices, in packaging materials, as a chemical
intermediate, as a filler in plastics, rubber, cosmetics and paper, as a soft abrasive
for brass and plastics, as a glass additive to increase mechanical strength and
resistance to thermal shock, weathering, and chemicals, and in ceramics.
Aluminium hydroxide is also used pharmaceutically to lower the plasma
phosphorus levels of patients with renal failure.
3.6.8 Spinel
agnesium aluminium is the large member of the spinnel group minerals. It
has the formula MgAl2O4. Spinel crystallizes in the isometric system commonly
in the form of crystal octahedral. It has an imperfect octahedral cleavage and a
conchoidal fracture. Its hardness is 8, its specific gravity is 3.5-4.1 and it is
transparent to opaque with a vitreous to dull luster. It may be colorless, but is
usually various shades of red, blue, green, yellow, brown or black.
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3.6.9 Salt of Oxyacids

Aluminium Sulfate is an aluminium oxy-acid salt that is extremely soluble
in water. An anhydrous form exists but it is relatively unimportant. Aluminium
sulfate (Al2(SO4)3), commonly called alum, is produced as white crystals which
are non-combustible and soluble in water. This dry hydrate (Al2(SO4)3.14H2O) is
17% Al2O3 and is also sold as a 47% aluminium sulfate solution which is 8%
Al2O3. It is also sold in solid form as kibbled, ground or dust. Aluminium sulfate
has been used by man since 2000 BC, when the Egyptians used a mineral alum as
a mordant in dyeing. It has long been used in paper sizing to improve durability
and ink receptivity and in water treatment to clarify water. Other uses for alum
include wastewater treatment, as a waterproofing agent and accelerator in
concrete, as a clarifier for fats and oils and as a foaming agent in fire foams. In
paper making the alum reacts with rosin sizes of various types, helping to attach
the newly formed rosin aluminates to fibres. Sizing makes the paper water
resistant. Alum, which exhibits a cationic charge, is also used to flocculate anionic
trash including paper fines and other anionically charged material by
neutralization, in a similar way to water treatment, improving drainage, retention
and strength of the material. Aluminium sulfate is produced according to the
following exothermic reaction: 2Al(OH)3 + 3H2SO4 + 8H2O → Al2(SO4)3 .14H2O
ΔfH = -156 kJ mol-1 Alum is generally produced batch wise in a reactor. The
reactor is a stirred vessel made of materials resistant to the acidity and heat of the
reaction(Mathers, 2006).
3.7 SUMMARY
Aluminium is the most abundant metal in the earth crust (8.3% by weight),
it is exceeded in abundance only by O (45.5%) and Si (25.7%) and is approached
only by Fe (6.2%) and Ca (4.6%). Aluminium was obtained by Humpry Davy
followed by Oersted in 1825, Deviller and Wohler in 1827 and have important
roles in industry, pharmacy, chemistry, electronic, etc. Aluminium have physical
and chemical properties that make aluminium is uniqueness metal. There are two
process isolation of aluminium such as by Bayer and Hall-Heroult Processes.
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Aluminium has several compounds such as Hydrides and their complexes include
of AlH3. Carbides and nitrides include of Al4C3 and AlN. Halides and their
complexes of aluminium included of AlF3, AlCl3,AlI3, and its dimmers. Oxide of
aluminium is Al2O3 that called alumina. Chacogenides of aluminium is the
compound that bond with oxygen group . the most stable chalcogenides of
aluminium are Al2S3, Al2se3, and Al2Te3. The hydroxides of aluminium is called
called hydrate of alumina that has formula AlO(OH). Spinel of aluminium is
magnesium aluminate that has chemical formula of MgAl2O4. Spinnel can be
obtained in minerals in the form of rocks that has several colors and the salt of
oxyacid is aluminium sulfate in white crystal.
STUDY QUESTIONS
3.1 Explain the finding history of aluminium metal.
3.2 Explain the isolation manner of aluminium metal from its corresponding
minerals.
3.3 Explain the natural abundance and distribution of the aluminium in the earth
crush.
3.4 Explain the uses of aluminium.
3.5 Explain the properties of aluminium.

3.6 Explain the properties and reactions of aluminium compounds: hydrides and
hydride complexes, carbides, nitrides, halides and halide complexes, oxides
and chalchonides, hydroxides, spinel and aluminates, and salts of oxyacides.
3.7 Explain the preparation methods of the aluminium compounds: hydrides
and hydride complexes, carbides, nitrides, halides and halide complexes,
oxides and chalchonides, hydroxides, spinel and aluminates, and salts of
oxyacides.
3.8 Explain the uses of the aluminium compounds: hydrides and hydride
complexes, carbides, nitrides, halides and halide complexes, oxides and
chalchonides, hydroxides, spinel and aluminates, and salts of oxyacides.
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CHAPTER 4
FIRST PERIOD OF TRANSITION METALS
GROUP ELEMENTS
4.1 INTRODUCTION
Among the elements of group IIA and IIIA are ten column elements of
group B. These elements are called transition elements. The transition elements
may be strictly defined as those that, as elements, have partly filled d or f shells.
The main transition group or d block includes those elements that have partially
filled d shells only. Transition elements, series of chemical elements that share
similar electron orbital structures and hence similar chemical properties. The
transition elements are commonly defined as the 30 elements with atomic number
21 to 30, 39 to 48, and 71 to 80. The transition elements exhibit multiple valences
or oxidation states typically ranging from +1 to +8 I compounds. In
organometallic compounds, consisting of metal bonded to organic species,
transition metals sometimes take on negative oxidation state. The transition
elements have such typically metallic properties as malleability, ductility, high
conductivity of heat and electricity, and metallic luster. They tend to act as
reducing agents (donors of electrons), but are less active in this regard than the
alkali metals and alkaline earth metals, which have valences of +1 and +2,
respectively. Transition elements in general have high densities and melting points
and exhibit magnetic properties. They form both ionic and covalent bonds with
anions (negatively charge ions), and such compounds are in general brightly
colored.
Thus, the element Sc, with the outer-electron configuration 4s2 3d, is the
lightest member. The eight succeeding elements (the first transition series) Ti, V,
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Cr, Mn, Fe, Co, Ni, and Cu, all have partly filled 3d shell either in the group state
of the free atom (all except Cu) or in one or more of their chemically important
ions (all except Sc). Transition elements have distinctive properties that
distinguish them from the main group elements, such as: high melting and boiling
points, paramagnetic properties, colored compounds, more than one oxidation
number, and able to form complex compounds. In this course, all of those
properties that owned by transition metals will be discussed briefly.
4.2 ELECTRON CONFIGURATION

The electron configuration of an atom is the representation of the
arrangement of electrons that are distributed among the orbital shells and sub
shells. Commonly, the electron configuration is used to describe the orbital of an
atom in its ground state, but it can also be used to represent an atom that has
ionized into a cation or anion by compensating with the loss of or gain of
electrons in their subsequent orbital. Many of the physical and chemical properties
of elements can be correlated to their unique electron configurations. The valence
electrons, electrons on the outer most shell, become the determining factor for the
unique chemistry of the element.
Based on Aufbau’s rule, the filling of electrons in d orbital started from the
electron in orbital 4s2 is occupying. Therefore, the elements of the transition
started in the fourth period in the periodic table, according to the largest principal
quantum number (4s 3d). Therefore, the maximum d orbital occupied by ten
electrons there will be ten elements in the fourth period, starting from Sc with
electron configuration [Ar] 3d1 4S2 to Zn with the electron configuration [Ar] 3d10
4S2. Electron configuration of the elements of the first period of transition can be
seen in table.
Table 4.1 Electron Configuration of the First Period of Transition Metal Elements
Element Electron Configuration Group Number
21 2 2 6 2 6 1 2
Sc 1s 2s 2p 3s 3p 3d 4s IIIB
22 2 2 6 2 6 2 2
Ti 1s 2s 2p 3s 3p 3d 4s IVB
V23 1s2 2s2 2p6 3s2 3p6 3d3 4s2 VB
Cr24 1s2 2s2 2p6 3s2 3p6 3d5 4s1 VIB
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Mn25 1s2 2s2 2p6 3s2 3p6 3d5 4s2 VIIB
Fe26 1s2 2s2 2p6 3s2 3p6 3d6 4s2 VIIIB
27 2 2 6 2 6 7 2
Co 1s 2s 2p 3s 3p 3d 4s VIIIB
28 2 2 6 2 6 8 2
Ni 1s 2s 2p 3s 3p 3d 4s VIIIB
29 2 2 6 2 6 10 1
Cu 1s 2s 2p 3s 3p 3d 4s IB
Zn30 1s2 2s2 2p6 3s2 3p6 3d10 4s2 IIB
According to the Aufbau rule, the electron configuration of chromium is

[Ar] 3d4 4S2, but the fact is different with the theory [Ar] 3d5 4S1. That is same as
the electron configuration of copper atoms, [Ar] 3d10 4S1. This is due to the
stability of the full d sub shell or half full.
The transition metal has certain common properties, namely they are all
metals. They are practically all hard, strong, high-melting, high-boiling metals
that conduct heat and electricity well. They form alloys with one another and with
other metallic elements. Many of them are sufficiently electropositive to dissolve
in mineral acids, although a few are “noble”, that is, they have such low electrode
potentials that they are unaffected by simple acids. With very few exceptions, they
exhibit variable valence, and their ions and compounds are colored in one if not
all oxidation states. Because of partially filled shells they form at least some
paramagnetic compounds (Cotton & Wilkinson, 1995).
All these transition elements have metal properties. These properties
influenced by the easy of transition elements release valence electrons. In
addition, the presence of electrons in the d-block that have not occupy it cause the
transition element more than electron unpaired. Unpaired electrons will move
freely to form a stronger metallic bond than the main element. The presence of
this metallic bonding resulting the melting point, boiling point and the density of
transition element large enough to be hard and strong.
For the Cr and Cu elements, charging in subshell electrons deviate from
Aufbau role. It is described in the following:
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3d1 4s2
21Sc : (Ar)
3d2 4s2
22Ti : (Ar)
3d3 4s2
23V : (Ar)
3d5 4s1
24Cr : (Ar)
3d5 4s2
25Mn : (Ar)
3d6 4s2
26Fe : (Ar)
3d7 4s2
27Co : (Ar)
3d8 4s2
28Ni : (Ar)
3d10 4s1
29Cu : (Ar)
3d10 4s2
30Zn : (Ar)
The explanation about the Cr and Cu elements is deviate from Aufbau role.
3d4 4s2
24Cr : (Ar)
In the fact:
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3d5 4s1
24Cr : (Ar)
So, 4s1 3d5 more stable than 4s2 3d4. In this case, it is not cause by electron
excited but it is caused the filling for get more stable.
3d9 4s2
29Cu : (Ar)
In the fact:
3d10 4s1
29Cu : (Ar)
So, 4s1 3d10 more stable than 4s2 3d9. In this case, it is not cause by electron
excited but it is caused the filling for get more stable.
From the table above it can be seen that there is an increase in the shell in
d electrons of Sc to Zn elements, it is caused in an attractive force of the nucleus
increases. So the atomic radius of Sc to Zn tends to become smaller. The more
unpaired electrons in the orbital, the stronger the metallic bond and the higher
melting point. Based on the valence configuration, shows that the element of
chromium has a more unpaired electrons number, while zinc has no unpaired
electrons. This is because chrome have high melting point, while zinc have low
melting point.
It should be no surprise to find similar chemical properties, because
chemical reactions always involve the outer electrons, and the atoms in each
transition series have the same outer most electron shell (4s, 5s, or 6s), nearly
always containing two electrons.
Physical properties also depend on the outer electrons (especially metallic
conductivity), and also on the way electron arrangement determines atomic radius.
Similar atomic radius generally gives rise to similar physical properties.
The density of scandium: 3 gcm-3 is much lower than of the other
transition metals (mostly 7-8 gcm-3), and the melting point of zinc: 4200C is much
lower than the melting point of the other transition metals (mostly above 15000C).
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Their anomalous physical properties provide another reason, in addition to the

absence of partly filled d-orbital in compounds, for excluding scandium and zinc
from the transition metals.
Table 4.2 Characteristic of Transition Metals
Characteristic Sc Ti V Cr Mn Fe Co Ni Cu Zn
Atomic Number 21 22 23 24 25 26 27 28 29 30
Electron Valence 4s2d1 4s2d2 4s2d3 4s1d5 4s2d5 4s2d6 4s2d7 4s2d8 4s1d10 4s2d10
Configuration
Density (g/cm3) 3.0 4.51 6.1 7.19 7.43 7.86 8.9 8.9 8.96 7.14
0
Melting Point C 1539 1668 1900 1845 1245 1536 1495 1453 1083 420
Boiling Point 0C 2730 3260 3450 2665 2150 3000 2900 2730 2595 905
Atomic Radii (M) (pm) 162 147 134 130 135 126 125 124 128 138
First Ionization Energy
(kJ/mol)
- First 631 658 650 652 717 759 760 736 745 906
- Second 1235 1309 1414 1591 1509 1561 1645 1751 1958 1733
- Third 2389 2650 2828 2986 3250 2956 2231 3393 3578 3833
Electronegativity 1.3 1.5 1.6 1.6 1.5 1.8 1.9 1.9 1.9 -
Standard Potential -2.08 - -1.2 -0.74 -1.18 -0.44 -0.28 -0.25 +0.34 -0.76
Reduction 1.63
Hardness - - - 9.0 5.0 4.5 - - 2.8 2.5
Oxidation Number 3 2,3,4 2,3,4,5 2,3,6 2,3,4,7 2,3 2,3 2 1,2 2
There is generally a decrease in radii, both metallic and ionic, from Ti to

Cu. This is because the additional electrons are accommodated in the same sub-
shell, which is drawn closer to the nucleus by the higher nuclear charge.
There is in general, through irregular, an increase in first ionization energy
from Ti to Cu. The electron removed in ionization, through always removed from
the same sub-shell, is progressively more tightly bound because it is always
partially shield from the increasing nuclear charge. There is general small increase
in electronegativity from Ti to Cu (ignoring the smaller value for Mn). This
parallel is the decrease in atomic radius.
4.3 DENSITY OF TRANSITION ELEMENTS

The densities of the transition elements are generally higher, (except for
scandium), than the densities of the s-block metals are generally low; especially
Group I.
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Densities of individual atoms increase markedly across a period because

the atomic radii decrease while the atomic masses increase. Bulk densities
increase similarly for the same packing arrangements.
The difference in densities between transition metals and group I metals is
accentuated by the fact that most transition metals have close-packed structures
while group I metals do not.
Atoms of most of the transition metals have small radii and pack in
closest-packed structures with a coordination number of 12. They are relatively
dense compared with the metals of Group IA and Group IIA whose larger toms
pack in body-centered structures with coordination number 8.
4.4 MELTING POINT AND BOILING POINT

The melting point of transition metals are generally high (>15000C),
except for zinc. The melting point of s-block is generally low, especially for group
I. Melting point is an approximate indicated of the strength of the bonding
between particles. Strong bonding occurs in the transition metals where the atomic
radius is small and the atomic structures are close-packed.
In the s-block metals metallic bonding weaker because the atomic radius
larger. The differences is again most marked when comparing transition metals
with group I metals, which have the largest atomic radii and do not have close-
packed structures. In addition, they have only one valence electron per atom to
contribute to the ‘sea of electrons’.
Boiling point of transition metals is generally high (~20000C), except for
zinc again, compared to the s-block metals, which are generally low. This is for
the same reason as for melting point, vaporization separates the particles
completely.
When compared with the alkali and alkaline earth elements, transition
elements at first period have a greater electronegativity. As a result, the element is
more difficult to react than with the alkali and alkaline earth elements. Almost all
of the elements in the transition group, period of four is easy to oxidized (having
E0red negative) except Cu are easily oxidized. This is means that theoretically;
almost all of the elements of the four periods can react with strong acids to
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produce hydrogen gas. But in fact, the elements of the transition period of four
slow to react with strong acids. This is caused by the formation of an oxide layer
that prevents further reaction.
In this period, between adjacent elements, ionization energy difference is
not too big. Although there is fluctuations, it can be concluded there is an
increasing the ionization energy from Sc to Zn. Both are occurs because of a
certain uniqueness in the filling shell electrons in the orbital elements of the
transition period of four groups. Where after filling electrons in sub shell 3s and
3p, charging does not proceed to the 3d sub shell but rather directly to the 4s and
4d sub shell. So when there is a change metal to ions, electrons in the 4s sub shell
is the first ionized.
Almost all of the electrons in the d orbital of transition elements can be
used together with electrons in s orbital in forming compounds. The difference in
energy of the electron in the 4s and 3d sub shell is small enough so that the
electrons in the 3d sub shell is also released during ionization besides electrons in
the 4s sub shell. This has resulted in the transition elements have multiple
oxidation numbers. The fourth period transition elements are electropositive
(easily release electrons) that have positive oxidation numbers. The maximum
oxidation number is an element of the transition state the number of electrons in
the sub shell 3d and 4s.
Tabel 4.3 Oxidation State of Transition Metals
Sc Ti V Cr Mn Fe Co Ni Cu Zn
+3 +2 +1 +2 +2 +2 +2 +2 +1 +2
Oxidation +3 +2 +3 +3 +3 +3 +3 +2
Number +4 +3 +6 +4 +4
+4 +6 +6
+5 +7
All electrons from scandium to manganese in its d orbital are unpaired

electrons thus relatively easy to remove. This resulted in the atoms tend to achieve
maximum oxidation. In elemental iron to zinc, electrons in its d orbital begin
pairing and fully charged. Thus, these elements tend to be more difficult to
achieve the maximum oxidation. Orbital electrons are more strongly bound to this
charge. Generally, the period four transition elements have a +2 oxidation state
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because the two electrons in the 4s sub shell is very easy to form cations are
released beforehand.
The element scandium and zinc have only one kind of oxidation number.
Scandium = +3 oxidation state is due to release 3 electrons (2 electrons in the 4s
orbital and one electron in the 3d orbital) to have a stable electron configuration.
Meanwhile, zinc = +2 oxidation number due to release two electrons alone (from
4s orbital), zinc has achieved stability without removing electrons from the 3d sub
shell.
Transition elements have unique properties such as have different color of
each ions. Most of the transition elements form colored compounds both in solid
state as well as in aqueous solution. Table below present the color of transition
elements in form of ions.
Table 4.4 Oxidation State and Color of Transition Metals
Oxidation State +2 +3 +4 +5 +6 +7
Scandium (Sc) - Colorless - - - -
Titanium (Ti) - Violet Blue - - -
Vanadium (V) Violet Green - Red Orange -
Chromium (Cr) Blue Green - - Green -
Manganese (Mn) Pink - - - - Violet
Iron (Fe) Bluish Yellow - - - -
green
Cobalt (Co) Pink Blue - - - -
Nickel (Ni) Green - - - - -
Copper (Cu) Blue - - - - -
Zinc (Zn) Colorless - - - - -
It is already studied that the transition metals have incomplete d-orbital.

The electrons are to be promoted from a lower energy level to a higher energy
level. Some amount of energy is required for this process and the radiations of
light are observed in the visible region. The compounds absorb a particular color
from the radiation and the remaining ones are emitted. For example Cu2+ is bluish
green in color due to absorption of red light wavelength. As Zn has completely
filled d-orbital it cannot absorb radiation and hence Zn2+ salts are colorless.
Transition metals form many complex ions. They are the electrically
charged complexes with a metal ion in the center which is surrounded and linked
by a number of neutral molecules or negative ions. These neutral molecules or
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negative ions are called as ligands. As the transitions metals are small in size they
form large number of complexes.
Ligand that is Lewis base at least must have a pair electron in bond orbital.
Ratio size of ligand and centre atom will determine the maximum ligand that can
be bind. Coordination number of covalent bonds that can be formed in the
formation of a complex called the coordination number of the central ion.
Atoms, ions, and molecules with unpaired electrons are attracted to a
magnet. This property is known as paramagnetism. Magnet of small electron
causes the atom or molecule as a whole acts as a tiny magnet. If they are placed in
a magnetic field tends to give up (align) with and drawn towards the field.
However, the thermal motion scrambles toward small magnets electron. Only part
of an electron magnetic that success field delivered by paramagnetic substances
only drawn so weakened by an external magnetic field. Any substance which is
weakly attracted by a magnetic field is said to be paramagnetic, while if it is
repelled it is diamagnetic. Substances in which all the electrons are paired are
repelled by magnet and are said to be diamagnetic.
Transition elements and their ions are generally paramagnetic, whereas
most others are diamagnetic. The greater the number of unpaired electrons, the
more paramagnetic is the ion.
Paramagnetism in transition elements is associated with unpaired electrons
found in their partially filled d-orbitals, because there is a magnetic moment
associated with the spinning electron. The magnetic moment rises with the
number of unpaired electrons and this gives a good indication of the number of
unpaired electrons present in the atom/ions; maximum number of unpaired
electrons in Mn+2.
Transition elements and their compounds have d orbital are not full yet, so
many of them have paramagnetic properties. To predict the magnetic properties of
transition metal compounds require bond theory can be applied to the substance.
Discussion about the paramagnetic properties of transition metal compounds will
be discussed in more detail in topic compound/ion complex.
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Based on the magnetic properties, the transition elements in first period are
grouped into diamagnetic and paramagnetic. Diamagnetic and paramagnetic are
magnetic properties when we talk about atomic.
a. Diamagnetic is transition element that not attract each other the magnetic
field. This property has transition element that whole of electron in the orbital
pair. For example Zn element with the electron configuration namely,
30Zn: [Ar] 3d10 4s2
3d10 4s2
All of the Zn electron in orbital s and d has been paired so have no magnetic
properties.
b. Paramagnetic is transition element is can be stretched slightly magnetic fields.
This property has transition element that have paired electron in the orbital.
For example scandium with the electron configuration namely,
21Sc : [Ar] 3d1 4s2
3d1 4s2
There is one electron in d orbital of scandium so this element has

paramagnetic properties.
4.5 SUMMARY
The first series of transition metals belong to the fourth period in the
Periodic Table of Elements beginning from Scandium (Sc) with the outer-electron
configuration 4s2 3d. The element is the lightest member. The eight succeeding
elements, Ti, V, Cr, Mn, Fe, Co, Ni, and Cu have partly filled 3d shell either in
the group state of the free atom (all except Cu) or in one or more of their
chemically important ions (all except Sc). Transition elements have distinctive
properties that distinguish it from the main group elements, such as: (1) All of
transition elements have high melting and boiling points; (2) Almost have
paramagnetic properties; (3) These elements can form colored compounds; (4)
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Transition elements have more than one oxidation number; and (5) They can form
complex compounds.
STUDY QUESTIONS
4.1 Explain why the transition metal elements have commonly more than one
oxidation states!
4.2 Explain why the compounds of the transition metal elements have colors!
4.3 Compare and contrast the melting points as well as boling points of the
transitions metals and those of the main groups metal elements!
4.4 Explain the magnetic properties of transition metals elements and their
compounds in terms of paramagnetism, diamagnetism, ferromagnetism,
ferrimagnetism, and anti ferromagnetism!
4.5 Explain the roles of the transition metal elements to the development of
nowdays advanced technologies according to their distinctive properties!
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CHAPTER 5
TITANIUM AND ZIRCONIUM
5.1 INTRODUCTION
Titanium and zirconium are two elements that belong to transition metal
group of elements. Both of them are placed in IVB group in periodic table of
elements. Generally, titanium is symbolized as Ti and has atomic number 22.
Zirconium is symbolized as Zr and has atomic number 40. Both metals play
important role for our living.
This is to explain the nature of titanium and zirconium including their
history and existences, abundance, elemental properties and uses, their
compounds and complexes.
5.2 HISTORY
The existence of titanium is begun in 1791, when William Gregor, a
Cornish vicar and amateur chemist, found the element. He examined sand from
the local river Helford, and by using magnet, he extracted a black material from
which he removed iron by treatment of hydrochloric acid. The residue, which
dissolved in only with difficulty in concentrated sulfuric acid, was the impure
oxide of new element. Gregor proceeded to discover the reactions which were to
form the basis of the production of virtually all titanium oxide (TiO2) up to 1960.
Then, in 1795, German chemist M.H. Klaproth in independent discovered the
same oxide, in a sample of ore now known as rutile. The name “titanium” itself is
come from “Titans” that exist in Greek mythology as children of heaven and earth
condemned to live amongst hidden fires of the earth. Klaproth also had previously
isolated the oxide of zirconium from a sample of zircon, ZrSiO4 in 1789. The
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name “zirconium” itself is come from the name of its mineral, zircon. Impure
samples of the two metals were prepared by Jons Jakobs Barzelius in 1824 for
zirconium and in 1825 for titanium.

Titanium, which comprises 0,63% (i.e 6320 ppm) of earth’s crustal rocks,
is very abundance element (ninth of all elements, second of the transition
elements), and, of the transition elements, only Fe, Ti, and Mn are more
abundance than Zirconium (0, 016%, 162 ppm) (Greenwood et al., 1997). Both of
them are not widely known because of the difficulties in preparing the pure metals
and also their rather diffuse occurrence. They are generally occur in form of
minerals. The two most important minerals of titanium are ilmenite (FeTiO3) and
rutile (TiO2) (Greenwood et al., 1997). They are mostly mined in Canada, the
USA, Australia, Scandinavia and Malaysia. Zirconium also has its minerals.
Zirconium’s main minerals are zircon (ZrSiO4) and baddeleyite (ZrO2). They are
mainly mined in Australia, Republic of South Africa, USA and the former Union
Soviet.
5.4 ISOLATION
The existence of minerals as the only form of titanium and zirconium in
nature force the expert to make methods that can produce elemental titanium and
zirconium. And there was Wilhelm Kroll of Luxembourg in 1932, made the
method to produce titanium by reducing TiCl4 with calcium and then later with
magnesium even sodium. The Kroll’s way to produce titanium known as Kroll
method. In the Kroll method, ilmenite and rutile is heated with chlorine and
carbon, e.g.:
2FeTiO3 + 7Cl2 + 6C → 2TiCl4 + 2FeCl3+6CO
The TiCl4 is fractionally distilled from FeCl3 and other impurities and then
reduced with molten magnesium in sealed furnace under Ar,
TiCl4 + 2Mg → Ti + 2 MgCl2
Molten MgCl2 is tapped of periodically and after cooling, residual MgCl2
and any excess of magnesium are removed by leaching with water and dilute
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hydrochloric acid or by distillation, leaving titanium “sponge” which after

grinding and cleaning with aqua regia (1:3 mixture of concentrated nitric and
hydrochloric acid), is melted under argon or vacuum and cast into ingots
(Greenwood & Earshaw, 1997). The produced titanium metal has a very low
density, (≈57% that of steel) combined with good mechanical strength and in fact,
when alloyed with small quantities of such metals as Al and Sn, has the highest
strength weight ration of any of engineering metals.. The properties of Titanium
which has the highest weight-to-strength ratio of any metal, makes it useful for a
variety of industries in which parts must have superior strength but not add to the
overall weight of the product. Titanium is as strong as steel but 45 percent lighter.
It is also corrosion resistant, which makes it a preferred metal for a number of
outdoor uses. Titanium could also replaces aluminum when operating
temperatures exceeds 130oC, which is the maximum operating temperature of
aluminum. These condition exist, for example, in the nacelle and auxiliary power
unity (APU) areas and anti-icing system for airframe structures. Those facts of
titanium makes the major uses of titanium are in the aircraft industry for the
production of both engine and airframes.
Zirconium is also produced commercially by the Kroll method. There also
another method in producing zirconium, namely the van Arkel-de Boer process. In
this later method, the crude zirconium is heated in an evacuated vessel with little
iodine, to a temperature of about 200o C when ZrI4 volatilizes. A tungsten or
zirconium filament is simultaneously electrically heated to about 1300oC. This
decomposes the ZrI4 and pure zirconium is deposited in the filament.
5.5 ELEMENTAL PROPERTIES AND USES

Zirconium is ideal metal for inside nuclear reactors and nuclear
submarines. It does not corrode at high temperatures, nor absorb neutrons to form
radioactive isotopes. Zirconium metal has an oxidized surface which is both hard
and impervious to chemical attack making it ideal not only for chemical plants but
for body implants such as hip replacement joints. Even today the nuclear industry
buys almost all of the metal that is produced and some nuclear reactors have more
than 100 kilometres of zirconium tubing.
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Titanium and zirconium have several properties that makes both of them
are different and special. The table below summarizes a number of properties of
these elements.
Table 5.1 Properties of Titanium and Zirconium
Properties Titanium (Ti) Zirconium (Zr)
Atomic number 22 40
Number of naturally occurring isotopes 5 5
Atomic weight 47, 867 91,224
Electronic configuration [Ar] 3d24s2 [Kr]4d25s2
Electronegativity 1,5 1,4
Metal radius/pm 147 160
Ionic radius (6-coordinate)/pm M(IV) 60,5 -
M(III) 67,0 -
M(II) 86 -
Melting point/oC 1667 1857
Boiling point/oC 3285 4200
∆Hfus/kJ mol-1 18,8 19,2
∆Hvap/kJ mol-1 425 (±11) 567
Density (25oC)/gr cm-1 4,50 6,51
Electrical resistivity (20oC)/µohm cm 42,0 40,0
Sources: Greenwood et al., 1997
Generally, the titanium and zirconium are all lustrous, silvery metals with
high mps and they typically metallic hep structures which transform to bcc at high
temperatures (882oC, 870oC for Ti, Zr). They all are good conductors. Titanium
and zirconium also have a number of naturally occurring isotopes and, in the case
of zirconium, the least abundant of these is radioactive, though with a very long
half-life (9640 Zr, 2.76%, 3.6 x 1017 y; 17472). Here are some trends of properties of
elements group of titanium and zirconium.
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(a) Melting and boiling points (b) Enthalpies of atomization
Figure 5.1 Properties Trends of Titanium and Zirconium in Their Groups
The titanium and zirconium are generally electropositive. If heated to high

temperatures they react directly with most non-metals, particularly oxygen,
hydrogen (reversibly) and in this case of titanium, nitrogen (Ti actually burns in
N2). Another important thing in these elements is the group oxidation state of +4.
This is too high to be ionic, but zirconium, being larger has oxides which are more
basic than that of titanium and give rise to a more extensive and less hydrolyzed
aqueous chemistry. In this oxidation state, particularly in the case of the dioxide
and tetrachloride, titanium shows many similarities with tin which is of much the
same size (Greenwood et al., 1997). Lower oxidation states are rather sparsely
represented for Zr. Even for Ti they are readily oxidized to +4 but they are
undoubtedly well defined and, whatever argument may be advanced against
applying to description to Sc, there is no doubt that Ti is a “transition metal”.
Previously, we have known that “transition metal” have many oxidation
states. So, here are some data of oxidation states and stereo chemistries of
titanium and zirconium.
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Table 5.2 Oxidation States and Stereochemistry of Titanium and Zirconium

Oxidation Coordinati
Stereochemistry Ti Zr/Hf
state on number
-1 (d5) 6 Octahedral [Ti(bipy)3] -
[Zr(bipy)3]-
0 (d3) 6 Octahedral [Ti(bipy)3] [Zr(bipy)3]-
2 (d2) 6 Octahedral TiCl2 Layer structures and
clusters
12 - [Ti(η5-C5H5)2(CO)2] [M(η5-
C5H5)2(CO)2]
3 (d1) 3 Planar [Ti{N(SiMe3)2}3]
5 Trigonal [TiBr3(NMe3)3}2]
bipyramidal
6 Octahedral [Ti(urea)6]3+ ZrX3(Cl,Br,I), HfI3,
0
4 (d ) 4 Tetrahedral TiCl4 ZrCl4 (g) (solid is
octahedral)
5 Trigonal [TiOCl2(NMe3)2] -
bipyramidal
Square pyramidal [TiOCl4]2- -
6 Octahedral [TiF6]2- [ZrF6]2-, ZrCl4(s)
7 Pentagonal [TiCl2(S2CNMe3)2] [NH4]+3[ZrF7]3-
bipyramidal
Capped trigonal [TiF5(O2)]3- [Zr2F13]5-
prismatic
8 Dodecahedral [Ti(η2-NO3)4] [Zr(C2O4)4]4-
Square - [Zr(acac)4]
antiprismatic
11 - [Ti(η5- [Zr(η5-
C5H5)(S2CNMe3)2] C5H5)(S2CNMe3)2]
12 - - [M(η3-BH4)4
5.6 TITANIUM AND ZIRCONIUM COMPOUNDS

Titanium and zirconium are difficult to find in pure element. They are
mostly found in form of minerals, in other words, they are mostly found in form
of compounds. There are many compounds of titanium and zirconium. Some of
them are oxides and sulfides, mixed oxides, halides and complexes.
The main oxides of titanium and zirconium are dioxides. The most known
oxide is titanium oxide (TiO2). Titanium oxide are known because of it uses as a
pigment. It melts at 1892±300C when heated in an atmosphere of O2; when
heated in air the compound tends to lose oxygen and the melt at 1843±150oC..
TiO2 exists at room temperature in three forms rutile, anatase, and brookite. Rutile
is the most common form, which contains 6 coordinate titanium. The coordinate
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titanium has structure octahedral and the oxygen structure is trigonal planar. It can
be seen in the figure below.
Figure 5.2 The Structure of Rutile (TiO2). The picture is

taken from Greenwood & Earnshaw, 1997.
TiO2 commonly is unreactive. But the TiO2 can be difficultly reduced and
produce nonstoichiometric oxide, and the most important of those are the Magneli
type phase TinO2n-1 (4≤ n ≤ 9) ), the lower oxides Ti3O5 and Ti2O3 and the broad,
nonstoichiometric phase TiOx (0.70 ≤ x ≤ 1.30). The Magneli phase TinO2n-1 are
built up of slabs of rutile-type structure with a width of nTiO6 octahedral and with
adjacent slabs mutually related by a crystallographic shear which conserves
oxygen atoms by an increased sharing between adjacent octahedral. The crystals
of TinO2n-1 having the composition between Ti2O3 and TiO2 are transferred from
the mother phase rutile TiO2 with decrease of value x of TiO2-x (Yun et al.,
2012). Other, Ti4O7 is metallic at room temperature but the other members of the
series tend to be semiconductors. The Ti4O7 is obtained by annealing of TiO2 in
the atmosphere hydrogen at 1050oC during four hours. Other ways, Annealing of
the mechanically mixture of Ti + TiO2 for one hour at 1000oC in air resulted into
the highly conductive Ti4O7 (Gusev et al., 2003).
The lower oxide, Ti3O5 is a blue-black material. It is prepared by reducing
TiO2 with H2 at the temperature of 900oC. It shows a transition from
semiconductor to metal at 1750o C (Greenwood & Earnshaw, 1997). The other
lower oxide, Ti2O3 is a dark-violet material with the corundum structure. It is
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prepared by reacting TiO2 and Ti metal at 16000C and is generally inert, being
resistant to most reagents except oxidizing acids. It has a narrow composition
range (x = 1.49 – 1.51 in TiOx) and undergoes a semiconductor-to-metal transition
above -2000C.
TiO is bronze colored and oxidized material. It is prepared by the reaction
of TiO2 and Ti metal. It has a defect rock-salt structure which tolerates a high
proportion of vacancies (schottky defects) in both Ti and O sites and so is highly
nonstoichiometric with a composition range at 17000C of TiO0.75 to TiO1.25. This
range diminishes somewhat at lower temperature and, at equilibrium below about
9000C, various ordered phase separate with smaller ranges of composition-
variation, TiO0.9-TiO1.1 and TiO1.25. In this latter compound the tetragonal unit cell
can be thought of as being related to the NaCl-type structure: there are 10 Ti sites
and 10 oxygen sites but 2 of the Ti sites are vacant in a regular or ordered way to
generate the structure of Ti4O5. A high temperature (>30000C) form of TiO has
been prepared with the unusual feature of Ti2+ in a trigonal prismatic array of
oxygen atoms.
The compound of zirconium is can’t be observed comprehensively
because there is little evidence of stable phase other than MO2, and at room
temperature ZrO2 (baddeleyite). ZrO2 gas at least two more high temperature
modifications (tetragonal above 11000C and cubic, fluorite type, above 23000C)
but it is notable that, presumably because of greater size of Zr compared to Ti,
neither of them has the 6-coordinate rutile structure. ZrO2 is unreactive, has a low
coefficient of thermal expansion, and a very high melting point (2710 ± 25 0C) and
is therefore a useful refractory material, being used in the manufacture of
crucibles and furnace cores. ZrO2 has also recently been produced fibrous form
suitable for weaving into fabrics, as already mentioned for Al2O3, and its chemical
inertness and refractivity coupled with an apparent lack of toxicity can be
expected to lead to increasing applications as an insulator and for the filtration of
corrosive liquids. Production of ZrO2 concentrates in 1991 was about 870.000t,
Australia being the most important source. The sulfides have been less thoroughly
examined than the oxides but it is clear that a number of stable phases can be
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produced and nonstoichiometric is again prevalent. The most important are the
disulfides, which are semiconductor with metallic lustre.
Beside the oxides, titanium and zirconium also have mixed oxides. Mixed
oxides mean the oxides of titanium or zirconium that mixed with other metals.
The common dioxide, MO2, is inert, and it produces a number of a number of
“titanates”, “zirconates” if they have been heated, fusion or firing at high
temperatures (sometime up to 25000C) with the stoichiometric amounts of
appropriate oxides. There are two types of titanates: the orthotitanates M 2II TiO4
and metatitanates M2II TiO3.
Figure 5.3 Two representations of the structure of perovskite,

