Group 14

Element

symbol

Electron configuration

Nature

Carbon Silicon Germanium Tin Lead

C Si Ge Sn Pb

2.4 [He]2s22p2 2.8.4 [Ne]3s23p2 2.8.18.4 [Ar]3d104s2 4p2 2.8.18.18.4 [Kr]4d105s2 5p2 2.8.18.32.18.4 [Xe]4f14 5d106s2 6p2

Non- metal

Metalloid

Metal

All have four electrons in their valence shell with configuration : ns2np2

ns2

np2

Take note : group 14 : p block elements the similarity between elements in the same group

Variation in the physical properties Atomic radius First ionisation energy Melting point Electrical conductivity

Atomic Radius
Group 14 ( going down the group ) Nuclear charge & screening effect increases But, increasing of screening effect LARGER than nuclear charge Why ? : Each electron has more one shell filled with eThus, effective nuclear charge decreases The attraction bet. Nucleus and electron become weaker Atomic size increase

First Ionisation Energy

1st ionisation energy dec , proton number inc When atomic radius increase Effective nuclear charge decrease Easy to remove e-

Element 1st ionisation energy/ KJ mol -1

C 1090

Si 970

Ge 760

Sn 710

Pb 720

C Si : 1st ionisation energy decreases is big number Si Pb : Decrease more gradual Why ? After Si ; the nuclear charge increase + the filling of the d orbital and f sub- orbital + increase in atomic radius = effective nuclear charge dec more gradual

Question : why 1st Ionisation energy of Pb is HIGHER than Sn ? Ans : Ineffective screening effect by the 4f electrons in Pb atom. Thus, a slight increase in the effective nuclear charge Sn to Pb
50Sn :

[Kr] 4d105s25p2 82Pb : [Kr] 4f145d106s26p2

( Sn : 2.8.18.18.4 ) ( Pb : 2.8.18.32.18.4 )

32 proton & electron screening effect does not counter -balance the in nuclear chargebecause the shielding provided by the 4f electrons is less than expected

Melting point
Element Melting point/oC Structure C 3730 Si 1410 Ge 937 Sn 232 Pb 327 Giant molecular(diamond-type) Giant metallic

Strength of covalent bond in lattice decrease : C > Si > Ge

smallest size strong covalent bond

Sn and Pb - metal , form metallic bond ( solid ) Hence, the melting point is lower than C, Si, Ge Melting point of Pb > Sn = atoms of Pb are closely packed ( face centred cubic stucture ) than atoms of Sn (tetragonal structure ) Also same trend in boiling points & enthalpy of vapourisation
Inc strength of metallic bond

Electrical conductivity
going down the group structure of elements changes ( covalent to giant metallic ) = electrical cond. Increases Carbon ( diamond ) a conductor Si & Ge ( metalloids ) semi conductors Sn & Pb Good conductor (due to delocalised e- in metallic bonds )

Oxidation states of +2 and +4

Elements have valence shell configuration of ns2 np2 Oxidation state of : +2 involves only p electrons : +4 involves both s and p electrons ? None of G14 forms simple M 4+ ions the ionisation energy is too high ( +4 oxidation state of all element are covalent )* For oxidation state of +2 : C , Si , Ge are covalent while Sn and Pb are ionic = due to in ionisation energy with proton number

Relative stability of the +2 and +4 oxidation state

The +4 oxidation state involves the promotion of an s electron to an empty p orbital. Oxidation state +2
Energy absorbed

Oxidation state +4

If the energy is needed to promote s electron is compensated by the energy release when the covalent bonds are formed, element will show a stable covalency of 4 .

Going down the group Strength of covalent bonds formed with other element decreases ( due to inc in size ) Thus , the stability of the +4 oxidation state tendency for G14 to show a valency of +2
The behaviour of later members of G14 show a valency of less than 2 in the group valency through a failure to use their s electrons and known as the inert pair effect

Relative stability :
C , Si , Ge : +4 > +2 Sn : +4 > +2 Pb : +2 > +4

When E0 value become inc positive ( down the group ), tendency for M4+ state get to convert to M 2+ state inc C to Ge : +4 oxidation state is very stable compared to +2 ox. state

+2 oxidation state will change to +4 ox.state = the +2 oxidation state are strong reducing agents ( electron donors ) M2+ -> M4+ + 2 e-

In Sn : +4 oxidation state is slightly more stable than +2 ox.state Thus, tin ( 2) compounds are midly reducing. In Pb : +2 oxidation state more stable than +4 ox.state. Pb (7) oxide is a strong oxisiding agent, Pb ( 2 ) oxide is stable

