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PRE U CHEMISTRY SEMESTER 2 CHAPTER 5 : GROUP 14 & COMPOUNDS

Physical properties of group 14 elements


Element Classification Valence electron Atomic radius(nm) Melting point(C) Boiling Point(C) First ionisation energy(kJ mol)
Conductivity (Heat) Conductivity (Electrical) Stability of oxidation states

Carbon Nonmetal 2s2p 0.77 3700 4620 1085


Diamond (X) Graphite ( )

Silicon

Germanium

Tin

Lead Metal

Metalloid 3s3p 1.17 1410 2680 788


Nonconductor

4s4p 1.22 936 2820 760


Conductor

5s5p 1.48 232 2270 705

6s6p 1.55 328 1730 714

Semiconductor

Good conductor of heat and electricity

Stability of +4 oxidation state decrease Stability of +2 oxidation state increase

Introduction Group 14 is the only group which contain all 3 major classification of elements: metal, metalloid and non metal The variation of Group 14 is based on the characteristic of each elements Atomic radius Atomic radius increase when goes down to Group 14. When the number of electrons increases, the number of shell required to fill in the electrons increase. This will increase the screening effect of the atom causing the effective nuclear charge decrease. As the attraction forces between the outermost electron and the nucleus decrease, atomic radius become larger.

3.1.2

Melting point

As the metallic properties of Group 14 elements are different, it has different molecular structure. Carbon, silicon and germanium have gigantic molecular structure. The melting point decrease when goes down to from carbon to germanium. This is due to bonding length of C C ; Si Si ; and Ge Ge become longer, so the covalent bond become weaker as the length increase. As for tin (Stanum) and lead (Plumbum), they have strong metallic bond. Lead has lower melting point than tin, as the arrangement of the metallic atom of lead are more closely packed (faced centered cubic) than tin (tetragonal structure) in solid lattice. The close packing of increase the strength of the metallic bond in lead.

3.1.3 Ionisation energy Generally the 1st ionisation energy decrease when going down to Group 14. This is due to the increase of atomic size as the number of electron shells filling in increased. When this happened, it will gradually increase the screening effect thus decrease the effective nuclear charge of the atom. When this occur, electron is easier to extract out from the atom. However the 1st ionisation energy of tin is lower than lead despite that the atomic radius of Pb is larger than Sn. The electronic configuration of Sn and Pb are as follow: Sn : 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 5s2 5p2 Pb : 1s2 2s2 2p6 3s2 3p6 3d10 4s2 4p6 4d10 5s2 5p2 4f14 5d10 6s2 6p2 This is due to the ineffective screening by 4f electrons in lead atom. The nuclear charge of lead is far greater than tin. So, the effective nuclear charge of lead will be slightly higher than tin, causing the ionisation energy of lead is higher than tin.

3.1.4 Electrical conductivity Since carbon is a non metal, theres no conductivity of carbon (diamond) that occur on carbon. If the allotrope of carbon is graphite, it can conduct electricity as it has one delocalised electron on carbon (sp2 hybridisation). As for silicon and germanium, both of them are semiconductor as they are metalloid. The conductivity of semiconductor can be increase by increasing the temperature, or silicon doped with germanium. As for tin and lead, since both of them are metal, they can delocalise electron thus conducting electricity. The electrical conductivity increase from tin to lead as the electron delocalised by lead is easier than tin.

3.2 Chemical Properties of Group 14 3.2.1 Stability of +2 and +4 oxidation state of Group 14 Group 14 elements can exhibit 2 oxidation states, which is +2 and +4 The valence electron of Group 14 elements are ____ ____ ____ ____ ns2 np2 Even though the number of valence electron of Group 14 is 4, but it will never form M4+ ions due to its very high successive ionisation energy to remove 4 electrons. Still, the +4 oxidation state involve the involvement in the 1 s and 3 p orbital. Whenever the energy is absorbed ____ ns2 ____ ____ ____ np2 ____ s ____ ____ ____ p3