CaTiO3, showing (a) the octahedral coordination of Ti, and (b) the
twelve-fold coordination of Ca by oxygen. The picture is taken
from Greenwood & Earnshaw, 1997.
The M2II means the metal that mixed with titanium oxide. The M2II can be
calcium, barium and strontium. Because of the M2II is Ca, Ba and Sr, the preferred
structure is perovskite. The structure of perovskite is shown above.
M2II TiO4 (M = Mg, Zn, Mn, Fe, Co) have the spinel structure (MgAl2O4)
which is the third important structure type adopted by many mixed metal oxides:
in this the cations occupy both octahedral and tetrahedral sites in a ccp array of
oxide ions. Ba2TiO4, although having the same stoichiometry, is unique amongst
titanates in that it contains discrete [TiO4]4- ions which have the somewhat
distorted tetrahedral structure.
High temperature reduction of Na2TiO3 with hydrogen produces
nonstoichiometric materials, NaxTiO2 (x = 0,20 – 0,25), called titanium “bronzes
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by analogy with the better-known tungsten bronzes. They have a blue-black,

metallic appearance with high electrical conductivity and are chemically inert (
even hydrofluoric acid does not attack them).
“Zirconates” can be prepared by firing appropriate mixtures of oxides,
carbonates or nitrites. None of the are known to contain discrete [MO4]4- or
[MO3]2- ions.Compounds MIIZrO4 frequently adopt the spinel structure.
The other compounds of titanium and zirconium are halides. The most
important halides is tetrahalides. Titanium halides shows an interesting gradation
in color, the charge-transfer band moving steadily to lower energies ( absorbing
increasingly in the visible region of the spectrum) as the anion becomes more
easily oxidized (F- or I-) by the small, highly polarizing titanium cation. Here are
some physical properties of titanium tetrahalides.
Table 5.3 Some Physical Properties of Titanium Tetrahalides
Compound Colour Mp Bp
TiF4 White 284 -
TiCl4 Colourless -24 136,5
TiBr4 Orange 38 233.5
TiI4 Dark brown 155 377
Sources: Greenwood & Earnshaw, 1997
The importance of those tetrahalides is proportional with the way to
produce them. Tetrafluorides is prepared by the action of anhydrous HF on the
tetrachloride. Tetrachlorides and tetrabromides are prepared by passing the
halogen over the heated dioxide in the presence of a reducing agent such as
carbon ( this reaction is central to the chloride process for manufacturing TiO2).
Tetraiodides is prepared by the iodination of the dioxide with aluminium triiodide
at a temperature of 130-400 depending on the metal (3MNO2 + 4AlI3→ 3MI4 +
2Al2O3).Generally, the tetrahalides of titanium have structure of monomeric
(tetrahedral) in vapor phase. Probably, zirconium also has the monomeric
structure in vapor phase.
All the trihalides HfF3 have been prepared, the most general ,method being
the high temperature reduction of the tetrahalide with the metal, though the variety
of other methods habe been used especially for the titanium compound. Since the
tetrahalides are quite stable to reduction, lower halides are not easily prepared in a
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pure state, incomplete reaction and the presence of excess metal being common.
Apart from TiF3, which as expected for a d1ion, has a magnetic moment of 1.85
BM at room temperature, and only shows signs of magnetic interactions below
about 60 K, all compound have low magnetic moment, indicative of appreciable
M-M bonding. They are coloured halogen bridged polymers in which one third of
the octahedral interestices of an hcp lattice of halide ions is occupied by metals
atoms. In the cases of α-TiCl3 and α-TiBr3 this take the form of the “BiI3”
structure which is comprised of layers of edge-sharing octahedra; the remainder
adopt the “β-TiCl3” structure, comprised of chains of face-sharing octahedra. In
most, if not all, of the latter case M-M bonds occur between pairs of metal atoms
as a result of distortion leading, in the case of ZrI3 for istance, to alternate Zr-Zr
distances of 317.2 and 350.7 pm. TiF3 also differs in being stable in air unless
heated whereas the others show the reducing properties; indeed, ZrX3 anf HfX3
reduce water and so no have aqueous chemistry, but aqueous colution of TiX3 are
stable if kept under and inert atmosphere. Hexahydrates TiX3.6H2O are well
known and the chloride is notable in that, like its chromium(III) analogue, it
exhibits hydrates isomerism, existing as violet [Ti(H2O)6]3+Cl3- and green
[TiCl2(H2O)4]+Cl-.2H2O.
TiX2 (X= Cl, Br I) have been prepared by reduction of TiX4 with Ti metal
and are black solids with the CdI2 structure but their low magnetic moments again
indicate extensive M-M bonding. They are very strongly reducing and decompose
water Ti7X16 (X= Cl,Br) have also been prepared. They are black crystalline
solide sensitive to hydrolysis and oxidation and can be regarded as being
composed of octahedrally coordinated TiIV and TiII in the ratio of 1:6
(TiCl4.6TiCl2) eith the bivalent metal ions arranged in triangular groups involving
Ti-Ti bonds. Incorporation of KCl in the chloride reaction mix yield the
structurally related KTi4Cl11 but the structural diversity of reduced Ti halides does
not yet match that of Zr.
Products of the high temperature (typically 750-8500C) reduction of ZrX4
(X=Cl,Br,I) with Zr ,metal in various proportios, have provided intriguing
structural problems. Black phases initially thught to be ZrX2 and made up of
Zr6X12 clusters, isostructural with the well-known [M6X12]n+ cluster of Nb and Ta,
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were subsequently shown to contain impurity atoms situated inside the Zr6
octahedra which they actually stabil;ize. The materials are correctly formulated as
Zr6X12Z and, if alkali metal halides are incorporated in the reaction mix a wole
series of phases base on the [Zr6X12Z] cluster unit is obtained, of which chlorides
and iodides have so far been most thoroghly studied. Z is most commonly H, Be,
B, C or n ( dark orange to red product), but may also be Cr, Mn, Fe, or Co (green,
blue or purple products). In all cases the same basic Zr6X12Z cluster unit is
involved , though several structure types result from the differing ways in which
there are connected. In most cases it appears that stability is attained when 15
electrons are available for cluster bonding (total number of valence electrons from
Zr6 and Z, adjusted for overall charge, less 12 required by X-12) where z is main
group element, but 18 electrons where Z is transition element. It has been
suggested that the presence of Z is essential for the stabilisation of these clusters,
but Zr6Cl12(Me2Ph6) appears to consist entirely of empty Zr6Cl12 clusters with a
phosphine attached externally to each Zr atom.
By contrast, ZrCl and ZrBr, also prepared by high temperature reduction
of ZrX4 with the metal, appear to be genuine binary halides. They are comprised
of hcp double layers of metal atoms surrounded by layers of halide ions, leading
to metallic conduction in the plane of the layers, and they are thermally more
stable than the less reduced phases. ZrI has not been obtained, possibly because of
large size of the iodide ion, and less surprisngly, attempts to prepare reduce
fluorides have been unsuccessful.
The compounds of oxoanions, means compounds of titanium and
zirconium that contains oxides and anions, commonly produce salts. Many
oxoanions form in oxidation state +4. The known oxoanions such as
Zr(NO3)4.5H2O and Zr(SO4)2.4H2O can only be isolated if the solution is
sufficiently acidic, whilst basic salts and anionic complexes are readily obtained.
Some of the oxometals compounds being polymeric state in solid state. Other
titanium anhydrous nitrate cm be prepared by the action of N2O5 on MCl4.
Ti(NO3)4 is a white sublimable and highly reactive compounds. The structure
shows that the nitrate ion disposed tetrahedrally around titanium (Figure 4).
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Figure 5.4 The molecular structure of Ti(NO3)4. The picture is

taken from Greenwood & Earnshaw, 1997.
There also compound of Zr(NO3)4, Zr(HPO4)2.2H2O and may there also more
compounds exists. In oxidation state lower that +4, there only Ti III forms sulfate
that gives MTi(SO4)2.12H2O.
The titanium also has carbides. Titanium bond with the carbon produce
titanium carbides. The titanium carbides is considered as interstial carbides.
Interstial carbides are infusible, extremely hard, refractory materials that retain
many characteristic properties of metals (lustre, metallic conductivity)
(Greenwood & Earnshaw, 1997). Interstial carbide got their name from the fact
that the C atoms occupy octahedral interstices in a close packed lattice metal
atom. The example of titanium carbides is Ti18C22 like the figure below.
Figure 5.5 (a) Proposed pentagonal decahedral structure of Ti18C22.

(b) The same structure viewed as a Ti8 cube with each face capped
by C2 group. The picture is taken from Greenwood & Earnshaw,
1997.
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The interstial carbide commonly is very inert, do not react with water, react with
air when heated above 1000o C and most degraded with concentrated HNO3 or
HF.
Next compound that will be explained is the nitrides. Titanium and
zirconium can form nitrides (metallic nitrides) of general formulae MN, M2N and
M4N. he compounds are usually opaque, very hard, chemically inert, refractory
materials with metallic lustre and conductivity. The melting points is very high,
2950oC for titanium nitride (TiN) and 2980oC for zirconium nitride (ZrN).
Hardness of these compounds on the Mohs scale is 8 and sometimes above 10 like
a diamond. These properties result in the use of these compounds as crucibles,
high temperature reaction vessel, thermocouple sheaths and other related
applications.
And the last compounds of titanium and zirconium that will be explained
are complexes. Firstly, the common complexes exists is complexes that form form
titanium that have +4 oxidation state. Titanium shows very large number of these
complexes, that usually has coordination number 6, but 7- and 8-coordination
number is possible. The titaniumIV largely form the complexes from the halides,
i.e. TiCl4 that will be adducts with O or the other ligands. There also TiF4 that
adducts mainly with O- and N-donor ligands and TiCl4 and TiBr4 that form mainly
yellow to red adducts type [MX4L2] and [MX4L2] with ligands such as ethers,
ketones OPCL3, amines, imines, nitriles, thiols and thioethers. There also many
complexes of titanium occur, likes titanium tartrate and many more.
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Figure 5.6 Molecular structure of [TiCl4(diars)2].

(The picture is taken from Greenwood &
Earnshaw, 1997)
Zirconium form many complexes. Zirconium mainly forms octahedral

structure in anionic complexes. Na3ZrF7 the anion has the 7-coordinate pentagonal
bipyramidal structure; in Li6[BeF4][ZrF8] the zirconium anion is 8-
coordinate,dodecahedral (distorted); in Cu6 [ZrF8].12H2O it is 8-coordinate,
square antiprismatic, and in Cu3[Zr2F14 ].18H2O dimerization by the edge-sharing
of two square antiprisms maintains 8-coordination. There also Monocarboxylate
of the types [Zr(carbox)4],[ZrO(carbox)3(H2O)x] and [ZrO(OH)(carbox)-(H2O)x
are well known, as are the corresponding dicarboxylates.It is interesting that the
tetrakis (oxalates),Na4[M(C2O4)4].3H2O, adopt the dodecahedral stereochemistry
in contrast to the square-antiprismatic stereochemistry of [M(acac)4],possibly
because the smaller “bite” of the oxalate ion compared to that of acac favours the
dodecahedral form.
For oxidation state III (d1), the titanium is the main concern, although there
also ZrIII. There are many of TiIII complexes. It is shown in the table below.
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Table 5.4 Some Compelexes of Titanium (III)

Complex Colour 2
Eg←2T2g µ(room
temperature)/BM
[Cs(H2O)6][Ti(H2O)6[SO4]2 Red-purple 19 900, 18 000 1,79
[Ti(urea)6][I3 Blue 17 550, 16 000 1.77
[TiCl3(NCMe)3] Blue 17 100, 14 700 1,68
[TiCl3(NC5H5)3] Green 16 600, Asym(a) 1.63
[TiCl3(thf)3] Blue-green 14 700, 13 500 1.70
[TiCl3(dioxan)3] Blue-green 15 150, 13 400 1,69
[NH4]3[TiF6] Purple 19 000, 15 100 1,78
[C5H5NH]3[TiCl6] Orange 12 750, 10 800 1,78
[C5H5NH]3[TiBr6] Orange 11 400, 9 650 1.81
[N ]3[Ti(NCS)6] Dark violet 18 400, Asym(a) 1,81
For the lower oxidation states, there are not well established chemistry to
explained it well. There also no aqueous chemistry for TiII because of its ready
oxidation (Cotton, et al., 1995). Addition compounds of the type [TiCl2L2] can be
formed with difficulty woith ligands such as dimethylformamide and acetonitrile,
but their magnetic properties suggest that they also are polymeric with appreciable
metal-metal bonding.However, the electronic spectra of TiII in TiCl2/AlCl3 melts
and also of TiII incorporated in NaCl crystal (prepared by the reaction of CdCl2
and titanium an molten NaCl and subsequent sublimation of Cd metal) have been
shown to be as expected for a d2 ion in an octahedral field.
The versatility of cyanide and bipyridyl ligands has been used to stabilize
low oxidation statess. By using potassium in liquid ammonia,K3TiIII(CN)6 is
reduced to K2TiII(CN)4. With ZrBr3 and M1CN (M1=K,Rb) in liquid
ammonia,ammonolysis occurs and zerovalent Zr is produced;
4ZrBr3 + 5M1CN + 6NH3  Zr(CN)5 +3ZrBr3(NH2) + 3NH4Br
Reduction of MCl4 (M=Ti,Zr) in tetrahydrofuran by lithium in the presence
of bipyridyl yields a series of darkly coloured, very air-sensitive compounds of the
types [M(bipy)3], Li[M(bipy)3] and Li2[M(bipy)3] with varying amounts of
solvent of crystalization, implying oxidation states of 0,-1,and -2.However,
delocalization of charge in the π* orbitals of the ligands facilitates reduction of the
ligands and assigning oxidation states to the metals under these circumstance is a
purely formal exercise.A more “realistic” claim to zero oxidation state in Zr and
Hf compounds is provided by [M(η-PhMe)2(PMe3)]. Metal vapour was produced
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from an “electron-gun furnace” and condensed with an excess of toluene and

trimethylphosphine at -196 C. On warming up, a dark-green solution was
produced from which the pure solids were isolated. And
5.7 SUMMARY
Based on the explanation above, it can be summarized that titanium as
well as zirconium has many usefulness for human being. Titanium and zirconium
have very unique properties. They also have various compounds, such as oxides,
sulfides, halides, mixed oxides, oxoanions, carbides, nitrides and complexes.
Every compound have its own properties and usefulness. So it is needed more
study and research to wisely use their special and unique properties for the the
human being in the future.
STUDY QUESTIONS
5.1 Compare the finding histories of titanium and zirconium!
5.2 Explain the isolation of titanium using Kroll’s process and zirconium using
van der Boer’s process!
5.3 Explain the properties and uses of Ti as well as Zr metal elements!
5.4 Explain the polymorphic structures of titanium oxide, TiO2 in correlation of
their properties and uses!
5.5 Explain the structure of zirconium oxide, ZrO2 and its properties and uses!
5.6 Compare the structure, properties, and uses of spinel M2TiO4 and MZrO4!
5.7 Compare the structure, properties, and uses of halides TiX4 and ZrX4!
5.8 Compare the structure, properties, and uses of carbides as well as nitrides of
titanium and zirconium!
5.9 Explain the structure, properties, and uses of octahedral complex
compounds of titanium by giving one example!
5.10 Explain the structure, properties, and uses of octahedral complex
compounds of zirconium by giving one example!
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CHAPTER 6
VANADIUM AND NIOBIUM
6.1 INTRODUCTION
Vanadium and niobium is a chemical element that is included into group
5B. Vanadium in the periodic table has the symbol V and its atomic number is 23.
The electron configuration of vanadium is [Ar] 3d3 4S2. One of compounds that is
containing vanadium such as pentaoksida vanadium (V2O5). Niobium is a
chemical element in the periodic table that has the symbol Nb and atomic number
41. The electron configuration of niobium is [Kr] 4d4 5S1. Vanadium and
Niobium is a solid state at a temperature of 298K. Therefore, that these two
elements are classified into groups metallic. This is to explain about history,
isolation, natural abundance, properties and uses of vanadium and niobium as well
as their compound.
6.2 HISTORY
The discoveries of vanadium and niobium elements were made at the
beginning of the nineteenth century and were marked by initial uncertainty and
confusion due, in the case of the heavier pair of elements, to the overriding
similarity of their chemistries.
A.M. del Rio in 1801 claimed to have discovered the previously unknown
element 23 in a sample of Mexican lead ore, and because of the red colour of the
salts produced by acidification, he called it erythronium. Unfortunately, he
withdrew his claim 4 years later, it was (incorrectly) suggested by the Frenchman,
H. V. Collett-Desotils, that the mineral was actually basic lead chromate. In 1830
the element was "rediscovered" by N. G. Sefstrom in some Swedish iron ore.
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Because of the richness and variety of colours found in its compounds he called it
vanadium after Vanadis, the Scandinavian goddess of beauty.
One year later F. Wrhler established the identity of vanadium and
erythronium. The metal itself was isolated in a reasonably pure form in 1867 by
H. E. Roscoe who reduced the chloride with hydrogen, and he was also
responsible for much of the early work on the element.
C. Hatchett examined a mineral which had been sent to England from
Massachusetts and had lain in the British Museum since 1753. He found it in the
same year that del Rio found his erythronium, From it he isolated the oxide of a
new element which he named columbium from the mineral columbite, in honour
of its country of origin. Meanwhile in Sweden A. G. Ekeberg was studying some
Finnish minerals and in 1802 claimed to have identified a new element which he
named tantalum because of the difficulty he had had in dissolving the mineral in
acids. It was subsequently thought that the two elements were one and the same,
and this view persisted until at least 1844 when H. Rose examined a columbite
sample and showed that two distinct elements were involved.
One was Ekeberg's tantalum and the other he called niobium (Niobe was the
daughter of Tantalus). Despite the chronological precedence of the name
columbium, IUPAC adopted niobium in 1950, though columbium is still
sometimes used in US industry. Impure niobium metal was first isolated by C. W.
Blomstrand in 1866 by the reduction of the chloride with hydrogen, but the first
pure samples of metallic niobium and tantalum were not prepared until 1907 when
W. von Bolton reduced the fluorometallates with sodium.

The abundances of these elements decrease by approximately an order of
magnitude from V to Nb. Vanadium has been estimated to comprise about 136
ppm (i.e. 0.0136%) of the earth's crustal rocks, which makes it the nineteenth
element in order of abundance (between Zr, 162 ppm, and Cl, 126ppm); it is the
fifth most abundant transition metal after Fe, Ti, Mn and Zr. It is widely, though
sparsely, distributed; thus although more than 60 different minerals of vanadium
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have been characterized, there are few concentrated deposits and most of it is
obtained as a coproduct along with other materials. Its major commercial source is
the titanoferrous magnetites of South Africa, the former USSR and China. One of
its important minerals is the polysulfide, patronite, VS4, but, being a class a metal,
it is more generally associated with oxygen. For example, vanadinite
approximates to lead chloride vanadate, PbCl2.3Pb3 (VO4)2, and camotite to
potassium uranyl vanadate, K(UO2)(VO4).l.5H2O. Vanadium is also found in
some crude oils, in particular those from Venezuala and Canada, and can be
recovered from the oil residues and from flue dusts after burning.
The crustal abundances of niobium and tantalum are 20 ppm and 1.7 ppm.
Of course, in view of their chemical similarities, Nb and Ta usually occur
together, and their most widespread mineral, (Fe,Mn)M2O6 (M = Nb, Ta), is
known as columbite or tantalite, depending on which metal preponderates. Until
the 1950s, this was the major source of both metals, with significant amounts
obtained also as a byproduct of the extraction of tin in SE Asia and Nigeria. The
discovery of a huge, high grade (2.5% Nb2Os) deposit of pyrochlore,
NaCaNb206F, in Brazil totally changed the pattern. Nb is now obtained chiefly
from Brazil; Ta from Australia, Canada and SE Asia but its production is heavily
dependent on demand for Sn.
6.4 ISOLATION AND USES OF THE METALS

Vanadium is usually produced along with other metals; therefore the
availability of vanadium and the economics of its production are intimately
connected with the particular coproduct involved.
The first step to isolate vanadium metal in other to get its oxidation form,
V2O5, from its ore through certain process and reaction. The usual extraction
procedure is to roast the crushed ore, or vanadium residue, with NaC1 or Na2CO3
at 850o C. It will produces sodium vanadate, NaVO3, which is leached out with
water. Acidification with sulfuric acid to pH 2-3 precipitates "red cake", a
polyvanadate which, on fusing at 700oC, gives a black, technical grade vanadium
pentoxide, V2O5.
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After that, the reduction of V2O5 that in generally is differentiated into two
treatments according to its purpose. Reduction is then necessary to obtain the
metal, but, since about 80% of vanadium produced is used as an additive to steel,
it is usual to effect the reduction in an electric furnace in the presence of iron or
iron ore to produce ferrovanadium, which can then be used without further
refinement. Carbon was formerly used as the reductant, but it is difficult to avoid
the formation of intractable carbide, and so it has been superseded by aluminum
or more commonly ferrosilicon in which case lime is also added to remove the
silica as a slag of calcium silicate. If pure vanadium metal is required it can be
obtained by reduction of VC15 with H2 or Mg, by reduction of V2O5 with Ca, or
by electrolysis of partially refined vanadium in fused alkali metal chloride or
bromide.
The benefit of vanadium as an additive in steel is that it forms V4C3 with
any carbon present, and this disperses to produce fine-grained steel which has
increased resistance to wear and is stronger at high temperatures. Such steels are
widely used in the manufacture of springs and high-speed tools.
Production of niobium and tantalum is on a smaller scale and the processes
involved are varied and complicated. Alkali fusion or digestion of the ore with
acids can be used to solubilize the metals, which can then be separated from each
other. The process originally developed by M. C. Marignac in 1866 and in use for
a century utilized the fact that in dilute HF tantalum tends to form the sparingly
soluble K2TaF7, whereas niobium forms the soluble K3NbOFs.2H2O. Nowadays it
is more usual to employ a solvent extraction technique. For instance, tantalum can
be extracted from dilute aqueous HF solutions by methyl isobutyl ketone, and
increasing the acidity of the aqueous phase allows niobium to be extracted into a
fresh batch of the organic phase. The metals can then be obtained, after
conversion to the pentoxides, by reduction with Na or C, or by the electrolysis of
fused fluorides.
Niobium is used in the production of numerous stainless steels for use at
high temperatures, and Nb/Zr wires are used in superconducting magnets.
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6.5 ATOMIC AND PHYSICAL PROPERTIES OF THE ELEMENTS

Some of the important properties of Group 5 elements are summarized in
Table 6.1. Having odd atomic numbers, they have few naturally occurring
isotopes; Nb only 1 and V and Ta 2 each, though the second ones are present only
in very low abundance (50V 0.250%, 180
Ta 0.012%). As a consequence their
atomic weights have been determined with considerable precision. On the other
hand, because of difficulties in removing all impurities, reported values of their
bulk properties have often required revision.
Table 6.1 Atomic and Elemental Properties of V and Nb
All three elements are shiny, silvery metals with typically metallic bcc
structures. When very pure they are comparatively soft and ductile but impurities
usually have a hardening and embrittling effect. When compared to the elements
of Group 4 the expected trends are apparent. These elements are slightly less
electropositive and are smaller than their predecessors, and the heavier pair Nb
and Ta are virtually identical in size as a consequence of the lanthanide
contraction. The extra d electron again appears to contribute to stronger metal-
metal bonding in the bulk metals, leading in each case to a higher mp, bp and
enthalpy of atomization. Indeed, these quantities reach their maximum values in
this and the following group. In the first transition series, vanadium is the last
element before some of the (n- 1)d electrons begin to enter the inert electron-core
of the atom and are therefore not available for bonding. As a result, not only is its
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mp the highest in the series but it is the last element whose compounds in the
group oxidation state (i.e. involving all (n - 1)d and ns electrons) are not strongly
oxidizing. In the second and third series the entry of (n - 1)d electrons into the
electron core is delayed somewhat and it is molybdenum and tungsten in Group 6
whose mps are the highest.
6.6 CHEMICAL REACTIVITY AND TRENDS

The elements of Group 5 are in many ways similar to their predecessors in
Group 4. They react with most non-metals, giving products which are frequently
interstitial and nonstoichiometric, but they require high temperatures to do so.
Their general resistance to corrosion is largely due to the formation of surface
films of oxides which are particularly effective in the case of tantalum. Unless
heated, tantalum is appreciably attacked only by oleum, hydrofluoric acid or,
more particularly, a hydrofluoric/nitric acid mixture. Fused alkalis will also attack
it. In addition to these reagents, vanadium and niobium are attacked by other hot
concentrated mineral acids but are resistant to fused alkali.
The most obvious factor in comparing the chemistry of the two elements is
again the very close similarity of the second and third members although, in this
group, slight differences can be discerned as will be discussed shortly. The
stability of the lower oxidation states decreases as the group is descended. As a
result, although each element shows formal oxidation states from +5 down to -3,
the most stable one in the case of vanadium under normal conditions is the +4,
and even the +3 and +2 oxidation states (which are admittedly strongly reducing)
have well- characterized cationic aqueous chemistries; by contrast most of the
chemistries of niobium and tantalum are confined to the group oxidation state +5.
Of the halogens, only the strongly oxidizing fluorine produces a pentahalide of
vanadium, and the other vanadium (V) compounds are based on the oxohalides
and the pentoxide. The pentoxide also gives rise to the complicated but
characteristic aqueous chemistry of the polymerized vanadates (isopolyvanadates)
which anticipates the even more extensive chemistry of the polymolybdates and
polytungstates; this is only incompletely mirrored by niobium and tantalum.
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Table 6.2 Oxidation states and stereochemistry’s of vanadium and niobium
The +4 oxidation state, which for Nb and Ta is best represented by their

halides, is most notable for the uniquely stable VO2+ (vanadyl) ion which retains
its identity throughout a wide variety of reactions and forms many complexes.
Indeed it is probably the most stable diatomic ion known. The M TM ions have
only slightly smaller radii than those of Group 4, and, again, coordination
numbers as high as 8 are found. In the +5 state, however, only Nb and Ta are
sufficiently large to achieve this coordination number with ligands other than
bidentate ones with very small "bites", such as the peroxo group. Table above
illustrates the various oxidation states and stereochemistries of compounds of V,
Nb and Ta.
Niobium and tantalum provide no counterpart to the cationic chemistry of
vanadium in the +3 and +2 oxidation states. Instead, they form a series of
"cluster" compounds based on octahedral M6X12 units. The occurrence of such
compounds is largely a consequence of the strength of metal-metal bonding in this
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part of the periodic table (as reflected in high enthalpies of atomization), and
similar cluster compounds are found also for molybdenum and tungsten.
Compounds containing M-C a-bonds are frequently unstable and do not
give rise to an extensive chemistry. Vanadium forms a neutral (paramagnetic)
hexacarbonyl which, though not very stable, contrasts with that of titanium in that
it can at least be prepared in quantity. All three elements give a number of 5 -
cyclopentadienyl derivatives.
6.7 OXIDES
Main oxide compounds for both of those elements (vanadium and
niobium) namely V2O5 & Nb2O5 for oxidation state +5 , VO2 & NbO2 for
oxidation state +4, V2O3 for oxidation state +3 and VO & NbO for oxidation state
+2.
Table 6.3 Oxides of Vanadium and Niobium
Oxidation Oxid Properties Ion Name of ion Color of
State e and color ion
+2 (3d3) VO base V2+ Vanadium (II) Violet
black-grey
+3 (3d2) V2O3 base black V3+ Vanadium (III) green
+4 (3d1) VO2 amphoteric VO2+ Oxovanadium (IV) brown
dark blue [V4O9]2- Vanadite
+5 (3d0) V2O5 amphoteric VO2+ Dioxovanadium Yellow
yellow- (V)
orange VO43- Vanadate Colorless
With long-range oxidation state, it can be understood that the alkaline
properties of the oxide will weaken with increasing oxidation state. VO and V2O3
are alkaline while VO2 and V2O5 are amphoteric with vanadate anion form, VO43-
or sometimes formulated VO3- for vanadium (V), while for vanadium (IV) anion
forms does not found as simple ions but very varied.
6.7.1 Vanadium Pentoxide, V2O5
On the basis of simple radius ratio arguments, vanadium (V) is expected to
be rather large for tetrahedral coordination to oxygen, but rather small for
octahedral coordination. It is perhaps not surprising therefore that, though the
structure of V2O5 is somewhat complicated, it consists essentially of distorted
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trigonal bipyramids of VO5 sharing edges to form zigzag double chains. But
species of oxo anion , tetraoxovanadate (V) , VO43- has tetrahedral structure
(Greenwood & Earnshaw, 1998 : 981).
V2O5 is homogeneous over only a small range of compositions but loses
oxygen reversibly on heating, which is probably why it is such a versatile catalyst.
For instance, it catalyses the oxidation of numerous organic compounds by air or
hydrogen peroxide, and the reduction of olefins (alkenes) and of aromatic
hydrocarbons by hydrogen, but most importantly it catalyses the oxidation of SO2
to SO3 in the contact process for the manufacture of sulfuric acid. For this purpose
it replaced metallic platinum which, besides being far more expensive, was also
prone to "poisoning" by impurities such as arsenic (Greenwood & Earnshaw,
1998 : 981).
Vanadium Pentoxide (V2O5) is orange yellow when pure (due to charge
transfer) and is the final product when the metal is heated in an excess of
oxygen, but contamination with lower oxides is then common and a better method
is to heat ammonium "metavanadate":
2NH4VO3 (s) NH3 (g) + V2O5 (s) + H2O(g)
V2O5 solid formed has a melting point of about 650 C and solidifies on
cooling by forming needle-shaped crystals. This oxide can also be obtained from
the addition of dilute acid solution into a solution of ammonium vanadate.
Solubility of this oxide in water is very small (approximately 0.007 g L-1)
and V2O5 is more amphoteric. Therefore, V2O5 soluble in strong base, such as
sodium hydroxide to produce a colorless of vanadite ions. If into this solution is
then added acid to about pH = 6.5 solution became bright orange. If the addition
of acid is continued until approximately pH = 2, it brown precipitate is obtained
V2O5, but this precipitate dissolved back on adding more acid to form oxo cations,
the complex ion of dioksovanadium (V), VO2+. The simple reaction equation can
be written as follows:
In addition of base
V2O5(s) + 6OH- (aq) 2[VO4]3- (aq) + 3H2O(l)
colorless
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In addition of acid until pH = 6.5

2[VO4]3- (aq) + 2H3O+ (aq) [VO2(OH)2]-(aq) + 2H2O(l)
Yellow-orange
In addition of acid until pH= 2
2[VO2(OH)2]-(aq) + 2 H3O+ (aq) V2O5(s) + 5 H2O(l)
Brown
The addition of further acid
V2O5(s) + 2 H3O+ (aq) 2[VO2]+ (aq) + 3 H2O(l)
So, there are two ions of oxovanadium (V) namely complex form of anion
tetraoxovanadate(V) ,[VO4]3- and cation dioxovanadium(V) ,[VO2]+
Vanadium pentoxide is very useful as catalyst in contact process. The
contact process produces a purer, more concentrated acid but requires purer raw
materials and the use of expensive catalysts. In both processes sulfur dioxide is
oxidized and dissolved in water. There are four steps to the contact process which
starts with elemental sulfur.
Step 1: Pure sulfur is burned in air to give sulfur dioxide (SO2), which is familiar
to as rotten egg gas. This reaction happens at about 10000C. The air used
for the burning must be dust free as the presence of dust in the second
part of the process will cause damage to the catalyst.
S(g) + O2(g) SO2(g)
Step 2: The sulfur dioxide is passed into a tower made of stacked vertical beds of
catalyst material, usually vanadium oxide (V2O5) but sometimes
platinum. Here the sulfur dioxide reacts with oxygen once again to give
sulfur trioxide. The purpose of the catalyst is to reduce the temperature
needed for the reaction to occur. This is used because the reaction of SO2
with O2is more productive at the lower temperature of 3000C.Sulfur
Trioxide cannot be immediately converted into Sulfuric acid by
absorbing water, as happens in acid rain. If allowed to absorb water the
SO3 becomes a fine mist that is very difficult to collect.
SO2(g) + ½ O2(g) SO3(g)
Step 3: In order to produce sulfuric acid in liquid form, the sulfur trioxide gas
from the converter is bubbled through very high purity liquid H2SO4.
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This is a very efficient process that results in virtually complete

absorption of the SO3 gas. The resulting liquid chemical is called oleum
and has the formula H2S2O7.
SO3(g) + H2SO4(l) H2S2O7(l)
Step 4: Finally the oleum is converted into highly concentrated H2SO4 by the
addition of dilute H2S2O7 and water. This reaction gives off a lot of heat
and so the resulting acid needs to be cooled before it is sent to storage.
H2S2O7(l) + H2O(l) H2SO4(aq)
6.7.2 Vanadium (IV) Oxide, VO2

Vanadium dioxide has dark blue color and it can be obtained from
reduction of solid V2O5 or by directly heating with oxalic acid. At room
temperature VO2 has a rutile-like structure distorted by the presence of pairs of
vanadium atoms bonded together. Above 700C, however, an undistorted rutile
structure is adopted as the atoms in each pair separate, breaking the localized V-V
bonds and releasing the bonding electrons, so causing a sharp increase in electrical
conductivity and magnetic susceptibility. It is again amphoteric, dissolving in
non-oxidizing acids to give salts of the blue oxovanadium(IV) (vanadyl) ion[VO]
2+,
and in alkali to give the yellow to brown vanadate(IV) (hypovanadate) ion
[V4O9] 2- , or at high pH [VO4] 4-(Greenwood & Earnshaw , 1998).
6.7.3 Vanadium (III) Oxide, V2O3

V2O3 has a corundum structure and is notable for the transition occurring
as it is cooled below about 170 K when its electrical conductivity changes from
metallic to insulating in character. Vanadium trioxide has black color which is
obtained from reduction of V2O5 with H2 or CO continuously. Chemically it is
entirely basic, dissolving in aqueous acids to give blue or green vanadium(III)
solutions which are strongly reducing. The reaction can be seen as follows:
V2O3(s) + 6H3O+(aq) 2V3+(aq) + 9H2O(l)
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6.7.4 Vanadium (II) Oxide, VO

Vanadium oxide (VO) has black-grey color and it can be obtained from
reduction of V2O3 with its metal (V). This oxide has alkaline properties as V2O3,
soluble in acid to form V2+ ion which has violet color. The reaction equation can
be seen as follows.
VO(s) + 2 H3O+(aq) V2+(aq) + 3H2O(l)
6.7.5 Niobium Oxide

Niobium also forms various oxide phases but they are not so extensive or
well characterized as those of vanadium. Its pentoxide (Nb2O5) has white color
and relatively much more stable and difficult to reduce. As it is attacked by
concentrated HF and will dissolve in fused alkali, it may perhaps be described as
amphoteric, but inertness is the more obvious characteristic (Greenwood &
Earnshaw , 1997) .
High temperature reduction of Nb2O5 with hydrogen gives the bluish-
black dioxide NbO2 which has a distorted rutile structure. As in VO2 the distortion
is caused by pairs of metal atoms evidently bonded together, but the distortion is
in a different direction. Further reduction produces the grey monoxide NbO which
has a cubic structure and metallic conductivity (Greenwood & Earnshaw, 1997).
6.8 STRUCTURE OF OXIDE AND ISOPOLYMETALATES

V2O5 adopts a distorted chain structure of trigonal bypiramida allied to
each other on the two sides, one corner point, and one vertex to another freely,
therefore form a double zig-zag chain which seems rather complicated.
VO2 adopt the rutile structure (TiO2) and V2O3 adopts the structure of
corundum ( -Al2O3). VO has a natural structure of NaCl or rock salt (Greenwood
& Earnshaw, 1997).
Analogous to phosphate ions, are ortho-vanadate VO43- adopting
tetrahedron structure and pyro vanadate which is built from two VO4 tetrahedron
are allied on one corner point. Meta vanadate adopts a structure built by VO3- ion,
but depends on the hydration state, eg anhydrous metavanadate NH4VO3
composed of chains (infinite tetrahedron units of VO4 allied on the corners but
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metavenadat hydrated as KVO3.H2O composed by trigonal bipyramid unit chain

VO5, while yellow crystals as Na6V10.18H2O decane venadate containing anions
[V10O28] is composed by 10 octahedron VO6 aligned on the sides.
NbO2 has a distorted rutile structure, and NbO has structure of each six Nb
atom forming up in a octahedron in cube with O atoms occupying the mid-rib of
each cube. With sizes larger than the metal vanadium, Nb2O5 and Ta2O5 in niobat
species [NbO3] - and tantalat [TaO4] 3 -
, adopts a structure that varies with MO6
octahedron units aligned at the corner points and sides such as the hexa-metalat,
[M6O19] 8 - (M = Nb, Ta).
6.9 SULFIDES, SELENIDES AND TELLURIDES

All two metals form a wide variety of binary chalcogenides which
frequently differ both in stoichiometry and in structure from the oxides. Many
have complex structures which are not easily described. The various sulfide
phases are listed in phases approximating to the stoichiometry MS have the NiAs-
type structure whereas MS2 have layer lattices related to MoS2 , CdI2, or CdC12 .
Sometimes complex layer-sequences occur in which the 6-coordinate metal atom
is alternatively octahedral and trigonal prismatic. Most of the phases exhibit
metallic conductivity and magnetic properties range from diamagnetic for
example VS4, through paramagnetic (VS, V2S3), to antiferromagnetic (V7S8)
(Greenwood & Earnshaw, 1997).
Selenides and tellurides show a similar profusion of stoichiometries and
structural types. In addition to these binary chalcogenides, many of which exist
over wide ranges of composition because of the structural relation between the
NiAs and CdI2 structure types. Some, like BaVS3 and BaTaS3 have three-
dimensional structures in which the Ba and V(Ta) are coordinated by 12 and 6 S
atoms respectively (Greenwood & Earnshaw, 1997).
Table 6.4 Sulfides of Vanadium and Niobium
V3S Nb21S8 V2S3 -
- - V5S8 Nb1+xS2
V5S4 - - NbS2
VS NbS1-x - NbS3
V7S8 - VS4 -
V3S4 Nb3S4
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Table 6.5 Selenides and tellurides of vanadium, niobium
V2Se - - -
V5Se4 Nb5Se4 V5Te4 Nb5Te4
Vse NbSe VTe1+ x -
V7Se8 - - -
V3Se4 Nb3Se4 V3Te4 Nb3Te4
V2Se3 Nb2Se3 V2Te3 -
V5Se8 - V5Te8 -
- Nb1+ xSe2 V1 + x Te2 Nb1+ xTe2
Vse NbSe VTe2 NbTe2
- - - -
- NbSe4 - NbTe4
6.10 HALIDES
There are some known halides of vanadium and niobium as well as their
appearance are listed in the table below.
Table 6.6 Some Halides of Vanadium and Niobium
Oxidation Fluorides Chlorides Bromides Iodides
states
+5 VF5 - - -
Colorless
mp 19.5o, bp
48.3o
NbF5 NbCl5 NbBr5 NbI5
White yellow Orange Brass colored
mp 79 o, bp 234o mp 203o, bp mp 254o, bp
247o 230o
+4 VF4 VCl4 VBr4 -
Lime green Red-brown Magenta
(subl> 150 o) mp 26o, bp 148o
Black Violet Black Dark Brown Dark Grey
mp 503o
+3 VF3 VCl3 VBr 3 VI3
Yellow-green Red-violet Grey-Brown Brown-black
mp 800o
Blue black Dark Brown
+2 VF2 VCl2 VBr2 VI2
Blue Pale green Orange-brown Red violet
(subl 910 o) (subl 800 o)
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All pentahalides of Vanadium and Niobium can be prepared by direct

action of the appropriate halogen on the heated metal. All pentahalides is
relatively volatile and hydrolysable solid. VF5 is polymer that contains of
octahedron units with both of the corner in one of its side allied each other so it
will form infinite chain. It is different in NbF5 that form tetrameric (M4X20) from
octahedron units, NbCl5 and NbBr5 form dimer (M2X10) from two units of
octahedron. The structure of pentahalides of Vanadium and Niobium are given in
the picture below.
Figure 6.1 Infinite chain of vanadium atoms in VF5
Figure 6.2 Tetramer structures of NbF5
Figure 6.3 Dimeric structure of NbCl5 and NbBr5

