Tuesday, 10 September 2013

The chemistry of metals



METALS AND CHEMISTRY OF METALS

‘Metal’ is derived from the Greek word ‘metallon’, which directly translates to ‘mine’ or ‘quarry’. Generally, metals are usually defined as solid materials (element, compound or alloy) that are typically hard, shiny and possess features such as the ability to conduct electricity and heat, etc. the meaning of the term ‘metal’ differs for various communities. For instance, astronomers use the blanket term ‘metal’ for convenience to describe all elements other than hydrogen and helium (the main components of stars , which in turn comprise most of the visible matter in the universe) collectively. Therefore, in astronomy and physical cosmology, the metallicity of an object is the proportion of its matter made up of chemical elements other than hydrogen and helium. In addition, many elements and compounds that are not normally classified as metals become metallic under high pressure, these are known as metallic allotropes of non-metals. Many metals such as aluminium foil have a shiny silvery appearance.

Generally, all the elements in the periodic table can be classified either as metals or non-metals, based on their properties (physical and chemical). Although there is no clear-cut division between the two groups, metals show certain characteristics which distinguish them from non-metals. In this case, the metallic bracket covers semi-metals (metalloids).

Most elements are metals and currently, 91 out of the 118 total elements in the periodic table are classified as metals. On the periodic table, metals are separated from non-metals by a zig-zag line stepping through carbon, phosphorus, selenium, iodine and radon. These elements and those to the right of them are non-metals. Elements just to the left of the line may either be metals or metalloids (semi-metals). Metalloids are elements or substances that possess some metallic properties; that is, they are intermediate between metals and non-metals. Examples of such metals (metalloids) include boron and silicon.

STRUCTURE AND BONDING OF METALS

Some elementary features used to distinguish between metals and non-metals are their physical and chemical properties as well as their structure and bonding. The two former will be discussed later.

Structure may generally be defined as the shape, pattern or lattice arrangement of metals. In fact, the lattice arrangement which depends on the type of bonding between atoms or molecules is directly responsible for the structural framework of any element, compound or more generally, substance.

The atoms of metallic substances are closely positioned to the neighbouring atoms in one of two common arrangements. The first arrangement is known as body centred cubic. In this arrangement, each atom is positioned at the centre of eight others. The other is known as face centred cubic. Here, each atom is positioned in the centre of the six faces of the cube. The on-going arrangements of atoms in these structures form a crystal. Some metals adopt both structures depending on the temperature. Other types of packing structures are primitive cubic structure, the hexagonal closest packing (hcp), body centred tetragonal, etc.

Find attached, the structures of fcc and bcc
 
At room temperature, elements like Li, Na, K, Rb, Ba, V, Cr and Fe have the bcc structure. Silver exhibits fcc structure. Atoms of metals readily lose their outermost shell electron(s), resulting in a free flowing cloud of electrons within their otherwise solid arrangement. This provides the ability of metallic substances to easily transmit heat and electricity. While this flow of electrons occur, the solid characteristic of the metal is produced by electrostatic interactions between its  atom and electron cloud. This type of bond is called a metallic bond.

METALS IN NATURE

As loosely stated previously, three quarters of all known chemical elements are metals. The most abundant varieties in the earth’s crust are aluminium, iron, calcium, sodium, potassium and magnesium. The vast majority of metals found in ores (mineral bearing substances), but, a few such as copper, gold, platinum and silver frequently occur in the free state because they do not readily react with other elements.

Metals are usually crystalline solids. In most cases, they have a relatively simple crystal structure distinguished by a close packing of atoms and a high degree of symmetry. Typically, the atoms of metals contain less than half the full complement of electrons in their outermost shell. Because of these characteristic, metals tend not to form compounds with each other. They .do however combine more readily with non-metals (example, oxygen and sulphur), which generally have more than half the maximum number of valence electrons. Metals differ widely in their chemical reactivity. The most reactive include lithium, potassium, radium; whereas those of low reactivity are gold, silver, palladium and platinum. We shall make more reference to the nature of metals when we discuss the extraction of metals.

PROPERTIES/CHARACTERISTICS OF METALS

Properties of metals simply refer to the things that are common to metals. It simply entails certain factors or conditions which metals share. Properties or characteristics of metals can be sub-divided into physical and chemical properties.