This can be done at lower energy level as the gaps between the s and p is not far. When goes down to Group 14, the stability of +4 decrease due to the far level between the s and p orbital. For example, in lead, the 6s and 6p is separated by large d10 and f14 orbital. This effect is called as inert pair effect. This will cause +2 oxidation states to be more stable as the 2 electron is p orbital are easier to be removed. The graph below shows the relative stability of +2 and +4 oxidation state in Group 14

Si

Ge

Sn

Pb

From the graph, we can conclude that +4 more stable than +2 for carbon, silicon, germanium and tin while +2 more stable than +4 for lead From the angle of electrochemistry, the standard reduction potential, E0red, of +4 to +2 oxidation state of Group 14 elements is shown below Ge4+ (aq) + 2 eGe2+ (aq) E0red = 1.60 V Sn4+ (aq) + 2 eSn2+ (aq) E0red = + 0.15 V Pb4+ (aq) + 2 ePb2+ (aq) E0red = + 1.69 V As the E0red value become more positive, it mean from Ge2+ to Pb2+, the stability increase, Sn2+ and Pb2+ are preferably to stay as +2 oxidation state. Therefore, Pb4+ is a strong oxidising agent while Ge4+ is a strong reducing agent. Pb4+ (aq) + 2 ePb2+ (aq) (preferably to reduce) (oxidising agent) Ge2+ (aq) Ge4+ (aq) + 2 e- (preferably to oxidise) (reducing agent)

All Group 14 elements (except carbon) can make use of their empty d-orbitals to form complex ions. Example : SiF62- ; GeCl62- ; SnCl62- ; PbCl62- .

Central atom of Group 14 can use of the empty d orbital to expand their valency, from 4 to 6. carbon which contain only Carbon cannot form complex ions because . 2 shells can allocate a maximum of 8 electrons .

3.2.2 Catenation Catenation is the ability of an element to form bonds between atoms of the same element Carbon is unique in its ability to catenate to form stable long chain or even ring compound. For catenation to occur, the metal MM bond must be strong. The bond energy of the MM must must be similar in strength to those between M and other particular element, e.g. MO bond.
Element Carbon Silicon Germanium MM 350 222 188 M=M 610 MM 840 MO 360 464 360

Carbon, with the smallest size formed the strongest MM bonds, plus it is as strong as in MO bond. The MM for other elements are too weak. Furthermore Carbon can form double and even triple bond. So, only carbons are able to catenate to form series of long chain known as organic compounds. However, for silicon, since the SiO bonds are stronger than SiSi, hence SiO catenates to form the following chain as found in SiO2. The ability to catenate decrease as the size of atom increase

3.3 Oxide of Group 14 Group 14 elements form oxides with the formulae XO and XO2 in relation with the +2 and +4 oxidation states. The tendency to form dioxides, XO2 , decreases down the group showing the increases stability of the +2 oxidation states.
+2 oxidation state Element Formula Carbon CO Structure and bonding Simple covalent molecule Simple covalent molecule Ionic compound Ionic compound State of matter Gas Formula CO2 +4 oxidation state Structure and bonding Simple covalent molecule Giant covalent molecule Molecular/ ionic Ionic compound Ionic compound State of matter Gas Solid with high melting and boiling points Solid Solid with high melting and boiling points Solid, Easily decompose

Silicon Germaniu m Tin

SiO

Unstable gas -

SiO2

GeO

GeO2

SnO

Solid

SnO2

Lead

PbO

Solid

PbO2

3.3.1 Carbon Oxides Carbon monoxide, CO can be produced by passing carbon dioxide gas,CO2, over heated carbon. CO2 (g) + C (s) 2CO (g) An alternative method is by reducing the methanoic acid using concentrated sulphuric acid. HCOOH (l) CO (g) + H2O (l) In industry, it is prepared in a big scale by passing steam over heated coke. The mixture of hydrogen and carbon monoxide gases produced formed water gas and used as fuel C (s) + H2O (l) CO (g) + H2 (g) [ Water gas ] Carbon monoxide is a toxic gas. Chemically, it is neutral and dissolves partially in water. Carbon monoxide can exists in three possible structures. The main covalent bond in the molecule is in sp hybridisation.