(Greenwood & Earnshaw, 1997)
The color of halides compound of vanadium and niobium vary from
fluorine to iodine. The decreasing energy of the charge-transfer bands responsible
for these colors (Greenwood & Earnshaw, 1997). All pentahalides of vanadium
and niobium conduct sublimation in atmosphere and then they form monomeric
that probably a trigonal bipyramidal.
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The tetrahalides of vanadium and niobium can be prepared by direct action

of the elements. VCl4 and VBr4 tend to form VX3 +½V2; they need the presence
of excess halogen. VF4 is bright-green hygroscopic solid, probably consisting of
fluorine-bridged octahedral VF6. VCl4 is red-brown oil that quickly hydrolyzed by
water to produce oxovanadium (IV) chloride. The products have been proven that
contains of unassociated tetrahedral molecule. The magenta-coloured VBr4 is the
same.
The tetrahalides of niobium (except NbI4 which is prepared by thermal
decomposition of NbI5) are generally prepared by reduction of the appropriate
pentahalides, they also readily to hydrolyzed. NbF4 is a black involatile solid and
its low magnetic moment cause big metal-metal interaction. The remains halogen
are brown to black solid and have chain structure , where the metal’s atom pair are
displaced toward each other. It is abridging interactions that cause diamagnetic
properties.
Figure 6.4 Sheet Structure of NbF4
Figure 6.5 Chain Structure of NbCl4, NbBr4, NbI4

(Greenwood & Earnshaw, 1997)
All of the trihalides of vanadium is in the form of crystal, where the
vanadium is 6-coordinate. All of them are colored and have magnetic moments. A
haft of trifluoride is not very readily oxidized nor very soluble in water. This
trifluoride are easily oxidized by air and very hygroscopic, and form aqueous
solution of [V(H2O)6]3+. The remaining five known trihalides are dark colored and
little uncreative materials.
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The dihalides of vanadium are prepared by reduction of the appropriate

trihalides and have simple structures according to close-packing of halide ions.
They are strongly reducing and hygroscopic, dissolve in water to form lavender-
colored solution of [V(H2O)6]2+.
6.11 OXOHALIDES
Generally, oxohalides of vanadium and niobium are prepared from the
oxides, but not all is known. It is caused by the limited almost entirely to the
oxidation states of +4 and +5. Vanadium and niobium with former oxidation state
are stable, but the other are specially hygroscopic and hydrolyze vigorously to the
hydrous pentoxides. The oxohalides of Nb(V) is more volatile than the
pentahalides. NbOCl3 is well known, because it is tends to form as unwanted
impurity in the preparation of VCl5 if O2 is not rigorously excluded or if V2O5 is
used in that preparation. The well-known oxoanions or oxohalides of vanadium
and niobium as well as their appearance are listed in the table below.
Table 6.7 Oxohalides of Vanadium and Niobium
Oxidation
Fluorides Chlorides Bromides Iodides
State
+5 VOF3 VO2F VOCl3 VO2Cl VOBr3
Yellow Brown Yellow Orange Deep red
mp 300o mp -77o
bp 480o bp 127o
NbO2F NbOCl3 NbO2Cl NbOBr3 NbO2Br NbOI3 NbO2I
white white white yellow- brown black red
brown
+4 VOF2 VOCl2 VOBr2
yellow green yellow-
brown
NbOCl2 NbOBr2 NbOI2
black Black
+3 VOCl VOBr
yellow- Violet
brown
bp 127o
6.12 OXOANIONS
Vanadium and niobium with oxidation state of +5 is too high to allow the
formation of simple ionic salt. These heavy metals have lower oxidation states
that causing higher sublimation energy, they also easy to oxidize, therefore they
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difficult to form simple ionic salt of oxoacids. The simplest oxoanions salts are
the sulfates of vanadium in oxidation states of +3 and +2. This oxoanions salts can
be crystallized from aqueous solution as hydrates and both is strong reducing
agent. They give blue-violet alums MV(SO4)2.H2O and reddish-violet Tutton’s
salts M2V(SO4)2.6H2O.
The higher oxidation states species, which partially hydrolyzed will
dominate the aqueous chemistry; the most important is oxovanadium(IV) or
vanadyl, ion VO2+. This species will give VOSO4.5H2O. While, oxovanadium(V)
is not well characterized. But, in strong acid solution, VO2+ is formed to gives
VO2(NO3). VO2+ also found in anionic complexes such as [VO2(oxalate)2]3-.
Niobium produce variety of complicated, extremely readily hydrolyzed,
and polymeric species which include nitrates such as MO(NO3)3, sulfates such as
Nb2O(SO4), and double sulfates such as (NH4)6Nb2O(SO4)7
6.13 CARBIDES
The appearance of Vanadium carbide (VC) is grey metallic powder with
crystalline cubic in the centre of cubic. Vanadium carbide is insoluble in water.
While, niobium carbide appear as brownish-grey metallic powder.
6.14 COMPLEXES
Oxidation state V
Vanadium (V) has big affinity for O-donors; the complexes formed are
without oxygen, for example white diamagnetic hexafluorovanadates, MVF6 that
susceptible to hydrolyze. If H2O2 is added to aqueous solutions of [VO4]3- a series
of substituent products is founded depend on pH. It have been proven that the red-
brown in acidic solution contain [VO(O2)(H2O)4]+ and in more alkaline solution,
[Vo(O2)2(H2O)]-, [VO2(O2)2(H2O)]3-, [VO(O2)3]3- and [V(O2)4]3- are formed. From
strongly alkaline solution, blue-violet crystal of MI3[V(O2)4].nH2O where MI can
be Li, Na, K, NH4 are precipitate. [V(O2)4]3- in such high coordination number is
not common for vanadium. But, niobium can produce similar peroxo-compounds,
for example pale yellow K3[Nb(O2)4].
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Most complexes of Nb (V) is derived from the pentahalides. NbF5 dissolve

in aquaeous HF to produce [NbOF5]2- and in more concentration of HF, it
[produce [NbF6]-. However, with appropriate controlling concentration of metal,
Fluoride ion and HF, octahedral [MF6], covered trigonal prismatic [MF7]2-, and
quare-antiprismatic [MF8]3- salt can be found. Aquaeous NbCl5 and NbBr5
produce only oxochloro- and oxobromo-complexes.
Generally, niobium (V) is considered to be a class-a metal, but the SCN-
ligand produce a series of both N-bonded thiocyanatee amd S-bonded
isothiocyanato complexes, for example [Nb(NCS)n(SCN)6-n]- where n= 0, 2, 4,
5, 6. The other known complexes of niobium is dithiocarbarnater, dodecahedral
[M(S2CNR2)4]+, and dithiolates [M(SCH2CH2S)3]-. The pentahalides of
niobium act as lewis acid and form complexes of the type MX5L with O, S, N, P,
and As as donor ligan
Oxidation state IV
The tetrahalides of vanadium and niobium are Lewis acid and produce
some variety of donor atoms. The most common is [VF4L] where L is NH3, py. It
is insoluble in common organic solvent, have magnetic moment about 1.8 BM,
and considerably being fluorine-bridged polymer. [VCL42L] (L is py, MeCn,
Aldehydes, etc.) and [VCl4L-L] ( L-L is bypy, phen, diars) are brown
paramagnetic and readily hydrolyzed compounds. Similar compounds of niobium
are also paramagnetic and the metal-metal bonding led to the diamagnetism.
Hexahalo-complexes [MX2]2- is known (M =V, X=F,Cl the vanadium being
sensitive to moisture though stable to air; M=Nb, X= Cl, Br).
Oxidation state III
Only vanadium has significant MIII coordination chemistry that form
easily oxidized complexes. Complexes of Nb prepared by reduction of
pentahalides by Na or Mg, it has particularly S and P-donor ligans. Some
complexes of vanadium and their properties are available in the table below.
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Table 6.8 Typical octahedral complex of vanadium (III)

Complex Colour V1/cm-1 V2/cm-1 10Dq/cm-1 B/cm-1 µ/BM
(RT)
[NH4][V(H2O6)][SO4]2.6H2O Blue-violet 17800 25700 19200 620 280
[VCl3(MeCN)3] Green 14400 21400 15500 540 279
[VCl3(thf)3] Orange 13300 19900 14000 553 280
K3[VF6] Green 14800 23250 16100 649 279
[pyH]3[VCl6] Purple-punk 16650 18350 12650 513 271
Little trinuclear oxo-centered carboxilates [V3O(RCOO)6L3]+, more

common for transition metal have been isolated, as well as
[Nb3O2(RCOO)6(thf)3]+. Only differ by the two bridging O atoms above and
below Nb3 plane. The complexes with S- and P-donor ligans such as SMe2 and
PMe3, Nb2Cl6L4 consisting of a pair of edge-sharing octahedral are also known.
Orange derivatives of Li4[Nb4S2(SPh)12] and [Nb4S2(SPh)8(PMe2R)4] (R = Me,
Ph) show common and rather stable central unit of four Nb atoms. The
diamagnetism and average Nb-Nb separations of approximately 282pm are
consistent with single bonds between adjacent Nb atoms
Oxidation state II
The complexes of this oxidation state are not developed well. Blue-purple
solutions, vanadium (II) complexes that are prepared by electrolytic or zinc
reductions of acidic solution in one of its higher oxidation states is strong
reducing agent, and the reduction of water is only prevented by acid. Several salt
and double sulfates that contain [V(H2O)6]2+ are also known. Other complexes of
[VCl2L2] are differentiating by its color (green) and the magnetic moment also the
halogen-bridged oligomors. No niobium (II) complexes are known.
6.15 SUMMARY
Although vanadium and niobium take place in the same group, instead of
their similarities, they have also some distinctive properties in terms of their
elemental properties as well as their compound properties.
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STUDY QUESTIONS
6.1 Explain the brief history of finding the elements of vanadium and niobium!
6.2 Explain the natural abundance and distribution of the compounds of
vanadium and niobium in the earth’s crust!
6.3 Explain the isolation methods, properties and uses of vanadium and
niobium!
6.4 Explain the properties of oxides of vanadium and niobium!
6.5 Explain the properties of poymetalates of vanadium and niobium!
6.6 Explain the properties of sulfides, selenides dan tellurides of vanadium and
niobium!
6.7 Explain the properties of halides and oxohalides of vanadium and niobium!
6.8 Explain the properties of oxoanion compounds of vanadium and niobium!
6.9 Explain the properties of carbides of vanadium and niobium!
6.10 Explain the properties of complex compounds of vanadium and niobium
with oxidation numbers of V, IV, III and II!
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CHAPTER 7
CHEMISTRY OF CHROMIUM
7.1 INTRODUCTION
Chromium (Cr) is one metal element of the first transition series belong to
group VIB (group 16). At ordinary temperature, chromium metal is resistant to
chemical attack (although dissolves in dilute HCl and H2SO4). At high
temperatures the metal is reactive; it decomposes into steam and combines with
oxygen, halogens and most other non-metals. Chromium metal is used namely in
the production of non-ferrous alloys, but the use of pure chromium being limited
because of its low ductility at ordinary temperatures. Chromium has more than
one oxidation state namely +6, +5, +4, +3, and +2. Many compounds of
chromium can be found. This is to briefly discuss the history, abundance,
isolation, properties, uses, chromium alloys and its compound namely the oxides;
the metallates; the sulfides, selenides and tellurides; the halides and oxohalides;
and the complexes.
7.2 HISTORY OF CHROMIUM

Chromium ores as well as its compounds were used extensively long
before the pure metal was prepared. As early as 1800, it was used to make
pigments and chemicals for leather tanning, and in 1879 it was successfully used
as refractories for the lining of steelmaking furnaces (Britannica Encyclopedia,
2012).
Chromium metal was discovered by the French chemist Louis-Nicolas
Vauquelin in 1797; the following year he isolated the metal by the carbon
reduction of crocoite, or red lead, a chromate mineral whose brilliant hue inspired
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Vauquelin to give the metal its current name (from Greek chrōmos, “colour”).
Iron containing chromium was first produced in the mid-19th century, and the
first use of chromium as an alloying agent in the manufacture of steel took place
in France in the 1860s. In 1893 Henri Moissan smelted chromium ore and carbon
in an electric furnace and produced ferrochromium; this has remained the basis of
the modern commercial method of producing the alloy even while that method has
continuously evolved under the influence of changing markets, technology, and
raw materials. In 1898 Hans Goldschmidt, a German chemist, produced pure
chromium by the aluminothermic reduction of chromium oxide. The silicothermic
process for producing low-carbon ferrochromium was developed in 1907.
Chromium metal was produced by electrolysis in 1854, but this method did not
find wide commercial acceptance until a century later.
7.3 TERRESTRIAL ABUNDANCE AND DISTRIBUTION

Chromium metal is relatively rare in the earth's crust suspected implies
only about 0.0122% or 122 ppm, lower than the vanadium (136 ppm) and chlorine
(126 ppm). The most important ore source of any commercial chromium is
chromite, FeCr2O4 which is produced principally in Russia, Southern Africa
approximately 96% of the known reserve, the former Soviet Union and the
Philippines. Chromium is also found in other minerals, including
magnesiochromite (MgCr2O4). Other sources of chromium obtained in fewer
numbers are crocoite, PbCrO4 and chrome ochre, Cr2O3. Gemstones such as
emerald and ruby containing chromium trace as contaminant.
Chromium forms over 20 different isotopes. Three of them are considered
stable while nineteen are considered to be radioactive, and many have half lives
shorter than 24 hours. The ones listed below are the most stable and the most
commonly found.
Table 7.1 The Commonly Isotope of Chromium
Isotopes Half-life
48
Cr 21.56 hours
49
Cr 42.3 mins
50
Cr 1.8 x 1017 years
51
Cr 27.7025 days
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52
Cr Stable
53
Cr Stable
54
Cr Stable
Source: chemwiki.ucdavis.edu
7.4 ISOLATION
Basically there are two kinds of chromium production based on its use,
namely as ferrochrome alloy (Cr-Fe) and a pure metal chromium. Ferrochrome
with low carbon content can be obtained from the reduction of chromite by using
ferrosilicon. As alloys, ferrochrome is made from reduction of chromite by using
coal coke in an electric furnace. The reaction equation is as follow:
FeCr2O4 + C →Fe.2Cr + 4CO(g)

To obtain pure chromium, chromite ore is first treated with molten alkali
and oxygen, converting all of the chromite to the alkali chromate, Na2CrO4. The
latter Na2CrO4 is dissolved in water and eventually precipitated as sodium
dichromate, Na2Cr2O7. The dichromate is then reduced with carbon to its oxide,
Cr2O3. Then it is continued by the reduction of Cr2O3 by using aluminium or
silicon. The reactions are as follow:
FeCr2O4 + 2Na2CO3 + O2(g) 2Na2CrO4(aq) + 2CO2(g) + Fe(s)
2Na2CrO4(aq) + H2O Na2Cr2O7(s) + 2NaOH
Na2Cr2O7(s) + 2C Cr2O3 + Na2CO3 + CO(g)
Cr2O3 + 2Al Al2O3(s) + 2Cr(l)

or
2Cr2O3 + 3Si SiO3(s) + 4Cr(l)
7.5 PROPERTIES OF THE CHROMIUM ELEMENT

The metal has properties steel-gray color, hard, lustrous, and brittle and is
extremely resistant to ordinary corrosive reagents. Chromium with symbol Cr has
atomic number of 24. At ground sate, electron configuration of chromium is
[Ar]3d54s1. The physical properties of chromium are shown in the following table.
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Table 7.2 Physical Properties of Chromium
Density 7.19 g cm–3
Molar volume 7.23 cm3
Melting point 1907 °C
Boiling point 2671 °C
Specific heat cp at 298 K 449 J K–1 kg–1
Molecular Weight 51.9961 gmol-1
Electronegativity 3.72 eV
Electron Affinity 64.3 kJ mol-1
Radius 124.9 pm
Ionization Energy(Cr Cr+) 652.7 kJ mol-1
Magnetic characterization Paramagnetic
(as susceptibility is positive)
Mass magnetic susceptibility at 293 K +44.5 · 10–9 m3 kg–1
–1 –1
Thermal conductivity Wm K
173 K 273 K 373 K 573 K 973 K
120 96.5 92 82 66
Coefficient of linear expansion K–1
100 K 293 K 500 K 800 K
2.3 · 10–6 4.9·10–6 8.8·10–6 11.8·10–6
Resistivity n m
78 K 273 K 373 K 573 K 973 K 1473 K
5 127 161 252 472 800
Source: Per Enghag, 2004: 573
Certain oxidizing agents produce a thin unreactive oxide layer on the
metal, rendering it passive also to dilute mineral acids, such as sulfuric, nitric, or
cold aqua regia. At elevated temperatures chromium unites directly with the
halogens or with sulfur, silicon, boron, nitrogen, carbon, or oxygen. At room
temperature, chromium slowly dissolves in hydrochloric and dilute sulfuric acids
(Britannica Encyclopedia, 2012)
Chromium metal dissolves in dilute hydrochloric acid to form solutions
containing the equated Cr (II) ion together with hydrogen gas.
Cr(s) + 2HCl(aq) → Cr2+(aq) + 2Cl-(aq) + H2(g)
7.6 USES
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Chromium has melting point of 1900oC and boiling point of about 2690oC.
This metal is highly resistant to corrosion due to the reaction with air produce
Cr2O3 layer of non-porous so it is able to protect the coated metal from further
reaction. With corrosion resistant metal properties, the main use of chromium is as
a plating of metal or steel. In the chromium plating through electro chromium
plating process can be used Cr2O3 dissolved in H2SO4 as electrolyte. Ions of Cr3+
at the cathode will be reduced to metallic chromium that plating another metal. If
the metal directly plated with chromium, typically the resulted layer is easy to
crack. To obtain good plating, the metal previously plated with copper and nickel,
and then it is plated with chromium.
Chromite is used as a refractory. A typical analysis of a chromite suitable
for refractory purposes is 38 to 48 percent Cr2O3, 12 to 24 percent Al2O3, 14 to 24
percent Fe2O3, 14 to 18 percent MgO, and less than 10 percent SiO2. The
usefulness of chromite as a refractory is based on its high melting point of 2180°
C, moderate thermal expansion, the stability of its crystalline form at elevated
temperatures, and its neutral chemical behaviour. The refractory products are
chrome brick, chrome-magnesite brick and plastic cement. Bricks of 100 percent
chromium ore have been largely replaced by bricks composed of mixtures of
chromite and added magnesia for greater refractoriness, volume stability, and
resistance to spalling. One of the refractories used in the fused-cast condition is
composed of 80 percent alumina and 20 percent chromite. This product is highly
resistant to the corrosive action of a variety of fluxes, slags, and glasses.
7.7 CHROMIUM ALLOYS

Ferrochromium is an alloy of iron and chromium. More than 80% of all
chromite ore is consumed in manufacturing this alloy. It is mainly used as the
chromium source for the manufacture of stainless steels and other chromium
steels (Enghag, 2004: 583). An alloy like stainless steel have a high resistance to
oxidation and atmospheric corrosion owing mainly to the presence of chromium,
which, at levels varying between 10 and 26 percent, forms a protective oxide film
on the surface of the steel (Britannica Encyclopedia, 2012). Chromium confers
oxidation resistance to stainless steel, making it ‘‘stainless.’’
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Nickel and chromium can make alloy. Wide solubility ranges between
iron, chromium, and nickel make possible many alloy combinations. The nickel-
chromium system shows that chromium is quite soluble in nickel. This is a
maximum at 47% at the eutectic temperature and drops off to about 30% at room
temperature. A range of commercial alloys is based on this solid solution. Such
alloys have excellent resistance to high temperature oxidation and corrosion. The
80/20 nickel chromium alloy is often used for wrought and cast parts for high
temperature applications, as it has better oxidation and hot corrosion resistance
compared to cheaper iron-nickel-chromium alloys. This nickel chromium alloy is
highly suited to applications that are subject to oxidation.
Those alloys are highly resistant to corrosion and oxidation due to the
reaction with air produces its oxide namely Cr2O3 layer of non-porous so it is able
to protect the coated metal from further reaction.
7.8 CHROMIUM COMPOUNDS

The main oxidation states of chromium are +6, +3, and +2. A few
compound of Cr (V), and Cr (IV) are known, but are unstable with respect to
disproportionation.
7.8.1 Oxides
The principle oxides formed by element of chromium are given in table
below.
Table 7.3 Oxides of Chromium
Oxidation state : +6 Intermediate +4 +3
Cr CrO3 Cr3O8, Cr2O5, Cr5O2, CrO2 Cr2O3
etc.
Source: Greenwood & Earnshaw, 1997: 1007
Chromium (VI) oxide, CrO3, as is to be expected with such a small cation,
is a strongly acidic and rather covalent oxide with a mp of only 197oC. It is
commonly called "chromic acid" and is generally prepared by the addition of
concentrated H2SO4 to a saturated aqueous solution of a dichromate. This purple-
red solid oxide is soluble in water and is highly poisonous. In basic solutions
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above pH 6, CrO3 forms tetrahedral yellow chromate ion, . Between pH 2

and 6, and the dichromate ion, are in equilibrium. At pH below 1,
the main species is H2CrO4. (Cotton, Wilkinson & Gaus, 1995: 559) The
equilibrium are:
This oxide melts with some decomposition and if heated above 220-250oC, it
loses oxygen to give a succession of lower oxides until the green Cr2O3 is formed.
4CrO3(s) → 2Cr2O3(s) + 3O2(g)
Chromium (III) oxide, Cr2O3, it finds wide applications as a green pigment.
Its dehydrate (Guignet’s green) is used in paints due to its the properties as follow:
Table 7.4 Properties of Cr2O3 as Green Pigments
Property Chromium (III) oxide
Refractive index 2.5
Opacity Good
Chemical stability Excellent
Solvent resistance Excellent
Heat Stability excellent1000°C
Light fastness and weatherability Excellent
So, the pigment is non toxic since the chrome is in the trivalent form, which is
inert. It therefore has no apparent toxicological or adverse environmental impacts.
This green oxide is a semiconductor and is antiferromagnetic below 35oC.
(Greenwood & Earnshaw, 1997: 1007) It is more conveniently obtained by
heating ammonium dichromate:
` (NH4)2Cr2O7(s) → Cr2O3(s) + N2(g) + 4H2O(l)
Although insoluble in water, it dissolves in acid to produce hydrated chromium
ions, [Cr(H2O)6]3+ which react with base to give salts of [Cr(OH)6]3-. It dissolves
in concentrated alkali to yield chromite ions. When heated with finely divided
carbon it can be reduced to chromium metal with release of carbon dioxide. When
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heated with finely divided aluminum it is reduced to chromium metal and

aluminum oxide by reaction
Cr2O3(s) + 2 Al(s) → 2 Cr(s) + Al2O3(s)
The third major oxide of chromium is the brown-black chromium (IV)
oxide, CrO2, which is an intermediate product in the decomposition of CrO3 to
Cr2O3. It has metallic conductivity and its ferromagnetic properties. This suggests
that the ferromagnetism in CrO2 is derived from a single unpaired chromium
valence electron. The ferromagnetic properties lead to CrO2 commercial
importance in the manufacture of magnetic recording tapes which are claimed to
give better resolution and high-frequency response than those made from iron
oxide. Unlike the spongy looking ferric oxides used in common tape, the
chromium dioxide crystals were perfectly formed and could be evenly and densely
dispersed in a magnetic coating; and that led to unparalleled low noise in audio
tapes.
7.8.2 Sulfides, Selenides and Tellurides
The sulfides tend to be more stable in the lower oxidation states of the
metals. Thus Cr forms no trisulfide. Chromium (III) sulfide, Cr2S3, is formed by
heating powdered Cr with sulfur, or by the action of H2S(g) on Cr2O3, CrC13 or
Cr. It decomposes to CrS on being heated, via a number of intermediate phases
which approximate in composition to Cr3S4, Cr5S6 and Cr7S8.
Cr2S3(s) → 2CrS(s) + S(g)
Of these various phases Cr2S3 and CrS are semiconductors, whereas Cr7S8, Cr5S6
and Cr3S4 are metallic, and all exhibit magnetic ordering. The corresponding
selenides CrSe, Cr7Se8, Cr3Se4, Cr2Se3, Cr5Se8 and Cr7Se12 are broadly similar, as
are the tellurides CrTe, Cr7Te8, Cr5Te6, Cr3Te4, Cr2Te3, Cr5Te8 and CrTe2.
(Greenwood & Earnshaw, 1997: 1017)
7.8.3 Metalletes
The formation of chromate and dichromate ion has been described in oxide
of chromium. Polymerization beyond the dichromate ion is apparently limited to
the formation of tri- and tetra-chromates ( and -), which can be
crystallized as alkali-metal salts from very strongly acid solutions. These anions,
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as well as the dichromate ion, are formed by the comer sharing of CrO4
tetrahedral giving Cr-O-Cr angles very roughly in the region of 123o.
O O
O O
Cr o Cr
Cr O 123
O O
O O O O
Figure 7.1 Structure of and ion

The limitation of this anionic polymerization of chromium is probably due to the
small size of Cr (VI). This evidently limits it to tetrahedral rather than octahedral
coordination with oxygen.
Sodium dichromate, Na2Cr2O7.2H2O, produced from the chromate is
commercially much the most important compound of chromium. It yields a wide
variety of orange-red pigments used in the manufacture of paints, inks, rubber and
ceramics. It is also the oxidant in many organic chemical processes. Besides,
acidified dichromate solutions are used as strong oxidants in volumetric analysis:
+ 14H+ + 6e- → 2Cr3+ + 7 H2O; Eo= 1.33 V
For this purpose the potassium salt, K2Cr2O7 is preferred since it lacks the
hygroscopic character of the sodium salt and may therefore be used as a primary
standard (Greenwood & Earnshaw, 1997: 1009).
7.8.4 Halides and Oxohalides
The oxidation state of +6 is attained by chromium only with the strongly
oxidizing fluorine, precisely the same is true in the +5 oxidation state and in the
+4 oxidation state the iodides have a unstable existence. In the lower oxidation
states all the chromium halides are known (Greenwood & Earnshaw, 1997:
1019).
Table 7.5 Halides of Chromium (mp/oC)
Oxidation State Fluorides Chlorides Bromides Iodides
+6 CrF6
yellow
+5 CrF5
Red (34o)
Bp 117o
+4 CrF4 CrCl4 CrBr4 CrI4
Violet-amethyst
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Green (1404o) Red-violet Very dark green Very dark
(1150o) (1130o) green
Green (894o) White (820o) White (842o) Red-brown
(868o)
The hexahalides can be prepared by direct action of the halogen on metal
(requires a temperature of 400oC and a pressure of 200-300 atms and reduction of
the pressure causes it to dissociates into CrF5 and F2 even at temperature as low as
-100oC. The pentahalides, chromium again forms only the fluoride which is a
strongly oxidizing, the bright red volatile solid prepared from the elements using
less severe conditions than for CrF6 at ≈ 297 K
The tetrahalides are scarcely more numerous or familiar than the hexa- and
penta-halides, the CrI4, CrBr4, CrCl4 being either of uncertain existence or
occurring only at high temperatures in the gaseous phase. The most stable
representatives are the fluorides, CrF4, is an unreactive solid. Pure CrF4 can be
made by fluorination of Cr using HF/F2 under solvothermal conditions. The pure
material is violet, but the color of samples prepared by different routes varies
(green, green-black, brown) with descriptions being affected by the presence of
impurities (Housecroft & Sharpe, 2008: 701). In the vapor, CrF4 exist as a
tetrahedral molecule.
Chromium trihalides, CrF3, CrCl3, CrBr3, CrI3 are known, this being much
the most stable oxidation state for chromium; they can be prepared by reacting the
halogen and the metal, though CrF3 is better obtained from HF and CrCl3 at
500oC. The fluoride is green, the chloride red-violet and the bromide and iodide
dark green to black. In all cases layer structures lead to octahedral coordination of
the metal. Stable hydrate forms of CrX3 can also be readily obtained from aqueous
solutions, and CrCl3.6H2O provides a well-known example of hydrate isomerism.
In view of this clear ability of Cr3+ to aquate it may seem surprising that
anhydrous CrCl3 is quite insoluble in pure water (though it dissolves rapidly on
the addition of even a trace of a reducing agent). It appears that the reducing agent
produces at least some Cr2+ ions. Solubilization then follows as a result of electron
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transfer from Cr2+(aq) in solution via a chloride bridge to Cr3+ in the solid, which
leaved Cr3+(aq) in solution and Cr2+ in the solid.
Anhydrous chromium dihalides are conveniently prepared by reduction of
the trihalides with H2 at 300-500oC, or by the action of HX (or I2 for the diiodide)
on the metal at temperatures of the order of 1000oC. They are all deliquescent and
the hydrates can be obtained by reduction of the trihalides using pure chromium
metal and aqueous HX.
The oxohalides are very susceptible to hydrolysis. They are yellow to red
liquid or volatile solid; probably the best known is the deep-red liquid, chromyl
chloride, CrO2Cl2. (Greenwood & Earnshaw, 1997: 1022)
Table 7.6 Oxohalides of Chromium (mp/oC)
Oxidation State Fluorides Chlorides Bromides Iodides
+6 CrOF4 CrO2Cl2 CrO2Br2
Red (55o) Red, bp 117o Red
CrO2F2
Violet (32o)
+5 CrOF3 CrOCl3
Dark red
+3 CrOCl CrOBr
Green
Fluorination of CrO3 with SeF4, SF4 or HF yields CrO2F2 (violet crystal,
mp 305 K), while CrO2Cl2 (red liquid, mp 176 K, bp 390 K) is prepared by
heating a mixture of dichromate and chloride in concentrated H2SO4. It is most
commonly encountered as the distillate in qualitative tests for chromium or
chloride; it is an extremely aggressive oxidizing agent; chromyl chloride is an
oxidant and chlorinating agent. It has a molecular structure (a) and is light
sensitive and readily hydrolyzed: CrO2Cl2 + 3H2O  [Cr2O7]2- + 4Cl- + 6H+. If
CrO2Cl2 is added to a concentrated KCl solution, K[CrO3Cl] precipitate.
(Housecroft & Sharpe, 2008: 700)
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Cl
O
Cr
Cr O
O
O O
Cl
Cl
o
O-Cr-O = (a) O-Cr-O = 111
(b)
108.5o Cl-Cr-O = 106o
Cl-Cr-Cl = 113o
Figure 7.2 Structure of CrO2Cl2 (a) and [CrO3Cl]- (b)
Source: Housecroft & Sharpe, 2008: 700
7.8.5 Complexes
Oxidation State VI
Complex formation by Cr (VI) requires strong π-donor ligands such as O2-
or [O2]2- (Housecroft & Sharpe, 2008: 700). When H2O2 is added to an acidified
solution of a chromate (VI) salt, the product (formed as a solution species) is a
deep violet-blue complex which contains both oxo and peroxo ligands (Cotton,
Wilkinson & Gaus, 1995: 560).
[CrO4]2- + 2H+ + 2H2O2  [Cr(O)(O2)2] + 3H2O
In aqueous solution, [Cr(O)(O2)2] rapidly decomposes to Cr3+ and O2, but it may
be extracted into ether where it is more stable. An ethereal solution is more stable
and, from it the pyridine adduct [Cr(O)(O2)2(py)] may be isolated. This and
related compounds (which are explosive when dry) have used as oxidants in
organic syntheses. Like other Cr (VI) compounds, [Cr(O)(O2)2(py)] has a very
small paramagnetic susceptibility (arising from coupling of the diamagnetic
ground state with excited states). The action of H2O2 on neutral or slightly acidic
solutions of [CrO7]2- (or reaction between [Cr(O)(O2)2] and alkalis) yields
diamagnetic, dangerously explosive, red-violet salts of [Cr(O)(O2)2(OH)]-.
Oxidation State V and IV
Complexes of chromium (V) may be stabilized by π-donor ligands, e.g.
[CrF6] , [CrOF4]-, [CrOF5]2-, [CrNCl4]2- and [Cr(NtBu)Cl3]. Peroxo complexes
-
containing [Cr(O2)4]3- are obtained by reaction of chromate(V) with H2O2 in

alkaline solution; [Cr(O2)4]3- has a dodecahedral structure. These salts are
explosive but are less dangerous than the Cr(VI) peroxo complexes. The explosive
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Cr(IV) peroxo complexes [Cr(O2)2(NH3)3] is formed when [Cr2O7]2- reacts with

aqueous NH3 and H2O2 which has a dark red-brown metallic lustre; a related
complex is [Cr(O2)2(CN)3]3-.
Oxidation State III
Chromium (III) forms stable salts with all the common anions and it
complexes with virtually any species capable of donating an electron-pair. These
complexes may be anionic, cationic, or neutral and with hardly any exceptions,
are hexacoordinate and octahedral, e,g.:
[CrX6]3- (X=halide, CN, SCN, N3)
[Cr(L-L)3]3- (L-L= oxalate)
[CrX6]3+ (X= H2O, NH3)
[Cr(L-L)3]3+ (L-L= en, bipy, phen)
[Cr(L-L)3] (L-L= β-diketonates, amino-acid anions)
(Greenwood & Earnshaw, 1997: 1027)
Large number of mononuclear octahedral Cr(III) complexes are known.
The electronic spectra of octahedral d3 complexes contain three absorptions due to
‘d-d’ transitions. Selected examples of octahedral chromium(III) complexes are
[Cr(acac)3], [Cr(ox)3]3-, [Cr(en)3]3+, [Cr(bpy)3]3+, cis- and trans-[Cr(en)2F2]+,
trans-[CrCl2(MeOH)4)+, [Cr(CN)6]3- and [Cr(NH3)2(S5)2]- ([S5]2- is bidentate). The
complex halides include [CrF6]3-, [CrCl6]3-, and [Cr2Cl9]3-. The violet Cs3[Cr2Cl9]
is made by reaction: 3CsCl + 2CrCl3  Cs3[Cr2Cl9]; the [Cr2Cl9]3- is isostructural
with [V2Cl9]3- and the magnetic data are consistent with the presence of three
unpaired electrons per Cr(III) center, i.e. no Cr-Cr interaction. Pale violet
[Cr(OH2)6]3+ is obtained in aqueous solution when [Cr2O7]2- is reduced by SO2 or
by EtOH and H2SO4 below 200K.
Oxidation State II
Complexes of Cr(II) include halide anions such as [CrX3]-, [CrX4]2-,
[CrX5]3-, and [CrX6]4-. Despite the range of formulae, the Cr(II) centers in the
solids are usually octahedrally sited, e.g. [CrCl3]- consists of chains of distorted
face-sharing octahedral, the distortion being a Jahn-Teller effect. Some of these
salts show interesting magnetic properties. For example, salts of [CrCl 4]2- show
ferromagnetic coupling at low temperatures, with Tc values in the range 40-60 K;
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communication between the metal centers is through Cr-Cl-Cr bridging

interactions.
Cyano complexes of Cr(II) include [Cr(CN)6]4- and [Cr(CN)5]3-.
K4[Cr(CN)6] may be prepared in aqueous solution, but only in the presence of
excess cyanide ion; octahedral [Cr(CN)6]4- is low-spin. The reaction of [Cr2(µ-
O2CMe)4] with [Et4N][CN] leads to the formation of [Et4N]3[Cr(CN)5].
Based on explanation above, it can be concluded that chromium (Cr) is the
metal element of the first transition series belong to group VIB (group 16).
Chromium has atomic number of 24 and at ground sate, electron configuration is
[Ar]3d54s1. It has more than one oxidation state namely +6, +5, +4, +3, and +2.
Chromium ores and compounds were used extensively long before the pure metal
was prepared. The metal was discovered by the French chemist Louis-Nicolas
Vauquelin in 1797. Chromium metal is relatively rare in the earth's crust
suspected implies only about 0.0122% or 122 ppm, lower than the vanadium (136
ppm) and chlorine (126 ppm). The metal has properties steel-gray color, hard,
lustrous, and brittle and is extremely resistant to ordinary corrosive reagents. With
corrosion resistant metal properties, the main use of chromium is as a plating of
metal or steel. This metal can form several alloys, such as with iron and nickel.
Those alloys are highly resistant to corrosion and oxidation due to the reaction
with air produces its oxide namely Cr2O3 layer of non-porous so it is able to
protect the coated metal from further reaction. Chromium is capable to form
compound with other elements. Its common oxides are CrO3, Cr2O3, and CrO2.
The sulfides are Cr2S3 and CrS with intermediate of Cr3S4, Cr5S6 and Cr7S8. The
dichromate ion can be crystallized as alkali-metal salts, such as Na2Cr2O7.2H2O
and K2Cr2O7. The known halides of chromium are exist in form of hexahalides,
tetrahalides, trihalides, and dihalides. It also forms the oxohalides such as CrOF4,
CrOCl3, and CrOBr. The chromium forms varied complexes in its oxidation
states. Different the oxidation state, different the kind and properties of the
complex.
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7.9 SUMMARY
Chromium is well-known as an color element. It has more than one
oxidation state namely +6, +5, +4, +3, and +2. Its distinctive properties makes the
metal widely used in industries. The multi oxidation states of chromium makes
the metal easily to form various compounds, ranging from various oxides,
hidroxides, halides, oxoanionic compounds, as well as a lot of complex
compounds.
STUDY QUESTIONS
7.1 Explain the brief history of finding the element of chromium!
chromium in the earth’s crust!
7.3 Explain the isolation methods, properties and uses of chromium!
7.4 Explain the superior properties of chromium alloys!
7.5 Explain the properties of the oxides of chromium!
7.6 Explain the properties of some metalate of chromium!
7.7 Explain the properties of sulfides, selenides dan tellurides of chromium!
7.8 Explain the properties of halides and oxohalides of chromium!
7.9 Explain the properties of complex compounds of chromium with oxidation
numbers of VI, V, IV, III and II!
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CHAPTER 8
MANGANESE CHEMISTRY
8.1 INTRODUCTION
Manganese is a chemical elements, designated by symbol of Mn. It has the
atomic number 25, with the electronis configuration is [Ar]3d54s2. It is found as a
free element in nature (often in combination with iron), and in many minerals.
Manganese is a metal with important industrial metal alloy uses, particularly in
stainless steels. Manganese is a silvery-gray metal that resembles iron. It is hard
and very brittle, difficult to fuse, but easy to oxidize.Manganese metal and its
common ions are paramagnetic.Manganese tarnishes slowly in air and "rusts" like
iron, in water containing dissolved oxygen.
This is to discuss all about manganese elements, such as the history of
manganese, abundance, isolation, the propertise, uses and its compounds.
8.2 THE HISTORY OF MANGANESE

Manganese (Mn) is known as an element in 1774. History found
manganese comes from magnesia region that is now the modern Greek regions
that manganese name when first taken from the Latin meaning Magnes
magnetized. In the 16th century, manganese dioxide is called manganesum by
glassmakers. In the mid-17th century, the German chemist Glauber obtained
permanganate, the first usable manganese salt. Nearly a century later, manganese
oxide became the basis for the manufacture of chlorine. Yet manganese was only
recognized as an element in 1771, by the Swedish chemist Scheele. It was isolated
in 1774 by one of his collaborators, J.G. Gahn. At the beginning of the 19th
century, both British and French scientists began considering the use of
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manganese in steel making, with patents granted in the UK in 1799 and 1808. In
1816, a German researcher observed that manganese increased the hardness of
iron, without reducing its malleability or toughness. Around the beginning of the
19th century, manganese widely is used both in industry and health care.
Manganese can be used in making steel. In1816, Johan Gottlieb Gahn reported
that the addition of manganese to iron will produce a louder mix. In 1837, British
academic James Couper noted the relationship between heavy exposure to
manganese in mines with a form of Parkinson's disease. In 1912, conducted of
layer of manganese phosphating electrochemical conversion of fire arms to
protect agains trust and corrosion were patented by the United States, and has
been used extensively since then. The invention of further Leclanchédry cell
battery in 1866.
8.3 THE ABUNDANCE OF MANGANESE

