INORGANIC CHEMISTRY PART-2-rev-print PDF
INORGANIC CHEMISTRY PART-2-rev-print PDF
INORGANIC CHEMISTRY PART-2-rev-print PDF
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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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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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1.3 ISOLATION
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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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-
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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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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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.
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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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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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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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Figure 1.2 Schematic representation of the Solvay process for the manufacture of
Na2CO3, and NaHCO3 from CaCO3, NH3 and NaCl.
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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.
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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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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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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).
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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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
Cl
Be Be
Cl
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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
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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
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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.
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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)
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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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
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Br I
Br Br I I
Al Al Al Al
Br Br I I
Br I
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
4 Al + 3 C Al4C3
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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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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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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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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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3.7 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.
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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.
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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
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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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- 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
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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
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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 - - - - -
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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
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.
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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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
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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titanium has structure octahedral and the oxygen structure is trigonal planar. It can
be seen in the figure below.
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.
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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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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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.
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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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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.
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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.
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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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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.
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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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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
NbF4 NbCl4 NbBr4 NbI4
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
NbF3 NbCl3 NbBr3 NbI3
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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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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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.
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!
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.
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.
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
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.
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.
7.8.1 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
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
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
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
Source: Greenwood & Earnshaw, 1997: 1023
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)
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
-
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!
7.2 Explain the natural abundance and distribution of the compounds of
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!
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.
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.
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.
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.
Manganese oxide that have extraction is mix with carbon and then heated, the
reaction as follow:
Mn3O4 + 4C → 3Mn + 4CO
MnO +2C → Mn + 2CO
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:
manganese (VI) oxide, MnO3; and manganese (VII) oxide, Mn2O7. Each of them
will be explained in detail below.
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
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.
8.7.7 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
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.
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
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!
8.2 Explain the natural abundance and distribution of the compounds of
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!
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
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).
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).
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.
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
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
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.
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
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.
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.
Fe3O4
FeOOH Fe2O3.4H2O
Fe(OH)2
Fe(OH)3
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
[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
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).
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
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
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.
9.17 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.
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!
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).
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.
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.
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
2Ag S 200
Ag2S
o
C
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
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)
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) + 4O22Cu2S(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) + SiO2FeSiO3
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
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).
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
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).
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
Zn2+ions will react with OH-ions to form Zn(OH)2 which is results in cell potential
of 1.5 volts.
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.
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
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.
"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:
10.8 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.
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!
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.
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).
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
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
8 Distorted [Zn(NO3)4]2-
dodecahedral
Distorted [Hg(NO2)4]2-
square
antiprismatic
Sources: Greenwood & Earnshaw, 1997
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
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.
11.6.1 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
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
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.
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)
Sources: Greenwood & Earnshaw, 1997
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.
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
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.
(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.:
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.
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)
Sources: Greenwood & Earnshaw, 1997
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)
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.
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.
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-
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.
(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.
Pi
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:
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
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:
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
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
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
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
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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