It is toxic since it will combines with hemoglobin to produce carboxyhemoglobin, which usurps the space in hemoglobin that normally carries oxygen, but is ineffective for delivering oxygen to bodily tissues. Furthermore, carbon monoxide is easily absorbed by lung.

All the structures of carbon monoxide show that oxygen atom possessing lone pair of electrons. That is why carbon monoxide is a good ligand. In a complex consisting of transition metals as the centre ion.

The carbon monoxide molecules form ligands by donating a lone pair of electrons through dative bonds. These complexes are known as carbonyl compounds. Example : tetracarbonylnickel (II) ion, [Ni(CO)4]2+

CO Ni OC CO CO

2+

Carbon dioxide, CO2. Carbon monoxide is an unstable molecule. In contact with air, it is easily oxidised to carbon dioxide gas and released into the atmosphere. 2 CO (g) + O2 (g) 2 CO2 (g) Carbon dioxide, CO2, is a colourless and odourless gas. Unlike carbon monoxide, carbon dioxide is non-toxic. It is slightly acidic and it forms non-polar linear molecule with structure O=C=O. The main covalent bond is also in sp hybridisation. The intermolecular forces are weak van der waals forces. Carbon dioxide has a low boiling point and sublimes at low temperatures. At room temperature pressure, carbon dioxide exists as a gas Common uses of carbon dioxide includes the following : Carbon dioxide used in fire extinguishers are stored under high pressure. So, when the gas is suddenly released into the atmosphere, sudden expansion and cooling of the gas causes a dense layer of inflammable gas to form on top of the flame, blocking off oxygen supply and thus halts burning.

Carbon dioxide is also used in making aerated drinks and beverages and in the manufacture of baking soda, NaHCO3. Solid carbon dioxide or dry ice is used as a refrigerant as well as for producing stage effects as it sublimes immediately to produce a cloudy and misty environment

3.2.2 Silicon Oxides Two well known silicon oxides are silicon monoxides, SiO,and silicon dioxide,SiO2. Silicon monoxide, SiO, is an unstable compound at room temperature. When silicon dioxide, SiO2, and silicon, Si, are heated together under a vacuum to a high temperature (1250C), silicon monoxide will be produced. However, the reaction is reversible when the temperature cools down. The reverse reaction is a disproportionation reaction in which the same element, Si, is reduced and oxidised at the same time. 2 SiO (g) Si (s) + SiO2 (s) Oxidation state : +2 0 +4 Silicon dioxide, SiO2, is a very stable compound with high boiling and melting points. It exists in three different forms at different temperatures. The three forms, namely quartz, tridimite and cristobalite exist simultaneously at different temperatures as shown below.

In the silicon dioxide structures, each silicon atom is connected to four oxygen atoms and each oxygen atom shares two tetrahedrons. The basic unit of the structure is a SiO4 tetrahedron but since each oxygen atom is shared between two basic units, the empirical formula is again SiO2 with coordination ratio of 4 : 2 The cristobalite structure shows similarities to the diamond structure. It is simply inserting an oxygen atom in the middle of each Si-Si bond. Silicon dioxide is an important component in ceramics because of its unique properties. It is inert to attacks from acids and alkalis, do not corrode, hard but brittle & stable as a lot of heat energy is required to break the strong bonds. All these properties resemble diamond in many aspects

3.2.3 Germanium oxide Germanium (II) oxide, GeO, is obtained from the reduction of germanium (IV) ion. Reduction must be carried out under inert conditions because any presence of air will easily oxidise germanium (II) ions back to the more stable germanium (IV) ions. As in the case of all divalent compounds of germanium, disproportionation occurs during oxidation. 2 Ge (II) Ge (IV) + Ge Germanium oxide, like all the other lower metal oxides of the group, is more basic and ionic than their dioxide counterparts. Germanium oxide shows certain acidic properties, however tin (II) oxide and lead (II) oxide are amphoteric. The basic properties become prominent with increase in proton number. Germanium dioxide, GeO2, is more stable than germanium oxide. Germanium dioxide shows both acidic and basic properties (amphoteric). As going down Group 14, the acidic properties of the dioxide decreases giving a decreasing order of acidity, GeO2 > SnO2 > PbO2. GeO2 (aq) + 4 HCl (aq) GeCl4 (aq) + 2 H2O (aq) GeO2 (aq) + 2 NaOH (aq) Na2GeO3 (aq) + H2O (l)