Manganese is a naturally occurring substance found in some types of rock
and soil. Pure manganese is a silver-colored metal. Therefore manganese metal is
reactive with oxygen, thus this element does not exist freely in nature. In the
nature, manganese is found in the formS of MnO2 (pirolusit e); Mn3O4 or
MnOMn2O3 (hausmannite); Mn2O3 (braunite); Mn2O3.H2O (mangganite);
MnCO3 (rhodochrosite); and BaMn9O16(OH)4 (psilomelan). Rocks containing
manganese crust is approximately 0.11% by mass.
Manganese is the twelfth most abundant element and the third most
abundant transition element (exceeded only by iron and titanium). It is found in
over 300 different and widely distributed minerals of which about twelve are
commercially important. As a class a metal it occurs in primary deposits as the
silicate. Of more commercial importance are the secondary deposits of oxides and
carbonates such as pyrolusite (MnO2), which is the most common, hausmannite
(Mn3O4), and rhodochrosite (MnCO3). These have been formed by weathering of
the primary silicate deposits and are found in the former USSR, Gabon, South
Africa, Brazil, Australia, India and China (Greenwood,1997:1041).
Manganese is also present as nodules, namely sediment resemble to rock
with a composition approximately 15-30% Mn in oxide form together with oxides
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of Fe, Co, Cu, and Ni. The forms of nodules aregranules ball with a diameter are
few millimeters until 15 cm, and accumulates in the bottom of the ocean, most of
the region, the southeastern islands of Hawaii.
Potential of manganese ore reserves in Indonesia is quite large, but are
located in different locations spread through out Indonesia, among others on the
Sumatra, Riau, Java, Kalimantan, Sulawesi, Nusa Tenggara, Maluku, and Papua.
Manganese also spreads through out the body tissues. Manganese concentration is
the highest in the liver, thyroid gland, pituitary, pancreas, kidney, and bone. Total
amount of manganese in men who weighs 70 kg, is approximately 12-20 mg.
Number of daily intake has yet to be certainly determined, however, several
researchs suggest that the amount of manganese is at least about 2.5 to 7 mg per
day to sufficient human needs.
8.4 ISOLATION OF MANGANESE

Manganese is found in the formed of MnO2 in pyrolusite mineral. There
some steps to get the manganese element. Manganese is used in steel application
that in mixture of iron-manganese. This mixture is obtained by heating the
mixture of MnO2 with Fe2O3 and carbon.
feromanganate
If the pyrolusite mineral containes silicon, it can be remove by addition of
Ca(OH)2. The silicon will change into potassium silicate. To get the pure of
manganese metal, pyrolusite is proccesed through thermite process. In the
process, pyrolusite (MnO2) is is reduced into Mn3O4. Addition of aluminum
metals is produce manganese metal that can separated as it melts. the purity of
manganese can be obtained distillation process.
By heating process of MnO2 become mangano-mangani oxide.
Then, manganese oxide is mixed with aluminium powder and burned.
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Manganese oxide that have extraction is mix with carbon and then heated, the
reaction as follow:
Mn3O4 + 4C → 3Mn + 4CO
MnO +2C → Mn + 2CO
8.5 PROPERTIES OF MANGANESE

Manganese is an important trace element in life and has a role in
photosynthesis. There are 4 allotropes of Mn of which the -form is the one stable
at room temperature. This has a bcc structure in which, for reasons which are not
clear, there are 4 distinct types of Mn atom. It is hard and brittle, and noticeably
less refractory than its predecessors in the first transition series (Greenwood,
1997:1043)
Manganese is reactive when pure, and as a powder it will burnt in oxygen.
It reacts with water (it rusts like iron) and dissolves in dilute acids. Evidently the
3d electrons are more tightly held by the Mn atomic nucleus and this reduced
delocalization produces weak metallic bonding. Below are some characteristics of
manganese:
Table 8.1 The Physical Properties of Manganese
Atomic number 25
-1
Atomic weight 54.9380 g.mol
Electronegativity according to Pauling 1.5
-3
Density 7.43 g.cm at 25°C
Melting point 1244 °C
Boiling point 2060 °C
Vanderwaals radius 0.126 nm
Ionic radius 0.08 nm (+2) ; 0.046 nm (+7)
Isotopes 7
5 2
Electronic configuration [ Ar ] 3d 4s
-1
Energy of first ionisation 716 kJ.mol
-1
Energy of second ionisation 1489 kJ.mol
2+
Standard potential - 1.05 V ( Mn / Mn )
Electrical resistivity 185 at 20 C/ ohm. cm
(monoatomic gas) 281 ( 6)kJ/mol
221( 8)kJ/mol
13.4 kJ/mol
Heat capacity 0,48 J/g·K
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Like other transition metals, manganese has more than one common
oxidation state. The oxidation state of +2, which is a pale pink color in aqueous
solutions. Also important is +4, brown/black, which is found in manganese
dioxide, and +7 found in the purple permanganate anion MnO4-. Manganese's +6
oxidation state is green.
Manganese metal and its common ions are paramagnetic. This is because
of the electron configuration d orbitals of manganese, there are atoms that have an
unpaired electron, the atom will be paramagnetic. Paramagnetic properties mean
that can be affected by magnetic fields, which each unpaired electron has a spin
that generates a magnetic moment. Magnetic moment is what behaves like a
magnet. Therefore manganese unpaired electrons in the electron spin magnetic
moment produces no abolish that manganese has a magnetic moment and are
paramagnetic. In a pure state, manganese metal is hard but brittle (easily broken).
Manganese is easily oxidized by air but reacts slowly with water.
Chemical properties of Manganese
1. Reaction with water
Manganese reacts with water can turn into base and the hydrogen gas are
slowly will be released according to the reaction:
Mn(s) + 2H2O → Mn(OH)2 +H2
2. Reaction with air
Manganese metal burns in air according to the reaction:
3Mn(s) + 2O2 → Mn3O4(s)
3Mn(s) + N2 → Mn3N2(s)
3. Reaction with halogen
Manganese reacts with halogens to form manganese (II) halides. Reaction
are follows:
Mn(s) +Cl2 → MnCl2
Mn(s) + Br2 → MnBr2
Mn(s) + I2 → MnI2
Mn(s) + F2 → MnF2
Besides reacting with fluorine to form manganese (II) fluoride, also
produces manganese (III) fluoride according to the reaction:
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2Mn(s) + 3F2 → 2MnF3(s)

4. Reaction with acid
Manganese metal reacts with dilute acids rapidly produce hydrogen gas
according to the reaction:
Mn(s) + H2SO4 → Mn2+(aq) + SO42-(aq) + H2(g)
8.6 USES OF MANGANESE

Dry-cell batteries, flashlight batteries, are important applications for
manganese. Its dioxide is used as a depolarizer. The electrolyte is a paste of
ammonium chloride and zinc chloride, a zinc can is the anode and a carbon rod,
surrounded by manganese dioxide, the cathode. During work (discharge)
hydrogen is released at the cathode – a gas film is formed on the electrodes and
cuts off the current. manganese dioxide is used in battery application because it
can oxidize hydrogen into water. Natural manganese dioxide can be used in
standard cells while electronic manganese dioxide or chemical manganese dioxide
are required for high-performance cells. An alternative to the Leclanché cell is the
alkaline MnO2 zinc cell with an increased service life (introduced in the 1950s).
The cathode is an MnO2/C powder mixture on the inside wall of a steel container,
the anode is zinc powder and the electrolyte is potassium hydroxide
(Enhag:639:2004).
8.7 OXIDES AND CHALCOGENIDES OF MANGANESE

Manganese oxide is a generic term used to describe a variety of
manganese oxides such as: manganese (II) oxide, MnO; manganese (III) oxide,
Mn2O3; manganese (II,III) oxide, Mn3O4; manganese (IV) oxide, MnO2 ;
manganese (VI) oxide, MnO3; and manganese (VII) oxide, Mn2O7. Each of them
will be explained in detail below.
8.7.1 Manganese(II) Oxide

Manganese (II) oxide is used in the fertilizer industry as a source of
manganese in fertilizers; in feedstuff formulations; and as an intermediate in the
production of several manganese compounds.
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The properties of manganese are green cubic crystal, refractive index of

2.16, density of 5.37 g/cm3 at 23°C, Moh’s hardness of 5.5, melts at 1945°C,
and insoluble in water.
Manganese (II) oxide is obtained commercially from manganese (IV)
oxide (manganese dioxide) by the reduction with hydrogen, carbon monoxide or
methane at elevated temperatures (>800°C):
MnO2 + CO → MnO + CO2
MnO2 + H2 → MnO + H2O
The oxide also can be made by thermal decomposition of manganese (II)
carbonate or manganese(II) oxalate in the absence of air:
MnCO3 → MnO + CO2
Also, careful dehydration of manganese(II) hydroxide, Mn(OH)2, under controlled
conditions in the absence of air yields MnO.
Manganese(II) oxide is the lowest oxide of manganese and it is purely a
basic oxide. It reacts with acids to form their manganese(II) salts:
MnO + H2SO4 → MnSO4 + H2O
MnO + 2HCl → MnCl2 + H2O
The compound also is oxidized by air or oxygen to higher oxides of manganese.
When heated cautiously in air, the product is manganese sesquioxide or
manganese(III) oxide:
4MnO + O2 → 2Mn2O3
8.7.2 Manganese (III) Oxide

Manganese (III) Oxide is a dark brownish-black powder (left), Mn2O3
thermite (right).
Black cubic (or rhombic) crystals; density of 4.50 g/cm3; Moh’s hardness
of 6–6.5 (for braunite); decomposes at about 875°C; insoluble in water; insoluble
in alcohol and acetone; soluble in acids.
Manganese(III) oxide is obtained by heating manganese(II) oxide in air at
600 to 850°C. It also may be prepared by igniting manganese(II) salts in air or
oxygen. The oxide also is produced by cautious heating of manganese(II) oxide in
oxygen. Manganese(III) oxide also can be made by dehydrating manganese( III)
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metahydroxide, MnO(OH), in a vacuum at 250°C. In such preparation, an

unstable tetragonal modification, beta-Mn2O3, is first obtained which on
prolonged heating converts to the stable cubic modification, alpha- Mn2O3.
Mn2O3 is also formed in redox raction of alkali cell, as the reaction below
2 MnO2 + Zn → Mn2O3 + ZnO
8.7.3 Manganese(II,III) Oxide

Manganese(II,III) oxide occurs in nature as the mineral hausmannite
[1309-55-3]. The properties of Manganese(II,III) oxide are black tetragonal
crystal, exhibit two allotropic modifications—a stable alpha phase, occurring in
tetragonal crystalline form (a hausmannite) and an unstable beta modification,
density of 4.85 g/cm3, Moh’s hardness of 5.5, melts at 1,567°C, insoluble in
water, and soluble in hydrochloric acid.
Manganese(II,III) oxide is made by heating manganese(IV) oxide, MnO2,
or manganese(III) oxide, Mn2O3, above 950°C. When Mn2O3 is heated in air, the
temperature should be above 940°C, but if heated in oxygen, the temperature
should be above 1,090°C. Also, heating manganese(III) oxide at 230°C in
hydrogen yields Mn3O4. However, further heating above 300°C converts Mn3O4
formed to green manganese(II) oxide, MnO. Manganese(II,III) oxide also is
obtained by heating the dioxide, MnO2, with carbon at 600 to 700°C.
Manganese(II,III) oxide reacts with dilute acids forming the corresponding
manganous salt and manganese(IV) oxide, MnO2:
Mn3O4 + 2H2SO4 → 2MnSO4 + MnO2 + 2H2O
The oxide, however, dissolves slowly in cold sulfuric acid forming a red solution
that also contains manganic sulfate, Mn2(SO4)3:
Mn3O4 + 4H2SO4 → MnSO4 + Mn2(SO4)3 + 4H2O
Reaction with acetic acid yields manganese(II) acetate and manganese(III) oxide:
Mn3O4 + 2CH3COOH → Mn(CH3COO)2 + Mn2O3 + H2O
Manganese(II,III) oxide is reduced to manganese metal when heated with
powdered aluminum (the Thermite process). The reaction is vigorous and
exothermic:
3Mn3O4 + 8Al → 4Al2O3 + 9Mn
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8.7.4 Manganese(IV) Oxide

Manganese(IV) Oxide is a black powder. Manganese(IV) oxide is used to
produce manganese metal, most manganese salts, and also manganese steel and
other alloys. The metallurgical applications of manganese(IV) oxide mainly
involve making ferromanganese and special manganese alloys. Another important
application of manganese(IV) oxide is in manufacturing dry-cell batteries and
alkaline cells. The oxide also is a colorant in brick, tile, porcelain and glass; a
drier for paints and varnishes; a preparation for printing and dyeing textiles; a
curing agent for polysulfide rubbers; an adsorbent for hydrogen sulfide and sulfur
dioxide; an oxidizing agent in many organic syntheses such as quinone and
hydroquinone; and a catalyst in laboratory preparation of oxygen from potassium
chlorate. Manganese(IV) oxide also is used to make welding rods and fluxes, and
ceramic magnets (ferrites); and is an additive to fertilizers.
Black tetragonal crystals; density 5.08 g/cm3; Moh’s hardness 6.3;
decomposes at 535°C; insoluble in water.
Pure manganese(IV) oxide (precipitate form) may be prepared by reducing
permanganate ion with a manganous salt:
2KMnO4 + 3MnSO4 + 2H2O → 5MnO2 + K2SO4 + 2H2SO4
Manganese(IV) oxide can also be precipitated by oxidation of a manganese( II)
salt using an oxidizing agent such as hypochlorite or peroxydisulphate:
Mn2+ + S2O82– + 2H2O → MnO2 + 2SO42– + 4H+
Manganese(IV) oxide may also be made by thermal decomposition of manganese(
II) nitrate; or from roasting manganese(II) carbonate in air:
Mn(NO3)2 → MnO2 + 2NO2
MnCO3 + ½ O2 → MnO2 + CO2
A highly active gamma-MnO2 can be produced by treating manganese(III) oxide
with hot sulfuric acid:
Mn2O3 + H2SO4 → MnO2 + MnSO4 + H2O
Mn2O3 is derived from pyrolusite by heating the mineral at 600–800°C or
reducing with powdered coal at 300°C.
The preparation of MnO2 by using dirty manganese oxide and changes into
manganese (II) solution with dinitrogentetraoxide and water. The evaporation of
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water will make nitrate salt is crystalize. In the temperature of 4000C , it salt will
decompose and release N2O4.
MnO2 +N2O4 → Mn(NO3)2
Mn(NO3)2 → MnO2+N2O4
Thermal decomposition of manganese(IV) oxide at 600 to 800°C yields
manganese( III) oxide:
4MnO2 → 2Mn2O3 + O2
MnO2 also is reduced to Mn2O3 at 300°C in the presence of a reducing agent
such as hydrogen, methane or carbon. Treatment with concentrated hydrochloric
acid forms manganese(IV) chloride which readily decomposes to manganese(III)
chloride and manganese(II) chloride, successively liberating chlorine:
MnO2 + 4HCl → MnCl4 + 2H2O
MnCl4 → MnCl3 + ½ Cl2
MnCl3 → MnCl2 + ½ Cl2
When heated with concentrated sulfuric acid, manganese(IV) oxide yields
manganese(II) sulfate, evolving oxygen:
MnO2 + H2SO4 → MnSO4 + H2O + ½ O2
When the solution is heated at 135°C, MnSO4 is oxidized to Mn2(SO4)3. Reaction
with sulfuric acid in the presence of oxalic acid yields manganese(II) sulfate and
carbon dioxide:
MnSO2 + (COOH)2 + H2SO4 → MnSO4 + 2CO2 + 2H2O
While the reaction with sulfuric acid in the presence of sodium chloride evolves
chlorine:
MnO2 + 2NaCl + 2H2SO4 → MnSO4 + Na2SO4 + 2H2O + Cl2
When heated with potassium hydroxide, manganese(IV) oxide partially
decomposes to manganese(III) oxide and potassium manganate:
3MnO2 + 2KOH → Mn2O3 + K2MnO4 + H2O
However, in the presence of oxygen or other oxidizing agents, all manganese is
oxidized to manganate:
MnO2 + 2KOH + ½ O2 → K2MnO4 + H2O
Manganate(VI) can further oxidize to manganate(VII) (or permanganate) in
alkaline solution with a strong oxidizing agent such as hypochlorite, chlorine or
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perchlorate, or under anodic oxidation. Alternatively, in less alkaline media

(where the KOH concentration is less than about 15%), the manganate ion MnO42–
hydrolyzes, disproportionating to permanganate MnO4¯ and forming back
manganese(IV) oxide:
3MnO42– + 2H2O → 2MnO4¯ + MnO2 + 4OH¯
The green color of manganate solution turns purple due to the permanganate
formed. Manganese(IV) oxide is an oxidizing agent. In acid medium, it oxidizes
iodide to iodine:
MnO2 + 2I¯ + 4H+ → Mn2+ + 2H2O + I2
Thus, in the presence of dilute acids, MnO2 is readily attacked by strong reducing
agents. Similarly, reaction with sulfurous acid forms manganese(II) dithionate:
MnO2 + 2H2SO3 → MnS2O6 + 2H2O
Or with nitrous acid in the presence of nitric acid, manganese(II) nitrate is formed:
MnO2 + HNO2 + HNO3 → Mn(NO3)2 + H2O
Reaction with potassium bifluoride in the presence of hydrofluoric acid creates a
stable complex fluoride, K2MnF6 in which Mn is in +4 oxidation state:
MnO2 + 2KHF2 + 2HF → K2MnF6 + 2H2O
When fused with basic oxides such as calcium oxide, manganites or manganate(
IV) salts such as CaO•MnO2, 2CaO•MnO2, CaO•3MnO2 are formed. The
stoichiometric compositions of these manganites vary. Manganese(IV) oxide
reacts with aniline in the presence of sulfuric acid
formingquinone, an intermediate product in the manufacture of hydroquinone:
4MnO2 + 2C6H5NH2 + 5H2SO4 → 2C6H4O2 + 4MnSO4 + (NH4)2SO4 + 4H2O
8.7.5 Manganese (VII) Oxide

Manganese (VII) oxide (manganese heptoxide) is an inorganic compound
with the formula Mn2O7. This volatile liquid is highly reactive. It is a dangerous
oxidizer and was first described in 1860. The crystalline form of this chemical
compound is dark green. The liquid is green by reflected light and red by
transmitted light. It is soluble in carbon tetrachloride, and decomposes when in
contact with water. It melts at only 5.9 °C and sublimes at −10 °C. These
properties indicate a nonpolar molecular species, which is confirmed by its
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structure. The molecules consist of pair of tetrahedral that shares a common

vertex. The vertices are occupied by oxygen atoms and at the centers of the
tetrahedral are the Mn (VII) centers. The connectivity is indicated by the formula
O3Mn-O-MnO3. The terminal Mn-O distances are 1.585 Å and the bridging
oxygen is 1.77 Å distant from the two Mn atoms. The Mn-O-Mn angle is 120.7°.
It contains manganese in its highest oxidation state. This oxidation state, +7, is
shared by permanganates, which are more stable compounds.
Mn2O7 arises as dark green oil by the addition of concentrated H2SO4 to
KMnO4. The reaction initially produces permanganic acid, HMnO4 (structurally,
HOMnO3), which is dehydrated by sulfuric acid to form its anhydride, Mn2O7.
2 KMnO4+(cold) 2 H2SO4 → Mn2O7 + H2O + 2 KHSO4
Mn2O7 can react further with sulfuric acid to give the remarkable cation MnO3+,
which is isoelectronic with CrO3.
Mn2O7 + 2 H2SO4 → 2 [MnO3]+[HSO4]− + H2O
Mn2O7 decomposes near room temperature, explosively at 55 °C.
8.7.6 Potasium permanganate, KMnO4

KMnO4 is used frequently for permanganometry titration.
Permanganometry titration is performed based titration reaction by potassium
permanganate (KMnO4). This reaction is focused on oxidation and reduction
reactions that occur between KMnO4 with certain materials. Permanganometry
method based on the reaction of permanganate ion oxidation. This oxidation can
take place under acidic, neutral and base conditions.
(1) In the neutral condition, the reaction become:
MnO4 + 4H+ + 3e → MnO4 +2H2O
(2) In the acid condition, the reaction become:
MnO4- + 8H+ + 5e → Mn2+ + 4H2O
(3) In the base condition, the reaction become:
MnO4- + 2H2O + 3e → MnO2 +4OH
Permanganometry is titration based on a redox reaction. In this reaction,
MnO4- ion acts as an oxidant. MnO4- ion will be changed to Mn2+ ions in acidic
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conditions. Titration technique is used to determine the levels of oxalate or iron in

a sample. At permanganometry tiration, titrant used is potassium permanganate.
Potassium permanganate is easy to obtain and does not require an indicator unless
used very dilute solutions and has been used extensively as an oxidizing reagent
for a hundred years. A drop of permanganate gives a clear pink color to the
volume of the solution in a titration. This color is used to indicate the excess
reagent. Potassium Permanganate standardized using sodium oxalate or as arsenic
(III) oxide is the primary standards. End of the titration is marked by the onset of
pink caused excess permanganate.
KMnO4 solution should be freshly prepared just before its use because
KMnO4 reacts rapidly with air or exposed to light so that it will break down into
MnO2 so the endpoint will be obtained brown precipitate formation is a solution
that should have been red rosa.
8.7.7 Chalcogenides
The chalcogens are the chemical elements in group VIA of the periodic
table. This group is also known as the oxygen family. It consists of the elements
oxygen (O), sulfur (S), selenium (Se), tellurium (Te), the radioactive element
polonium (Po). The synthetic element livermorium (Lv) is predicted to be a
chalcogen as well. The word chalcogen comes from the Greek word chalkos,
meaning "bronze" or "ore", and the word genēs, meaning "born". While sulfur has
been known since antiquity, oxygen was only recognized as an element in the
18th century. Selenium, tellurium and polonium were discovered in the 19th
century, while livermorium was discovered in 2000.
The chacogenides of manganese are manganese sulfide, manganese disulfide,
manganeseselenide and manganese telluride.
a. Manganese sulfide MnS
MnS is the chalcogenide of manganese with the number of oxidation is +2,
it is red or green solid
b. Manganese disulfide, MnS2
MnS2is the compoun of mangansesesulfde with oxidation numbe is +4
c. Manganese selenide, MnSe
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Manganese selenide is crystal that has grey color with oxidation number of
+2
d. Manganese Teluride, MnTe
This compound is solid crystal with oxidationnumber of +2.
8.8 HALIDES AND OXYHALIDES OF MANGANESE

8.8.1 Halides of Manganese
Manganese can formed manganese halides that bond with the halogens,
namely F, Cl, Br, and I. Fluoride compounds of manganese contained in the 3
oxidation state, namely MnF2(+2), MnF3(+3) and MnF4(+4). While the chloride
compound exists only in the +2 oxidation state namely MnCl2. They are the
compounds of halides manganese.
Manganese(II) fluoride, MnF2 is the chemical compound composed of
manganese and fluoride with the formula of MnF2. It is a light pink crystalline
solid, the light pink color being characteristic for manganese(II) compounds. The
compound has 856 °C of melting point and 1820 °C of boiling point. Has the
density of 3.98 g/cm3 and 92.93 g/mol of molar mass. MnF2 made by treating
manganese and diverse compounds of manganese(II) in hydrofluoric acid (HF).
Manganese(III) fluoride, MnF3 also known as manganese trifluoride is the
inorganic compound with the formula MnF3. The color of MnF3 compound is
purple-pink powder color, molar mass of 111.938 g/mol, density of 3.54 g/cm3,
melting point of > 600 °C and soluble in water. MnF3 can be prepared by treating
a solution of MnF2 in hydrogen fluoride with fluorine, with the reaction:
MnF2 + 1/2 F2 → MnF3
It can also be prepared by the reaction of elemental fluorine with a manganese(II)
halide at -250°C. MnF3 reacts with sodium fluoride to give the octahedral
hexafluorate anion.
3NaF + MnF3 → Na3MnF6
Manganese tetrafluoride, MnF4 is the highest fluoride of manganese. Has a
blue solid color, molar mass of 130.93 g mol−1, density of 3.61 g cm−1, melting
point of 70 °C. Preparations of MnF4 include the fluorination of MnF2 with
krypton difluoride, or with F2 in liquid hydrogen fluoride solution under
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ultraviolet light. Manganese tetrafluoride has also been prepared between

antimony pentafluoride and K2MnF6 as part of a chemical synthesis of elemental
fluorine, as a reaction:
K2MnF6 + 2 SbF5 → MnF4 + 2 KSbF6
Manganese tetrafluoride is in equilibrium with manganese(III) fluoride and
elemental fluorine, as the reaction:
MnF4 MnF3 + ½ F2
Decomposition is favoured by increasing temperature, and disfavoured by the
presence of fluorine gas.
The anhydrous manganese (II) chloride, MnCl2 is a pink solid; cubic
crystals; deliquescent; density 2.977 g/cm3 at 25°C; melts at 650°C; vaporizes at
1,190°C; very soluble in water (-72g/100 mL at 25°C); soluble in alcohol;
insoluble in ether. The tetrahydrate has a rose color; monoclinic crystal structure;
deliquescent; density 2.01 g/cm3; melts at 58°C; loses one molecule of water at
106°C and all water at 198°C; highly soluble in water (151 g/100mL at 8°C) and
extremely soluble in boiling water (656 g/100mL at 100°C); soluble in ethanol;
insoluble in ether. Manganese(II) chloride is prepared by heating manganese(II)
oxide, manganese dioxide, manganese(II) carbonate or manganese(II) hydroxide
with hydrochloric acid:
MnO2 + 4HCl → MnCl2 + 2H2O + Cl2
MnCO3 + HCl → MnCl2 + H2O + CO2
When the product mixture is evaporated below 58°C, the tetrahydrate salt,
MnCl2•4H2O is obtained. Manganese(II) chloride is a by-product in the
manufacture of chlorine from manganese dioxide and hydrochloric acid (the
Weldon process). Anhydrous chloride can be prepared by heating manganese(II)
oxide or manganese(II) carbonate with dry hydrogen chloride; or by burning the
metal in chlorine at 700°C to 1,000°C. The anhydrous salt can also be obtained by
slowly heating the tetrahydrate, MnCl2•4H2O in a rotary drier above 200°C or by
dehydration in a stream of hydrogen chloride gas. Manganese(II) chloride forms
adducts with ammonia, hydroxylamine and many other nitrogen compounds.
Many adducts are stable at ordinary temperatures. Examples are MnCl2•6NH3 and
MnCl2•2NH2OH. An aqueous solution can readily undergo double decomposition
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reactions with soluble salts of other metals, producing precipitates of insoluble

salts of Mn(II) or other metals.
Manganese(II) bromide, MnBr2 is the chemical compound composed of
manganese and bromine with the formula MnBr2. MnBr2 has pink crystalline
color, has a density 4.385 g/cm3, melting poing of 698 °C (anhydrous) and 64 °C
(tetrahydrate), boiling point of 1027 °C, and soluble in water.
Manganese(II) iodide, MnI2 can be used as a pink pigment or as a source
of the manganese ion or iodide ion. It has molar mass of 308.747 g/mol, density of
5.01 g/cm3, melting point of 701°C (anhydrous) and 80 °C (tetrahydrate), boiling
point of 1033 °C and soluble in water.
8.8.2 Oxyhalides of Manganese

The oxohalides of manganese are green liquids (except MnO2Cl2 which is
brown) they are notable for their explosive instability. MnO3F can be prepared by
treating KMnO4 with fluorosulfuric acid (HSO3F) whereas reaction of Mn2O7
with chlorosulfuric acid yields MnO3Cl + MnO2Cl2 + MnOCl3.
8.9 COMPLEXE COMPOUNDS OF MANGANASE

Some complex compounds of manganese can be explained in terms of
their oxidation states of manganese as the center atom of the complexes as shown
on Table 8.2 below.
Table 8.2 Complex Compounds of Manganese
Ox. Oxide Hydroxide Properties Ion Name Complex Color

state Compound
+2 MnO Mn(OH)2 Moderate Mn2+ Manganese [Mn(H2O)6]2+ Pink
base (II)
+3 Mn2O3 Mn(OH)3 Weak Mn3+ Manganese [Mn(H2O6)] 3+ Violet
base (III) Or
K3[Mn(C2O4)3].
3H2O
+4 MnO2 MnO(OH)2 Amphoter MnO32- Manganite K2[MnX6], X= F, Brown
or H2MnO3 or weak Cl, IO3, and CN
acid
+6 MnO3 H2MnO4 Moderate MnO42- Manganite K2MnO4 Green
acid
+7 Mn2O7 HMnO4 Strong MnO4- Permangan KMnO4 Purple
acid ate
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Based on potential reduction, manganese (II) complex compound is stable

species of manganese, it depend on the electro configuration half full of 3d5. The
reduction with hydrogen toward of manganese oxide will produce the oxide of
manganese with lowest oxidation number, such as MnO that has green grey color.
Manganese (II) in it salt compound like chloride, sulfate and nitrate in water
solution can state as Mn2+ ion or perspective of complex ion as [Mn(H2O)6]2+ and
it has pale pink color.
The addition of alkali hydroxide in Mn2+ solution can obtained Mn(OH)2
as white gelatin close to the color pale pink, but in the open air this hydroxide fast
to oxidize become manganese (III) oxyhydroxyMn(OH) that has dark brown
color. The reaction as follows:
Mn2+(aq) +2 OH-(aq) Mn(OH)2(s)
4Mn(OH)2(s) + O2(g) 4MnO(OH)(s) +2 H2O(l)
Only a part of manganese (II) is precipitate with ammonia solution. The
precipitate of Mn(OH)2 is dissolve in ammonium salt solution. The reaction as
follows:
Mn(OH)2(s) + 2 NH4+(aq) Mn2+(aq) + 2 NH3 (g) +2 H2O(l)
Mn(OH)2 is moderate base , so that in it is dissolve in acid solution and not
dissolve in alkali base. The heating this base without air can produce it oxide
(MNO) that has green grey color. The reaction as follow;
Mn(OH)2(s) MnO(s) +H2O(g)
Manganese (III) is obtained in it oxide namely Mn2O3 and MnO(OH)
which occur in nature, but Mn3+ ion in water solution is unstable, it is easily to
reduction become Mn2+. The mixture of Mn(II) and Mn(III) oxide is obtained as
Mn3O4, the mineral that has black color. It will formed if heated approximately
10000C in the air. For the example MnCl3 salt can be obtained in it solution from
the reaction MnO2 with HCl in low temperature, but it will decompose on the
temperature -400C, the reaction as follows;
2MnO2(s) + 8HCl(aq) 2 MnCl3(aq) + 4 H2O +Cl2(g)
2MnCl3 (aq) 2 MnCl2(aq) +Cl2(g)
Manganese (IV) is obtained as MnO2 that has antiferromagnetic properties,
under temperature approximately 92K. MnO2 is not the stable oxide because it
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can decompose become Mn2O3 in the temperature 5300C. It is the most important
oxide and very useful as an oxidation agent. Exactly, this oxide is amphoteric but
relative inert toward acid or base. It can be seen it the result of the reaction with
concentrated hydrochloric acid in cool condition, green solution from Mn4+ ion
that has unstable properties change into pink solution because it formed Mn2+ ion.
Mn(SO)4 is unstable ,the reaction MnO2 with concentrated sulfuric acid will
produce MnSO4. The reaction as follows;
MnO2(s) + 4 HCl(aq) MnCl4(aq) +2H2O (l)
MnCl4(aq) MnCl2(aq) +Cl2(g)
MnO2(s) + 2H2SO4(aq) Mn(SO4)2(aq) +2H2O(l)
2Mn(SO4)2(aq)+ 2H2O(l) 2MnSO4(aq) + 2H2SO4(aq) +O2(g)
Mn(IV) in some complex compound is stable and not easily to decompose, for
example in complex K2[MnF6] that has yellow color and Rb2[MnCl6] that has
dark red color. Hydroxide from Mn(IV) is weak acid, so each hydroxide molecule
can release one molecule of H2O , the empirical equation as follow MnO(OH)2 or
H2MnO3. MnO32- is presented by the molten reaction of MnO2 and CaO that
produce potassium manganite(CaMnO3) that has brown color. The reaction as
follow:
MnO2 +CaO CaMnO3
Manganese (VI) is stable species of manganite (MnO42-), with the structure
tetrahedron and dark green color. For example potassium manganite can be
obtained from molten reaction of MnO2 and alkali base with air or KNO3 as an
oxidator, the reaction as follow;
2 MnO2(s) +4KOH(s) + O2 (g) 2K2MnO4(s) + 2 H2O (g)
In it solution, manganite ion only stable in base condition, but in the water and
acid condition it will disproportionation become permanganate ion and MnO2. In
acid condition MnO42- is an oxidator. The reaction as follows;
MnO42-(aq) + 8H3O+ + 4e Mn2+(aq) + 12 H2O (l) E0= 1.74 V
K2MnO4 is isomorphic with K2SO4 and KCrO4. Manganite acid (H2MnO4) is
unstable to isolation.
Manganese (VII) is called manganese heptoxide (Mn2O7) as green oil that
easily to explosive and obtained from the reaction of manganese (VII) salt with
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concentrated H2SO4. Only one oxoanion compound Mn (VII) is important namely

potassium permanganate (KMnO4) that has violet color. This compound is stable
in it solution and act as an well oxidator in acid, neutral or base condition.
Commercially, the preparation of potassium permanganate is from oxidation of
potassium manganite by chlorine in base condition. The purple crystal can get in
the process of concentrated. The reaction as follow:
2 K2MnO4(aq) + Cl2(g) 2KMnO4 (aq) + 2KCl(aq)
The reduction of KMnO4 with Na2So3 will produce light blue color from
hipomanganate that has unstable properties
8.10 SUMMARY
Manganese is very important for our life. It is used not only for materials
supporting our technologies but also for our body especially for our liver, thyroid
gland, pituitary, pancreas, kidney, and bone. Wide various compounds of
manganese are well-known and those are very useful for our life, namely oxides,
halides, oxoanionic salts, and complexes.
STUDY QUESTIONS
8.1 Explain the brief history of finding the element of manganese!
manganese in the earth’s crust!
8.3 Explain the isolation methods, properties and uses of manganese!
8.4 Explain the properties of oxides and chalconides of manganese!
8.5 Explain the properties of halides and oxohalides of manganese!
8.6 Explain the properties of complex compounds of manganese with oxidation
numbers of VI, V, IV, III and II!
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CHAPTER 9
IRON, COBALT AND NICKEL
9.1 INTRODUCTION
Group VIIIB in the periodic system are divided into 3 sub groups. That
vertically called triad transition. In the modern periodic system, this third triad
transition was given new classification, namely no. 8, 9, and 10. But the tendency
of properties especially their chemical properties horizontally have more
similarities than vertically. So it is grouped again into 3 groups of horizontal, each
consisting of 3 elements. Iron, cobalt, and nickel are an element contained
horizontally in the transition group VIIIB. These elements tends to have similar
properties so that they can mix and form an alloy.
This is briefly to discuss about the history, abundance, isolation,
properties, uses, iron, cobalt and nickel alloys and its compound namely the
oxides; the metallates; the sulfides, selenides and tellurides; the halides and
oxohalides; and the complexes.
9.2 HISTORY
Iron beads dating from around 4000 BC were no doubt of meteoric origin,
and later samples, produced, by reducing iron ore with charcoal, were not cast
because adequate temperature were not attainable without the use of some form of
bellows. Instead, the spongy material produced by low temperature reduction
would had to be shaped by prolonged hammering. It seems that iron was first
smelted by the Hittites in Asia. Minor sometime in the third millennium BC, but
the value of the process was so great that its secret was carefully guarded and it
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was only with the eventual fall of the Hittite empire around 1200 BC that the
knowledge was dissapear and the “ Iron Age” began. The name “iron” is Anglo
Saxon in origin (iren, cf. German Eisen). The symbol is Fe and words such as
“ferrous” derive from Latin ferrum, iron. (Greenwood et al., 1997:1070).
Although harldy any metallic cobalt was used until the twentieth century,
its ores have been used for thousand of years to impart a blue color to glass and
pottery. It is present in Egyptian pottery dated at around 2600 BC and Iranian
glass beads of 2250 BC. The source of the blue colour was recognized in 1735 by
the Swedish chemist G.Brandt, who isolated a very impure metal, or “regulus”,
which he named “cobalt rex”. In 1780 T.O. Bergman showed this to be a new
element. Its name has some resemblance to the Greek word for “mine” but is
almost certainly derived from the German word Kobold for “goblin” or “evil
spirit”. The miners of northern European countries thought that the spitefulness of
such spirits was responsible for ores which on smelting (Greenwood et al., 1997).
An alloy of nickel was known in China over 2000 years ago, and Saxon
miners were familiar with the reddish-coloured ore, NiAs, which superficially
resembles Cu2O. These miners attributes their inability to extract copper from this
source to the work of the devil and named the ore “Kupfernickel” (Old Nick’s
copper). In 1751 A. F. Cronstedt isolated an impure metal from some Swedish
ores, and identifying it with the metallic component of Kupfernickel, named the
new metal “nickel”. In 1804 J.B. Richter produced a much purer sample and so
was able to determine its physical properties more accurately (Greenwood et al.,
1997).
9.3 NATURAL ABUNDANCE AND DISTRIBUTION