Formation of complex ions

All g14 ( EXCEPT C ) can make use of their empty orbitals to form complex ions. The central atoms make use of the empty d-orbitals to expand their valency from 4 to 6 C cannot form complex ions -> no empty d-orbitals in valence shell. Thus, the coordination number of C never excees 4

Catenation
Catenation = ability of an element to form bonds bet. Atoms of the same element. Carbon : ability to catenate to form stable long chain and ring compunds. For catenation to occur : 1. the bond must strong, M-M 2. Similar in strength to those between M and other elements M-O
Element C Si Ge M-M 350 222 188 M=M 610 M M 840 M-O 360 464 360

Carbon ; smaller size ; strongest M-M bonds C-C almost as strong as C-O M-M bond for other element are weak Carbon can form double and triple bonds bet. Carbon atoms. Thus, only carbon can catenate to form a series of compounds known as organic atoms Remember ! Silicon , Si O bond is twice as strong as strong as Si- Si bond. Thus, silicon catenates can form SiO2 chain.

The allotropes of Carbon

Element can exist in more than one form and exhibit allotropy is called allotropes. Diamond o Each carbon atom undergoes sp3 hybridisation and bonded to four other carbon atom through strong covalent bonds ( tetrahedral arrangement ) o Repeated three dimensional structure o High melting point o All the four valence electrons of C atom involves in the formation of covalent bonds - no free e- ( delocalised e- ) in solid structure. o Thus, non- conductor of electricity o Metastable

Graphite Example of a layered structure in the hexagonal crystalline system C atom undergoes sp2 hybridisation and covalently bonded to three other C atom to form hexagonal ring The weak Van der Walls force allow the layer to slide over one another Thus , it is soft and slippery High melting point The more open structure of graphite as compared to diamond ; graphite less dense then diamond Stable

Relative Stability of Graphite and Diamond Monotropy = all the allotropes can exist under a particular set of condition.
Only one particular allotrope is more stable than the others. No transition temperature

The transformation of diamond into graphites must be done by release heat energy.
Graphite is stable Diamond is energetically unstable but kinetically stable

Uses of Carbon Diamond -> use in the making of high speed drilling material & precious stones Graphite -> Used as lubricants, electrodes and moderator in nuclear reactor Lead in pencil Graphite -> a component in the composite materials of bullet-proof vests & in bodies of air crafts

Tetrachlorides
Group 14 element exist as the simple MCl4 molecule with a tetrahedral shape( 109.5o) Dry chlorine gas into liquid carbon disulphide boiling under reflux Catalyst : iodine / iron 3Cl2 (g) + CS2 (l) CCl4 (l) + S2Cl2 (l) Tetrachlorides of Si, Ge , Sn : react with chlorine gas and reflux Pb tetrachoride : lead dioxide on cold and concentrated HCl ( < 5o) - to prevent the decomposition of lead tetrachloride PbO2 ( s) + 4HCl (aq) PbCl4 (l) +2H2O (l)

Physical properties of tetrachlorides

The intermolecular force between tetrachloride molecules: weak van der Waals forces ( all in liquids ) ( down the group ) Size of molecules & total number of e- increases Strength of van der Waals forces increases Melting & boiling point increases * CCl4 show abnormal behaviour

Thermal stability of the tetrachlorides

( down the group ) Length of M-Cl bond increases ( due to Inc size of elements & covalent bond gets weaker ) Thermal stability decreases CCl4 , SiCl4 , GeCl4 are stable even at high temperatures SnCl4 decomposes on strong heating to form tin (II) chloride PbCl4 decomposes on slight warming to give lead (II) choride

Oxides of Group 14
Monoxides, MO ( oxidation state of +2) Dioxides, MO2 ( oxidation state of +4) Thermal Stability of the monoxides CO2 burn with a blue flame in air to produce dioxide SiO only exists in gas phase at temperature above 20000c When cooled, silicon dioxide and silicon are formed. GeO & SnO oxidised to its dioxides PbO > 4000c ( converted to triplumbum tetraoxide, Pb3O4 ) on continuous heating, triplumbum tetraoxide is converted back to lead monoxide. * When heated with nitric acid,triplumbum tetraoxide form a colourless solution and brown soled of lead ( IV ) oxide is left.