3.2.4

Tin Oxide

Tin (II) oxide, SnO, is a deep green solid compound which is relatively unstable at room temperature. When heated up in air, it is easily oxidised to tin (IV) oxide, SnO2. Tin (IV) oxide exists naturally in the Earths crust as a mineral ore from which tin can be mined or extracted from it. Carbon is used to extract tin. SnO2 (s) + C (s) Sn (s) + CO2 (g) Tin (IV) oxide, SnO2, is only slightly more stable than tin (II) oxide. Both are amphoteric. Only Sn4+ can exist as free ions. Tin can exist in 2 oxides, which is tin (II) oxide (SnO) and tin (IV) oxide (SnO2). Both of the oxides of tin are amphoteric oxide.

When tin (II) oxide, SnO react with acid and base SnO (s) + 2H+ (aq) Sn2+ (aq) + H2O (l) SnO (s) + OH- (aq) + H2O (l) [Sn(OH)3]- (aq) Trihydroxystannate (II) ion When tin (IV) oxide, SnO2 react with acid and base SnO2 (s) + 4 H+ (aq) Sn4+ (aq) + 2H2O (l) SnO2 (s) + 2 OH- (aq) + 2 H2O (l) Sn(OH)62- (aq)

Lead Oxide Lead exists in different states of oxides, lead (II) oxide, PbO, lead (IV) oxide, PbO2, and trilead tetroxide, Pb3O4. Lead (II) oxide, PbO is the most stable form of all the lead oxides. All the other oxides are unstable and easily decompose on heating to form the more stable lead (II) oxides. 2PbO2 (s) 2 PbO (s) + O2 (g) Brown Yellow 2Pb3O4 (s) 6 PbO (s) + O2 (g) Red Yellow When lead (II) oxide is heated in air to a temperature of 400oC, it will form Pb3O4 first. On further heating to 470oC, Pb3O4 will revert back to lead (II) oxide. 3 PbO2 (s) + O2 (g) Pb3O4 (s) 6PbO (s) + O2 (g) Lead (IV) oxide is a powerful oxidising agent as it readily loses its oxygen atom to form a more stable lead (II) oxide. 2 PbO2 (s) 2 PbO (s) + O2 (g)

One of the example of this oxidising reaction is the oxidation of the iodide ion,I- to iodine, I2. Trilead tetroxide is also known as red lead because of its brilliant scarlet colour. It consists of a mixture of two moles of lead (II) oxide and one mole of lead( (IV) oxide. Thus, it behaves chemically like a mixture of the two. It is an oxidising agent which easily reduced to its metal. It is used as a red pigment in oil paints,especially as a first coating for structural steelworks, putty with linseed oil for joints in pipes and plates, making glass and pottery-glazes, and matches

Like tin oxide, Lead (II) oxide is also an amphoteric oxide. When react with acid or base,
In acidic solution : PbO (s) + 2H+ (aq) Pb2+ (aq) + H2O (l) In alkaline solution : PbO (s) + 2OH- (aq) + H2O (l) [Pb(OH)4]2- (aq) Tetrahydroxyplumbate(II) ion Lead (IV) oxide is also an amphoteric oxide In acidic solution : PbO2 (s) + 4 H+ (aq) Pb4+ (aq) + 2 H2O (l) Cold, concentrated In alkaline solution : PbO2 (s) + 2 OH- (aq) PbO32- (aq) + H2O (l) Hot, concentrated Plumbate (IV) ion