In the earth’s crustal rocks, iron metal can be found about 6.2% or 62000
ppm, it is the fourth most abundant element after oxygen, silicon, and aluminium;
and the second most abundant metal. Its also widely distributed, as oxides and
carbonates, of which the chief ones are haematite (Fe2O3), magnetite (Fe3O4),
limonite (2Fe2O3.3H2O )and siderite (FeCO3). Iron pyrite (FeS2) is also common
but is not used as a source of iron because of the difficulty in eliminating the
sulfur. The distribution of iron has been considerabely influenced by weathering.
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Leaching from sulfide and silicate deposits occurs readily as FeSO4 and Fe(HCO3)
respectively. In solution, these are quickly oxidized, and even mildly alkaline
conditions cause the precipitation of iron (III) oxide. Because of their availability,
production of iron ores can be confined to those of the highest grade in gigantic
operations (Greenwood & Earnshaw, 1997:1071).
Most of our stone and soil contain an iron. Iron isotopes are mainly used in
nutritional studies, with Fe-57 and Fe-58 being the two most commonly used Fe
isotopes. Studies have included iron-loss by human adolescents, conditions for
effective iron absorption, interventions for anemia and genetic iron control. The
Fe-54 isotope is used for the production of radioactive Fe-55 which in turn is used
as an electron capture detector and in X-ray fluorescence. Fe-56 can be used for
the production of radioactive Co-55 which is used as a tumor seeking agent in
bleomycin. An iron ore that able to be an material must contain the high
persentage of iron compound.
Pure cobalt is not found in nature, but compounds of cobalt are common.
Small amounts of it are found in most rocks, soil, plants and animals. It is the 33rd
most abundant element and has been found in a variety of media, including air,
surface water, leachate from hazardous waste sites, groundwater, soil, and
sediment. Small amounts of metallic cobalt are present in meteorites but it is
usually extracted from ore deposits worked in Canada, Morocco, Zaïre, Zambia,
Russia, Australia, and Cuba. It is present in the minerals cobaltite (CoAsS),
smaltite (CoAS2), chloranthite, lemacite (Co3S4) and erythrite but also associated
with copper and nickel as sulfides and arsenides.
Cobalt is present in nature where it represents approximately 0.002% of
the earth’s crust. Unlike its neighbors in the Periodic Table, iron, nickel, and
copper, cobalt is not widespread in nature. It has an average abundance in Earth's
crust of 25 parts per million (ppm); in ultrabasic rocks, where cobalt is most
common, the average concentration is 110 ppm. Cobalt minerals may be
concentrated by a range of geological processes to produce workable ores that
typically contain 1,000–2,000 ppm. The isotope cobalt-60 (60Co) is an artificially
produced isotope used as a source of γ rays (its high energy radiation is useful for
sterilisation in medicine and of foods).
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Nickel is the seventh most abundant transition metal and the twenty-
second most abundant element in the earth’s crust. It is aboout 99 ppm. It is
commercially important ores are of two types:
(1) Laterites, which are oxide/silicate ores such as garnierite
(Ni,Mg)6Si4O10(OH)8, and nickelliferous limonite (Fe,Ni)O(OH).nH2O,
which have been concentrated by weathering in tropical rainbelt in New
Caledonia, Cuba and Queensland.
(2) Sulfides such as pentlandite (Ni,Fe)9S8, associated with copper, cobalt and
precious metals so that the ores typically contain about 1.5% Ni. It can be
found in the Canada, the former Soviet Union and South Africa.
Nickel is composed of five stable isotopes, such as: 58Ni, 60Ni, 61Ni, 62Ni and 64Ni.
Nickel-61 is the only stable isotope of nickel.
9.4 METAL ISOLATION

It is not normally necessary to make iron in the laboratory as it is available
commercially. Small amounts of pure iron can be made through the purification of
crude iron with carbon monoxide. The intermediate in this process is iron
pentacarbonyl, Fe(CO)5. The carbonyl decomposes on heatingto about 250°C to
form pure iron powder.
Fe + CO → Fe(CO)5 (250°C) → Fe + 5CO
The Fe(CO)5 is a volatile oily complex which is easily flushed from the
reaction vessel leaving the impurities behind. Other routes to small samples of
pure iron include the reduction of iron oxide, Fe2O3, with hydrogen, H2.
Nearly all iron produced commercially is used in the steel industry and
made using a blast furnace. Most chemistry text books cover the blast furnace
process. In essence, iron oxide, Fe2O3, is reduced with carbon (as coke) although
in the furnace the actual reducing agent is probably carbon monoxide, CO.
2Fe2O3 + 3C → 4Fe + 3CO2
This process is one of the most significant industrial processes in history
and the origins of the modern process are traceable back to a small town called
Coalbrookdale in Shropshire (England) around the year 1773. In 1995, world
produce 20000 tonnes of cobalt, considerably below capacity. The major
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producing countries are Zaire, Zambia, Canada, Finland and former Soviet Union
(Greenwoodand Earshaw, 1997:1114).
Pure cobalt is produced when hydroxide and sodium hypochlorite
(NaOCl) based on the reaction:
2Co2+(as) + NaOCl(as) + 4OH-(as) + H2O → 2Co(OH)3(s) + NaCl(as)
Co(OH)3(s) which is formed is heated to form oxide and then adding by
carbon to form a pure metal.
2Co(OH ) 3   Co2 O3  H 2 O
Heated
2Co2 O3  3 C  4 Co( s )  3CO2( g )
Cobalt also is obtained by heating its ore (cobaltite) to produce the cobalt
oxide. That compound is then heated with aluminum to free the pure cobalt metal
by the following reactions:
( cobaltite) FeS  CoS 
, O2 Co3O4 Al
Co metal
(CoAsS  FeS ) O2
  Fe2O3  Na3 AsO4
NaNO3

SiO2

Fe2O3  SiO2  Na3 AsO4
Na2CO3
Production for nickel is complicated and dependent on the particular ore

involved. Therefore only be sketched in outline. In this case of nickel the oxide
ores are not generally amenable to concentration by normal physcical separations
and so the whole ore has to be treated. (Greenwood et al., 1997:1145)
Nickel occurs more abundantly than cobalt but only a few deposits are
economically useful for extraction. The metal is obtained by heating with sulphur
compounds to give the sulphide, which is roasted to form the oxide. And then, it is
reduced directly by heating with the coke or dissolved to give a solution
containing nickel (II) from which nickel can be deposited electrolytically. The
metal obtained by reduction cab be purified by the Mond process. It is heated to
320 K with carbon monoxide to give the pure volatile tertacarbonyl Ni(CO)4. And
then when heated to 500 K gives the pure metal and carbon monoxide is
recorvered (Chambers & Holliday, 1975:405)
Ni + 4CO ⇌ Ni(CO)4
Reduction that occurs in this process only a portion of the iron that can be
tied into slag, and most are still in the form of ferro-nickel alloy. In this case to
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separate the iron from the nickel smelter is added to the reaction of some sulfur-
containing materials (Gypsum or Pyrite). Because of differences in iron and nickel
holding capacity of the oxygen and sulfur, so the process is obtained which is an
alloy metal FeS and Ni3S2 and most of the iron can be slagged.
The resulting metal was still contain more than 60% Fe and the subsequent
metal that remains in the liquid state continue to be processed again in the
converter. Converter processes given the added material to the silicon oxide slag
the iron. The results of slag still contain nickel converter is high enough, so the
slag is usually in the back on the smelting process (resmelting). The next process
is in the roast to separate metal sulfur. Nickel oxide obtained from the subsequent
reduction roasting with charcoal added material (charcoal), in order to get the
nickel metal.
9.5 METAL PROPERTIES

Iron is a silvery, lustrous metal but chemically active. After a short time in
moist air it changes from silvery to rusty as reddish-brown FeOOH is formed.
Water and soluble electrolytes such as salt accelerate the reaction. Iron with
symbol Fe has atomic number of 26. At ground sate, electron configuration of Fe
is [Ar]3d64s2.
Table 9.1 The Physical Properties of Iron
Melting point 1811 K
Boiling point 3134 K
Electronegativity 1.7 eV
Electrode potential
M2+ + 2e M -0,44
M3+ + e M2+ +0,74
Magnetic characterization Ferromagnetic
Thermal conductivity Wm–1K–1
173 K 273 K 373 K 573 K 973 K
99 83.5 72 56 34
100 K 293 K 500 K 800 K
5.6 · 10–6 11.8 10–6 14.4 10–6 16.2 10–6
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Resistivity n m
78 K 273 K 373 K 573 K 973 K 1473 K
7 89 147 315 855 1220
Source: Enghag, 2004: 169
Several chemical properties of iron are:
(1) With hot water vapor can react to produce hydrogen gas, but wit cold water
can not react.
3Fe(s) + 4H2O(g) → Fe3O4(s) + 4H2(g)
(2) Iron will corrosion and the color change to brown if react with wet air.
4Fe(s) + 3O2(g) + nH2O → 2Fe2O3.n H2O
(3) If it is burned with sulfur will form iron (II) sulfides (FeS).
Fe(s) + S(s) → FeS(s)
(4) With halogen group will form FeX3 (X=F, Cl, Br, dan I) compound, except
with iodium will form FeI2.
(5) Reaction with acid
Reaction with hydrochloric acid to produce hydrogen gas and iron (II)
chloride.
Fe(s) + HCl(aq) → FeCl2(aq) + H2(g)
Reaction with dilute sulfuric acid will form H2 gas but with concentrated
sulfuric acid will produce SO2 gas. It can be occurred because besides
acidic, sulfuric acid also acts as an oxidizing agent.
As the acid:
Fe(s) + 2H+(aq) → Fe2+(aq) + H2(g)
As oxidizing agent:
Fe(s) + SO42-(aq) + 4H+(aq) → Fe2+(aq) + SO2(g) + 2H2O(l)
Reaction with nitric acid
With dilute nitric acid will form NO and NO2 gas, but with concentrated
nitric acid will produce NO2 gas. It can be occurred because the oxidizing
properties of concentrated nitric acid stronger than dilute nitric acid.
Cobalt is a bluish silvery metal with magnetic properties similar to those
of iron. Its salts give glass a beautiful deep-blue color. Cobalt with symbol Co has
atomic number of 27. At ground sate, electron configuration of Fe is [Ar]3d74s2.
The physical properties of cobalt are shown in the following table.
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Table 9.2 Physical Properties of Cobalt

173 K 273 K 373 K 573 K 973 K
130 105 89 69 53
–1
Coefficient of linear expansion K
100 K 293 K 500 K 800 K
–6 –6
6.8 10 13 10 15 10–6 15.2 10–6
Resistivity n m
78 K 273 K 373 K 573 K 973 K 1473 K
9 56 95 197 480 885
The chemical properties of cobalt are; (a) cobalt is less reactive element. It
combines slowly with oxygen in the air, but does not catch fire and burn unless it
is in a powder form; (b) reacts with most diluted mineral acids to produce
hydrogen gas. It does not react with water at room temperatures; (c) forms the
complex compounds, (d) in water solution exist as Co2+ (red colored), and (e)
resistance to the corrosion, and (f) Co3+ is not stable, but its complexes are stable
in solution and in solid state, and (g) dissolves in diluted mineral acids.
Nickelis a moderately lustrous, silvery metal, and extensively used in
alloys. It is a malleable and ductile metal, ferromagnetic up to 354°C. Iron
meteorites contain metallic iron with up to 20% nickel. The main nickel source is
the mineral pentlandite. Nickel with symbol Ni has atomic number of 28. At
ground sate, electron configuration of Ni is [Ar]3d84s2. The physical properties of
nickel are shown in the following table.
Table 9.3 Physical Properties of Nickel
Electron Affinity 112 kJ mol-1
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173 K 273 K 373 K 573 K 973 K
113 94 83 67 71
100 K 293 K 500 K 800 K
–6
6.6 10 13.4 10–6 15.3 10–6 16.8 10–6
Resistivity n m
78 K 273 K 373 K 573 K 973 K 1473 K
5.5 62 103 224 400 -
The combination of nickel, chromium and iron produce stainless steel
(stainless steel) are widely applied to kitchen utensils (spoons, and cooking
equipment), home ornaments and buildings, and industrial components. At room
temperature, nickel can not be attacked by air or water. Some of the reactions of
nickel:
1. Very slow to react with hydrochloric acid or dilute sulfuric acid
2. Reacts rapidly with dilute nitric acid, but with concentrated nitric acid,
noickel is passive.
Hydrochloric acid (both dilute and concentrated) and dilute sulphuric acid
dissolve nickel with the formation of hydrogen:
Ni + 2H+  Ni2+ + H2 
Ni + 2HCl  Ni2+ + 2Cl- + H2 
These reaction accelerate if the solution is heated. Concentrated, hot
sulphuric acid dissolves nickel with the formation of sulphur dioxide.
Ni + 2H2SO4 + 2H+  Ni2+ + SO2 + 2H2O
Dilute and concentrated nitric acid dissolve nickel readily in cold:
Ni + 2HNO3 + 6H+  3Ni2+ + 2NO + 4H2O
9.6 USES OF IRON, COBALT AND NICKEL

Iron is the basic metal for the production of the steel family. This is very
diversified and plays a crucial role in modern human life, from the load-bearing
functions in large steel buildings and bridges to the small springs in precision
mechanics, special steels for the surgeon’s scalpels to all steel components in
household and kitchen (Enghag, 2004: 168).
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Iron is an important micronutrient for living things. Iron largely stable in the
metal bound with protein (metalloprotein), because the iron in a free state can
cause the formation of free radicals that are toxic to cells. Iron is a major
constituent of the survival of living beings and works as a carrier of oxygen in
hemoglobin. FeSO4 is used as a mineral source for therapeutic mineral deficiency/
iron deficiency and is used to make ink powder. Fe3SO4 used for textile dyeing
and testing of aluminum.
But iron also has some weaknesses especially the corrosive properties.
Corrosion that mension before is an interaction between an iron with water and
air. We can modify iron becomes a steel in order to make an iron uncorrosively,
but ussualy has a high cost to do that. To minimalize the corrosive in iron there
are several ways to do protection for iron from the water and air:
(1) Painting the fence or bridge also everythink that made from an iron. Paint
can protect iron from water and air because if we painted them, water and
air can’t directly attract with water and air. The better paint that recomended
to used is paint that contained lead and zinc.
(2) Coat with plastic, for example on a plate rack
(3) Coated with lead, for example on packaging cans
(4) Coating with Zn, for example on iron pipe
(5) Coating with chromium, for example, motors bumper
(6) Coating with Mg, for example in the steel pipe in the ground
(7) Making bridge construction, tranports body, train rel, etc.
Cobalt is used as stainless steel and steel magnet. Because cobalt has
positive value of E0 so difficult to oxidize. . The artificially produced isotope
60Co, where as an important source of light, and is extensively used as a
radiotherapeutic agent. Cobalt-60 can emit gamma rays that kill viruses, bacteria,
and other pathogenic microorganisms without damaging the product. Cobalt-60 is
used for irradiating the cancer cells. With a controlled radiation dose given, the
cancer cells will be killed, while normal cells will not be affected and will
withstand the radiation.
Nickel is used on a large scale for the manufacture of stainless steel and
other alloys that are corrosion resistant (used in all types of corrosive
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environments and also on our kitchen sinks) contains, as well as 18% chromium,
also 8% nickel. It is also used to make coins; the US 5-cent coin (whose nickname
is “nickel”) contains 25% nickel.
9.7 ALLOYS OF IRON, COBALT AND NICKEL

Alnico is an alloy containing aluminum (Al), nickel (Ni), cobalt (Co) hence
its name Alnico. But Alnico actually contains more than just these three elements.
It also contains iron and copper with some versions also containing titanium and
even niobium (the titanium versions were sometimes called Ticonal, derived from
the elements TiCoNiAl). Alnico magnets were developed in the 1930’s and was
the first “Real” performance permanent magnets (the first “magnets”, called
magnetic steels, were quickly replaced by the vastly superior Alnico).
Alnico is produced by either a sintering method or, more commonly, a
casting method. The as cast or as sintered shape is acceptable for many
applications but surfaces may need to be ground for a smoother surface finish.
The as cast look has darkened edges with a slightly rough texture (due to the sand
mold edges); a machined face of an Alnico magnet has a bright silvery metallic
surface and is usually extremely smooth as it is often precision ground.
The other alloy is kovar. Kovar is the alloy of iron, cobalt and nickel with a
coefficient of thermal expansion similar to that of hard (borosilicate) glass. It is an
alloy with 29% Nickel, 17% Cobalt and the remaining balance is Iron.This makes
it especially suitable for uses which require a matched-expansion seal between
metal and glass parts. Thus kovar finds wide usage in the electronics industry for
metal parts bonded to hard glass envelopes for such devices as power tubes, x-ray
tubes, etc., and other applications requiring glass-to-metal seals.
9.8 OXIDES AND CHALCONIDES OF IRON

9.8.1 Iron (II) oxide (FeO)
Although the formula for iron (II) oxide is written as FeO, there is usually
a deficiency in iron, which is not surprising because this is the oxide is lowest
oxidation state. It is the oxide residing farthest from the oxygen in term of the
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phase present corrosion. The oxide of FeO can be found as a black flour that has a
pirofor properties with flaming the oxide of Fe(II) oxalate.
9.8.2 Iron (III) Oxide (Fe2O3)

Rust is a general term for describing iron oxides. In colloquial usage, the
term is applied to red oxides, formed by the reaction of iron and oxygen in the
presence of water or air moisture. There are also other forms of rust, such as the
result of the reaction of iron and chloride in an environment deprived of oxygen,
such as rebar used in underwater concrete pillars, which generates green rust.
Several forms of rust are distinguishable visually and by spectroscopy, and
form under different circumstances. Rust consists of hydrated iron(III) oxides
Fe2O3·nH2O and iron(III) oxide-hydroxide (FeO(OH), Fe(OH)3). Given sufficient
time, oxygen, and water, any iron mass will eventually convert entirely to rust and
disintegrate. Surface rust provides no protection to the underlying iron, unlike the
formation of patina on copper surfaces. Rusting is the common term for corrosion
of iron and its alloys, such as steel. Many other metals undergo equivalent
corrosion, but the resulting oxides are not commonly called rust.
The rusting of iron is an electrochemical process that begins with the
transfer of electrons from iron to oxygen. The rate of corrosion is affected by
water and accelerated by electrolytes, as illustrated by the effects of road salt on
the corrosion of automobiles. The key reaction is the reduction of oxygen:
O2 + 4 e- + 2 H2O → 4 OH-
Because it forms hydroxide ions, this process is strongly affected by the
presence of acid. Indeed, the corrosion of most metals by oxygen is accelerated at
low pH. Providing the electrons for the above reaction is the oxidation of iron that
may be described as follows:
Fe → Fe2+ + 2 e−
The following redox reaction also occurs in the presence of water and is
crucial to the formation of rust:
4 Fe2+ + O2 → 4 Fe3+ + 2 O2−
In addition, the following multistep acid-base reactions affect the course of
rust formation:
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Fe2+ + 2 H2O ⇌ Fe(OH)2 + 2 H+

Fe3+ + 3 H2O ⇌ Fe(OH)3 + 3 H+
As do the following dehydration equilibria:
Fe(OH)2 ⇌ FeO + H2O
Fe(OH)3 ⇌ FeO(OH) + H2O
2 FeO(OH) ⇌ Fe2O3 + H2O
The transformation of FeO, Fe2O3, Fe3O4, FeOOH will be explained by
figure below:
Fe3O4
FeO α-Fe2O3 -Fe2O3
FeOOH Fe2O3.4H2O
Fe(OH)2
Fe(OH)3
Figure 9.1 Oxide-Hydroxide Transformation of Iron

Fe3+ more stable than Fe2+. Ion Fe2+ in form [Fe(H2O)6]2+, has the function is as a
weak acid in water and which as light blue. The reaction as follow:
[Fe(H2O)6]2+ + H2O ⇌ [Fe(H2O)5OH]+ + H3O+
On the other hand the compound of Fe3+ is [Fe(H2O)6]3+ which has
colorless in strong acid condition and greenish yellow in weak or strong base
condition. The reaction as follow:
[Fe(H2O)6]3+ + H2O ⇌ [Fe(H2O)5OH)+2 + H3O+
[Fe(H2O)6]3+ + H2O ⇌ [Fe(H2O)4(OH)2]+ + H3O+
At pH above 3, the properties is more gel and form FeO(OH). The reaction
as follow:
[Fe(H2O)6]3+ + H2O → FeO(OH) (gel) → Fe2O3.n5H2O (red)
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9.8.3 Iron (II) sulfate

Iron(II) sulfate or ferrous sulfate is the chemical compound with the formula
FeSO4. Known since ancient times as copperas and as green vitriol, the blue-green
heptahydrate is the most common form of this material. All iron sulfates dissolve
in water to give the same aquo complex [Fe(H2O)6]2+, which has octahedral
molecular geometry and is paramagnetic.
9.9 HALIDES AND OXOHALIDES OF IRON

In spite of its having an electron configuration that suggest a possible
oxidation state of +6, iron form no halogen compound in which it has an
oxidation state higer that +3. The halogen compound of iron consist of the series
FeX and FeX3. The three halides of iron can be prepared by the general reaction
Fe + 3 X2 → 2FeX3
9.9.1 Iron (II) Chloride (FeCl2)

Iron (II) Chloride, the form of this compound is greenish yellow crystal
which has melting point 670-6740C. This compound has cadmium chloride’s
structure, and dissolves in water and hydrates, which is coordinated with a number
of water precipitated from FeCl2 solution in hydrochloric acid. The reaction as
follow:
Fe + 2 HCl (aq) → FeCl2 + H2
Yields the dichloride, which is obtained upon evaporation as the
tetrahydrate, FeCl2.4H2O. Anhydrous FeCl2 can be obtained by reaction of the
metal with gasseous HCl.
Fe + 2HCl(g) → FeCl2(s) + H2
9.9.2 Iron (III) chloride (FeCl3)

Iron (III) chloride, the form of this compound is dark brown crystal which
has melting point 3060C. Iron (III) chloride has lamellar structure. In gas phase,
FeCl3 has dimer structure.
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9.9.3 Iron (II) bromide (FeBr2)

Iron (II) bromide (FeBr2) can be obtained by excess iron heats in bromide
vapor. Excess iron can be used to discourage the formation of iron (III) bromide.
9.9.4 Iron (II) Iodide (FeI2)

Iron (II) iodide (FeI2) can be obtained in the same way with FeBr2 namely by
heating iron and iodine but do not use excessive iron. Halide Fe(+2) can react
with anhydrous NH3 gas, forming salts containing octahedral complex ion [Fe
(NH3)6]2+.
9.10 COMPLEX COMPOUNDS OF IRON

9.10.1 Iron (II) Complexes
Their complex is octahedral, in general has paramagnetic properties and
strong enough ligan field to be a spin pair. Diamagnetic complex iron are
[Fe(CN)6]4- dan [Fedipy3]2+. Formation of complex 2,2- red bypyridin and 1,10
fenantrolyn are used to obtain Fe2+ ion.
Some tetrahedral complex like FeCl42- is obtained. For iron complex
compound that most important are that used in our biological system and the most
important iron complex compound ferrocena.
One reaction to obtain Fe2+
K4[Fe(CN)6] + Fe3+ KFe(III)[Fe(II)(CN)6
(berliner blue and not soluble)
K4[Fe(CN)6] + Fe2+ K2Fe[Fe(CN) 6]
(colorless and soluble)
9.10.2 Iron (III) Complexes

Iron (III) was found in crystaline salt with high anion container beside
iodide that has high reductor properties:
Fe3+ + I- = Fe2+ + ½ I2
Salts that contain ferriaquo ion, [Fe(H2O)6]3+ like Fe(ClO4)3.10H2O has soft
pink color, but aquo ion has orange color. FeCl3, this matter used as source for
any iron compound sythesis. Ferrochloride unhydrate can be made with flowed
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HCl gas or hot iron powder by reducing FeCl3 with Fe in tetrahydrofuran, or by

reflucting FeCl3 in chlorobenzene (soft green solid).
The reaction as follow:
K3[Fe(CN)6] + Fe3+ FeFe(CN) 6
(ligth brown and soluble)
K3[Fe(CN)6] + Fe2+ KFe[Fe(CN) 6]
(turnbull blue and not soluble)
9.11 OXIDES AND CHALCOGENIDES OF COBALT

9.11.1 Cobalt (II) oxide (CoO)
Cobalt (II) oxide with the formula CoO, is a pink solid, has NaCl structure.
This compound which has m.p. 1935°C and density 6.45 g/cm3. The compound is
readily oxidized in air to form tricobalt tetraoxide, Co3O4, and is readily reduced
by hydrogen to the metal. It is readily oxidized with water and oxygen to form
brown cobalt (III) hydroxide (Co(OH)3. It is obtained by heating its ore in air or
vapor water, of hydroxide, carbonate, and nitrate without air.
9.11.2 Cobalt (III) oxide (Co2O3)

Cobalt (III) oxide (cobalt sesquioxide) is a black grey insoluble solid with
the formula Co2O3. This compound is hexagonal or rhombic and decomposes at
895°C. It is produced by the ignition of cobalt nitrate; the product however never
has the composition corresponding exactly to cobalt (III) oxide. On heating it
readily forms Co3O4, which contains both Co (II) and Co (III), and is easily
reduced to the metal by hydrogen. Cobalt (III) oxide dissolves in strong acid to
give unstable brown solutions of trivalent cobalt salts. With dilute acids cobalt (II)
salts are formed.
9.11.3 Cobalt (II) sulfide (CoS)

Chalcogenide of cobalt consist of Cobalt (II) sulfide, CoS is formed by the
reaction of Co2+ and H2S to form black ppt of CoS, with reaction as follow:
Co2+ + H2S → CoS↓
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Cobalt sulphides form a group of II–IV semiconductor materials with

considerable potential for application in electronic devices. It is one of the more
complicated metal sulphide systems, with a number of phases and differing
chemical compositions, including Co4S3, Co9S8, CoS, Co1−xS, Co3S4, Co2S3 and
CoS2. Other chalcogenides of cobalt are cobalt (II) selenide, CoSe, cobalt (II)
selenite, CoSeO3, and cobalt (II) telluride, CoTe.
9.12 HALIDES AND OXYHALIDES OF COBALT

9.12.1 Cobalt (II) chloride (CoCl2)
Cobalt (II) chloride with the formula CoCl2 is a blue crystal (mp 735 0C
and bp 1049 °C), density 1.924 g/cm3, and solubility 76.7. CoCl2 is a hygroscopic
and become red color when absorb water. It dissolves in ethanol and acetone. Its
hexahydrate has red color and as a coordination compounds with water as a
ligand. It is prepare by the reaction of Cobalt (II) and chlorine gas (Cl 2) with the
reaction:
Co(s) + Cl2 (g) → CoCl2
9.12.2 Cobalt (III) fluoride (CoF3)

Cobalt (III) fluoride with the formula CoF3 is a brown-black compound
which is used in several fluorination reactions, and strongly react with water. It is
formed by the reaction of HF and CoCl2.
9.12.3 Cobalt (II) bromide (CoBr2)

Cobalt (II) bromide with the formula CoBr2 is a green crystal which has
hexagonal structure, density 4.909 g/cm3, solubility 60.7 (at 500C).
9.12.4 Cobalt (II) iodide (CoI2)

Cobalt (II) iodide with the formula CoI2 is a black powder which has
hexagonal structure and hygroscopic, density about 5.66 g/cm3 and the solubility
is 59.
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9.13 COMPLEX COMPOUND OF COBALT

9.13.1 Cobalt (III) Complexes
A complex ion of hexanitrocobaltate (III), [Co(NO2)6]3- has a yellow color
and usually is synthesized as its sodium salt. For example, Na3[Co(NO2)6]
dissolves in water, but its potassium salt is difficult to dissolve in water. It is
caused of the relative ionic size, where the potassium ion has a relative size more
closer to the anion size of its complex so that its crystal has high lattice energy
and low of solubility. The reaction as follow:
3K+ (aq) + [Co(NO2)6]3+ (aq) → K3[Co(NO2)6] (s) (yellow)
The difference of ligand causes a significant different of reduction
potential, so that it causes the stability of oxidation state of the complexes ion. For
example:
[Co(H2O)6]3+ (aq) + e [Co(H2O)6]2+ (aq) E0 = +1.82 V
[Co(NH3)6]3+ (aq) + e [Co(NH3)6]2+ (aq) E0 = +0.10 V
The reduction potential of [Co(NH3)6]3+ ion (+ 0.01 V) is too lower than
that of oxygen (+ 1.23 V):
O2 (g) + 4H3O+(as) + 4e → 6H2O (l) E0= +1.23 V
Other compounds are most easily prepared by substitution of ligands on a
complex already formed. The following is a set of typical conversions:
Co 2 
 O2
CO32    Co( NH 3 ) 4 CO3 
 
HCl
 Co( NH 3 ) 5 ( H 2 O) 3
NH 3
NH 4 OH 
( purplechelate) ( pink)
2
Co( NH 3 ) 5 ( H 2 O) 3 
 Co( NH 3 ) 5 Cl 2 
HCl
 Co( NH 3 ) 5 NO2
HNO3
( pink) ( violet ) ( brown)
9.13.2 Cobalt (II) Complexes

In water solution, cobalt (II) salt has a pink color due to octahedral ion,
[Co(H2O)6]2+. However, tetrahedral of cobalt (II) ion has a blue color, and this can
be occurs for example with Cl- ligand. So, the addition of concentrated HCl into
[Co(H2O)6]2+ion will form a blue solution of tetrahedral ion of [CoCl4]2- with the
reaction:
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[Co(H2O)6]2+ (as) (pink) + 4Cl- (aq) [CoCl4]2- (aq) (blue) + 6H2O (l)
At the equilibrium state that is exactly when the color change, the
equilibrium shifting of color is sensitive to the temperature, namely has blue color
at heating, but become after the cooling process.
[Co( H 2 O) 6 ] 2 ( aq)  4 Cl  ( aq)  [CoCl 4 ) 2 ( aq)  6H 2 O(l )
heating
( pink) cooling ( violet )
The addition of hydroxide ion into cobalt (II) ion solution in water will form
a precipitate of cobalt (II) hydroxide which first has a blue color, but become a
pink after keeping for a view times, with the reaction:
[Co(H2O)6]2+ (as) + 2OH- (aq) → Co(OH)2 (s) + 6H2O (l)
This cobalt (II) hydroxide is a amphoteric because the addition of
concentrated of hydroxide ion will form a blue tetrahydroxocobaltate (II) ion:
Co(OH)2 (s) + 2OH- (aq) → [Co(OH)4]2- (aq)
Gradually, cobalt (II) hydroxide is oxidized by dioxygen in air to become
cobalt (III) oxide hydroxide, CoO(OH).
9.14 OXIDES AND CHALCONIDES OF NICKEL

9.14.1 Nickel Hydroxide
If Nickel (II) reacts with NaOH, it will form green precipitation of nickel
(II) hydroxide. The reaction is follow:
Ni2+ + 2OH-  Ni(OH)2
The precipitate is insoluble in excess reagent. No precipitation occurs in
the presence of tartrate or citrate, owing to complex formation. Ammonia
dissolves the precipitate in the presence of excess alkali hydroxede, ammonia salts
will also dissolve the precipitate
Ni(OH)2 + 6 NH3 [Ni(NH3)6]2+ + 2OH-
Ni(OH)2+ 6 NH4+ + 4OH- [Ni(NH3)6]2+ + 6 H2O
The solution of hexamminenickelate (II) ions is deep blue it can be easily
mistaken for copper (II) ions, which form the blue tetrammineucuprate(II) ions in
an analogous reaction. The solution does not oxidize on boiling with free
exposure to air or upon the addition of hydrogen peroxide. The green nickel (II)
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hydroxide precipitate can be oxidized to black nickel (III) hydroxide with sodium
hypochlorite solution
2Ni(OH)2 + ClO- + H2O 2Ni(OH)3 + Cl-
In addition, the action of Br2 on alkaline solutions of Ni2+ gives a black
hydrous oxide, NiO(OH). Other black substances can be obtained by electrolytic
oxidation, so the Edison or nickel-iron battery, which use KOH as the electrolyte,
is based on the reaction of them contain alkali metal ions.
discharge
Fe + 2 NiO (OH) + 2H2O ⇆ Fe(OH)2 + 2Ni (OH)2 (1.3 V)
charge
9.14.2 Nickel (II) Oxide (NiO)

Nickel (II) oxide is the chemical compound with the formula NiO. It is
notable as being the only well characterized oxide of nickel (although nickel(III)
oxide, Ni2O3 and NiO2 have been claimed). The mineralogical form of NiO,
bunsenite, is very rare. It is classified as a basic metal oxide. Several million
kilograms are produced in varying quality annually, mainly as an intermediate in
the production of nickel alloys. NiO can be prepared by multiple methods. Upon
heating above 400 °C, nickel powder reacts with oxygen to give NiO. In some
commercial processes, green nickel oxide is made by heating a mixture of nickel
powder and water at 1000 °C, the rate for this reaction can be increased by the
addition of NiO.
The simplest and most successful method of preparation is through
pyrolysis of a nickel (II) compounds such as the hydroxide, nitrate, and carbonate,
which yield a light green powder. NiO was also a component in the Nickel-iron
battery, also known as the Edison Battery, and is a component in fuel cells. It is
the precursor to many nickel salts, for use as specialty chemicals and catalysts.
More recently, NiO was used to make the NiCd rechargeable batteries found in
many electronic devices until the development of the environmentally superior
Lithium Ion battery. Heating nickel oxide with either hydrogen, carbon, or carbon
monoxide reduces it to metallic nickel. It combines with the oxides of sodium and
potassium at high temperatures (>700 °C) to form the corresponding nickelate.
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Nickel oxide reacts with chromium(III) oxide in a basic moist environment to

form nickel chromate:
2 Cr2O3 + 4 NiO + 3 O2 → 4 NiCrO4
In addition, the stable nickel (II) salts are derived from nickel (II) oxide,
NiO, which is a green substance. The dissolved nickel (II) salts are green, owing
to the colour of the hexaquonickelate (II) complex [Ni(H2O)6]2+; in short,
however, this will be regarded as the simple nickel(II) ion Ni2+. A brownish-black
nickel(III) oxide Ni2O3 also exist, but this dissolves in acids forming nickel(II)
ions. With dilute HCl this reaction yield chlorine gas:
Ni2O3 + H+ + 2Cl-  2Ni2+ + Cl2+ 3H2O
9.14.3 Nickel Telluride (NiTe)

Nickel Telluride (NiTe) is a crystal grown product generally immediately
available in most volume. The melting point of NiTe is 860 oC. Nickel Telluride is
insoluble in H2O (water). The appearance is grey granules and it is no odor.
Nickel tellurium has relatively low toxicity. It is converted in the body to
dimethyl telluride which imparts a garlic- like odor to breath and sweat. Heavy
exposures may, in addition, result in headache, drowsiness, metallic taste, loss of
appetite, nausea, tremors, convulsion, and respiratory arrest (Sax, Dangerous
Properties of Industrial Materials, eighth edition).
9.14.4 Nickel sulphide

Nickel sulphide is also includes charconides. The reaction is as follow
Ni2+ + S2- NiS
In above reaction, it produces NiS which has black precipitate of nickel
sulphide from neutral or slightly alkaline solution. If the reagent is added in
excess, a dark-brown colloidal solution is formed which runs though the filter
paper. If the colloidal solution is boiled or if it is rendered slightly acid with acetic
acid and boiled, the colloidal solution (hydrosol) is coagulated and then filtered.
The presence of large quantities of ammonium chloride usually prevents the
formation of the sol. Nickel sulphide is pratically insoluble in cold dilute
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hydrochloric acid (distinction from the sulphides of manganese and zinc) and in
acetic acid, but dissolves in hot concentrated nitric acid and in aqua regia with the
separation of sulphur:
3NiS + 2HNO3 + 6 H+ 3 Ni2+ + 2NO + 3S  + 4 H2O
NiS + HNO3 + 3HCl Ni2+ + S  + NOCl + 2 Cl- + 2 H2O
9.14.5 Nickel (II) selenide

Nickel (II) selenide or penroseite is a rare selenide mineral with formula
NiSe2. It has a gray-steel color and black streak with a hardness of 3. It is an
isometric mineral, 2/m3. Penroseite was first discovered in 1925 in a Bolivian
rhyolite. It was named for Richard Penrose (1863-1931), an economic geologist.
It used to be found in fissure veins in the extrusive igneous rhyolite rock.
It is considered as a member of the pyrite group from the perspective of its
structure, with a cubic space group. Penroseite makes extensive solid solutions
with other minerals. Its composition have mixture of elements, some of them are
primary elements such as nickel that make with each other a substitution in
different amounts. Penroseite has a high content of selenium like no other mineral,
and as a result it was reported as the first nickel selenide mineral discovered.
Penroseite is a massive mineral. It can have radiating, columnar, or granular
structure. It shows a dull lead-gray to steel-gray color with a black streak. It has a
metallic luster and thought to have a weak chemical bonding and that what makes
it with a low hardness around 3. When it reacts with HNO3 or KCN, a fumes
tarnish to brown are resulted. But if it reacts with HCl, FeCl3, or HgCl2, it is not
react.
9.15 HALIDES AND OXYHALIDES OF NICKEL

Nickel halides can include nickel fluoride, nickel chloride, nickel bromide,
and nickel iodide. Nickel pseudo-halides include nickel cyanide, nickel cyanate,
nickel thiocyanate, nickel azide, and nickel ferrocyanide.
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9.15.1 Nickel (II) chloride (NiCl2)

Nickel (II) chloride (or just nickel chloride), is the chemical compound
NiCl2. Nickel chloride hexahydrate is formed by the reaction of nickel powder or
nickel oxide with hot mixture of water and HCl. The anhydrous salt is yellow, but
the more familiar hydrate NiCl2·6H2O is green. It is very rarely found in nature as
mineral nickel bischofite.
In general nickel (II) chloride, in various forms, is the most important
source of nickel for chemical synthesis. Nickel salts are carcinogenic. They are
also deliquescent, absorbing moisture from the air to form a solution. Probably the
largest scale production of nickel chloride involves the extraction with
hydrochloric acid of nickel matte and residues obtained from roasting refining
nickel-containing ores. NiCl2·6H2O is rarely prepared in the laboratory because it
is inexpensive and has a long shelf-life. The hydrate can be converted to the
anhydrous form upon heating in thionyl chloride or by heating under a stream of
HCl gas. Simply heating the hydrates does not afford the anhydrous dichloride.
The dehydration is accompanied by a color change from green to yellow.
NiCl2·6H2O + 6 SOCl2 → NiCl2 + 6 SO2 + 12 HCl
Nickel chloride hexahydrate is an important material in nickel
electroplating. The reaction of nickel chloride or nickel bromide with
dimethoxyethane yields ether-soluble NiX2. 2C2H4(OCH3)2 compounds which are
useful as nickel-containing reagents for a variety of reactions used to form
coordination compounds of nickel.
9.15.2 Nickel (II) Bromide (NiBr2)

Nickel (II) bromide (NiBr2) is the nickel salt of hydrobromic acid. Nickel
bromide NiBr2.6H2O is made by the reaction of black nickel oxide and HBr. The
reaction of hydriodic acid with nickel carbonate yields nickel iodide (NiI2.6H2O).
Nickel bromide has limited use in nickel electroplating. It can be made by
reacting nickel, nickel (II) oxide, nickel (II) carbonate, or nickel (II) hydroxide
with hydrobromic acid. It can also be made by reacting nickel with bromine. It is a
weak reducing agent. It is yellow-brown, rhombohedral, hygroscopic, and is
soluble in water and in ethanol. It dissolves in water to make a blue-green solution
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typical of soluble nickel (II) compounds. It can be used as a source of the bromide
ion. It reacts with bases to make nickel(II) hydroxide. Nickel(II) bromide, like
most nickel compounds, is toxic and a suspected carcinogen. It can cause contact
dermatitis in skin. The bromide ion is also mildly toxic.
9.15.3 Nickel Fuoride Tetrahydrate (NiF2.4H2O)