Dioxides of G14
Dioxide Structure Physical state Thermal stability Acid/ base nature React with acid CO2 Simple molecule Gas SiO2 Giant molecule Solid Decomposes GeO2 SnO2 PbO2 Intermediate between giant molecule and giant ionic

Stable even at high temperature Acidic NaOH (to form carbonate ) Hot & con. NaOH ( to form Silicate ) Amphoteric Hot & con. HCl ( to form salts)

Hot & con. HCl ( to form Lead ( II) chloride and Cl2 gas )

Alkali

Hot and c. NaOH

Silicon(IV ) Oxide
Found in crystalline and amorphous form. Quartz Hard , brittle , clear and colourless In solid state, each silicon atom is bonded covalently to 4 oxygen atom in tetrahedral manner Ratio Si to O2 is 1 :2 . Thus, empirical formula is SiO2 Quartz
870oc

tridymite

1470 oc

cristobalite

Uses of Silicon Oxide Make glass and lenses for optical Component in electronic devices Make cement , concrete and ceramics Extraction of phosphorus Glass Melts at 1710 oc Soda lime glass : bottles , window panes Potash glass / hard glass : combustion tubes Borosilicate glass : make test tubes , laboratory glassware Aluminosilicate glass : cooking utensils Fibre Glass : car panels and aircraft components Coloured glass : metallic oxides into the glass

Oxidation state of +2 and +4

http://prezi.com/k50ijaicdn2b/group-14/

Silicates
Make up about 75% of the Earth s crust. Silicate minerals include asbestos, mica, clay ,granite ,feldspar and sand. Silicates are tetrahedral SiO4-4 anions.

 These tetrahedral units can share oxygen atoms at their vertices to generate a large variety of structures.

Primary Structural Unit Silicates

a)Silicates with Discrete 4- ion. SiO4 b)Silicates With Discrete 6- ion. Si2O7 c)Silicates with Discrete 6- ion. Si3O9

a) Simple silicates such as Mg2SiO4 , Fe3Al2(SiO4)3 and (BE)2SIO4 contain the 4- ions . simple SiO4 b) When 2 SiO44- units link together by one of the oxygen atom, a silicate with 6- is formed. formula of Si2O7 c) When 3 SiO44- units link together by sharing 2 oxygen atoms, a ring anion with the formula of Si3O96- is formed.

Chain Silicates
There are 2 types of chain silicates: single chain silicates (pyroxene) and double chain silicates ( amphiboles)

Amphiboles
An example is

asbestos.

It is brittle and hard Widely used in the building industry as heat insulators. Asbestos dust is highly poisonous and can cause lung cancer.

Sheet/Layer Silicates
General structure similar to that of the amphiboles . Have the empirical formula of [Si2O5]2- . Found in mica and talcum. Sheet can easily slide over one another making it soft and slippery. Other examples are clay (eg.kaolinite and montmorillonite).

Giant
Structure Silicates (Framework Silicates)

Aluminosilicates
Si4+ ions are replaced by Al3+ ions, Aluminosilicates are formed. To maintain electrical neutrality another cation eg. ; Al3+ Na+ , K+ or Ca2+ ,must be incorporated. Clay is a hydrated aluminosilicate with sheet/layer structure. One example is KAOLINITE. Some alu loose water on heating forming an open structure that has large surface area and are porous(space in between). They are called zeolites.

Clay Minerals
Mica is an example of a sheet structure formed by the tetrahedral SiO44- units. It is possible for aluminium and oxygen to form a sheet structure. Aluminium ion surrounded octahedrally by 6 oxides or hydroxide ions.

 It is possible for the silicon/oxygen tetrahedral sheet to link with the aluminium/oxygen octahedral sheet by sharing oxygen atoms. Layer structures of combination of these 2 types of sheet are called SILICATE CLAYS.

Kaolinite
Found mainly in Kao-Ling ,China. There is 1 octahedral sheet and 1 tetrahedral sheet in each layer. Layers are held together by hydrogen bonding between the oxygen(tetrahedral) and the hydroxide(octahedral) forming a giant structure. So , water cannot enter between the layers making it in expandable when wet.

Kaolinite and Montmorillonite sandwich structures.

Uses of Kaolinite

Use as modelling clay, making ceramics and as fillers for paint, rubber and plastic.

Montmorillonite
An example of a 2:1 clay. Composed of the octahedral aluminium/oxygen sheet sandwiched between 2 tetrahedral silicon/oxygen sheets. As such,water can enter the space between the layers pushing them apart causing the clay to expand.

Uses Of Silicon And Its Compounds

Use widely in making of microelectronic devices. Used in the making of silicone. Silicones are oils, greases or resin or rubbery materials. Used as oils , lubricants, hydraulic fluids , car polishes, elastomers , paints etc.

Chlorosilicanes can also be produced by using Grignard reagents.Example : 2C2H5MgCl +SiCl4 (C2H5)2SiCl2 + 2MgCl2

Uses of tin
Used in the plating of iron/steel in food containers. Iron /steel which are clean is dipped into molten tin. Widely used in making alloys. Examples are : pewter,solder and bronze.