3.4 Group 14 Chlorides All the Group 14 elements form tetrachloride with formula MCl4 and have a tetrahedral structure. The MCl are simple molecules which held together by weak van der waals forces.Hence,all the compounds have low boiling points and are liquids under room conditions. The stability of the MCl compounds decreases down the group as the MCl covalent bond becomes weaker when the atom becomes larger. This is due to the bond energy decreases when the bond length becomes longer. The inert pair effect of bigger atoms like lead gives rise to stable +2 oxidation states. The electrons in the s orbitals show extra stability and are harder to be removed. Ions like Pb are stable compared to its Pb4+ ions. Tetrachloromethane or carbon tetrachloride,CCl,is very stable to heat whereas lead (IV) chloride, PbCl, (yellow liquid) is unstable and will slowly decompose to lead (II) chloride (white solid) and chlorine gas, even at low temperatures. PbCl4 PbCl2 + Cl2

3.4.1 Physical properties and thermal stability of Group 14 chloride All Group 14 chlorides are liquid at room temperature. They are mostly volatile liquid with high vapour pressure
Tetrachloride Melting points (oC) CCl4 -23 SiCl4 -70 GeCl4 -50 SnCl4 -33 PbCl4 -15

The melting points of Group 14 chlorides generally increase as the molecular mass increase. Though, carbon tetrachloride shows greater melting point than most of the Group 14 chlorides due to the short bond length between CCl, which required a higher temperature is required to overcome the forces of attraction between the CCl4 molecules. the atomic size of Br and I are too big for MBr4 or MI4 does not exist as Carbon. So the product formed will not be stable. (steric hindrance) ..................................................................... When goes down to Group 14, the bond length of M Cl increase as the atomic size of group 14 increase. This will causes the covalent bond to be weakened and decrease the stability.

CCl4, SiCl4 and GeCl4 are stable at high temperature and does not decomposed easily. Tin (IV) chloride, SnCl4 and lead (IV) chloride, PbCl4, on the other hand, decomposed when heated SnCl4 (l) PbCl4 (l) 3.4.2 Hydrolysis of Group 14 chloride All Group 14 chloride can undergoes hydrolysis except carbon tetrachloride, CCl4.

Hydrolysis of Group 14 chloride involves the attachment of water molecules in empty d-orbital first before the Cl is removed from the SiCl bond. Then, the hydrogen atom from the water attract the chlorine atom from SiCl4 away and left oxygen atom attached to silicon to form silicon (IV) oxide

3.4.4 Freons Freon is a trade name given to a group of chlorofluorocarbon compounds normally known as CFC. Freon is formed when one or more chlorine atoms from the tetrachloromethane, CCl, is/are substituted by one or more fluorine atom/atoms. The common freons produced are freon-11, freon-12, freon-13, and freon14. When only one chlorine atom is substituted by the fluorine atom, the compound formed is known as trichlorofluoromethane, CFCl or freon-11. Freon-12 refers of two substitution of the chlorine atoms in CCl to form CFCl. Same as freon-11 and freon-12, freon-13, CFCl and freon-14, CFCl, are all volatile liquids , readily liquefied, relatively inert, nontoxic and non-combustible. They are used as coolants in refrigerators and air conditioners. Large quantities of CFC are also used as aerosol propellants in spray cans like hair spray and insecticide. The harmful and destructive effects of these chlorofluoro compounds on the ozone layer in the stratosphere have attracted much study on these CFC compounds since the mid 1970s

The harmful and destructive effects of these chlorofluoro compounds on the ozone layer in the stratosphere have attracted much study on these CFC compounds since the mid 1970s In the stratosphere, the UV radiation has a wavelength of 175-220nm that is strong enough to dissociate the CFC compounds CFCl3 (g) CFCl2 + Cl The chlorine radical, Cl, is very reactive and will continue to attack the ozone molecules in the stratosphere Cl + O3 ClO + O2 .. (1) ClO + O Cl + O2 .. (2) Although the ClO species acts only as an intermediate, its presence is greatly responsible for the destruction and hence the depletion of the ozone layer The ozone layer absorbs the harmful ultraviolet (UV) radiation from the sun so that only a minimal amount penetrates through to reach the atmosphere. Too much UV radiation is harmful as it causes skin cancer and damages vegetation