Nickel fluoride (NiF2) are the only known stable binary compound of
nickel and fluorine. The former is greenish light yellow crystal or powder
prepared by the addition of nickel carbonate to 30 – 50% aqueous HF solution.
The nickel fluoride formed first goes into solution and then precipitates out as the
tetrahydrate as the concentration of nickel fluoride increases and that of HF
decreases. When the addition of nickel is complete, the solution and the
precipitates are dried at 75 – 1000C until all the water is expelled.
Anhydrous nickel fluoride, is a light yellow colored powder is prepared by
the action of anhydrous HF on anhydrous NiCl2, or nickel fluoride tetrahydrate at
3000C. It is also prepared by heating a mixture of NH4HF2 and NiF2.4H20. The
other methods include the fluorination of metal salts using excess SF4 or using
ClF3 at elevated temperatures, or the reaction of NiCO3 and anhydrous HF at
2500C. NiF2 is prepared by treatment of anhydrous nickel(II) chloride with
fluorine at 3500C.
NiCl2 + F2 → NiF2 + Cl2
Nickel (II) fluoride reacts with strong bases to make nickel (II) hydroxide
which has green color compound.
NiF2 + 2 NaOH → Ni(OH)2 + 2 NaF
9.15.4 Nickel (II) Iodide (NiI2)

Nickel (II) iodide is an inorganic compound with the formula NiI2. This
paramagnetic black solid dissolves readily in water to give blue-green solutions of
the aquo complexes. This blue-green colour is typical of hydrated nickel (II)
compounds. Nickel iodides has important rule in some applications of
homogeneous catalysis.
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9.15.5 Nickel Oxyhalides

Nickel oxyhalides include nickel oxychloride and nickel oxybromide.
9.15.6 Nickel Oxychloride (NiOCl)

Nickel oxychloride, NiOCl, is produced in powder form as an active
fungicidal agent for pest control. One of the aqueous suspension concentrates
(Flowbrix) developed by Montanwerke Brixlegg AG is distinguished by its
especially high level of effectiveness. A method for processing nickel ores with
ammoiun chloride is also considered. The result of thermodinamic calculations for
the reactions of the oxide component or nickel oxychlrode of nickel ore with
ammnium chloride are given.
9.15.7 Nickel Oxybromide (NiOBr2)

Nickel oxybromide can form the 3D open framework of Ni5(SeO3)4Br2
which is built from 2D nickel (II) oxybromide layers bridged by Se and additional
Ni atoms. It has magnetic property measurements which indicate that compounds
display antiferromagnetic interactions between nickel (II) centers. Nickel
oxybromide can be prepared through the reaction of nickel dioxide and nickel
tetrabromide. Nickel dioxide is reacted with bromine to form nickel monobromide
and nickel tetrabromide. Dissolving the nickel dioxide in the tetrabromide will
produce the nickel oxybromide. The reaction are as follows:
2 Ni + 2 Br → Ni2Br2
Ni2Br2 + 6 Br → NiBr4
NiBr4 + NiO2 → 2 NiOBr2
9.16 COMPLEX COMPOUNDS OF NICKEL

9.16.1 Complexes of Nickel (II)
The binary compounds, such as NiO and NiCl2, need no special comment.
Nickel (II) forms a large number of complexes with coordination numbers six,
five, and four having all the main structural types: octahedral, trigonal
bipyramidal, square pyramidal, tetrahedral, and square. It is characteristic that
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complicated equilibria, which are generally temperature dependent and sometimes

concentartion dependent, often exist between there structural types.
Six-Coordinate Complexes
The commonest six-coordinate complex is the green aqua ion,
[Ni(H2O)6]2+, that is formed on dissolution of Ni, NiCO3, and so on, in acids and
gives salts like NiSO4. 7 H2O.
The water molecules in the aqua ion can be readily displaced especially by
amines to give complexes, such as-[Ni(H2O)2(NH3)4]2+, [Ni (NH3)6]2+, or [Ni
(en)3]2+. These amine complexes are usually blue or purple because of shifts in
absorption bands when H2O is replaces by a stronger field ligand.
Four-Coordinate Complexes
Most of the four coordinate complexes are square. This is a consequence
of the d8 configuration, since the plananr ligand set causes one of the d
orbitals( ) to be uniquely high in energy, and the eight electrons can occupy
the other four d orbitals but leave this strongly antibonding one vacant. In
tetrahedral coordination, on the other hand, occupation of antibonding orbitals is
unavoidable. With the congeneric d8 system PdII and PtII this factor becomes so
important that no tetrahedral complex is formed.
Planar complexes of NiII are thus in variable diamagnetic. They are
frequently red, yellow, or brown owing to the presence of an absorption band of
medium intencity ( in the range 450-500 nm.
Similar square complexes are - ketoenolates as well as unidentate -acid
ligands [example, NiBr2(Pet3)2], and by CN- and SCN-. The cyano complex,
[Ni(CN)4]2- is readily formed on addition of CN- to Ni2+ (aq). The green Ni(CN)2
which is first precipitated reddissolves to give the yellow ion, which can be
isolated as, for example, Na2[Ni(CN)4] .3 H2O. On addition of an excess of CN-
the red ion, [Ni(CN)5]3-, is formed, which can be precipitated only by use of large
cations.
Tetrahedral complexes
Tetrahedral complexes are less common than planar complexes, and are all
paramagnetic. These complexes are of the types (NiX4)2- , NiX3L-, NiL2X2, and
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Ni(L-L)2 where X is halogen, L is a neutral ligand and L-L is a bidentate positive

ligand, [NiL4]2+ , is known, where L = Hexamethylphosphoramide.
Five-Coordinate Complexes
Five-Coordinate Complexes usually have trigonal-bipyramidal geometry
but some are square pyramidal. Many contain the tetradentate “tripod” ligands,
such as N[CH2 CH2N(CH3)2]3.
9.16.2 Complexes of Nickel (III)

There are several authentic complexes of nickel (III). Oxidation of
NiX2(PR3)2 with the appropriate halogen gives NiX3(PR3)2
Nickel (IV) complexes are even rarer, and the dithiolene complexes, which
could formally be regarded as containing Ni4+ and S2CR2- ligands are best
regarded as NiII complexes.
9.17 SUMMARY
Iron, cobalt, and nickel have several physical and chemical properties. They are
included of ferromagnetic. While very similar in magnetic properties and reaction,
these elements are also very unique and used differently in both nature and
industry. In the nature, iron was found in the form of haematite (Fe2O3), magnetite
(Fe3O4), limonite (2Fe2O3.3H2O) and siderit (FeCO3). Cobalt is present in the
minerals cobaltite (CoAsS), smaltite (CoAS2), chloranthite, lemacite (Co3S4) and
erythrite but also associated with copper and nickel as sulfides and arsenides.
Nickel is the seventh most abundant transition metal and the twenty-second most
abundant element in the earth’s crust. It is aboout 99 ppm. It is commercially
important ores are of two types, Laterites, which are oxide/silicate ores such as
garnierite (Ni,Mg)6Si4O10(OH)8, and nickelliferous limonite (Fe,Ni)O(OH).nH2O,;
Sulfides such as pentlandite (Ni,Fe)9S8. In addition, they are commonly combined
with others elements and each other to create various types of alloys. Iron, cobalt,
and nickel also have oxides and chalconides, halides and oxohalides, and complex
compound for their compound.
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STUDY QUESTIONS
9.1 Explain the brief history of finding the element of iron, cobalt and nickel!
9.2 Explain the natural abundance and distribution of the compounds of iron,
cobalt and nickel in the earth’s crust!
9.3 Explain the isolation methods, properties and uses of iron, cobalt and nickel!
9.4 Explain the superior properties of iron, cobalt and nickel alloys!
9.5 Explain the properties of oxides and chalconides of iron, cobalt and nickel!
9.6 Explain the properties mixed oxides and oxoanion compounds of iron,
cobalt and nickel!
9.7 Explain the properties of halides and oxohalides of iron, cobalt and nickel!
9.8 Explain the properties of complex compounds of iron, cobalt and nickel
with various oxidation states!
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CHAPTER 10
COPPER, SILVER AND GOLD
10.1 INTRODUCTION
This course is to discuss thet finding history, isolation, natural abundance,
properties and uses of the elements of copper, silver and gold as well as their
compounds.
10.2 HISTORY
Copper is a chemical element in the periodic table that has the symbol Cu
and with atomic number 29. The symbol Cu comes from the LatinCuprum. In the
Greek, copper known as chalkos. To the Greeks and Romans this metal is known
as Cyprium because these metals in the mine area Cyprus. From those terms, so
was named as Cuprum. Copper has important role in the history of mankind,
easily obtained as long as10,000 years. Copper objects have been found among
the remains of many ancient civilizations, including those of Egypt, Asia Minor,
China, south eastern Europe, Cyprus (from which the word copper is derived),
and Crete (Kríti). It was known to Native Americans, and American ores were
found by the European explorers. It is also found in the pure state. Copper was
known to some of the oldest civilizations on record, and has a history of use that
is at least 10,000 years in northern Iraq have found copper pendant made
approximately around 8700 BC. This is reinforced by the discovery that states that
in 5000 BC already there are signs of coppers melting and refining.
Besides copper, silver has been in use since prehistoric times. It has a
special place in the history of the elements because it is one of the first five metals
discovered and used by humans. Silver objects dating from before 4000 BC have
been found in Greece and from slightly later in Anatolia (in modern Turkey).
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Silver artifacts have been found in the Sumerian city of Kish dating from about
3000 BC. Silver is formed in nature as argentile, Ag2S and horn silver,
AgCl.Silver comes from the Latin is Argentum and in Greek word is Argos, which
means "shiny" or "white”.
Gold was discovered around 40,000 BCin the form of pieces of natural
gold in the European region, especially in the caves of Spain by Paleolithic
humans. Then in 4000 BC, in the Eastern Europe gold began to be used as a
decorative medium and jewelry tools, while at that time the kingdom of ancient
Egypt used gold as decorative tombs of the kings. Knowledge of gold continues to
expand to Asia especially in Iraq and the Asian countries east around. In 3000
Bcgold was used gold coins as a medium of exchange in Iraq. Gold exchange rate
is very high at the time, so by the time it was known by Menes code Egyptian
founder of the dynasty, which means that one part of gold equal to two and one-
halfpart of the value of silver which at that time silver also familiar as the material
that expensive anyway.
The first use of gold as money in commercial occurred around 700 BC,
when Lydian merchants produced the first coins. It is only made of 63% gold and
27% silver it is a mixture known as "Electrum", while the Roman Empire began
issuing gold coins called "Aureus" in the year 50 BC. Because the price and value
of gold has increased, so many nations vying for a gold mining area that it is
caused the war. Untill now gold remains an expensive item and jewelry are much
in demand.

Copper is found naturally, such as those found in minerals namely, pyrite
or chalcopyrite (CuFeS2), copper glance or chalcolite (Cu2S), cuprite (Cu2O),
malaconite (CuO) and malachite (Cu2(OH)2CO3). According to the data mining
world in 2005, the largest copper producer is Chile then followed by the U.S. and
Indonesia. In nature, copper is mined with underground mines and mining
methods ground. The concentration of pure copper in nature is around 2.3%.
Copper ore in Indonesia are generally formed by magmatic. Deposit formation
magmatic or hydrothermal processes can be meta somatisme.
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Silver is widely distributed in sulfide ores of which silver glance

(argentite), Ag2S, is the most important. Native silver is sometimes associated
with these ores as a result of their chemical reduction, while the action of salt
water is probably responsible for their conversion into "horn silver", AgC1, which
is found in Chile and New South Wales. The Spanish Americas provided most of
the world's silver for the three centuries after about 1520, to be succeeded in the
nineteenth century by Russia. Appreciable quantities are now obtained as a
byproduct in the production of other metals such as copper, and the main
producers are Mexico, the former Soviet Union, Peru, the USA and Australia
(Greenwood & Earnshaw, 1997).
The abundance of silver in the earth's crust of approximately: 0,008 ppm.
(Greenwood & Earnshaw, 1997). The minerals containing silver, namely: native
silver (silver-content100%); sulfide bond such as argentite (Ag2S) with silver-
content 87% and stromecrite (CuAgS) with silver-content 49-53%; sulfo salts
such as polibasite (Ag, Cu) 16Sb2S11 with silver-content of 61-74%, pearccite
Ag16As12S11 with silver-content of 57-77%, pyrargyrite or dark ruby, (Ag3SbS3)
with silver-content 60-61%, proustite or light ruby, (Ag3AsS3) with silver-content
64-65%, tetrahedrite or freibergite; silver-content of 0-7%, tennantite (Cu1Fe1Ag)
12As4S13 with silver-content of 0-4%, stephanite (Ag5Sb4) with silver-content of
68-69%; chloride minerals such as cerargeyrite (AgCl) with silver-content of 67-
75%; as tellurides such as silvanite (Ag1An) TE2 with silver-content of 9-14%,
hassite (Ag2Te) with silver-content of 59-63%, and petzite (Ag3AnTe2) with
silver-content of 41-45%.
Usually silver is found joined with base metals, such as copper, zinc and
lead; with very varied silver-content of low grade to a high grade (Hurlburt.
1971). Silver produced in Indonesia are generally obtained together with gold.
Metallic gold (Au) are widely distributed in nature. Gold is generally
found in the form of free metals in quartz rock cracks and in the form of the
mineral. Abundance of gold in nature is 0.004 ppm in the earth's crust. Gold ore
rock that eligible to be exploited as a gold mine industry is with a gold content
approximately 25 g/ton (25 ppm). Largest gold deposits found in the Precambrian
Witwatersrand, South Africa, with hundreds miles of area mines and a depth of
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more than two miles. Since the 1880s, South Africa has become the world's
largest source of gold supply. In 1970, production reached up to 70% of the world
supply, which is producing about 1000 tons. Here is the location of today's biggest
gold mining:
(1) Kalgoorlie Super Pit (Australia)
Kalgoorlie Super Pit was first discovered in 1893, and this is a giant crater
in Western Australia. This crater stretched open along 3.5 km, width 1.5 km
and depth of 360 m.
(2) The Big Hole (South Africa)
Bigholein Kimberly, South Africa, is a very large hole ever excavated by
human hands. But mine was closed in 1914. During the productive period
of43years, estimated 50,000 workers they only use pick sands hovels to
excavate 22.5 million tonnes of soil and produces nearly 3 tonnes of gold.
(3) Diavik Diamond Mine (Canada)
Diavik Diamond Mine is located in the North Slave Region Canada. This is
a mine that was left open. The mine site is located on an island with an area
of 220 km2. With life span productivity of16-22years, the crater is estimated
to have produced 8,000,000 carats (1600 kg) of gold.
(4) Gasberg Mine (Tembagapura, Indonesia).
This mine opened in 1973, Indonesia's Grasberg Mine is the largest gold
mine andt hird largest copper mine.

Elemental properties of three elements Cu, Ag, Au are presented in the
table below.
Table 10.1 Elemental Properties of Cu, Ag, and Au
Characteristic 29Cu 47Ag 79Au
10 1 10 1
Electron configuration [Ar] 3d 4s [Kr] 4d 5s [Xe] 4f 5d106s1
14
Electronegativity 1.9 1.9 2.4

Metallic radii/pm 128 144 144
Ionic radii/pm 73 (+2); 77 (+1) 115 (+1) 137 (+1)
First ionization energy/kj.mol-1 745.3 730.8 889.9
Melting point/ C 1083 961 1064
Boiling point/ C 2570 2155 2808
Density (20 0C) / g cm-3 8.95 10.49 19.32
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Because of its many desirable properties, such as its conductivity of

electricity and heat, its resistance to corrosion, its malleability and ductility, and
its beauty, copper has long been used in a wide variety of applications. The
principal uses are electrical, because of copper's extremely high conductivity,
which is second only to that of silver. Because copper is very ductile, it can be
drawn into wires of any diameter from about 0.025 mm (about 0.001 in) upward.
The tensile strength of drawn copper wire is about 4200 kg/sq cm (about 60,000
lb/sq in). It can be used in outdoor power lines and cables, as well as in house
wiring, lamp cords, and electrical machinery such as generators, motors,
controllers, signaling devices, electromagnets, and communications equipment.
Copper, a comparatively inactive metal, is slowly corroded by air and
water in the presence of such weak acids as carbonic acid, producing a green,
porous, basic carbonate of copper.
A good conductor is one that has low resistance. A good insulator has a
very high resistance. At commonly encountered temperatures, silver is the best
conductor and copper is the second best. Electric wires are usually made of
copper, which is less expensive than silver.
Copper have several chemical properties, namely:
(1) Copper is an element that is relatively non-reactive so resistant to corrosion.
In moist air the copper surface is covered by a green layer of copper
carbonate Cu(OH)2CO3.
(2) Hot copper can react with sulfur and halogen vapor. Reacts with sulfur to
form copper (I) sulfide and copper (II) sulfide and for reactions with
halogens to form copper (I) chloride, chlorine is produced specifically
copper (II) chloride.
(3) Generally, copper layer is the base layer should be coated with nickel or
Chrome. In principle this is a process of electrochemical deposition of
metals, used electric direct current (DC). Type of electrolyte used is the type
of alkaline and acid type
Copper is widely used as one of the techniques, either in a pure state and
alloys. Copper has a tensile strength up to 150N/mm2 in the form of molten
copper and can be increased up to 390N/mm2 through cold working process and
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for the type of casting hardness numbers only reached 45 but can be up graded to
HB 90 HB through cold working, where the cold working process this will reduce
there silience, tenacity however can be improved through the process of annealing
(see the process of heat treatment) can reduce the rate of violence and tension or a
process called "temperature" which can be achieved through controlling distance
workman ship afterv annealing.
Copper has a thermal and electrical properties conductivity number two
after Silver. Copper is used as an electrical conductor widely used in a high state
of purity up to 99.9%. Other properties of copper are the nature of resistance to
atmospheric corrosion as well as a variety of other corrosion media attacks.
Copper is very easily connected through selection process, Brazing and welding.
Copper belongs to a class of heavy metal which has a specific gravity of 8.9kg/m3
with a melting point of 10830C.
The uses of copper are as follows:
(1) As a material for electrical wires and coil dynamo.
(2) Metal alloys. Alloy of 70% copper with 30% zinc is called brass, while 80%
copper alloy with tin 20% is called bronze. Containing a number of
phosphor bronze used in the watch industry and galvanometer. Brass has a
golden color like so much used as jewelry or ornaments. While a lot of
bronze used as jewelry and used also in theart of sculpture.
(3) Currency and instruments made of gold and silver have always containing
copper to increase the strength and hardness.
(4) As a barrier to building materials and some parts of the ship.
(5) Copper powder is used as a catalyst to oxidize methanol to methanal.
On the other hand, silver also is the best conductor of heat, electricity and
strong. It is malleable and ductile (can be beaten and drawn into a wire).Silver can
keep extreme temperature ranges, and very good reflector of light.Silver is harder
than gold but softer than copper.Silver tarnishes easily, as you willsee if you look
at some neglected silverware. Silver is shiny.
Chemical properties of silver can be seen when it is reacted with the other
compounds. Some reactions are as follows:
(1) Silver reacts with H2S
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4Ag  2H2S  O2  2H2O  2Ag2S

(2) Silver reacts with halogen
2Ag  Cl 2  2AgCl (in Hot Condition)
2Ag  Br 2  2AgBr (in Hot Condition)
(3) Silver reacts with sulfur
2Ag  S 200
  Ag2S
o
C
(4) Silver reacts with acid

2Ag  2H 2SO 4(s)  Ag2SO 4  SO 2  2H 2 O
3Ag  4HNO3  3AgNO3  2H2O  2NO
Ag  2HNO3(s)  AgNO 3  H 2 O  NO2
2Ag  2HCl  2AgCl  H 2

(5) Silver reacts with alkali cyanide
4Ag  8NaCN  2H2O  O2  4NaAgCN2   4NaOH
Photography was known in the sixteenth century that silver salts were
photosensitive, but it was not until the beginning of the nineteenth century, when
Herschel found that silver chloride was soluble in sodium thiosulphate, that
photography became possible. The plate or film of celluloid is coated with a
colloidal gelatinized solution when the unchanged bromide is dissolved to form a
chloride because of its greater sensitivity). During photographic exposure,
decomposition of the bromide occurs to form minute particles of silver. These
particles are too small to be seen by the naked eye and are only detectable with the
electron-microscope. The number of such nuclei of decomposition in a given area
of plate or film depends on the intensity of light falling on the area.
When the film is developed (the developer being a reducing agent), the
unchanged silver bromide immediately surrounding these nuclei is reduced to give
a visible blackening of the film. The film is now fixed by washing in sodium
thiosulphate ('hypo') solution when the unchanged bromide is dissolved to form
the complex ion
AgBr+ 2S2 →[Ag(S2O3)2]3- + Br-
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The fixed plate is now a negative', for those patches on which most light
fell are black. The process is reversed in printing to make the 'positive'—the
printing paper having a covering of silver chloride or bromide or a mixture of the
two. This, in turn, is developed and fixed as was the plate or film. The formation
of minute specks of silver when silver bromide is exposed to light is known to be
aided by the presence of gelatin, which acts as a sensitiser. Very pure gelatin does
not act in this way; but ordinary gelatin contains a trace of sulphur; because of
this, a few sulphide ions, S2-, are introduced into the silver bromide lattice, which
is made up of silver and bromide ions. Now a sulphide ion, S2-, must replace two
bromide ions to keep the crystal electrically neutral, but it only occupies the space
of one.
Hence a 'vacant anion site', i.e. a "hole' is left in the crystal. When the
crystal is exposed to light, electrons are released from the crystal, and move
through it; and some of these, when they reach a "hole', become "trapped'. When
this happens, neighbouring silver ions unite with these electrons, so forming a
nucleus or speck containing a few neutral silver atoms. These nuclei then grow
when the silver bromide is reduced by the developer, and form the dark patches of
silver where exposure has occurred.
Gold is highly conductive to electricity, and has been used for electrical
wiring in some applications. This is because gold has the electron configuration
[Xe] 4f14 5d10 6s1 valence electrons are 6s1 5d10, indicating that gold is in a
transition group, seen from the d orbitals of the valence electrons and d orbitals
have a great energy in the electrons. Material will be a conductor if the material
has free electrons (electrons are located at the outside) that move and conduct
electricity. Conductive properties is better if the outermost electron has
considerable energy and numerous as is the case with gold. Therefore gold is
widely used in various electronic items.
Gold is an excellent conductor material, copper is more commonly used as
a good conductor than gold because gold is expensive. Conductivity good gold
and general resistance to oxidation and corrosion in other environments (including
resistance to non-chlorinated acids) has led to the widespread industrial use in the
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electronic era as a thin layer coating electrical connectors of all kinds, thereby
ensuring good connection.
Gold has unique properties not shared by other metals, which makes it
unique and a lot of metal used.
a. The most commonly used gold as jewelry, such as necklaces, rings, bracelets,
etc. This is because gold has a beautiful yellow color, and gold belong inert
metal that is not easily react with other elements that cause corrosion
resistant.
b. Gold is used as wires in electronic devices, such as satellite in outer space, to
coat electrical connectors, thus ensuring a better connection, it is because gold
is a very good conductor.
c. Gold is a very rare metal that causes the value of the gold itself is very
expensive, so it is often used as a gold coin as a medium of exchange. Gold is
widely used as a financial standard in many countries as well as foreign
exchange reserves, and until now gold is a means of payment in the world.
d. Gold investment is now a promising business choice. This is because the
price of gold tends to be stable even getting up from the previous price,
despite the money crisis or inflation.
e. Gold is used as dentures. Once combined with other metals, will form a hard
mix, and has many advantages, such as not react with acids and bases, and
corrosion resistance.
Gold is chemically quite inert so called precious metals. It is because gold
has the highest reduction potential value(in the voltaic series lies in the right most
position) so that the resulting metalis always present in nature in free state. Gold
is difficult to react with other elements and can not be corroded. Gold also does
not react with any acid or base, but gold in cyanide solution decomposes and
reacts with halogen gold and aqua regia.
Gold metal reacts with chlorine (Cl2), or bromine (Br2) to form trihalides
gold(III) chloride(AuCl3), or gold(III) bromide(AuBr3).
2Au(s) + 3Cl2(g) → 2AuCl3(s)
2Au(s) + 3Br2(g) → 2AuBr3(s)
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AuCl3 soluble in concentrated acid produces hydroxide ions tetrachloroaurate(III)

[AuCl4]-, anion which is one component ofthe"liquid gold".
Moreover, a gold metal reacts with iodine, I2to form monohalide, gold(I)
iodide, AuI.
2Au(s) + I2(g) → 2AuI(s)
Gold can be dissolved in aquaregia (concentrated hydrochloric acid and
nitric acid in the ratio 3:1) where HNO3 serves as an oxidant and HCl as a
complexing agent. Gold in aquaregia produces HAuCl4 solution. The overall
reaction involved in aquaregia is:
Au(s) + 4HCl (aq) + HNO3(aq) → HAuCl4(aq) + NO (g) + 2H2O(l)
10.5 METAL ISOLATION AND PURIFICATION

Copper ores often contain very low concentrations of the metal. Because
of this, many stages of the production process focus on eliminating impurities.
The ore is crushed and milled before entering a flotation chamber, in which
copper will concentrate at the top while unwanted fragments sink. Next, the
concentrate, now called charge, will enter reverberatory furnace, where more
impurities are removed. During smelting, waste gases are removed, and the
material forms a molten pool of copper and iron, called the matte, at the bottom of
the furnace. The orange layer of impure metal on top of the matte is slag, which is
drained off while the copper matte continues on to a converter. Molten copper
from the converter is cast and must be refined once more by electrolysis before it
is ready for use in the manufacture of products such as electrical wire and utensils.
a. Flotation
Flotation process is begin by reduction size of ore and then milled to form vine
grains. Ore that has been crushed put into a mixture of water and certain oil. Then
air is blown into the mixture to produce air bubbles. Ore containing metal parts
that do not bind to the water will bind to the oil and stick to the air bubbles which
then float to the surface. Further air bubbles that carry the metal particles and the
floats are separated and then concentrated.
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b. Roasting
Concentrated ore flotation results subsequently baked in a limited air at a
temperature below its melting point in order to remove water that may still exist at
the time of concentration and sulfur are lost as sulfur dioxide.
2Cu2FeS(s) + 4O22Cu2S(s) + 2FeO(s) + 3SO2(s)
Mixture obtained from the roasting process is called calcine, that contain Cu2S,
FeO and possible contain a little FeS. After that FeO is reacted with SiO2 to form
FeSiO3. The reaction can be written as follows:
FeO(s) + SiO2FeSiO3
Copper(I) sulfide obtained at this stage is called matte and possible contain a little
iron(II) sulfide
c. Reduction
Then, Cu2S or matte that have been gained is reduced by heating with air
controlled, according to the reaction
2Cu2S(s) + 3O2(g) → 2Cu2O(s) + 2SO2(g)
Cu2S(s) + 2Cu2O(s) → 6Cu(s) + SO2(g)
Copper obtained at this stage is called blister or blister copper because it contains
cavities filled with air.
d. Electrolysis
Blister still contains Ag, Au, Pt and then purified by electrolysis. On copper
electrolysis (not pure) installed as the anode and the cathode used pure copper,
with an electrolyte solution of copper (II) sulfate (CuSO4). During the electrolysis
process takes place at the copper in anode is oxidized to Cu 2 + and then reduced
at the cathode to Cu metal.
Cathode: Cu2+(aq) + 2e → Cu(s)
Anode: Cu(s) → Cu2+(aq) + 2e
In this process the anode is decrease and cathode (pure copper) increase, while the
impurities in the form ofAg, Au, and Pt settle as sludge.
Silver contained mostly as free elements and silver(I) sulfide(Ag2S). One
method to isolation is the extraction ofthese metalsby reacting Ag2S and the
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cyanide solution, which will produce silver as ions disianorgentat complex(I),

[Ag(CN)2]- :
2 Ag2S (s) + 8CN (aq) + O2(g) + H2O (l) → 4[Ag(CN)2]-(aq) + 2S (s) + 4OH (aq)
The addition of metallic zinc resulted in crowding reaction Ag+ions by
zinc, forming a very stable complex ions [Zn(CN)4]2- :
2[Ag(CN)2]-(aq) + Zn (s) → [Zn(CN)4]2-(aq) + 2Ag (s)
Next, pure silver can be carried out electrolysis with acidified silver nitrate
electrolyte.
Isolation process to obtain which performed on an industrial gold from gold
ore rocks, which the gold ore rocks that deserves to be exploited as the gold
mining industry is rock gold content of approximately 25 g/ton. There
areseveralwaysormethods used toisolategold, namely:
1. Cyanide Method
Gold can be in isolated by using cyanide method. Cyanide method consists of
two important processes, i.e. the gold leaching process and the process of
separating the gold from the solution.
In the process of dissolution, solvent commonly used in the cyanide process
is NaCN, KCN, Ca(CN)2 or a mixture of all three. The most commonly used
solvents are NaCN, because it is able to dissolve gold better than other solvents.
In general, Au dissolution reaction is as follows:
4Au + 8CN- + O2 + 2H2O 4Au(CN)-2 + 4OH-
In of the separation of gold from the solution is done by metal deposition using Zn
powder (zinc precipitation). Reactions that occur are as follows:
2 Zn + 2 NaAu(CN)2 + 4 NaCN +2 H2O  2 Au + 2 NaOH + 2 Na2Zn(CN)4 + H2
The use of Zn powder is an effective way to a solution containing small gold
concentrations. Zn powder is added to the solution to precipitate metallic gold.
2. Amalgamation Method
Amalgamation is the process of extracting gold ore by mixing gold with
mercury (Hg). In this process will form a bond between the gold compounds, and
mercury itself is commonly known as amalgam (Au-Hg). Mercury form
amalgams with metals other than iron and platinum. Amalgam is still the gold
extraction process is the most simple and inexpensive, but gold amalgamation will
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be effective on the larger particle size of 200 mesh (0.074 mm). The three main
forms of amalgam are AuHg2, Au2Hg and Au3Hg. After amalgam formed, further
amalgam heated so it will decompose into the elements mercury and gold.
Amalgam can be decomposed by heating in a retort (place of heating amalgam, its
shape resembles a drum), the water will evaporate and mercury can be recovered
from the mercury vapor condensation. While gold remains behind in the retort as
metal.
This way of purification is becoming obsolete because it raises the Hg gas
that is harmful to human health, such as causing cancer, damage to the digestive
tract and respiratory and skin disorders.
10.6 ALLOYS
Alloy of copper as the most widely used engineering material because it
has many advantages, among others:
(1) It has good mechanical properties, electrical properties and high thermal
conductivity and resistance to corrosion and wear resistance.
(2) Easily formed by machining.
(3) Easily formed through heat processing and cold work.
(4) Easy tobe formed by connected by soldering, brazing and welding.
(5) Easy polished or depleting if desired.
(6) Pressing and forging temperature is lower than with the use of metallic
materials Ferro.
Copper alloy can be grouped into:
1) Low-alloy copper are included in this group are Silver-Copper, Cadmium-
Copper, Tellurium-Copper, Berylium-Copper and Copper-Nickel Alloy-
Silicon.
2) Copper alloy with high levels, namely Brass and Bronze (Cotton and
Wilkinson, 1971).
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10.7 COMPOUNDS OF COPPER, SILVER, AND GOLD

10.7.1 Copper (II)
Copper forms compounds with oxidation states +1 and +2, but only copper
(II) are stable and dominate in aqueous solution. In water solution, almost all the
salt of copper (II) colored blue, the color characteristics of ion coordination
complex 6, [Cu(H2O)6)]2+. Famous exception is copper (II) chloride greenish
because of the complex ion [CuCl4] 2-which has the basic geometry tetrahedral or
square depending on the cation partner.
In aqueous solution the color changes intobluebecausecrowding ofmetal-
ligand Cl- byH2O. Therefore, ifthe green colorto be maintained, in concentrated
CuCl2 is added by Cl- by adding NaCl solid.
[CuCl4]2- (aq) + 6H2O (l) → [Cu(H2O)6]2+ (aq) + 4Cl (aq)
10.7.2 Copper(I)
Basically copper is not reactive metal, but this metal can be attacked by
concentrated acids, especially, if it reacts with boiling concentrated hydrochloric
acid will produce a colorless solution and hydrogen gas. Ions of copper(I) occurs,
with chloride ions immediately form a colorless complex ion dichlorocuprate(I),
[CuCl2]-. The second stage of this reaction was expected to be extremely rapid,
triggering the first reaction step as follows:
Cu (s) + H3O+ (aq) → Cu+ (aq) + H2 (g) + 2H2O (l)
Cu (aq) + 2Cl- (aq) → [CuCl2]- (aq)
If this solution [CaCl2]-(aq) is reacted with distilled water it will form a white
precipitate of copper(I) chloride according to equation:
[CuCl2]-(aq) → CuCl (s) + Cl-(aq)
Copper chloride should be promptly separated, washed and kept free from
air, because the interaction with water vapor will produce copper(II).
Dichlorocuprate(I) is used to convert benzene into chlorobenzene from
diazoniumchloride by reaction below.
[C6H5N2]+ Cl- (aq) → C6H5Cl (l) + N2 (g)
Generally, compounds of copper(I) is colorless or white, because this ion has a
full electronic configuration, 3d10. In aqueous solution, copper ions(I) hydrated is
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unstable and having disproportionate to be copper ions(II) according to the

forecast diagram reduction potential frost.
2Cu+ (aq) → Cu2+ (aq) + Cu (s)
Table 10.1 Compounds of Copper
Copper (II) Name Copper (I) Name
CuO Copper (II) oxide Cu2O Copper (I) oxide
Cu(OH)2 Copper (II) hydroxide CuCl Copper (I) chloride
CuCl2 Copper (II) chloride CuI Copper (I) iodide
CuF2 Copper (II) fluoride
CuS Copper (II) sulfide
CuSO4.5H2O Copper (II)
sulphatepentahydrateor
Cu(NO3)2.3H2O vitriol blue
Copper (II) nitrate
trihydrate
As we know that the halides of copper (I) only fluoride that has not
obtained pure. Copper chloride and iodide be colored, even white colorless. The
compound is diamagnetic and and are in the form of crystals at room temperature,
where the tetrahedral Cu atom bound to four halogen atoms. Copper (I) chloride
and bromide salts in the production of acid by boiling a solution of copper (II)
with excess copper which will be formed when the dilution of the yellow CuCl or
CuBr which has pale yellow color. The addition of iodide to a solution of copper
(II) to form a precipitate of copper (I) iodide (Sugiyarto, 2003).
Copper(I) halide is slightly soluble in water and soluble copper in the
water is copper(II). Although the compound has little solubility of copper (I) will
increase if already bind halide ions. For more details, see the table below:
Table 10.2 Compounds of Copper (I)
Compound Color
CuCl White
CuBr White
CuI White
The third copper (II) halides can be identified despite rapid cupric iodide
decomposes into cuprous iodide and iodine. Copper (II) clorida has yellow and
copper (II) bromide almost black color. Copper (II) halide is moderate oxidizing
agent of the couple Cu (I)/Cu (II). In the water, copper (II) halide is moderate due
to the oxidizing agent Cu (I)/Cu (II) couple. Oxidation power level (halogenating)
can be arranged; CuF2<<CuBr2<<CuCl2 (Sugiyarto, 2003).
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Manufacture of Copper (II) halide can be prepared by direct reaction with

halogen.
Cu + F2 → CuF2
Cu + Cl2 → CuCl2 temperature 450C.
Cu + Br2 → CuBr2
Table 10.3 Compounds of Copper (II)
Compound Color
CuF2 White
CuCl2 Yellow
CuBr2 Almost black
At high temperatures, copper (I) oxide is more stable than copper (II)
oxide. Copper (I) oxide is formed in the shape of red cuprite. In the laboratory, the
addition of Fehling with reducing sugars such as glucose produces a red
precipitate. This test is sensitive enough to even 1 mg of sugar to produce the
characteristic red color of the compound. Cuprous oxide can also be prepared as a
yellow powder by controlled reduction of salt (II) copper base with hydrazine.
Thermal decomposition of copper (II) oxide also gives copper (I) oxide because
the latter has a greater thermal stability. The same method can be used to prepare
compounds of carbonate (II) copper nitrate, and hydroxide.
Copper(II) oxide occurs naturally as tenorite. This black solid crystal can
be obtained by pyrolysis of nitrate salts, hydroxide or carbonate. It is also formed
when copper powder is heated in air or oxygen. The table below shows some of
the characteristics of copper oxide.
Silver oxide, Ag2O is odorless, darkbrown, and used in batteries contained
in watches, calculators, and other electronic devices. This battery uses silver
oxide in cathode and zinc in anode, and electrolyte of KOH-shaped pasta.
Reaction takes place:
anode : Zn(s)  Zn2 (aq)  2e 
cathode : Ag 2 O (s)  H 2 O (l)  2e   2Ag(s)  2OH  (aq)
Zn2+ions will react with OH-ions to form Zn(OH)2 which is results in cell potential
of 1.5 volts.
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While the chloride, bromide and iodide are insoluble in water, the fluoride,
AgF, is very soluble. The insoluble halides can be prepared by adding the
respective halide ion to silver ions:
Ag+ + X- → AgX↓
The chloride is white, the bromide pale yellow and the iodide deeper
yellow. These are examples (uncommon) of a colored compound being obtained
from colorless ions. The silver(I) ion intensifies color in other cases, for example
silver chromate(VI), Ag2CrO4, is brick-red while potassium chromate(VI).
K2CrO4 is yellow.
Silver chloride is readily soluble in ammonia, the bromide lesreadily and
the iodide only slightly, forming the complex cation [Ag(NH3)2]+. These halides
also dissolve in potassium cyanide,forming the linear complex anion [Ag(CN)2]-
and in sodium thiosulphate forming another complex anion, [Ag(S2O3)2]3-.All the
silver halides are sensitive to light, decomposing eventuallyto silver. In sunlight,
silver chloride turns first violet and finallyblack. The use of these compounds in
photography depends on this(photography). (All silver salts are, in fact
photosensitive the neckof a silver nitrate bottle is black owing to a deposit of
silver). Silver chloride is reduced to the metal by zinc. One of the methods of
recovering silver from "silver residues' depends on this. Theresidue is first treated
with concentrated hydrochloric acid and thensulphuric acid and zinc added:
2AgCl + Zn → 2Ag + 2C1- + Zn2+
Compounds of halides, AgF, AgCl, AgBr, andAgI (except silver fluoride)
sparingly soluble in water it is due to the interaction between water molecules
(polar) with the ion charge; decreasing or increasing the ionic nature of the
covalent nature of the silver-halide lead to weakening of the interaction tends
soluble. But for silver fluoride, the small size of the fluoride ion causes a lack of
polarized nature of silver cations to the most ionic properties compounds than
other silver halides, silver and lead fluoride readily dissolves in water. AgCl,
AgBr, and AgI are very sensitive to light, and is easily reduced than Ag+ ions to
metallic Ag resulting in a dark-colored solids. That's why silver compound
deposited and the solution stored in dark bottles. On the other hand silver also can
form complexes with several oxidation state.
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10.7.3 Silver(III) (d8)
Silver(III) is quite similar to copper(III) and analogous, though more

stable, periodate and tellurate complexes can be produced by the oxidation of Ag
I with alkaline S2O82-. The diamagnetic, red ethylene dibiguanide complex
(Figure 10.1) is also obtained by peroxodisulfate oxidation and is again quite
stable to reduction. However, yellow, diamagnetic, square-planar fluoro-
complexes such as K[AgF4], obtained by fluorinating AgNO3 + KC1 at 3000C,
are much less stable; they attack glass and fume in moist air.
Figure 10.1 Silver(III) ethylenedibiguanide

complex ion; the counter anion can be HSO4-
, C1O4-, NO3- or OH-. (Greenwood, 1998)
10.7.4 Silver (II) (d9)
Compounds of AgII are more familiar and are, in general, square planar
and paramagnetic (µe ~ 1.7-2.2BM); this is as expected for an ion which is
isoelectronic with CuII, particularly in view of the greater crystal field splitting
associated with 4d (as opposed to 3d) electrons.The AgII(aq) ion has a transitory
existence when AgI salts are oxidized by ozone in a strongly acid solution, but it is
an appreciably stronger oxidizing agent than MnO4-[E0(Ag2+/Ag+) = +1.980V in
4M HC1O4; E0(MnO4-/Mn2+) = 1.507 V] and oxidizes water even when strongly
acidic.Of the acidic solutions the most stable is that in phosphoric acid, no doubt
because of complex formation, and even NO3- and C1O4- ions appear to
coordinate in solution since the colors of these solutions depend on their
concentrations. A variety of complexes, particularly with heterocyclic amines, has
been obtained by oxidation of Ag I salts with [S2O8]2- in aqueous solution in the
presence of the ligand. They include [Ag(py)4]2+ and [Ag(bipy)2]2+ and are
comparatively stable providing the counter- anion is a non-reducing ion such as
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NO3 , C1O4- or S2O82-. Other complexes include some with N-, O-donor ligands
such as pyridine carboxylates, and also the violet Ba[AgF4].
10.7.5 Silver (I) (d10)
The +1 state is by far the best-known oxidation state of silver and salts
with most anions are formed. These reveal the reluctance of AgI to coordinate to
oxygen for, with the exceptions of the nitrate, perchlorate and fluoride, most are
insoluble in water. The last two of these salts are also among the very few AgI
salts which formhydrates and, paradoxically, their solubilities are actually noted
for their astonishingly high values (respectively 5570 and 1800g1-1 at 25oC). The
hydrated ion is present in aqueous solution and a coordination number of 4 has
been established. AgI forms 4- coordinate tetrahedral complexes less readily than
2-coordinate linear ones. A wide variety of the latter are formed with N-, P- and
S-donor ligands, some of them of great practical importance. The familiar
dissolution of AgC1 in aqueous ammonia is due to the formation of
[Ag(NH3)2]+;the formation of lag (S2O3)2]3- in photographic "fixing" has already
been mentionedandthe cyanide extraction process depends upon the formation
of[M(CN)2]-. AgCN itself is a linear polymer, {Ag-C N→Ag-C N→} but
AgSCN is non-linear mainly because the sp 3 hybridization of the sulfur forces a
zigzag structure; there is also slight non-linearity at the AgI atom.
Figure 10.2 The AgSCN is non-linear (Greenwood and Earnshaw,1998)
Because of their inability to form linear complexes, chelating ligands tend

instead to produce polymeric species, but compounds with coordination numbers
higher than 2 can be produced, e.g. the almost tetrahedral diphosphine and
diarsine complexes [Ag(L-L)2]+ and the almost planar 5-coordinate
[Ag(quinquepyridine)][PF6].Four-coordination is also found in tetrameric
phosphine and arsine halides [AgXL]4 which occur in "cubane" and "step" (or
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"chair") forms like their copper analogues. Indeed, [AgI(PPh3)]4 exists in both
forms. As with CuI, sulfur and S-donor ligands yield many complexesof high
nuclearity. [Ag4(SCH2C6H4CH2S)3]2-contains the same tetrahedral {M4S6} centre
found in [Cu4(SPh)6]2-, while in the dark-red Na2[Ag6S4] the metal atoms are
disposed octahedrally. The cyclohexanethiolato complex [Ag(SC6H11)]12
and(PPh3)4 [AgSBut]14 consist respectively of 24- and 28-membered puckered
rings of alternate Ag and S atoms.
In the formation of complex compounds of silver (Ag) as a central atom
and CN- as a ligand [Ag(CN)2] - based on the principle of energetics, the energy
level of the complex is the lowest when the repulsion between the two ligands
CN-minimal. This occurs when two CN-ligands in opposition so complex
[Ag(CN)2]- has a linear structure. The fact is experimentally proved that the
[Ag(CN)2]- is diamagnetic therefore this complex hybridization involvingsp
hybridization.
Gold has three oxidation states in its compounds, namely+1, +2and+3. But
for gold(II) compound is rarely to obtain in nature. The compounds of gold with
each oxidation state are as follows:
10.7.6 Gold(I) Compounds

