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    Content: P-Block Elements

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    sachinkurhekar
    Group IV elements exhibit varying properties down the group due to changes in bonding and structure. Carbon and silicon form giant covalent networks while tin and lead have metallic structures. Oxides show increasing ionic character, basicity, and stability of the +2 oxidation state. Melting points decrease as structures change from covalent networks to metallic. Silicates are important minerals formed from linking silicon-oxygen tetrahedra in chains, sheets, or 3D networks.

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    Content: P-Block Elements

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    sachinkurhekar
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    Group IV elements exhibit varying properties down the group due to changes in bonding and structure. Carbon and silicon form giant covalent networks while tin and lead have metallic structures. Oxides show increasing ionic character, basicity, and stability of the +2 oxidation state. Melting points decrease as structures change from covalent networks to metallic. Silicates are important minerals formed from linking silicon-oxygen tetrahedra in chains, sheets, or 3D networks.

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    Group IV elements exhibit varying properties down the group due to changes in bonding and structure. Carbon and silicon form giant covalent networks while tin and lead have metallic structures. Oxides show increasing ionic character, basicity, and stability of the +2 oxidation state. Melting points decrease as structures change from covalent networks to metallic. Silicates are important minerals formed from linking silicon-oxygen tetrahedra in chains, sheets, or 3D networks.

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    101 views8 pages

    Content: P-Block Elements

    Uploaded by

    sachinkurhekar
    Group IV elements exhibit varying properties down the group due to changes in bonding and structure. Carbon and silicon form giant covalent networks while tin and lead have metallic structures. Oxides show increasing ionic character, basicity, and stability of the +2 oxidation state. Melting points decrease as structures change from covalent networks to metallic. Silicates are important minerals formed from linking silicon-oxygen tetrahedra in chains, sheets, or 3D networks.

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    Group IV elements

    p-BLOCK ELEMENTS
    (Part II)

    variation in m.p. / b.p. dissimilarity in properties


    oxides chlorides

    Silicon & silicates [essay: 96-1-6]

    Group IV Elements
    The entire family consists of
    the elements
    Carbon, C Silicon, Si Germanium, Ge Tin, Sn Lead, Pb

    Group IV Elements
    Group IV exhibit the most contrasting properties among the same group, best illustrated by the
    increasing metallic character down the group
    C (non-metal graphite as conductor; diamond as insulator) Si, Ge (metalloid semi-conducting) Sn, Pb (metals conductor)

    their compounds (oxidation state = +4/+2)

    Outermost electronic configuration: ns2 np2

    oxide chloride

    variation in m.p. / b.p.


    b.p. m.p.

    Variation in m.p. / b.p.


    Interpretation of variation in m.p. / b.p. of elements in terms of structure & bonding
    C / Si / Ge : giant covalent structure
    melting involves breaking a large number of strong X-X covalent bonds between X atoms X-X bond strength decreases down the group
    atomic size of X increases

    Sn / Pb : metallic structure
    melting involves breaking a smaller proportion of metallic bonds between X2+ ions and delocalized electrons

    structure of Si
    sp3-hybridized / co-ordination no. = 4 / tetrahedral arrangement cubic unit cell similar to ZnS

    02-2-2c(i), 93-2-4b(i), 03-AS-7b/c, 06-AS-5a

    Carbon Allotropes

    Carbon Allotropes
    both have high m.p. / b.p.
    giant covalent network with millions of strong C-C bonds between C atoms graphite (3700C) has higher m.p. than diamond (3550C)

    diamond

    graphite

    C atoms in graphite & diamond are sp2- & sp3hybridized respectively


    C-C bond in graphite has multiple bond character owing to the sideway overlap of unhybridized p-orbitals e- being held more tightly more s-character

    allotrope: same element with different structures / forms / properties 06-1-2a, 98-2-2a, 00-1-1a, 03-AS-7

    Carbon Allotropes
    contrasting properties
    hardness
    strong & directional C-C bonds in diamond restricts the relative motion between C atoms weak van der Waals forces between layers of graphite allow the layers to slip over each other

    Group IV Oxides
    Formulae of Group IV oxides
    C : CO, CO2 Si : SiO2 only Ge / Sn / Pb : both XO2 (O.S. +4) & XO (O.S. +2)

    electrical conductivity
    all electrons in diamond are localized each C atom has a delocalized p-electron to conduct e- along the same layer

    Group IV Oxides
    Dissimilarity in properties as illustrated by the following trends down the group :
    increasing ionic character
    e.g. variation in m.p. / b.p.

    Variation in m.p. / b.p.


    increasing ionic character (or decreasing covalent character) as illustrated by the variation in m.p./ b.p.
    CO / CO2 : simple molecule SiO2 / GeO2 : giant covalent network SnO2 / PbO2 : ionic structure

    increasing basic nature


    e.g. rxn with H2O (hydrolysis)

    increasing stability of O.S. = +2


    e.g. thermal stability of divalent / tetravalent oxides

    [02-1-3c, 04-1-7a(ii), 04-AS-6, 95-AS-12b]

    Reaction with Water


    increasing basic nature as illustrated by rxn with H2O (hydrolysis)
    CO : neutral CO2 : acidic
    CO2 + H2O