3.5 Carbon composite in industry Composite compounds are formed when two or more materials are mixed or combined together to give improved qualities over the original substance. For example, substances like metal or alloy , ceramic and polymer when combined together will form composites that display all the good properties of the components Some common composite substances used in everyday like are concrete, high fibre plastics, superconductors and photochromatic glass. Composite compound is one type of solid that does not have a crystal lattice. Other such solid is the amorphous solid which include carbon black, glass and polymer. Carbon composites are formed when amorphous carbon is heated to a high temperature to form graphite fibres. This fibre then interwined with plastics to form a structure which is strong, stretchable and yet chemically stable known as carbon composites

Kevlar is one of the synthetic graphite fibres that is considerable importance in the plastic industry. It has high tensile strength and is more modulus than fibreglass. Kevlar is used for structures that require stiffness, high abrasion resistance and lightweight. Example of uses are Kevlar ropes used as lightweight boat hulls such as in canoes and aircrafts, and also canvas for tents. Kevlar maybe be used with epoxy or vinyl ester resin (polymer) as in fabrics for high performance reinforcement in automotive and marine applications. The firemen suits and the bulletproof jackets are all made of this type of material. Other composite compounds Concrete is another composite of Group 14 elements which is a mixture of cement, sand, brick and water. Concrete is hard but brittle and is able to withstand heavyweights. The structure of concrete can be further strengthened by laying steel wires to hold the components cement, sand, and brick closer together. Plastics, if strengthened by adding fiberglass to its structures, form a composite material that has broad uses in the building industry and in making sports equipment because composite material is light yet strong.

Photochromatic glasses are formed when photochromatic chemicals like silver chloride are added to transparent glass (silicon dioxide and silica ). This type of glass turns darker under sunlight and will revert back to its colourless state when out of the sun. This special property makes photochromatics glasses suitable for making sunglasses as they protect eyes from ultraviolet rays of the sun. Window screens of cars and glass window of residential houses also make use of this property of photochromatic glass to absorb unwanted rays so that the interior of cars and houses remain cool. Ceramics and a few metal compounds are able to conduct electricity with negligible resistance when cooled to a certain temperature. These are superconductors and are normally used in high technology facilities like the bullet train and some modern medical appliances.

3.6 Silicon and Silicates Silicon exists naturally in the Earths crust as - silicates,aluminosilicates and silica. Basic structural unit of silicates, SiO44- (Silicon atom is surrounded by 4 O atoms to form a tetrahedron). Silicon uses sp3 hybridisation in its bonding with oxygen. Different ways of arrangement will result in rings, single and double chains, sheets and 3-D network. Basic understanding to define silicates structures: (a) All structures are constructed from SiO4 tetrahedral. (b) The tetrahedral are joined to each other by corners only. (c) Resulting charges on the SiO44- anion depends on the number of corners shared

Most basic - consist only one simple SiO44- unit. The 4 electrons needed to complete the octet are obtained from metal atoms (like Mg2+ and Ca2+) and give the anion its quadruple negative charge. Examples: (a) zircon,ZiSiO4 (b) olivine, Mg2SiO4 (c) garnet,Ca2Al2(Si3O9)

Different Type of Silicates Pyrosilicates Its formed when 2 SiO44- unit joined together using an oxygen atom as the bridging atom. Also known as soro-silicates or disilicates. Examples: (a) thortveitite,Sc2Si2O7. (b) barycilite,Pb3Si2O7 Ring silicates / Cyclosilicates Its formed when 3 basic SiO44 units joined together by sharing 2 of its oxygen atoms in a compact manner. Unit cell - (SiO3)n2n- unit. Examples: (a) bentonite,BaTiSi3O9. (b) beryl, Al2Be3Si6O18

3.6.1 Single Chain Silicates/Pyroxenes Its formed when each SiO44- tetrahedral unit sharing 2 of its oxygen atoms with the next unit to form a long chain of (SiO3)n2n-. 2 pyroxene chains joined together by the corners will form amphiboles, with anionic structure [(Si4O11)6-]n. structure : 2-dimensional. Si-O bond is strong within the chain and weak between the chains. Hard but brittle (bonds between the chains can easily be broken). Asbestos is an important amphibole. Resistant towards heat and fire, inert towards attacks from acids and alkalis, fibrous (amphiboles sheets are separable),and not malleable. Tremolite is also an amphibole with formula Ca2Mg5(Si4O11)2(OH)2. can be cleft into strands,which is separated into thin fibres and later on woven into cloth. *layered structure contributes to its hardness and brittleness