These all tend to disproportionate into gold and gold(III) compounds, as
already stated. Some of those which are insoluble in water, for example gold(I)
sulphide, Au2S, are fairly stable; others, for example gold(I) oxide, Au2O, readily
decompose even on gentle heating. One of the most stable is gold(I) cyanide,
AuCN, which is formed when the ion, [Au(CN)2]-, is allowed to react with
hydrochloric acid. Gold(I) iodide, AuI, is also formed by the slow loss of iodine
from the gold(III) iodide, (AuI3)n. The stabilities of gold(I) cyanide and iodide
may be compared with those of the corresponding copper(I) salts.Gold(I) salts of
oxoacids are not known, but many complexes of gold(I) have been discovered
(Enghag, 2004).
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10.7.7 Gold(II) Compounds

Gold(II) compounds are rare and are represented by [AuXe4]2+, and trans-
and cis-[AuXe2]2+. For many years, AuSO4 has been formulated as the mixed
valence compound AuIAuII(SO4)2, but in 2001, a crystal structure determination
confirmed it to be an Au(II) compound containing an [Au2]4+ unit. This dinuclear
core is present in a range of complexes that formally contain Au(II) (Housecroft
and Sharpe, 2008).
10.7.8 Gold(III) Compounds

In the gold(III) halides (except the fluoride) there is evidence for the
formation of double molecules, Au2X6 so that the coordination is brought up to
four, but with a planar structure.
Figure 10.3 The structure of [AuCl4]-
Gold(III) chloride dissolves in hydrochloric acid to form tetrachlorauric

acid, HAuCl4. Here again, the gold(III) is 4-coordinate in the ion [AuCl4]-. If
alkali is added to this acid, successive replacement of chlorine atoms by hydroxyl
groups occurs, forming the unstable tetrahydroxoaurate(III) ion, [Au(OH)4]-:
[AuCl4]- [AuCl3OH]- [Au(OH)4]-
This ion is very easily reduced to gold, and hence alkaline solutions of
chloraurates(III) (often wrongly called gold chloride) are used with a reducing
agent to prepare colloidal gold. Other than the fluoride, no compounds of gold(III)
are known in which gold acts as a metal ion, i.e. there are no gold(III) salts.
Thereare, however, numerous complexes of gold(III) which are 4-coordinate, for
example the compound diethyl gold(III) sulphate [(C2H5)2Au]2SO4.4H2O, which
has the structure:
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Figure 10.4 Structure of [(C2H5)2Au]2SO4.4H2O

10.7.9 Electronic Spectra and Magnetic Properties of Copper (II)
Because the d9 configuration can be thought of as an inversion of dl,
relatively simple spectra might be expected, and it is indeed true that the great
majority of CuII compounds are blue or green because of a single broad absorption
band in the region 11000-16000cm-1. However, as already noted, the d9 ion is
characterized by large distortions from octahedral symmetry and the band is
unsymmetrical, being the result of a number of transitions which are by no means
easy to assign unambiguously. The free-ion 2D ground term is expected to split in
a crystal field in the same way as the 5D term of the d4 ion and a similar
interpretation of the spectra is likewise expected. Unfortunately this is now more
difficult because of the greater overlapping of bands which occurs in the case of
Cu.
In practice, moments of magnetically dilute compounds are in the range
1.9-2.2BM, with compounds whose geometry approaches octahedral having
moments at the lower end, and those with geometries approaching tetrahedral
having moments at the higher end, but their measurements cannot be used
diagnostically with safety unless supported by other evidence.
10.8 SUMMARY
Based on the explanation above, copper, silver, and gold elements and
compounds are largely use in our daily life. The precious metals have high
melting and boiling point. The metals can have more than one oxidation number
and show paramagnetic properties. Although they are commonly inert, they can
form complex ions. There are several method to isolation and purification of
copper, silver and gold. Those metals are good conductor. But copper is more
commonly used than gold and silver, because copper is cheaper than gold and
silver.
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STUDY QUESTIONS
10.1 Explain the brief history of finding the element of copper, silver and gold!
10.2 Explain the natural abundance and distribution of the compounds of copper,
silver and gold in the earth’s crust!
10.3 Explain the isolation methods, properties and uses of copper, silver and
gold!
10.4 Explain the superior properties of copper, silver and gold!
10.5 Explain the properties of oxides and chalconides of copper, silver and gold!
10.6 Explain the properties of high superconductor of copper, silver and gold!
10.7 Explain the properties of halides copper, silver and gold!
10.8 Explain the rules of respective copper, silver, and gold compounds in
photography!
10.9 Explain the properties of the complex compounds of copper, silver and gold
with oxidation number of III, II and I!
10.10 Explain the electronic spectra and magnetic properties of the complex
compound of copper (II)!
10.11 Explain the properties of cluster compounds of gold!
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CHAPTER 11
ZINC, CADMIUM AND MERCURY
11.1 INTRODUCTION
Zinc, cadmium and mercury are three elements that belong to transition
metal group of elements. Both of them are placed in II B group in periodic table of
elements. Generally, Zinc is Chemical element with symbol Zn and has atomic
number 30. Cadmium is a chemical element with symbol Cd and has atomic
number 48. Mercury is a chemical element with symbol Hg and has atomic
number 80.
This is to explain the nature of zinc, cadmium and mercury including their
history and existences, abundance, elemental properties and uses, their
compounds and complexes.
11.2 HISTORY
Zinc appeared since along-long time ago, approximately in present in
samples of early Egyptian copper no doubt simply reflect the composition of local
ores, but Palestinian brass dated 1400 – 1000 BC and containing about 23% Zn
must have been produced by the deliberate mixing of copper and zinc ores. The
origin of the name is obscure but may plausibly be thought to be derived from
Zinke (German for spike, or tooth) because of the appearance of the metal. The
second one, Cadmium start itself existence in 1817 when F. Stromeyer of
Gottingen noticed that a sample of “cadmia” (now known as “calamine”), used in
a nearby smelting works, was yellow instead of white. Mercury, more easily
isolated from its ore, cinnabar, and was used in the Mediterranean world for
extracting metals by amalgamation as early as 500 BC, possibly even earlier.
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Cinnabar, HgS, was widely used in the ancient world as a pigment (vermilion).
For over a thousand years, up to AD 1500, alchemists regarded the metal as a key
to the transmutation of base metals to gold and employed amalgams both for
gilding and for producing imitation gold and silver. Because of its mobility,
mercury is named after the messenger of the gods in Roman mythology, and the
symbol, Hg, is derived from hydrargyrum (Latin, liquid silver).

Zinc, cadmium and mercury exist in forms of their ores or minerals. Zinc
abundance is around 78 ppm, majorly exists in form of ZnS (which is known as
zinc blende in Europe and as sphalerite in the USA) and ZnCO3 (calamine in
Europe, smithsonite in the USA). Cadmium abundance is around 0,16 ppm,
majorly exist in form of greenockite, CdS, but its only commercially important
source is the 0.2-0.4% found in most zinc ores. Mercury abundance is around 0,08
ppm, majorly exist in form of Cinnabar, HgS, is the only important ore and
source of mercury and is found along lines of previous volcanic activity.
11.4 ISOLATION
The existence of zinc, cadmium and mercury as ores force the experts find
way to isolate the pure of them to use in another things. Zinc is isolated from its
sulfides ore. The sulfide ore is roasted until its produce the oxides, ZnO. The ZnO,
is then either treated electrolytically or smelted with coke. In the former case the
zinc is leached from the crude ZnO with dilute H2SO4, at which point cadmium is
precipitated by the addition of zinc dust. The ZnSO4 solution is then electrolyzed
and the metal deposited - in a state of 99.95% purity - on to aluminum cathodes. A
variety of smelting processes have been employed to effect the reduction of ZnO
by coke:
ZnO + C Zn + CO
For cadmium, it is usually separated from Zn by distillation or precipitation
sulfate solutions by Zn dust (Cotton et al., 1995). World production of zinc (1995)
is about 7 million tonnes pa: of this, about 1 million tonnes pa is produced by each
of Canada and Australia and 800000 tonnes pa by China. Cadmium is produced in
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much smaller quantities (-20000 tonnes pa) and these are dependent on the supply
of zinc (Greenwood & Earnshaw, 1997).
The isolation of mercury is comparatively straightforward. The most
primitive method consisted simply of heating cinnabar in a fire of brushwood. The
latter acted as fuel and condenser, and metallic mercury collected in the ashes.
Modem techniques are of course less crude than this but the basic principle is
much the same. After being crushed and concentrated by flotation, the ore is
roasted in a current of air and the vapour condensed:
6000C
HgS + O2 →Hg + SO2
Alternatively, in the case of especially rich ores, roasting with scrap iron or
quicklime is used:
HgS + Fe→Hg + FeS
4HgS + CaO → 4Hg + 3CaS + CaSO4
Blowing air through the hot crude, liquid metal oxidizes traces of metals such as
Fe, Cu, Zn and Pb which form an easily removable scum. Further purification is
by distillation under reduced pressure. About 4000 tonnest of mercury are used
annually but only half is from primary, mine production the other half being
secondary production and sales from stockpiles

Zinc, cadmium and mercury have several properties that makes both of
them are different and special. The table below summarizes a number of
properties of these elements.
Table 11.1 Properties of Zinc, Cadmium and Mercury
Properties Zn Cd Hg
Atomic number 30 48 80
Number of naturally occurring 5 8 7
isotopes
Atomic weight 65.39(2) 112.411(8) 200.59(2)
Electronic configuration [Ar]3d104s2 [Kr]4d105s2 [Xe]
4f145d106s2
Electronegativity 1.6 1.7 1.9
Metal radius (12 coordinate)/pm 134 151 151
Effective ionic radius/pm II 74 95 102
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I - - 119
Ionization energies/kj mol- 1st 906.1 876.5 1007
2nd 1733 1631 1809
3rd 3831 3644 3300
0 2+
E (M /M)/V -0.07619 -0.4030 +0.8545
Melting point / C0 419.5 302.8 -38.9
Boiling point / C0 907 765 357
ΔH fus /kJ mol- 7.28(±0,01) 6.4(±0.2) 2.30(±0.02)
ΔH vap /kJ mol- 114.2(±1.7) 100(±2.1) 59.1(±0.4)
ΔH monoatomic gas /kJ mol- 129.3(±2.9) 111.9(±2.1) 61.3
Density (250C)/g cm-3 7.14 8.65 13.534
Electrical resistivity (200C)/ohm 5.8 7.5 95.8
Their most noticeable features compared with other metals are their low
melting and boiling points, mercury being unique as a metal which is a liquid at
room temperature. Zinc and cadmium are silvery solids with a bluish lustre when
freshly formed. Mercury is also unusual in being the only element, apart from the
noble gases, whose vapour is almost entirely monatomic, while its appreciable
vapour pressure (1.9 x 10-3 mmHg, i.e. 0.25 Pa, at 25oC), coupled with its toxicity,
make it necessary to handle it with care. The electrical resistivity of liquid
mercury is exceptionally high for a metal, and this facilitates its use as an
electrical standard (the international ohm is defined as the resistance of 14.4521 g
of Hg in a column 106.300cm long and 1mm2 cross-sectional area at 0oC and
pressure of 760 mmHg.
All of the three elements can form alloy with another metals. These
elements show few of the characteristic properties of transition metals despite
their position in the d block of the periodic table. The zinc, cadmium mercury, as
other metals have tendency to form metal ion. Commonly they are form M II ion,
therefore they form MII compounds. Here are some stereo chemistries of M II ions
of zinc, cadmium and mercury.
Table 11.2 Stereochemistry of Zinc, Cadmium and Mercury
Coord. Stereo Zn Cd Hg
nr. chemistry
2 Linear ZnEt2 CdEt2 [Hg(NH3)2]2+
3 Planar [ZnMe(NPh3)]2 [HgI3]-
T-shaped [Hg(SC6H2Bu23)2(py)]
4 Tetrahedral [Zn(H2O)4]2+, [CdCl4]2- [Hg(SCN)4]2-
[Zn(NH3)4]2+
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Planar [Zn(glycinyl)2]
5 Triagonal [Zn(terpy)Cl2] [CdCl5]3- [Hg(terpy)Cl2]
bipyramidal
Square [Zn(S2CNEt2)2]2 [Cd(S2CNEt2)2 [Hg{N(C2H4Nme2)3}I]+
pyramidal ]2
6 Octahedral [Zn(en)3]2+ [Cd(NH3)6]2+ [Hg(C2H5NO)6]2+
7 Pentagonal [Zn(H2dapp)(H2 [Cd(quin)2(NO
bipyramidal O)2]2+ 3)2H2O]
2+
8 Distorted [Zn(NO3)4]2-
dodecahedral
Distorted [Hg(NO2)4]2-
square
antiprismatic
Zinc finds a wide range of uses. The most important, nearly 50% of the
total production in the worldwide is used for galvanizing to protect steel from
corrosion (Glinde et al., 2011). Other word, it can be said as an anti-corrosion
coating. This used occur due to the zinc properties. Zinc is resistant to corrosion.
Due to some special reactions with the air (first with oxygen then with CO2) zinc
can create a very special protective layer around its surface. (Almost like
aluminium). And because zinc creates this protective layer extremely fast, and
because this layer is virtually "air-tight" there is no time for the metal to "rust" and
the "rusting" of zinc stops almost instantaneously.
The major uses of cadmium are in batteries (67%), in the form of nickel
cadmium batteries (Ni-Cd batteries) (US Labor, 1992). Metallic cadmium is used
as anode in the batteries, while the nickel is used as cathode. This battery woks
with normal anode and cathode principles, similar to how all batteries work. A
nickel cadmium battery converts chemical energy to electrical energy upon
discharge and converts electrical energy back to chemical energy upon recharge.
In a fully discharged Ni-Cd battery, the cathode contains nickel hydroxide
[Ni(OH)2] and cadmium hydroxide [Cd(OH)2] in the anode. When the battery is
charged, the chemical composition of the cathode is transformed and the nickel
hydroxide changes to nickel oxy hydroxide [NiO(OH)]. In the anode, cadmium
hydroxide is transformed to cadmium. As the battery is discharged, the process is
reversed, as shown in the following formula.
Cd + 2H2O + 2NiOOH —> 2Ni(OH)2 + Cd(OH)2
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The major use of mercury is in extraction of gold. Since at least the time of
the ancient Romans, mercury has been used in the mining of gold and silver.
Precious metals are usually found in nature among sand and mud and mixed with
other nonmetallic elements like sulfur, a problematic condition for miners to
which mercury literally was the solution. Gold dissolves in mercury in a way not
dissimilar to the way salt dissolves in water. Thus, miners could submerge their
ore in mercury, roasting with which would take on the gold but not the other
impurities. This mercury amalgam could then be recollected and heated until the
mercury boiled away. A simple still like those used in alcohol production would
draw away the vaporized mercury, possibly collecting it for reuse, with relatively
pure gold remaining behind. Though the gold would have to be refined later for
even greater purity and minting, the amalgamation with mercury allowed the
efficient extraction of gold from low-yield ores that were not economical by other
means.
11.6 COMPOUNDS OF ZINC, CADMIUM, AND MERCURY

Zinc, cadmium and mercury are difficult to find in pure element. They are
mostly found in form of minerals, in other words, they are mostly found in form
of compounds. There are many compounds of zinc, cadmium and mercury. Some
of them are oxides and chalconides, halides and the cluster compound of mercury.
11.6.1 Oxides
Firstly, it will be explained about oxides. The normal oxide, formed by
each of the elements of this group, is MO, and peroxides MO2 are known for Zn
and Cd. Reported lower oxides, M2O, are apparently mixtures of the metal and
MO. ZnO is by far the most important manufactured compound of zinc and, being
an inevitable byproduct of primitive production of brass, has been known longer
than the metal itself. It is manufactured by burning in air the zinc vapour obtained
on smelting the ore or, for a purer and whiter product, the vapour obtained from
previously refined zinc. It is normally a white, finely divided material with the
wurtzite structure. The major industrial use of ZnO is in the production of rubber
where it shortens the time of vulcanization. As a pigment in the production of
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paints it has the advantage over the traditional “white lead” (basic lead carbonate)
that it is nontoxic and is not discoloured by sulfur compounds, but it has the
disadvantage compared to TiO2 of a lower refractive index and so a reduced
“hiding power”. It improves the chemical durability of glass and so is used in the
production of special glasses, enamels and glazes. Another important use is in
antacid cosmetic pastes and pharmaceuticals. In the chemical industry it is the
usual starting material for other zinc chemicals of which the soaps (i.e. salts of
fatty acids, such as Zn stearate, palmitate, etc.) are the most important, being used
as paint driers, stabilizers in plastics, and as fungicides. ZnO is amphoteric,
dissolving in acids to form salts and in alkalis to form zincates, such as
[Zn(OH)3]- and [Zn(OH)4]2-. The gelatinous, white precipitate obtained by adding
alkali to aqueous solutions of ZnII salts is Zn(OH)2 which, like ZnO, is
amphoteric.
The oxide of cadmium, CdO is produced from the elements and,
depending on its thermal history, may be greenish-yellow, brown, red or nearly
black. This is partly due to particle size but more importantly, as with ZnO, is a
result of lattice defects – this time in an NaCl lattice. It is more basic than ZnO,
dissolving readily in acids but hardly at all in alkalis.
HgO exists in a red and a yellow variety. The former is obtained by
pyrolysis of Hg(NO3)2 or by heating the metal in O2 at about 350°C; the latter by
cold methods such as precipitation from aqueous solutions of HgII by addition of
alkali (Hg(OH)2 is not known). The difference in colour is entirely due to particle
size, both forms having the same structure which consists of zigzag chains of
virtually linear O-Hg-O units with Hg-O 205 pm and angle Hg-O-Hg 1070. The
shortest Hg-O distance between chains is 282 pm.
11.6.2 Chalconides
The chalconides, firstly, zinc blende, ZnS, is the most widespread ore of
zinc and the main source of the metal, but ZnS is also known in a second naturally
occurring though much rarer form, wurtzite, which is the more stable at high
temperatures. The names of these minerals are now also used as the names of their
crystal structures which are important structure types found in many other AB
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compounds. In both structures each Zn is tetrahedrally coordinated by 4 S and

each S is tetrahedrally coordinated by 4 Zn; the structures differ significantly only
in the type of close-packing involved, being cubic in zinc-blende and hexagonal in
wurtzite.
Figure 11.1 Crystal structures of ZnS. (a) Zinc blende, consisting of two,
interpenetrating, ccp lattices of Zn and S atoms displaced with respect to each
other so that the atoms of each achieve 4-coordination (Zn-S = 235 pm) by
occupying tetrahedral sites of the other lattice. (b) Wurtzite. As with zinc blende,
tetrahedral coordination of both Zn and S is achieved (Zn-S = 236pm) but this
time the interpenetrating lattices are hexagonal, rather than cubic, close-packed.
The picture is taken from Greenwood & Earnshaw, 1997.
Pure ZnS is white and, like ZnO, finds use as a pigment for which purpose it is
often obtained (as “lithopone”) along with BaSO4 from aqueous solution of
ZnSO4 and BaS:
ZnSO4 + BaS→ZnS + BaSO4
Chalcogenides of Cd are similar to those of Zn and display the same
duality in their structures. The sulfide and selenide are more stable in the
hexagonal form whereas the telluride is more in the cubic form. CdS is the most
important compound of cadmium and, by addition of CdSe, ZnS, HgS, etc., it
yields themally stable pigments of brilliant colours from pale yellow to deep red,
while colloidal dispersions are used to colour transparent glasses. CdS and CdSe
are also useful phosphors. CdTe is a semiconductor used as a detector for X-rays
and γ-rays,(10) and mercury cadmium telluride(11) has found widespread
(particularly military) use as an ir detector for thermal imaging.
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HgS is polymorphic. The red α-form is then mineral cinnabar, or

vermilion, which has a distorted rock-salt structure and can be prepared from the
elements. β-HgS is the rare, black, mineral metacinnabar which has the zinc-
blende structure and is converted by heat to the stable α-form. In the laboratory
the most familiar form is the highly insoluble black precipitate obtained by the
action of H2S on aqueous solutions of HgII. HgS is an unreactive substance, being
attacked only by conc HBr, HI or aqua regia. HgSe and HgTe are easily obtained
from the elements and have the zinc-blende structure.
11.6.3 Halides
The other compouds of zinc, cadmium and mercury are halides. The
known halides are listed in table below.
Table 11.3 Zinc, Cadmium and Mercury Halides
Fluorides Chlorides Bromides Iodides
ZnF2 ZnCl2 ZnBr2 ZnI2
White White White White
(8720, 15000) (2750, 7560) (3940, 7020) (4460,d > 7000)
CdF2 CdCl2 CdBr2 CdI2
White White Pale yellow White
(10490, 17480) (5860, 9800) (5660, 8630) (3880 , 7870)
HgF2 HgCl2 HgBr2 HgI2
White White White (  red, β yellow
(d > 6450) (2800, 3030) 2380, 3180) (2570 , 3510)
Hg2F2 Hg2Cl2 Hg2Br2 Hg2I2
Yellow White White yellow
(d > 5700) (subl 3830) (subl 3450) (subl 1400)
All 12 dihalides are known and in addition there are 4 halides of Hg22+
which are conveniently considered separately. It is immediately obvious that the
difluorides are distinct from the other dihalides, their mps and bps being much
higher, suggesting a predominantly ionic character, as also indicated by their
typically ionic three-dimensional structures (ZnF2, 6:3 rutile; CdF2 and HgF2, 8:4
fluorite). ZnF2 and CdF2, like the alkaline earth fluorides, have high lattice
energies and are only sparingly soluble in water, while HgF2 is hydrolyzed to
HgO and HF. The anhydrous difluorides can be prepared by the action of HF (in
the case of Zn) or F2 (Cd and Hg) on the metal.
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The other halides of ZnII and CdII are in general hygroscopic and very
soluble in water (~400g per 100cm3 for ZnX2 and ~100g per 100 cm3 for CdX2).
This is at least partly because of the formation of complex ions in solution, and
the anhydous forms are best prepared by the dry methods of treating the heated
metals with HCI, Br2 or I2 as appropriate. Aqueous preparative methods yield
hydrates of which several are known. Significant covalent character is revealed by
their comparatively low mps, their solubilities in ethanol, acetone and other
organic solvents, and by their layer-lattice (2D) crystal structures. In all cases
these may be regarded as close-packed lattices of halides ions in which the ZnII
ions occupy tetrahedral, and the CdII ions octahedral, sites. The structures of
CdCl2 (CdBr2 is similar) and CdI2 are of importance since they are typical of MX2
compounds in which marked polarization effects are expected. Electron
diffraction studies show that ZnX2 (X= C1, Br, I) have linear X-Zn-X structures in
the gas phase.
Concentrated, aqueous solutions of ZnCl2 dissolve starch, cellulose (and
therefore cannot be filtered through paper), and silk. Commercially ZnCl2 is one of
the important compounds of zinc. It has applications in textile processing and,
because when fused it readily dissolves other oxides, it is used in a number of
metallurgical fluxes as well as in the manufacture of magnesia cements in dental
fillings. Cadmium halides are used in the preparation of electroplating baths and in
the production of pigments.
The halides are the most familiar compounds of mercury(I) and all contain
the Hg22+ ion (see below). Hg2F2 is obtained by treating Hg2CO3 (itself
precipitated by NaHCO3 from aqueous Hg2(NO3)2 which in turn is obtained by the
action of dil HNO3 on an excess of metallic mercury) with aqueous HF. It
dissolves in water but is at once hydrolysed to the “black oxide” which is actually
a mixture of Hg and HgO. On heating, it disproportionates to the metal and HgF2.
The other halides are virtually insoluble in water and so, being free from the
possibility of hydrolysis, may be precipitated from aqueous solutions of
Hg2(NO3)2 by addition of X- Alternatively, they may be prepared by treatment of
HgX2 with the metal. Hg2Cl2 and Hg2Br2 are easily volatilized and their vapour
densities correspond to “monomeric HgX”. However, the diamagnetism of the
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vapour (Hg in HgX would be paramagnetic) and the ultraviolet absorption at the
wavelength (253.7 nm) characteristic of Hg vapour, make it clear that
decomposition to Hg +HgX2 is the real reason for the halved vapour density.
Hg2I2 decomposes similarly but even more readily, and the presence of finely
divided metal is thought to be the cause of the greenish tints commonly found in
samples of this otherwise yellow solid.
Calomel, Hg2Cl2, has been widely used medicinally but possible
contamination by the more soluble and poisonous HgCl2 renders this a hazardous
nostrum.
11.6.4 Monovalent and Divalent Compounds

Firstly, it will be explained about mercury first. Mercury(I) compounds in
general may be prepared, like the halides just discussed, by the reduction of the
corresponding HgII salt, often by the metal itself, or by precipitation from
aqueous solutions of the nitrate. The nitrate is known as the dihydrate,
Hg2(NO3)2.2H2O, and is stable in water if this is acidified, otherwise basic salts
such as Hg(OH)(NO3) and Hg2(OH)(NO3) are precipitated. The perchlorate is the
only other appreciably soluble salt, the rest being either insoluble or, like the
sulfate, chlorate and salts of organic acids, only sparingly soluble. In all cases the
dinuclear Hg22+ ion is present rather than mononuclear Hg+. It is proven by some
reasons:
(1) In crystalline mercury(I) compounds, instead of the sequence of alternate
M+ and X- expected for MX compounds, Hg-Hg pairs are found in which
the separation, though not constant, lies in the range 250-270 pm which is
shorter than the Hg-Hg separation of 300 pm found in the metal itself.
(2) The Raman spectrum of aqueous mercury(I) nitrate has, in addition to lines
characteristic of the NO3- ion, a strong absorption at 171.7 cm-1 which is not
found in the spectra of other metal nitrates and is not active in the infrared;
it is therefore diagnostic of the Hg-Hg stretching vibration since
homonuclear diatomic vibrations are Raman active not infrared
active.Similar data have subsequently been produced for a number of other
compounds in the solid state and in solution.
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(3) Mercury(I) compounds are diamagnetic, whereas the monatomic Hg+ ion
would have a d10s1 configuration and so be paramagnetic.
(4) The measured emfs of concentration cells of mercury(I) salts are only
explicable on the assumption that a 2-electron transfer is involved. This
would not be the case if Hg+ were involved: [E = (2.303RT/n F ) log a1/a2
where n = 2 for Hg22+ and n = 1 for Hg+].
(5) It is found that "equilibrium constants" are in fact only constant if the
concentration [Hg22+] is employed rather than [Hg+]2, i.e. the equilibria must
be of the type:
2Hg + 2Ag+ Hg22+ + 2Ag
(rather than Hg + Ag+ Hg+ + Ag)
Or
Hg + Hg2+ Hg22+
(rather than Hg + Hg2+ 2Hg+)
In order to understand the formation and stability of mercury(I)
compounds it is helpful to consider the relevant reduction potentials:
Hg22+ + 2e- 2Hg( 1); Eo + 0.7889 V
and 2Hg2+ + 2e- Hg22+; Eo + 0.920V
From this it follows that
Hg2+ + 2e- Hg(1); Eo + 0.8545 V
and
Hg22+ Hg(1) + Hg2+; EO - 0.131 V
Now,
EO = (RT/nF) In K , i.e. EO = (0.0591/n)1og10K
Hence,
log10K = -(0.131/0.0591) = -2.217, i.e.
K = [ Hg 2+ ] / [ Hg22+] =0.006 1
Special for mercury, it will be discussed about Hg(II)-N and Hg(II)-S. The
Hg(II)-N, Mercury has a characteristic ability to form not only conventional
ammine and amine complexes but also, by the displacement of hydrogen, direct
covalent bonds to nitrogen, e.g.:
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Thus in the presence of an excess of NH4+, which suppresses this forward

reaction, and counteranions such as NO3- and CIO4-, which have little tendency to
coordinate, complexes such as [Hg(NH3)4]2+, [Hg(L-L)2]2+ and even [Hg(L-L)3]2+
(L-L = en, bipy, phen) can be prepared. But, in the absence of such precautions,
amino, or imino-compounds are likely to be formed, often together. Because of
this variety of simultaneous reactions and their dependence on the precise
conditions, many reactions between HgII and amines, although first performed by
alchemists in the middle ages, remained obscure until the application of X-ray
crystallography and, still more recently, spectroscopic techniques such as NMR,
infrared and Raman.
The action of aqueous ammonia on HgCl2, for instance, may be described
by the three reactions:
In general, all these products are obtained in proportions which depend on

the concentrations of NH3 and NH4+ and on the temperature, but more or less pure
products can be prepared by suitably adjusting the conditions. The di ammine
[Hg(NH3)2C12], descriptively known as “fusible white precipitate”, can be
isolated by maintaining a high concentration of NH4+, since reactions (2) and (3)
are thereby inhibited, or better still by using non-polar solvents. It is made up of a
cubic lattice of C1- ions with linear H3N-Hg-NH3 groups inserted so as to give the
common, distorted octahedral coordination about HgII (Hg-N = 203 pm, Hg-C1=
287 pm) figure below.
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Figure 11.2 (a) Crystal structure of Hg(NH3)2CI2 showing linear NH3-Hg-NH3 groups
inside a lattice of chloride ions. (b) Central Hg7S12Br2 core of [Hg7(SC6H11)12Br2] The
picture is taken from Greenwood & Earnshaw, 1997.
By using a low concentration of NH3 and with no NH4+ initially present,

the amide [Hg(NH2)Cl], “infusible white precipitate” is obtained. This consists of
parallel chains of {Hg(NH2)} as above, separated by C1- ions.
[Hg2NCI(H2O)] is the chloride of Millon's base, [Hg2N(OH).(H2O)2], and
can be obtained either by heating the diammine, or amide with water or, better
still, by the action of hydrochloric acid on Millon's base which is best prepared by
the method, used in 1845 by its discoverer, of warming yellow HgO with aqueous
NH3. Replacement of the OH- yields a series of salts, [Hg2NX(H2O)], the
structures of which (and that of the base itself) consist, with only minor variations,
of a network of {Hg2N}+ units linked so that each N is tetrahedrally linked to 4
Hg and each Hg is linearly linked to 2 N (Hg-N = 204-209pm depending on X).
The X- ions and water molecules are accommodated interstitially and these
materials behave as anion exchangers.
When Hg2C12 is treated with aqueous NH3 disproportionation occurs
(Hg2C12 → HgCl2 + Hg); the HgC12 then reacts as outlined above to give a
precipitate of variable composition. The liberated mercury, however, renders the
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precipitate black, as previously mentioned, and so forms the basis of a distinctive

qualitative test for Hg22+.
The next, mercury has compounds group consist of HgII –S. As indicated
by the insolubility and inertness of HgS, HgII has a great affinity for sulfur. HgO
reacts vigorously with mercaptans (which is why RSH were givet of n the name
mercaptans), displacing the H as with amines:
HgO + 2RSH  Hg(SR)2 + H2O
These mercaptides are low-melting solids, soluble in CHC13 and C6H6.
Though their structures depend on R and some, such as Hg(SR)2, (R =But Ph) are
polymers containing tetrahedral HgS4 units, most contain linear (or nearly linear)
S-Hg-S. Even in [Hg(SC6H2But3)2(py)] where the Hg is 3-coordinate and T-
shaped the S-Hg-S is still nearly linear (172o). Most of the thioether (SR2)
complexes which have been prepared are adducts of the Hg II halides and include
both monomeric and polymeric (i.e. X-bridged) species as is the case with mixed
thiolate-halide complexes. In [Hg7(SC6H11)12Br2], which is obtained as colourless
crystals when methanolic solutions of HgBr2 and sodium cyclohexanethiolate are
mixed, six Hg atoms are 4- coordinate but contain almost linear S-Hg-S (av.
angle = 159.3O) and the seventh Hg is tetrahedrally coordinated. The six Hg atoms
form a distorted octahedron around a central Br The dithiocarbamate
[Hg(S2CNEt2)2] exists in two forms, one of which has the same structure as the
corresponding ZnII and CdII compounds (while the other is polymeric).
Another special compounds of mercury is mercury cluster compounds.
Cluster means mercury has a marked ability to bond to other metals. In addition to
the amalgams already mentioned it acts as a versatile structural building block by
forming Hg-M bonds with cluster fragments of various types: e.g. reduction of
[RhCl(PMe3)3] with Na amalgams gives Hgs[Rh(PMe3)3]4 which consists of an
Hg6 octahedron, four faces of which are capped by Rh(PMe3)3 groups. Again, HgII
halides react with carbonylate anions yielding products such as [Os3(CO)IIHg]3
comprising a most unusual “raft” structure in which three Os3 triangles surround a
central Hg3 triangle in a planar array. From [Os10C(CO)24]2- it is possible to obtain
[Os20Hg(C)2(CO)48]2- the central portion of which is an HgOs2 triangle. Whereas
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the “raft” cluster has no redox chemistry, the {Os20Hg} cluster like the Osl0
cluster from which it is formed, gives rise to five different redox states.
Table 11.3 Comparison of Some Typical Organometallic Compounds MR2
Zn Cd Hg
o o o o o
R MP/ C BP/ C MP/ C BP/ C MP/ C BP/oC
Me -29.2 46 -4.5 105,5 - 92.5
Et -28 117 -21 64 - 159
(19 mmHg)
Ph 107 d 280 173 - 121.8 204
(subl) (10 mmHg)
After knowing all about the metallic and its compounds, the other most
important thing is the effect of human health. It is a remarkable contrast that,
whereas Zn is biologically one of the most important metals and is apparently
necessary to all forms of life, Cd and Hg have no known beneficial biological role
and are amongst the most toxic of elements.
The body of an adult human contains about 2g Of Zn but' has Zn enzymes
are present in most body cells, its concentration is very low and realization
of its importance was therefore delayed. The two Zn enzymes which have
received most attention are carboxypeptidase A and carbonic anhydrase.
Carboxypeptidase A catalyses the hydrolysis of the terminal peptide bond
in proteins during the process of digestion:
Figure 11.3 Catalyses the hydrolysis of the terminal peptide bond in proteins
during the process of digestion. The picture is taken from Greenwood &
Earnshaw, 1997)
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It has a molecular weight of about 34.000 and contains one Zn

tetrahedrally coordinated to two histidine N atoms, a carboxyl O of a glutamate
residue, and a water molecule. The precise mechanism of its action is not finally
settled in spite of the intensive study of model systems, but it is agreed that the
first step is coordination of the terminal peptide to the Zn by its group. This
is thereby polarized, giving the C a positive charge and making it susceptible to
nucleophilic attack. This attack is probably by the -OH of the attached water
molecule, followed by proton-rearrangement and breaking of the C-N peptide
bond, though alternative such as attack by the carboxyl group of a second
glutamate residue in the enzyme have also been considered. In any event it is
evident that the conformation of the enzyme provides a hydrophobic pocket, close
to the Zn, which accommodates the non-polar side-chain of the protein being
hydrolysed, and that this protein is, throughout, held in the correct position by H
bonding to appropriate groups in the enzyme.
Carbonic anhydrase was the first Zn metalloenzyme to be discovered
(1940) and in its several forms is widely distributed in plants and animals. It
catalyses the equilibrium reaction :
In mammalian erythrocytes (red blood-cells) the forward (hydration)