Physical properties

Physical properties as the name implies refers to the properties of metals that can be easily observed by the mere human eye. They can further be explained as properties that are dependent on:
I.                    The arrangement of their atoms or molecules in crystal lattices when in the solid state; and
II.                  The bond that binds the atoms of molecules in the solid, liquid or gaseous state.
Most metals are solids at room temperature and exist as crystal lattices in which their atoms are held together by strong metallic bonds. Thus, metals have the following physical properties:

i.                    High melting and boiling points: Metals generally usually have high melting and boiling point. This means that they must attain a very high temperature before boiling or melting can occur in the case of liquids or solids respectively. It is noteworthy that helium has the lowest melting point of about -2720c and tungsten has the highest melting point of about 35000C, though it is sometimes argued to be carbon. It is also noteworthy that mercury, sodium and potassium which are all metals have relatively low melting point of -390C, 970C and 630C respectively.

ii.                  Characteristic lustre: This property of metals means that most of them are shiny solids at room temperature (except mercury which is a shiny liquid metal/element)

iii.                Malleability: This may simply be defined as the ability of solid metals to be hammered into sheets.

iv.                 Ductility: This can be defined as the ability of metals to be drawn into thin wires under stress without cleaving. This can also be referred to as plastic deformation due to atomic rearrangement. This atomic rearrangement is due to an applied force/work. This force in turn can be tensile, compressive, shear or torsion.

v.                   Sonorous: This means that they give off sound notes when hit.

vi.                 Hard but not brittle: This means that whilst they are very strong/hard materials, they are not fragile or brittle (breakable)

vii.               They have great tensile strength: This simply means that by virtue of their strong/hard nature, they can withstand relatively high tension.

viii.               Relatively high density: This means that they are usually heavy for their size. Although most metals have higher densities than most non-metals, there is wide variations in their densities, for instance, lithium has the least density, while osmium has the highest density.

ix.                 Good conductors of heat and electricity: The electrical and thermal (heat) conductivities of metals originate from the fact that their outer electrons are delocalized, that is; they easily lose their valence electrons. This situation can be visualized by seeing the atomic structure of a metal as a collection of atoms embedded in a sea of highly mobile electrons. The electrical conductivity, as well as the electron’s contribution to the heat capacity and heat conductivity of metals can be calculated from the free electron model, which does not take into account the detailed structure of the ion lattice.

x.                   Opaque: This can simply be referred to as the ability of metals not to allow the passage of light (not radioactive) through them.


CHEMICAL PROPERTIES OF METALS

Chemical properties of elements generally are dependent on the number of valence electrons present in their atomic structure. An important property that is determined by valence electron is the tendency of the atoms of an element to ionize. This ionization pattern is used to define metals and non-metals. Based on its chemical properties, metals can be defined as an element whose atoms ionize by electron loss while a non-metal is an element whose atoms ionize by electron gain.

Metals are usually inclined to form cations (positive net charge) due to electron loss, while most non-metals usually form anions (negative net charge) due to electron gain. Hydrogen, which is usually considered as a non-metal, is the only exception to this as it is usually an electron donor.

Some characteristic chemical properties of metals are as follows:

i.                    Ionization behaviour:
Based on the fact that metallic atoms have few valence electrons, they have a great tendency to ionize and form positive ions by losing electrons, that is, they are electropositive, e.g.

            Na                    Na+ (univalent) + e-
            Zn                    Zn2+(divalent)  + 2e-
            Al                     Al3+(trivalent) + 3e-

By this virtue of metals, they majorly react or form compounds with non-metals (negative ions or radicals). Some of these radicals include:

            S + 2e-                   S2-(divalent)
            Cl2 + 2e-                  2Cl-(univalent)

These negative ions enter into chemical combination with positive ions or groups to form electrovalent compounds. Those atoms with four or five valence electrons share electrons during chemical reactions to form covalent compounds.

ii.                  Reduction and oxidizing agents:
Metals are reducing agents by definition because they tend to lose/donate their electrons readily during chemical reactions. On the other hand, non-metals are oxidizing agents because they accept electrons readily during chemical reactions. Thus, in the formation of sodium, it acts as a reducing agent while oxygen (non-metal) acts as an oxidizing agent.