Single chain in pyroxenes

Double chain in amphiboles

3.6.2

Silicate sheets

Silicate Its formed when 3 corners of the SiO44- unit are shared by 3 other units to form a 2-dimensional infinite sheet. Unit formula:(Si2O5)n2n- - found in clay substances like talc, mica and kaolinite. Pyrophyllite is forrmed when 2 layers of SiO4 tetrahedral and 1 layer of AlO6 octahedral are linked together in a ratio of 2:1. ideal composition:Al2Si4O10(OH)2. Talc is formed if the 2 aluminium ions in pyrophyllite are replaced by 3 magnesium ions. formula: Mg3Si4O10(OH)2. electrically neutral. its a giant molecule with strong covalent properties. The molecules in talc are arranged in parallel sheets giving the rise to flaky textures

Mica/Aluminosilicates consists of anion sheets held together by cations (K+ or Mg2+) present in between the sheets. Negative charge among the layers appears because 1/4 of the silicon ions in pyrophyllite is being replaced by an aluminium ion-[Al3Si3O10(OH)2] Example:muscovite (KAl2(OH)2[AlSi3O10]5-) *also known as white mica Kaolin higher quality kaolinite (clay soils). Its formed when some SiO2 units are removed from micas, [Al3Si3O10(OH)2]-,so that one layer of SiO4 tetrahedral share corners with one layer of AlO6 octahedral to form a ratio of 1:1 ,Al2Si2O3(OH)4 Clay is formed when its mixed with water.-making porcelain vases, cups, china plates and white ceramic tiles.It can also be used to treat indigestion

Montmorillonite Molecular formula: (Mg0.33Al1.67)(OH)2(Si2O5)20.33-. Consists of identical sheets. If one of the aluminium ion in it is replaced by one magnesium ion, the resulting unit cell will have a positive charge which can be balanced out by absorbing different ions into its structure. Forms semi-solid gel in the presence of water. Also acts as a cation exchange.(e.g. to exchange one mole of Na+ with one mole of H+ so that the surface becomes acidic, one mole of montmorillonite is required. At high temperature(150oC), montmorillonite loses its water molecules and acidity. The layered structure of its silicate will collapse. Because of this, zeolite is preferred to montmorillonite in industries especially when the reactions required high pressure and temperature

3.6.3

Three Dimensional Silicates / Framework Structure

Its formed when all the 4 angles of the silicate anion unit are shared by 4 other units to form 3-D lattice. Its found in quartz and cristobalite. Basic formula: (SiO2)n with neutral lattice. Quartz is regarded as a giant covalent molecule. Besides quartz,all the other members are aluminosilicates because of the presence of aluminium atoms in their structures. When silicon atoms are subsituted by aluminium atoms, the resulting structure is a giant anion because of the difference in charges (Al3+and Si4+). If 1/4 of the silicon atoms in 4 SiO2 is replaced by an aluminium atom, a big anion with formula [AlSi3O8]- is formed. The negative charge will be neutralised by cations as in orthoclase, K(AlSi3O8).

3.6.4 Silicones A group of polyorganosiloxanes containing the Si-C bond in long chains of -Si-O-Si- structures with alkyl or aryl groups attached to the silicon atoms. Its a long chain polymer and the structure varies when the conditions of reaction (hydrolysis and polymerisation)change. includes forming cross-links between the polymer chains by different alkyl groups. The type of alkyl groups attached can be determined by the types of Grignard reagents used. Polymers with cross-link bridges are harder and withstand heat better than single chain silicones. Silicones are prepared from silicon tetrachloride and methylmagnesium iodide (Grignard reagent) in ether

Step 1 : Reaction of silicon tetrachloride with Grignard reagent SiCl4 (l) + 2 CH3MgI (l) Si(CH3)2Cl2 + 2 MgClI

Step 2 : Dimethyldichlorosilane then undergoes hydrolysis to form hydroxyl compound Si(CH3)2Cl2 (l) + 2 H2O Si(CH3)2(OH)2 + 2 HCl