    Reaction with Water


    increasing basic nature as illustrated by rxn with H2O (hydrolysis)
    SnO / PbO : amphoteric react with alkali & acid SnO + 2 OH + H2O [Sn(OH)4]2SnO + 2 HCl SnCl2 + H2O PbO + 2 OH- + H2O [Pb(OH)4]2PbO + 2 HNO3 Pb(NO3)2 + H2O
    91-2-5a, 92-2-5b(iii), 94-2-6d(i), 97-AS-3c

    no rxn react with water & alkali


    CaCO3 + H2O Ca(HCO3)2

    2 H+ + CO32(turns limewater milky) (then clear again)

    CO2 + Ca(OH)2

    CaCO3 + CO2 + H2O

    SiO2 : acidic

    react with alkali

    SiO2 + 2 NaOH Na2SiO3 + H2O

    96-1-4a(ii), 91-2-5a, 95-AS-12b(i), 04-AS-2d

    Reaction with Water


    hydrolysis for basic oxides

    Thermal Stability

    Na2O + H2O 2 Na+ + 2 OHNa2O2 + 2 H2O 2 NaOH + H2O2 MgO + H2O Mg2+ + 2 OH-

    hydrolysis for acidic oxides

    SO2 + H2O 2 H+ + SO322 NO2 + H2O HNO2 + HNO3 F2O + H2O 2 HF + O2 Cl2O + H2O 2 HOCl Cl2O7 + H2O 2 HClO4 BeO + 2 H+ Be2+ + H2O / BeO + 2 OH- + H2O [Be(OH)4]2Al2O3 + 6 H+ 2 Al3+ + 3 H2O / Al2O3 + 2 OH- + 3 H2O 2 [Al(OH)4]-

    hydrolysis for amphoteric oxides

    01-2-3c, 07-2-4a(i), 08-2-1b

    increasing thermal stability of divalent (O.S.+2) or decreasing stability of tetravalent (O.S.+4) down the group

    Thermal Stability
    example 1
    PbO2 decomposes on heating to give PbO, whereas PbO does not : 2 PbO2(s) 2 PbO(s) + O2(g)
    observation :
    colorless gas relighting glowing splint solid turns brown when hot & yellow when cold

    Thermal Stability
    example 2
    redox strength :
    Sn2+ is a reducing agent Sn2+ Sn4+ + 2e PbO2 is an oxidizing agent PbO2 + 2e- Pb2+ 05-AS-9c, 93-1-1d, 91-1-3g, 98-AS-9b, 94-2-6e, 92-2-5b

    05-AS-9c, 98-AS-9b, 97-AS-3b, 95-AS-12b(iii)

    Thermal Stability
    explanation
    bond enthalpy
    M-Cl bond becomes weaker down the group MCl4 less stable than MCl2

    inert pair effect


    increasing stability of the n s2 electron pair to remain unremoved down the group O.S.+2 (n s2) more stable than O.S.+4 (n s2 n p2 )

    02-2-5b(v), 06-2-4d, 98-AS-9a, 95-AS-12b(iii)

    Group IV Chlorides
    all XCl4 are covalent molecules with tetrahedral shape, whereas XCl2 are ionic compounds with covalent character [96-2-4d] increasing stability of X2+ down the group
    only Sn & Pb forms XCl2 explanation: inert-pair effect 92-2-5b(vi)

    Group IV Chlorides
    All Group IV tetrachlorides (except CCl4) undergo hydrolysis XCl4 + 4 H2O X(OH)4 + 4 HCl

    hydrolysis involves nucleophilic attack of H2O molecules on the central atom of XCl4 X has vacant and low-lying d-orbitals to accept lonepair electrons from O atom in H2O C has no vacant & low-lying 2d-orbitals for H2O molecules to attack 06-2-1b(ii), 01-AS-5c, 97-AS-3a, 96-2-4d, 94-2-6d

    Silicon & Silicates


    Si : 2nd most abundant element in Earths crust (e.g. sand, rocks) Use of silicon
    semi-conductor
    e.g. computer chips

    Bonding & Structures of Silicates


    all silicates are built from the basic tetrahedral structural unit (SiO44-) with a Si atom at the centre and O atoms at each of the 4 corners

    construction materials
    e.g. concrete, bricks manufacture of glass & ceramic pottery

    abrasive [04-AS-6c] SiO44Si2O76-

    Bonding & Structures of Silicates


    the simplest form of silicates contain SiO44anions balanced by 2 M2+ cations properties similar to most ionic cpds

    Bonding & Structures of Silicates


    complicated silicates are built up from simple tetrahedral units by 3 ways:
    1) chain silicates
    each Si atom shares 2 O atoms with Si atoms in adjacent tetrahedra to form a long chain of silicates 2 chains can link laterally into a ribbon (e.g. asbestos) exist in fibres ( weak van der Waals forces % strands)

    tetrahedra join by corners only, never by edges / faces

    Ca2SiO4 (orthosilicate)

    Sc2Si2O7 (pyrosilicate)

    Bonding & Structures of Silicates


    2) sheet silicates
    each Si atom shares 3 of its 4 O atoms with other tetrahedra to form 2-dimensional layer (e.g. mica)

    Bonding & Structures of Silicates


    2) sheet silicates
    mica layers easily flake off
    ionic attraction within sheets is stronger than between sheets

    Bonding & Structures of Silicates


    3) network silicates
    each Si atom shares all 4 O atoms with other tetrahedra to form a 3-dimensional network of silicates (e.g. quartz) properties
    crystalline solid v. high m.p. quite hard non-conductor

    Bonding & Structures of Silicates


    3) network silicates
    feldspar is a group of minerals important in rock formation
    account for 60% of Earths crust result when some Si in the network are replaced by Al (aluminosilicate), plus some alkali & alkaline earth ions for charge balance

    Bonding & Structures of Silicates


    Why silicates occur in a wide variety of structures ?
    Si-O bond (466 kJ/mol) is very strong SiO44- tetrahedral units can join together by sharing O atoms in a variety of ways to form chains, rings, sheets & 3-D silicates some of the Si(IV) inside silicates can be replaced by other metal ions (e.g. Al3+) to form a wide variety of silicate analogues

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