            2Na(s)+1/2O2(g)                   Na2+O2-(s)

iii.                Reaction with acids to liberate or displace hydrogen:
Metals which are usually more electropositive than hydrogen readily displace hydrogen ion h+ from an acid. Non-metals cannot displace the hydrogen from acids. Most generally, metals, on reaction with acids liberate hydrogen whilst forming a salt; e.g.:

Zn(s)+2H+(aq)+2Cl(aq)-                Zn2+(Cl-)2(aq)+H2(g)
Zn(g)+H2+SO42-                   Zn22++SO42-(aq)+H2(g)

Also, it is noteworthy that it is noteworthy that in some special cases, for instance, when copper reacts with dilute tetraoxosulphate(vi) acid, water is being produced (H2O); while Cu2+ and SO42- will remain in solution as the salt CuSO4

iv.                 Reaction with oxygen:

Metals are usually inclined to form cations through electron loss, reacting with oxygen in the air to form oxides over various time scales (for instance, iron rusts over years, while potassium burns in seconds). Most metals react with oxygen to form basic oxides which are usually ionic compounds. Soluble basic oxides (with the ability to dissolve in H2O) form alkalis, e.g.;

            Ca(s)+1/2O2(g)                   Ca2+O2-(s)(Calcium oxide)
            Ca2+O2-(s)+H2O(l)                     Ca2+(OH-)2(aq)

Some metals like aluminium and zinc however form amphoteric oxides. Amphoteric oxides are oxides that can act either as an acid or base. They are usually of medium electronegativity.

Example:
            4Al + 3O2               2Al2O3 (Aluminium oxide)

Other examples of oxidizing of metals include:
            4Na + O2                  2Na2O (Sodium oxide)

The transition metals (such as iron, copper, zinc and nickel) are slower to oxidize because they form passivating layer of oxide that protects the interior. Others, like palladium, platinum and gold, do not react with the atmosphere at all. Some metals form a barrier layer of oxide on their surface which cannot be penetrated by further oxygen molecules and thus retain their shiny appearance and good conductivity for many decades (like aluminium, magnesium, some steels and titanium). The oxides of metals are generally basic, as opposed to those of non-metals, which are acidic. Blatant exceptions are largely oxides with very high oxidation states, such as CrO3, Mn2O7 and OsO4, which have strictly acidic reactions.
Painting, anodizing or plating metals are good ways of preventing corrosion. However, a more reactive metal in the electrochemical series must be chosen for coating, especially when chipping of the coating is expected. Water and the two metals form an electrochemical cell, and if the coating is less reactive than the coatee, the coating actually promotes corrosion.
Non-metallic oxides are covalent compounds formed by electron sharing. The non-metallic oxides in which the non-metal exercises its maximum valency dissolve in water to give an acidic solution, due to the formation of hydrogen ions, H+. Examples include carbon(iv)oxide[CO3] and sulphur(vi)oxide[SO3]

            CO2(g) + H2O(l)                    H2CO3(aq)                      2H+(aq) + CO32+(aq)

Other non-metallic oxides are either acidic, e.g. sulphur(iv)oxide[SO2], or neutral, e.g. carbon(ii)oxide[CO]

v.                   Few metals form compounds (hydrides) with hydrogen:

When hydrogen reacts with certain metals covalently (i.e. sharing of electrons), they form compounds referred to as hydrides. But few very reactive metals force hydrogen to accept electron to form their hydrides, which are salt-like solids.

                        Na(s) + 1/2H2                                  NaH

The hydride reacts with cold water to liberate hydrogen

                        H- + H2O                OH-(aq) + H2(g)

When in molten form, these hydride of metals act as electrolytes, liberating hydrogen at the anode.

vi.                 Reactions of metals with water:

The reactions of water with metals vary for a range of metals. Some have violent reactions, while others are somewhat mild. Some examples of these reactions include:
-   Place a piece of sodium metal on the surface of tap water in a trough; it darts about on the surface of the water. But, when a piece of paper interfaces the water and sodium piece, its movement is restricted. Thus, the sodium metal melts into a silvery white ball and then bursts into a yellow flame and finally explodes with a cracking sound. The sodium metal combines vigorously with water, liberating hydrogen and forming the hydroxide and heat is given off.
2Na + 2H2O               2NaOH + H2

-   Repeating the above experiment with potassium (K), the reaction is more rapid and violent than that of sodium. The heat produced in this reaction is enough to ignite the hydrogen liberated which then burns with a lilac flame, and the molten potassium ball explodes. This reaction is dangerous.