Step 3 : Product of hydrolysis undergoes condensation polymerisation to displace water molecules

Application of silicones
Its non-toxic, colourless, odourless and resists to physical and chemical changes caused by heat, cold and pressure. Has water repellant properties and is an electric insulator. Properties can be modified by attaching different organic groups to the main structure framework Silicone fluids- is used as lubricant in areas with low temperature as well as in hot areas.Its used over waterproofing fabrics and in polish for cars and furniture. Silicon rubbers- can be converted to elastomers by vulcanisation and crosslinking of the chains. Resins- insulation in electric motors and transformers. Its added to paints to increase the resistance against weather tear and heat. Form lacquers for coating frying pans so that food do not stick on the surface. Its also used as grease for lubricating glass tubes and burettes heads

3.7

Glass

Solids are most stable in crystalline form. However, if the solid is formed rapidly ( like sudden cooling of crystals), the crystals formed will not have a regular lattice. This type of solid is known as amorphous or noncrystalline. Glass is an amorphous solid as it does not have a regular three-dimensional arrangement of atoms. Glass is commonly referred to an optically transparent fusion product of inorganic materials cooled rapidly to a rigid state without undergoing crystallisation. Fusion process of mixing molten silicon dioxide, with its supplementary compounds such as sodium oxide, boron oxide or certain transition metals for colours and other properties. The main component of glasses is silicon dioxide, or simply sand. Other components are boron oxide, aluminium oxide and others are only supplementary additives, added to change the properties of the glasses produced. Some important glasses with special purpose are listed below

Quartz glass = silicon oxide SiO2. It has a low coefficient of thermal expansion but its important property lies in its transparency to a wide range of wavelengths. It is used in mirrors, glass rods and quartz lenses

Pyrex = borosilicate glass = boron + silicon oxides which give the glass a rather high coefficient of thermal expansion (more resistance towards thermal expansion when heated or cooled quickly). As such, the glass will not crack when heated to a high temperature or break when contracted in a freezer. This type of glass is used as test tubes and boiling flasks in the laboratory as well as cooking wares in the kitchen

Soda glass = sodium silicate + calcium silicate. Soda glass is passive to attack from chemical substances and is very brittle. Bottles made from soda glass are used to store non-reactive drinks and sauces like cordials and soya sauces. Since soda glass has a low melting point, it can be moulded into desired shapes and sizes. Bulbs, window-panes, drinking glasses, some cups and plates are made of soda glass. Products made from soda glass are cheaper and breakable. Some laboratory apparatus like microscopic glass plate, glass dish and glass tubing are all very fragile. The properties of soda glass can be upgraded by adding some metal oxides like lead oxide or boron oxide to enhance properties like colour and hardness

Lead glass = flint glass = potassium silicate and lead silicate which gives the glass a high refractive index. This type of glass is also known as crystal glass because of its glittering appearance. It is used in decorative glassware and windows. Lead glass is used in the laboratory as high refractive lens and prisms for optical studies

Bio glass = crown glass = phosphorus pentoxide + silicon oxide. It gives a smaller refractive index than flint glass but can be combined with flint glass to produce the desired refractive index. It is therefore important as implants in medical surgery at it has almost the same composition as bones

Water glass = fusion of sand, silicon oxide and sodium carbonate to produce sodium silicates which are soluble in water. The molten water glass is used to preserve eggs and as adhesives

3.9 Uses of Tin 1. This is a white metal with low melting point of 232 C. It is soft, ductile and malleable. It is widely used to make tin foil and wires. 2. Tin forms several alloys with other metals. For example, (a) bronze (90% copper, 10% tin) which is used in engines, electrical fuse and door knobs (b) pewter (75% tin, 25% lead) used for souvenirs (c) solder ( 50% tin, 50% lead) used for soldering 3. Pure tin is used in making cans for storing food ( so called canned food ) and tubes for storing toothpaste, creams and medicines. 4. Almost half of the tin produced is used to plate iron or mild steel to prevent the iron or steel from rusting. Tin plating is used in canned food as well. 5. Thin sheets of tin are used as wrapping in cigarette boxes

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