reaction occurs during the uptake of CO2 by blood in tissue, while the backward
(dehydration) reaction takes place when the CO2 is subsequently released in the
lungs. The enzyme increases the rates of these reactions by a factor of about one
million.
The molecular weight of the enzyme is about 30.000 and the roughly
spherical molecule contains just one zinc atom situated in a deep protein pocket,
which also contains a number of water molecules arranged in an ice-like order.
This Zn is coordinated tetrahedrally to 3 imidazole nitrogen atoms of histidine
residues and to a water molecule. Once again the precise details of the enzyme’s
action are not settled, but it seems probable that the coordinated H2O ionizes to
give Zn-OH- and the nucleophilic OH- then interacts with the C of CO2 (which
may be held in the correct position by H bonds to its two oxygen atoms) to yield
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HCO3-. This is equivalent to replacing the slow hydration of CO2 with H2O, by the
fast reaction:
The latter would normally require a high pH and the contribution of the
enzyme is therefore presumed to be the provision of a suitable environment,
within the protein pocket, which allows the dissociation of the coordinated H20 to
occur in a medium of pH 7 which would otherwise be much too low.
A more recently established function of zinc is in proteins responsible for
recognizing basesequences in DNA and so regulating the transfer of genetic
information during the replication of DNA. These so-called “zinc-finger’’ proteins
contain 9 or 10 Zn2+ ions each of which, by coordinating to 4 amino acids,
stabilizes a protruding fold (finger) in the protein. The protein wraps around the
double strand of DNA, each of the fingers binding to the DNA, their spacing
matching the base sequence in the DNA and thus ensuring accurate recognition.
Cadmium is extremely toxic and accumulates in humans mainly in the
kidneys and liver; prolonged intake, even of very small amounts, leads to
dysfunction of the kidneys. It acts by binding to the -SH group of cysteine
residues in proteins and so inhibits SH enzymes. It can also inhibit the action of
zinc enzymes by displacing the zinc.
The toxic effects of mercury have long been known, and the use of HgC12
as a poison has already been mentioned. The use of mercury salts in the
production of felt for hats and the dust generated in ill ventilated workshops by
the subsequent drying process, led to the nervous disorder known as “hatter’s
shakes” and possibly also to the expression “mad as a hatter”. The metal itself,
having an appreciable vapour pressure, is also toxic, and produces headaches,
tremors, inflammation of the bladder and loss of memory. The best documented
case is that of Alfred Stock whose constant use of mercury in the vacuum lines
employed in his studies of boron and silicon hydrides, caused him to suffer for
many years. The cause was eventually recognized and it is largely due to Stock’s
publication in 1926 of details of his experiences that the need for care and
adequate ventilation is now fully appreciated.
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Still more dangerous than metallic mercury or inorganic mercury

compounds are organomercury compounds of which the methyl mercury ion
HgMe+ is probably the most ubiquitous. This and other organomercurials are
more readily absorbed in the gastrointestinal tract than HgII salts because of their
greater ability to permeate biomembranes. They concentrate in the blood and have
a more immediate and permanent effect on the brain and central nervous system,
no doubt acting by binding to the -SH groups in proteins. Naturally occurring
anaerobic bacteria in the sediments of sea or lake floors are able to methylate
inorganic mercury (Co-Me groups in vitamin Bl2 are able to transfer the Me to
HgII) which is then concentrated in plankton and so enters the fish food chain.
The Minamata disaster in Japan, when 52 people died in 1952, occurred
because fish, which formed the staple diet of the small fishing community,
contained abnormally high concentrations of mercury in the form of MeHgSMe.
This was found to originate from a local chemical works where HgII salts were
used (inefficiently) to catalyse the production of acetylene from acetaldehyde, and
the effluent then discharged into the shallow sea. Evidence of a similar bacterial
production of organomercury is available from Sweden where methylation of Hg II
in the effluent from paper mills has been shown to occur. The use of
organomercurials as fungicidal seed dressings has also resulted in fatalities in
many parts of the world when the seed was subsequently eaten.
It is now apparent that bacteria have developed resistance to heavy metals
and the detoxifying process is initiated and controlled by metalloregulatory
proteins which are able selectively to recognize metal ions. MerR is a small DNA
binding protein which displays a remarkable sensitivity to Hg2+. The metal
apparently binds to S atoms of cysteine and this has been a major incentive to
recent work on Hg-S chemistry.
Public concern about mercury poisoning has led to more stringent
regulations for the use of mercury cells in the chlor-alkali industry. The health
record of this industry has, in fact, been excellent, but the added costs of
conforming to still higher standards have led manufacturers to move from
mercury cells to diaphragm cells, and this change has been made a legal
requirement in Japan.
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11.7 SUMMARY
Zinc, cadmium and mercury have many usefulness for human being. Zinc,
cadmium and mercury have very unique properties. They also have various
compounds, such as oxides, sulfides, halides, mixed oxides, oxoanions, carbides,
nitrides and complexes. Every compound has its own properties and usefulness.
So it is needed more study and research to wisely use their special and unique
properties for the the human being in the future. It is also important to know its
danger so as it can be wisely avoided.
STUDY QUESTIONS
11.1 Explain the brief history of finding the element of zinc, cadmium and
mercury!
11.2 Explain the natural abundance and distribution of the compounds of zinc,
cadmium and mercury in the earth’s crust.
11.3 Explain the isolation methods, properties and uses of zinc, cadmium and
mercury.
11.4 Explain the properties of oxides and chalconides of zinc, cadmium and
mercury.
11.5 Explain the properties of halides of zinc, cadmium and mercury.
11.6 Explain the properties of mercury (I) polycation compounds.
11.7 Explain the properties of the divalent compounds of zinc, cadmium and
mercury.
11.8 Explain the properties of Hg(II)-N and Hg(II)-S compounds.
11.9 Explain the properties of the mercury cluster compounds.
11.10 Explain the effect of zinc, cadmium, and mercury compounds on human
health and environment.
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CHAPTER 12
TIN AND LEAD
12.1 INTRODUCTION
The elements in group 14- carbon, silicon, germanium, tin, and lead. All
members of group 14 or IV A exhibit an oxidation state of +4, but +2 oxidation
state increases in stability as the group is descended.
This is to discuss two elements of this group namely tin and lead, in terms
of their finding history, natural abundances, isolation, properties, uses, and their
compounds.
12.2 HISTORY
Tin and lead have been used since ancient times (House, 2008). The
history about tin and lead will be explained briefly in this part. Tin has been
known since the Bronze Age. The Bronze Age spans the period from 2500 BC to
1500 BC. Bronze is an alloy of copper and tin was a prominent material used in
that period preceding the Iron Age. The addition of tin to bronze alloys improves
their properties compared with pure copper. The ancient Greeks obtained their tin
by sea-trade and referred to the source as 'The Cassiterides', meaning Tin Islands.
On ancient times, Robert Boyle published a description of his experiments
on the oxidation of tin in 1673. Cassiterite (SnO2), the tin oxide is formed of tin, it
was most likely the original source of tin. The name of tin comes from the Anglo-
Saxon word and the chemical symbol for tin is Sn comes from the Latin word for
tin, stannum that related to word ‘‘stagnum” (dripping), because tin melts easily.
Lead was used for thousands of years because it is widespread. Metallic
lead beads were dating back to 6400 BCE and it found in Çatalhöyük in modern-
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day Turkey. Lead was used with antimony and arsenic in the early Bronze Age.
The largest industry producer of lead was the Roman economy. Roman has
mining activities that occurred in Central Europe, Roman Britain, the Balkans,
Greece, Asia Minor; Hispania alone accounted for 40% of world production.
Lead (molten form) also used in the Romans for securing iron pins that
held together with large limestone blocks in certain monumental buildings. In
alchemy, lead was thought as the oldest metal and was associated with the planet
Saturn. Lead has symbol Pb and abbreviation of its Latin name plumbum for soft
metals originally it was plumbum nigrum (literally, "black plumbum"), where
plumbum candidum (literally, "bright plumbum") was tin.
12.3 NATURAL ABUNDANCE OF TIN AND LEAD

Next explanation is about the natural abundance and distribution of tin and
lead in the earth crush and nature. Tin is not exist as pure element in nature, so it
is extracted from various ores. In the other hand, pure lead is rare in nature. Tin is
the 49th most abundant element in the Earth's crust, representing 2 ppm compared
with 75 ppm for zinc, 50 ppm for copper, and 14 ppm for lead. Cassiterite (SnO2)
is the only commercially important source of tin, although small quantities of tin
are recovered from complex sulfides such as stannite, cylindrite, franckeite,
canfieldite, and teallite.
Sn of cassiterite, SnO2 mixed with graphite, sand and clay. It is formed as
primary tin precipitate in the granitic rocks and metamorphic sedimentary rock
contact areas are typically associated with tourmaline and quartz veins of tin, as
well as secondary sludge, which consists of alluvium deposits, eluvial, and
koluvium.
That’s the abundance of tin, next talk about lead. The most abundance of
208
lead is Pb (52.4%). Lead is the last result of natural radioactive decay and has
82 protons. This number of proton as symbol of atomic number is so important
because it is very stable number (Saito, 1996). So, Pb is the most abundance for
heavy element. Currently lead is usually found in ore with zinc, silver, copper and
it is extracted together with these metals. The main mineral of lead is Galena
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(PbS), which contains 86.6 % lead by weight. Other common varieties are
cerussite (PbCO3) and anglesite (PbSO4).
Lead is occur naturally in the environment. However, most lead
concentrations are found in the environment as a result of human activities. Due to
the application of lead in gasoline an unnatural lead-cycle has consisted. In car
engines lead is burned, so the lead salts (chlorines, bromines, and oxides) will be
formed and originated. The lead salts enter the environment through the exhausts
of cars. The larger particles will drop to the ground immediately and pollute soils
or surface waters, the smaller particles will travel long distances through air and
remain in the atmosphere. Part of this lead will fall back on earth when it is
raining. This lead-cycle which caused by human production is more extended than
the natural lead-cycle. It has caused lead pollution as worldwide issue.
12.4 ISOLATION OF TIN AND LEAD

Tin and lead can be isolated from its minerals in which tin is isolated from
cassiterite, SnO2 and lead is isolated from galena, PbS.
Tin is obtained from the tin dioxide, SnO2, by reducing it with coal as
following reaction:
SnO2 +2C  Sn + CO2
Before this treatment, the cassiterite content of the ore is increased by
removing impurities such as clay, by washing and by roasting which drives off
oxides of arsenic and sulphur. The crude tin obtained is often contaminated with
iron and other metals. Therefore, it is melted on an inclined hearth, the easily
fusible tin melts away, leaving behind the less fusible impurities. Finally, the
molten tin is stirred to bring it into intimate contact with air. Any remaining metal
impurities are thereby oxidized to form a scum ("tin dross') on the surface and this
can be skimmed off (Chambers & Holliday, 1975: 167).
In the extraction of lead, the galena (PbS) is first roasted together with
quartz in a current of air:
2 PbS +3O2  2PbO + 2SO2
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Lead(II) sulphate which formed in this process is converted to lead(II)

silicate by reaction with the quartz. The oxide produced is mixed with limestone
and coke, then heated in a blast furnace. The following reactions occur:
PbO + C  Pb + CO
PbO + CO  Pb + CO2
PbSiO3 + CaO + CO  Pb + CaSiO3 + CO2
The last equation explains the function of the limestone. An older process,
in which the ore was partially roasted, the air shut off and the temperature raised
so that excess sulphide reacted with the oxide produced to give lead, now it is not
used again.
12.5 ALLOTROPY OF TIN AND LEAD

Tin exists in three different forms of allotropes. First is Grey tin has a
diamond structure, a density of 5.75 g/cm3 and it is stable below 286 K. Second is
White tin exists as tetragonal crystals, has a density of 7.31 g/m3 and it is stable
between 286 and 434 K, the melting point of tin, 505 K. Third, rhombic tin which
has rhombic structure, it has a density of 6.56 g/cm3 (Chambers & Holliday,
1975:167).
Lead has only one form allotrope, a cubic metallic lattice. The change can
be seen from non-metal to metal in the physical structure of these elements,
occurring with increasing atomic weight of the elements carbon, silicon,
germanium, tin and lead (Chambers & Holliday, 1975:168).
Pi
Figure 12.1 White Tin, Gray tin and Lead
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12.6 PROPERTIES OF TIN AND LEAD

Tin and lead have their own characteristic to differentiate an element with
other elements in group IVA.
Tin is a silvery-white metal. It is soft, pliable and has a highly crystalline
structure. Tin is unreactive to water and oxygen, it is protected by an oxide film. It
reacts with acids and bases.
Lead is a bluish-white lustrous metal. It is very soft, highly malleable,
ductile, and a relatively poor conductor of electricity. It is very resistant to
corrosion but tarnishes upon exposure to air.
Table12.1 The physical properties of tin and lead
Property Sn Pb
Atomic number 50 82
Ground state electronic configuration [Kr] 4d105s2 5p2 [xe] 4f14 5d 106s2 6p2
Enthalpy of atomization (298 302 195
K)/ kj mol-1
Melting point mp/K 505 600
Boiling point bp/K 2533 2022
Standard enthalpy of fusion 7.0 4.8
First ionization energy, IE1/kJ mol -1 708.6 715.6

Second ionization energy IE2/kJ mol -1 1412 1450
Third ionization energy IE3/kJ mol -1 2943 3081
Fourth ionization energy IE4/kJ mol -1 3930 4083
Metallic radius, r metal /pm 158 175
Covalent radius, r cov/pm2 140 154
(Hausecrof & Sharpe, 2008)
12.7 TIN AND LEAD COMPOUNDS

12.7.1 Hydrides and Hydrohydrides
There are some compound of tin and lead in form oxide, hydride,
hydroxide, hydrohidride, and etc.
The hydride of tin and lead will be explained in this section. If the group
IVA elements are represented as E, the important hydrides are covalent or volatile
compounds that can be represented as EH4. The stability of the compounds
decreases in descending order for the series of elements Si, Ge, Sn, and Pb
(which, like PbH2 , is unstable). The names of the EH4 compounds are silane ,
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germane , stannane , and plumbane . Higher hydrides such as Si2H6 are named as
disilane and so on (James E.House, 2008).
Stannane (SnH4) is the hydride of tin. Variants of stannane can be found
as a highly toxic, gaseous, inorganic metal hydride. The molar mass of SnH4 is
122.71 gmol-1, density 5.4 g dm-3, melting point 127.15 K, boiling point 221.15 K
and it is colorless gas. The Stannane is an analogue of methane.
The reaction that occurred in producing SnH4 is:
SnCl4 + LiAlH4 SnH4 + LiCl + AlCl3

Plumbane (PbH4) is a metal hydride composed of lead and hydrogen.
Plumbane is an unstable colorless gas. Furthermore, plumbane has a tetrahedral
(Td) structure with an equilibrium distance between Pb and hydrogen of 1.73 Å.
By weight percent, the composition of plumbane is 1.91% hydrogen and 98.09%
lead. In plumbane, the formal oxidation states of hydrogen and lead are +1 and -4,
respectively, because the electronegativity of lead is higher than that of hydrogen.
The stability of metal hydrides with the formula MH4 decreases as the atomic
number of M increases. There are some properties of Plumbane, molar mass
211.23 g mol-1 and boiling point -130C (Chambers and Holliday, first publication
in1975).
12.7.2 Halides and Halides Complexes

Tin(II) chloride is a white crystalline solid with the formula SnCl2. It
forms a stable dehydrate, but aqueous solutions tend to undergo hydrolysis,
particularly if hot. The physical properties, it has molar mass of 189.60 g/mol
(anhydrous) and 225.63 g/mol (dehydrate), density 3.95 g/cm3 (anhydrous) and
2.71 g/cm3 (dehydrate), melting point 247 °C (anhydrous) and 37°C (dehydrate),
boiling point 623 °C (896 K), solubility 3.9 g/100 ml (0 °C).
Tin (II) chloride is prepared by dissolving tin in concentrated hydrochloric
acid, on cooling, the solution deposits crystals of hydrated. Tin (II) chloride,
SnCl2.2H2O (tin salt). The anhydrous chloride is prepared by heating tin in a
current of hydrogen chloride:
Sn + 2HCl  SnCl2 + H2
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The hydrated salt is decomposed by heat:

SnCl2.2H2O ⇌ Sn(OH)Cl + HCl + H2O
This reaction proceeds slowly in aqueous solution, so that the basic salt,
Sn(OH)Cl is slowly precipitated. Addition of excess hydrochloric acid gives the
acids of formula HSnCl3 and H2SnCl4. Salts of these acids are containing SnCl3-
and SnCl42- ions.
A solution of tin(II) chloride is a reducing agent. Hence it reduces:
Sn4+ (aq) + 2e-  Sn2+ (aq) E = 0.15V
Mercury (II) chloride, first to the white insoluble mercury (I) chloride and then, if
in excess, to mercury:
2HgCl2 + SnCl2  SnCl4 + Hg2Cl2
white
Hg2Cl2 + SnCl2  2Hg + SnCl4
It reduces iron (IIl) to iron (II) salts:
2Fe3+ + Sn2+  Sn4+ + 2Fe2+
This provides a method of estimating an iron(III) salt. After reduction the
iron (II) salt is titrated with manganate (VII) solution.
It reduces nitrobenzene (in the presence of hydrochloric acid) to
phenylammonium hydrochloride:
C6H5NO2 + 7HCl + SnCl2  C6H5NH2 .HCl + 2H2O +3SnCl4
It reduces phenyl diazonium chloride to phenylhydrazine hydrochloride :
[C6H5. N2]Cl + 4HCl + 2SnCl2  C6H5NH.NH2.HC1+ 2SnCl4
Tin (II) chloride is slowly oxidized in air, but keeping a piece of tin metal
in the solution prevents this (Chambers and Holliday, first publication in 1975).
The Sn atoms in SnX2- molecules have only three pairs of electrons that
surround them, so they behave as Lewis acids and react with halide ions to give
complexes.
SnX2- + X- → SnX3-
This compound is produced from the hydrolysis of tin (II) chloride. Tin
(II) chloride tend to undergo hydrolyze and aged solutions of these salts become
measurably acidic.
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Tin (IV) chloride has some properties are molar mass of 260.50 g/mol
(anhydrous) and 350.60 g/mol (penta hydrate), density 2.226 g/ml (anhydrous)
and 2.04 g/cm3 (pentahydrate), melting point -33 °C, boiling point 14.15 °C and
soluble in alcohol, benzene and toluene.
Stannic chloride is prepared by reacting metallic tin with chloride:
Sn + 2 Cl2  SnCl4
Uses of tin (IV) chloride are used as a chemical weapon in World War I,
as it formed as irritating (but non-deadly) dense smoke on contact with air: it was
substituted for a mixture of silicon tetrachloride and titanium tetrachloride near
the end of the War due to shortages of tin. It is also used in the glass container
industry for making an external coating containing tin (IV) oxide which toughens
the glass. It is a starting material for organo tin compounds. It is used in chemical
reactions with fuming (90%) nitric acid for the selective nitration of activated
aromatic rings in the presence of unactivated ones.
Lead (II) chloride (PbCl2) is an inorganic compound which is a white solid
under ambient conditions. It is poorly soluble in water. Lead (II) chloride is one of
the most important lead-based reagents. PbCl2 have some properties are has molar
mass 278.10 g/mol, density 5.85 g/cm3, melting point 501 °C, boiling point 950
°C, solubility 6.73 g/L (0 °C), 9.9 g/L (20 °C), 33.4 g/L (100 °C).
Lead(II) chloride precipitates from solution upon addition of chloride
sources (HCl, NaCl, KCl) to aqueous solutions of lead (II) compounds such as
Pb(NO3)2.
Pb(NO3)2(aq) + 2 NaCl (aq) → PbCl2(s) + 2 NaNO3 (aq)
Pb(CH3COO)2 (aq) + HCl (aq) → PbCl2(s) + 2 CH3COOH (aq)
PbCO3 + 2 HCl(aq) → PbCl2(s) + CO2(g) + H2O
Pb(NO3)2(aq) + 2 HCl(aq) → PbCl2(s) + 2 HNO3(aq)
Treatment of lead dioxide with hydrochloric acid gives lead (II) chloride
as well as chlorine gas:
PbO2 (s) + 4 HCl → PbCl2(s) + Cl2 + 2 H2O
Treatment of lead oxide with hydrochloric acid gives lead (II) chloride as
well as water
PbO (s) + 2 HCl → PbCl2(s) + H2O
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PbCl2(s) also forms by the action of chloride gas on lead metal:

Pb + Cl2 → PbCl2
Uses of lead (II) chloride are used in the synthesis of lead titanate
(PbTiO3) and barium lead titanate ceramics by cation replacement reactions:
xPbCl2(l) + BaTiO3(s) → Ba1-xPbxTiO3 + xBaCl2
PbCl2 is used in production of infrared transmitting glass, and ornamental glass
called aurene glass. Aurene glass has an iridescent surface formed by spraying
with PbCl2 and reheating under controlled conditions.
Lead (IV) chloride is formed from cold concentrated hydrochloric acid and
lead (IV) oxide as described earlier. It readily evolves chlorine by the reversible
reaction:
PbCl4 ⇄PbCl2 + C12
Hence, if chlorine is passed into a cold suspension (in hydrochloric acid) of lead
(II) chloride, lead (IV) chloride was formed.
PbCl2 dissolves in excess chloride ion as a result of the formation of a
complex ion, tetrachloroplumbate(II) ion:
PbCl2(s) + 2Cl-(aq) ⇌ [PbCl4]2-(aq)
12.7.4 Oxides
Tin (II) oxide (stannous oxide) is a compound of tin and oxygen where tin
has the oxidation state of +2. There are two forms, a stable blue-black form and a
meta stable red form. Tin (II) oxide has molar mass of 134,71 g/mole, density of
6.45 g/cm3 and melting point of 10800 C.
If a solution of a tin (II) salt is treated with a small amount of an alkali, tin
(II) hydroxide is precipitated, the reaction being represented by the equation:
Sn2+ + 2OH- Sn(OH)2
The precipitate obtained is in fact colloidal and has no definite composition.
Careful drying of the precipitate gives the anhydrous oxide, SnO, which may also
be prepared by heating tin(II) ethane dioate (oxalate):
SnC2O4  SnO + CO + CO2
Tin (II) oxide is a dark- colored powder which oxidizes spontaneously in air with
the evolution of heat to give tin (IV) oxide, SnO2:
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2SnO + O2  SnO2
It is amphoteric; it gives tin (II) salts with dilute acids and hydroxo-stannates(II)
with alkalis, for example:
SnO + 2HC1 SnCl2 + H2O
SnO + H2O + OH- ⇌ [Sn(OH)3]-
Stannate (II) ions are powerful reducing agents. Since, for tin, the stability of
oxidation state +4 is greater than that of oxidation state +2, tin(II) always has
reducing properties, but these are greater in alkaline conditions than in acid
(Chambers & Holliday, 1975).
Tin (IV) oxide is a colorless, diamagnetic solid. It is amphoteric, molar
mass 150.71g/mole, density 6.95 g/cm3, boiling point 1630 0C, melting point
1800-1900 0C and insoluble in water.
Tin (IV) oxide occurs naturally, clearly indicating its high stability. It can
be prepared either by heating tin in oxygen or by heating the hydrated oxide
obtained when metallic tin reacts with concentrated nitric acid:
Sn + 4HNO3  SnO2 + 4NO2 + 2H2O
Tin (IV) oxide is insoluble in water, but if fused with sodium hydroxide
and the mass extracted with water, sodium hexahydroxo-stannate (IV) is formed
in solution:
SnO2 + 2NaOH + 2H2O  Na2 [Sn(OH)6]
If a dilute acid is added to this solution, a white gelatinous precipitate of the
hydrated tin (IV) oxide is obtained. It was once thought that this was an acid and
several formulae were suggested. However, it now seems likely that all these are
different forms of the hydrated oxide, the differences arising from differences in
particle size and degree of hydration. When some varieties of the hydrated tin (IV)
oxide 'dissolve' in hydrochloric acid, this is really a breaking up of the particles to
form a colloidal solution a phenomenon known as peptisation (Chambers &
Holliday, 1975).
Lead (II) oxide has reddish yellow in color, molar mass 223,20 g/mole,
density 9.53 g/cm3, boiling point 1477 °C, 1750 K, 2691 °F, melting point 888°C,
1161 K, 1630°F, and have solubility 0.00504 g/100 mL
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Lead (II) oxide is the most stable oxide of lead; it exists in two crystalline
forms. One form is reddish yellow in color, with a tetragonal lattice, and is called
litharge. The other form, yellow in color, has a rather greater density and a
rhombic lattice; it is called massicot. Litharge was obtained when molten lead is
oxidized by a blast of air. B carefully heating, or by heating lead carbonate or lead
nitrate, massicot was obtained. Litharge is the stable form at room temperature,
but massicot changes very slowly to litharge under ordinary conditions.
Lead (II) oxide is the most basic oxide formed by a Group IV element. It
dissolves easily in acids to give lead (II) salts but it also dissolves slowly in alkalis
to give hydroxoplumbates (II) and must, therefore, be classed as an amphoteric
oxide, for example:
PbO + 2H+  Pb2+ + H2O
PbO + 4OH- +H2O  [Pb(OH)6]4-
Lead (II) oxide is easily reduced to the metal when heated with a reducing agent
such as hydrogen, carbon or carbon monoxide, for example:
PbO + H2 Pb + H2O
Uses of lead (II) oxide is used extensively in manufacturing of lead glasses
and ceramic glazes as well as in fine dinnerware. PbO is used in cathode ray tube
glass to block X-ray emission, but mainly in the neck and funnel because it can
cause discoloration when used in the faceplate. Strontium oxide is preferred for
the faceplate.
Lead (IV) oxide is an odorless dark-brown crystalline powder which is
nearly insoluble in water, molar mass 239.1988 g/mole, density 9.38 g/cm3,
melting point 290 °C, soluble in acetic acid and insoluble in alcohol.
Lead (IV) oxide can be prepared by the reaction of an alkaline chlorate (I)
solution on a solution of a lead (II) salt. The reaction can be considered in two
steps:
Pb2+ + 2OH- Pb(OH)2
White
The white precipitate of lead hydroxide (or hydrated lead (II) oxide) is then
oxidized by the chlorate (I) to the brown dioxide:
Pb(OH)2 + C1O-PbO2 + Cl-+ H2O
Brown
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Lead (IV) oxide is also obtained when red lead, Pb3O4 (see below), is treated with
dilute nitric acid:
Pb3O4 + 4HNO3 2Pb(NO3)2 + 2H2O + PbO2
When heated above 600 K lead (IV) oxide decomposes into the more stable lead
(II) oxide and oxygen:
2PbO2  2PbO + O2
Lead (IV) oxide is found to have a considerable oxidizing power, again indicating
that the oxidation state +2 is generally more stable for lead than oxidation state
+4. Concentrated hydrochloric acid, for example, reacts with PbO2 at room
temperature to form lead (II) chloride and chlorine:
PbO2 + 4HC1  PbCl2 + C12p + 2H2O
If this reaction is carried out at 273 K some unstable lead (IV) chloride is initially
formed. Other oxidizing reactions of lead (IV) oxide include the evolution of
oxygen when heated with concentrated sulphuric acid:
2PbO2 + 2H2SO4  2PbSO4 + 2H2O + O2
and the oxidation of sulphur to sulphur dioxide which then reacts with more
lead(IV) oxide to form lead(II) sulphate:
PbO2 + S  Pb + SO2
PbO2 + SO2  PbSO4
Lead dioxide is slightly soluble in concentrated nitric acid and concentrated
sulphuric acid, and it dissolves in fused alkalis. It therefore has amphoteric
properties, although these are not well characterized since it is relatively inert.
Uses of lead (IV) oxide are used in the production of matches,
pyrotechnics, dyes and the curing of sulfide polymers. Lead dioxide is used as
anode material in electrochemistry. The most important use of lead dioxide is as
the cathode of lead acid batteries.
12.7.5 Hydroxides
Tin (II) hydroxide, Sn(OH)2, also called stannous hydroxide is prepared by
reacting for example (CH3)3SnOH with SnCl2 in an aprotic solvent:
2Me3SnOH + SnCl2 → Sn(OH)2 + 2Me3SnCl
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It was believed that Sn(OH)2 was precipitated when a tin(II) salt is reacted
with an alkali hydroxide such as NaOH, but this product was determined
analytically to be hydrated tin(II) oxide, being either 5SnO.2H2O or 3SnO.H2O,
The structure of pure Sn(OH)2 is not known. Tin dissolves slowly in hot
concentrated alkali forming a hexahydroxostannate (IV):
Sn + 4H2O + 2OH- → [Sn(OH)6]2- + 2H2
Lead (II) hydroxide, Pb(OH)2, has molar mass of 241.21 g/mol. It has
density 7.41 g/cm3, the white amorphous powder form and the melting point is
1350C. Although it appears a fundamentally simple compound, it is doubtful if
lead hydroxide is stable as a solid phase. Lead basic carbonate (PbCO3.2Pb(OH)2)
or lead(II) oxide (PbO) is encountered in practice where lead hydroxide is
expected. This has been a subject of considerable confusion in the past.
When an alkali hydroxide is added to a solution of a lead (II) salt, then a
hydrated lead oxide PbO.XH2O (with x < 1) is obtained. Careful hydrolysis of
lead (II) acetate solution yields a crystalline product with a formula 6PbO.2H2O =
Pb6O4(OH)4. In solution, lead (II) hydroxide is a weak base, forming lead (II) ion,
Pb2+, under weakly acidic conditions. This cation hydrolyzes and under
progressively increasing alkaline conditions and forms Pb(OH)+,
Pb(OH)2(aqueous), Pb(OH)3−. Lead (II) hydroxide is usually used as stains to
enhance the electron-scattering properties of components of biological materials
examined in the electron microscope (Reynolds, 1963). Lead dissolves only very
slowly in hot concentrated sodium hydroxide and forms
hexahydroxoplumbate(II):
Pb + 4OH- + 2H2O  [Pb(OH)6]4- + H2
12.7.6 Oxyacids
Formula of metastannic acid is H2SnO3 and the molecular weight is
168.71 g/mol. A process for preparing H2SnO3 includes such steps as reaction
between Sn and nitric acid in sealed pressure reactor containing O2 to obtain the
intermediate of H2SnO3, neutralizing, washing, drying to obtain H2SnO3.
Lead (II) acetate, Pb(CH3COO)2•3H2O, a colorless or white efflorescent
monoclinic crystalline substance. It was made by treating lead (II) oxide with
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acetic acid. Like other lead compounds, it is toxic. Lead acetate is soluble in water
and glycerin. With water it forms the trihydrate, Pb(CH3COO)2.3H2O, a colorless
or white efflorescent monoclinic crystalline substance.
Uses of lead (II) acetate are the substance is used as a reagent to make
other lead compounds and as a fixative for some dyes. In low concentrations, it is
the principal active ingredient in progressive types of hair coloring dyes. Lead (II)
acetate is also used as a mordant in textile printing and dyeing, as a drier in paints
and varnishes, and in preparing other leads compounds.
12.8 SUMMARY
Tin and lead elements have been used since ancient times. They have
taken important roles in our life because of their properties. A lot of tin and lead
compounds were already developed to fullfill desire in advancing our
technologies to make our life more comfortable and more safety, namely hidrides,
hidrohydrides, halides, chalconides, oxides, hydroxides, and oxyacids.
STUDY QUESTIONS
12.1 Explain the brief history of finding the elements of tin and lead
12.2 Explain some ways in isolating the elements.
12.3 Explain the natural abundance and distribution of the compounds of tin and
lead in the earth’s crust
12.4 Explain the allotropy and structural transformation of tin and lead.
12.5 Explain the properties of the elements of tin and lead
12.6 Explain properties and reactions of the compounds of tin and lead.
12.7 Explain some preparation methods of some tin and lead compounds.
12.8 Explain some uses of some tin and lead compounds
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REFERENCES
Chamber, C & Holiday, H.K. (1975). Modern Inorganic Chemistry. Great Britain:
Butterworth & Co Publisher.
Chang, R. (2010). Chemistry Tenth Edition. New York: Mc Graw Hill Company.
Cotton, F. A., Wilkinson, G., & Gaus, P. (1995). Basic Inorganic Chemistry. New
York: John Willey & Sons.
Day, C. & Selbin, J. (1962). Theoritical Inorganic Chemistry. New York:
Reinhold Publishing Corporation
Encyclopædia Britannica. 2012. Alkaline Earth Metals. Encyclopædia Britannica
Ultimate Reference Suite. Chicago:Encyclopædia Britannica.
Enhag, P. (2004). Encyclopedia of The Elements. Sweden:Wiley VCH
Cotton, F.A, Wilkinson, G, and Gaus, P.L. (1995). Basic Inorganic Chemistry:
Third Edition. New York: John Wiley & Son
Gilinde, H., & Johan, I. (2011). Zinc and its Uses, Protective for Human and
Steels. United Kingdom: Galvanizers Association
Greenwood, N N, & Earnshaw, A. (1997). Chemistry of the Elements: Second
Edition. Great Britain: Elsevier Ltd.
Gusev, A.A., Avvakumov, E.G., Vinokurova, O.B. (2003). Synthesis of Ti4O7
Magneli Phase Using Mechanical Activation. Journal of Science of
Sintering, 35. pp 141-145.
Henriques, V. A. R. (2009). Titanium Production for Aerospace Applications.
Journal of Aerospace Technology and Management.
Housecroft, E. C. & Sharpe, A. G. (2008). Inorganic Chemistry. 3rd ed. London:
Pearson Education Limited
House, J. E. (2008). Inorganic Chemistry. Canada: Elseiver.
Johnson, G. (1972). Inorganic Chemistry of the Transition Elements Volume 2.
London: University Chemical Laboratory, Cambridge University
Knottnerus, J. (2009). Aluminium and aluminium compounds. Netherlands:
Gezondheidsraad Voorzitter
Mathers, G. (2002). The Welding of Aluminium and Its Alloys. New York : Wood
Head.
Miessler , G. L. & Tarr, D. A. (2004). Inorganic Chemistry. Third Edition.
Minnesota: Pearson.
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Ratcliff, B. et al. (2004). Chemistry: AS Level and A Level. England: Cambridge
University Press.
Saito, T. (1996). Inorganic Chemistry. Tokyo: Iwanami Shoten Publish.
US Department of Labor, Occupational Safety and Health Administration,
“Chemical Identification, Production, and Use of Cadmium,” in
Occupational Exposure to Cadmium, sec. 4, September 14, 1992, available
at
http://www.osha.gov/pls/oshaweb/owadisp.show_document?p_table=PRE
AMBLES&p_id=818
Yun, L., Matsuda, Y., Sagara, K., Hao, L., Otomitsu, T., Yoshida, H. (2012).
Fabrication and Thermoelectric Properties of Magneli Phases by Adding
Ti into TiO2. Journal of Advanced Materials Research Vols. 415-417. pp
1291-1296.
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from:http://www.amazingrust.com/Experiments/how_to/Thermite.html
223 I Wayan Karyasa

Inorganic Chemistry 2: Alkali Metal Chemistry

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Inorganic Chemistry 2: Alkali Metal Chemistry

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Inorganic Chemistry 2: Chemistry of Metal Elements

The term "alkali" (essentially the opposite of an acid) refers to a substance

basic building blocks. In 1807 he isolated potassium as potassium hydroxide

Alkali elements can be obtained by electrolysis and reduction. Lithium

The way to obtain cesium is through reduction method. Cesium can be

1.4 NATURAL ABUNDANCE

1.5 ELEMENTAL PROPERTIES

Table 1.1 Physical Properties of Alkali Metals

Dissociation enthalpy 110 74 55 49 44 -

Melting point, K 453.5 371 336 312 301.5 -

Standard enthalpy of 3.0 2.6 2.3 2.2 2.1 -

Ionization energy 520.2 495.8 418.8 403.0 375.7 -375

Metallic radius, 152 186 227 248 265 -

Standard entropy of -140 -110 -70 -70 -60 -

Standard Gibbs energy -477 -371 -300 -275 -253 -

Standard reduction -3.04 -2.71 -2.93 -2.98 -3.03 -

From the data we can see that:

group. Values of are related to energy changes accompanying the

3. In the gas phase, alkali metals are diatomic molecules.

1.6 USES OF THE ELEMENTS

Sodium metal is used in many synthesis of other metal compound, but

1.7 PROPERTIES OF ALKALI METAL COMPOUNDS

1.8 ALKALI METAL COMPOUNDS

K(s) + O2(g) → KO2(s)

2M(s)+ H2O(l) → 2MOH(aq)+ H2(g)

Figure 1.1 Uses of NaOH

Potassium hydroxide with melting point 633 K closely resembles NaOH in

The crystal structures of alkali metal hydroxides are usually complicated,

1.8.4 Salts of Oxoacids

Deposits of sodium nitrate (saltpeter) in great amount exist in Chile. This

Na2CO3(l) + xSiO2(s) → Na2O.x SiO2(l) + CO2(g)

1.8.6 Reaction with Ammonia

of metal ionization. For sodium, the ionization equation in ammonia solution is as

The influences of increasing in atomic and ionic size on physical and

Boiling point (oC) 2770 1170 1484 1380 1640

2.4 NATURAL ABUNDANCE

mixed metals carbonate dolomite as thermally decomposed to a mixture of CaO

cathode: Ba2+ + 2e- → Ba

Figure 2.1 The Chain Structure of BeCl2

Figure 2.2 The Dimer Structure of BeCl2

The lower members in Group II form essentially ionic halides, with

Figure 2.3 Tetrahedral complex ion of [Be(OH)4]2-

Source: Chambers & Holliday, 1975: 131

2.11 SALTS OF OXYACIDS

Ca(HCO3)2 (aq) + Ca(OH)2(aq) → 2CaCO3(s) + H2O(l)

3.2 HISTORY OF ALUMINIUM

3.3 NATURAL ABUNDANCE

Bayer process consist of three steps, namely extraction, precipitation, and

3.5 PROPERTIES AND USES

Table 3.2 Physical Properties of Aluminium

Aluminium is easily to burn and produce high of reaction heat. The

3.6 ALUMINIUM COMPOUNDS

3.6.2 Halides and Their Complexes

Aluminium chloride is one of compound of aluminium and chlorine.

Figure 3.2 The Structure of Al2Cl6

Al2Cl6 can dissociate became AlCl3, the reaction as follow:

2Al(s) + 3Br2(l) Al2Br6(s)

The structure of Al2Br6 The structure of Al2I6

Aluminium carbide is prepared by direct reaction of aluminium and carbon in an

An alternative reaction begins with alumina, but it is less favorable because of

oxide layer of Al2O3 in it surface; (2) Microelectronics (LSI circuits, sensor

Figure 3.3 The type of Corundum