-   If we put calcium metal on top of water in a beaker, it sinks to the bottom of the beaker, producing effervescence and liberating bubbles of gas, thus, forming calcium hydroxide which is slightly soluble in water.

Ca + H2O               Ca(OH)2 + H2

            Reaction of water (steam) on Mg, Al, Zn, Fe, Pb and Cu:
Magnesium, aluminium, zinc, iron, lead and copper on passing over steam in their red hot state, their oxides are formed and hydrogen is liberated in each case.

COMPARISON OF THE PROPERTIES OF DIFFERENT METALS

Metals differ in their ability to lose their valence electron(s) in their atoms to form positive ions. As a result, they can be arranged in a series according to their comparative tendencies to give up their valence electron(s) (i.e. according to their electropositivity). It is noteworthy that metals are reduction agents and as such are oxidized (i.e. lose electrons). The series of their arrangement by this virtue is called the replacement or electromotive or electrochemical series. Most textbooks refer to it generally as the electrochemical series. The relative position of a metal in this series indicates the chemical activity of the metal as well as the chemical properties of its compounds. A similar series is the activity series of metals.

Metals towards the beginning of the series, like caesium and lithium, are more readily oxidized than those towards the end, like silver and gold. In general, a metal will replace any other metal or hydrogen in a compound that it precedes in the series and under ordinary circumstances; it will be replaced by any metal or hydrogen that it follows. 

Find below a comprehensive tabulation, critically examining elements in the electrochemical series as well as their distinguishing properties


Find attached, the activity series of metals, to help us understand the electrochemical series in details 



EXTRACTION OF METALS     

Metals are often extracted from the earth’s crust by means of mining, resulting in ores that are relatively rich sources of the requisite elements. Ore is located by prospecting techniques, followed by the exploration and examination of deposits. Mineral sources are generally divided into surface mines, which are mined by excavation using heavy equipment, and subsurface mines.

More than 80 of the known elements are metals. They are widely distributed in the earth’s crust. The ore form in which metals exist in nature is related to its reactivity. The most reactive metals e.g. sodium and potassium, are found as chlorides or trioxocarbonate(iv)s, which are very stable compounds; the moderately reactive metals e.g. zinc and lead, are found as oxides or sulphides; while the least reactive metals like gold and silver are found in the uncombined forms of more or less definite chemical composition known as minerals. Often, these minerals are found mixed with earthly materials called ores. Generally, ores are usually concentrated and changed to oxides before extraction.

Once the ore is mined, the metals must be extracted, usually by chemical or electrolytic reduction. Pyrometallurgy uses high temperatures to convert ore into raw metals, while hydrometallurgy employs aqueous chemistry for the same purpose. The methods used depend on the metal and their contaminants. When a metal ore is an ionic compound of that metal and a non-metal, the ore must usually be smelted (heated with a reducing agent) to extract the pure metal. Many common metals, such as iron, are smelted using carbon as a reducing agent. Some metals, such as aluminium and sodium, have no commercially practical reducing agent, and are extracted using electrolysis instead. Sulfide and trioxocarbonate(iv) ores are not reduced directly to the metal but are roasted in air to convert them to oxides.

ALLOYS
An alloy is a mixture of two or more elements in which the main component is a metal. Most pure metals are either too soft, brittle or chemically reactive for practical use. Combining different ratios of metals as alloys modifies the properties of pure metals to produce desirable characteristics. The aim of making alloys is generally to make them less brittle, harder, resistant to corrosion, or have a more desirable color and luster. Of all the metallic alloys in use today, the alloys of iron (steel, stainless steel, cast iron, tool steel, alloy steel) make up the largest proportion both by quantity and commercial value. Iron alloyed with various proportions of carbon gives low, mid and high carbon steels, with increasing carbon levels reducing ductility and toughness. The addition of silicon will produce cast irons, while the addition of chromium, nickel and molybdenum to carbon steels (more than 10%) results in stainless steels.
Other significant metallic alloys are those of aluminium, titanium, copper and magnesium. Copper alloys have been known since prehistory (bronze gave the Bronze Age its name) and have many applications today, most importantly in electrical wiring. The alloys of the other three metals have been developed relatively recently; due to their chemical reactivity they require electrolytic extraction processes. The alloys of aluminium, titanium and magnesium are valued for their high strength-to-weight ratios; magnesium can also provide electromagnetic shielding. These materials are ideal for situations where high strength-to-weight ratio is more important than material cost, such as in aerospace and some automotive applications.
Alloys specially designed for highly demanding applications, such as jet engines, may contain more than ten elements.
Examples of alloys include:

Bronze = Copper + Tin
Brass = Copper + Zinc



METALLURGY
Metallurgy is the branch or domain of material science that studies the physical and chemical behaviour of metallic elements, their intermetallic compounds and their mixtures (i.e. alloys). Metallurgy can further be explained by examining the application of metals generally.
Applications of metals
Some metals and metal alloys possess high structural strength per unit mass, making them useful materials for carrying large loads or resisting impact damage. Metal alloys can be engineered to have high resistance to shear, torque and deformation. However the same metal can also be vulnerable to fatigue damage through repeated use or from sudden stress failure when a load capacity is exceeded. The strength and resilience of metals has led to their frequent use in high-rise building and bridge construction, as well as most vehicles, many appliances, tools, pipes, non-illuminated signs and railroad tracks.
The two most commonly used structural metals, iron and aluminium, are also the most abundant metals in the Earth's crust.
Metals are good conductors, making them valuable in electrical appliances and for carrying an electric current over a distance with little energy lost. Electrical power grids rely on metal cables to distribute electricity. Home electrical systems, for the most part, are wired with copper wire for its good conducting properties.
The thermal conductivity of metal is useful for containers to heat materials over a flame. Metal is also used for heat sinks to protect sensitive equipment from overheating.
The high reflectivity of some metals is important in the construction of mirrors, including precision astronomical instruments. This last property can also make metallic jewelry aesthetically appealing.
Some metals have specialized uses; radioactive metals such as uranium and plutonium are used in nuclear power plants to produce energy via nuclear fission. Mercury is a liquid at room temperature and is used in switches to complete a circuit when it flows over the switch contacts. Shape memory alloy is used for applications such as pipes, fasteners and vascular stents (used in hospitals).

CLASSIFICATION OF METALS BASED ON THEIR GROUP ON THE PERIODIC TABLE

Basically, the metals on the periodic table can be classified into five categories, viz;

i.                    Alkali Metals:
These are the group 1 metals. All the elements in this group are metals except hydrogen. They include lithium, sodium, potassium, rubidium, etc. They have one electron in their valence or outermost shell, thus, they are very electropositive and are very good reducing agents as they are easily oxidized.

ii.                  Alkaline Earth Metals:
These are the group 2 metals. It is noteworthy that all the elements here are metals. They include magnesium, calcium, strontium, barium and radium. They are less reactive than the alkali metals as they have 2 electrons in their valence shell.

iii.                Group 3 Metals:
All the elements in this group are metals, except boron which is a metalloid. Aluminium is a familiar group 3 metal. It has 3 valence electrons in each atom and tends to form covalent compounds than ionic/electrovalent ones.

iv.                 Group 4 Elements:
Group 4 elements change from non-metals (carbon) to metals(tin and lead) as we go down the group. Since the atoms of these elements have 4 valence electrons, they tend to form covalent compounds. Tin and lead form compounds in which they exist in the +2 and +4 oxidation states. The stable compounds of lead are the lead(ii)compounds which are mainly ionic.

v.                   Transition Elements:
The transition elements are all metals of economic importance. The first transition series (scandium to zinc) are particularly important industrially. The transition metals are found in the d-block of the periodic table between groups 2 and 3. They occupy three rows, with ten elements in each row. The term “transition elements” refer only to an element which has partially filled d-orbitals. For our level, we will make reference to only the first transition series. The first transition series contain the following metals: scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper and zinc. Each has a partially filled 3-d shell and a 4s shell containing 1 or 2 electrons. With the exception of zinc and copper which have completely filled 3-d orbitals and scandium which has no electron in its 3-d orbital.


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