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  3 Chemical Bonding

      This topic introduces the different ways by which chemical bonding occurs and the
      effect this can have on physical properties.

 3.1 Ionic Bonding

 3.4 Metallic Bonding

3.5   Bonding and physical properties

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Cambridge
                                            as simple       International
                                                      examples:            AS andCO
                                                                 BF3 (trigonal),  A Level  Chemistry 9701 syllabus Syllabus content
                                                                                    2 (linear), CH4 (tetrahedral), NH3
                                            (pyramidal), H2O (non-linear), SF6 (octahedral), PF5 (trigonal bipyramidal)
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                                        d) predict the shapes of, and bond angles in, molecules and ions analogous
                                           to those specified 10
                                                              in 3.2(b) (see also Section 14.3)

          3.3Chemical
          3   Intermolecular
                        bonding         a) describe hydrogen bonding, using ammonia and water as simple
              forces,
          This topic introduces the differentexamples
                                              ways by of   molecules
                                                        which  chemical containing
                                                                           bonding N–H   andand
                                                                                    occurs   O–Hthegroups
                                                                                                    effect this can have
              electronegativity
          on physical properties.       b) understand, in simple terms, the concept of electronegativity and apply
              and bond properties
                                            it to explain the properties of molecules such as bond polarity (see
                                            also Section
                                        Learning   outcomes3.3(c)), the dipole moments of molecules (3.3(d)) and the
                                            behaviour
                                        Candidates      of oxides
                                                     should  be ablewith
                                                                       to:water (9.2(c))
                                        c) explain the terms bond energy, bond length and bond polarity and use
          3.1 Ionic bonding                them to compare the reactivities of covalent bonds (see also Section
                                        a) describe ionic bonding, as in sodium chloride, magnesium oxide and
                                           5.1(b)(ii))
                                           calcium fluoride, including the use of ‘dot-and-cross’ diagrams
                                        d) describe intermolecular forces (van der Waals’ forces), based on
                                           permanent and induced dipoles, as in, for example, CHCl 3(l); Br2(l) and
          3.2 Covalent bonding          a) describe,
                                           the liquid including
                                                       Group 18 the  use of ‘dot-and-cross’ diagrams:
                                                                 elements
              and co-ordinate
                                           (i) covalent bonding, in molecules such as hydrogen, oxygen, chlorine,
              (dative covalent)
          3.4 bonding
              Metallic bonding                  hydrogen chloride, carbon dioxide, methane, ethene
                       including        a) describe metallic bonding in terms of a lattice of positive ions
              shapes of simple             (ii) co-ordinate
                                           surrounded       (dative covalent)
                                                         by delocalised       bonding, such as in the formation of the
                                                                        electrons
              molecules                         ammonium ion and in the Al 2Cl 6 molecule
          3.5 Bonding and               b) describe covalent bonding in terms of orbital overlap, giving σ and π
                                        a) describe, interpret and predict the effect of different types of     bonding
              physical properties          bonds, including the concept of hybridisation to form sp, sp2 and sp3
                                           (ionic bonding, covalent bonding, hydrogen bonding, other intermolecular
                                           orbitals (see also Section 14.3)
                                           interactions, metallic bonding) on the physical properties of substances
                                        c) explain the shapes of, and bond angles in, molecules by using the
                                        b) deduce the type of bonding present from given information
                                           qualitative model of electron-pair repulsion (including lone pairs), using
                                        c) as
                                           show   understanding
                                              simple  examples: BFof chemical   reactions in terms of energy transfers
                                                                     3 (trigonal), CO2 (linear), CH4 (tetrahedral), NH3
                                           associated  with  the breaking   and  making of chemical
                                           (pyramidal), H2O (non-linear), SF6 (octahedral),             bondsbipyramidal)
                                                                                               PF5 (trigonal
                                        d) predict the shapes of, and bond angles in, molecules and ions analogous
                                           to those specified in 3.2(b) (see also Section 14.3)

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          3.3 Intermolecular            a) describe hydrogen bonding, using ammonia and waterwww.cie.org.uk/alevel
                                                                                             as simple                         19
              forces,                      examples of molecules containing N–H and O–H groups
              electronegativity
                                        b) understand, in simple terms, the concept of electronegativity and apply
              and bond properties
                                           it to explain the properties of molecules such as bond polarity (see
                                           also Section 3.3(c)), the dipole moments of molecules (3.3(d)) and the
                                           behaviour of oxides with water (9.2(c))
                                        c) explain the terms bond energy, bond length and bond polarity and use
                                           them to compare the reactivities of covalent bonds (see also Section
                                           5.1(b)(ii))
                                        d) describe intermolecular forces (van der Waals’ forces), based on
                                           permanent and induced dipoles, as in, for example, CHCl 3(l); Br2(l) and
                                           the liquid Group 18 elements

          3.4 Metallic bonding          a) describe metallic bonding in terms of a lattice of positive ions
                                           surrounded by delocalised electrons

          3.5 Bonding and               a) describe, interpret and predict the effect of different types of bonding
              physical properties          (ionic bonding, covalent bonding, hydrogen bonding, other intermolecular
                                           interactions, metallic bonding) on the physical properties of substances
                                        b) deduce the type of bonding present from given information
                                        c) show understanding of chemical reactions in terms of energy transfers
                                           associated with the breaking and making of chemical bonds

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nding                                           The strong force of attraction between the oppositely
                                                                                 IONIC BONDING
                                                charged positive and negative ions results in an
med?                                            ionic bond. An ionic bond is sometimes called an
  atoms lose or gain electrons.    Ionic bondingelectrovalent
                                                     involvesbond.        In an ionic
                                                                   a transfer      ofstructure,
                                                                                       one or the
                                                                                                moreionselectrons
                                                                                                         are          from one atom to
med when an atom loses oneanother,  or          arranged in a regular repeating pattern (see Chapter 5).
                                            leading      to the formation of an ionic bond.
                                                As a result of this, the force between one ion and the ions
 al atoms usually lose electrons and
                                                of opposite charge which surround it is very great. In
                                   The strongotherelectrostatic          attraction that prevails between the oppositely
                                                       words, ionic bonding is very strong.
 med when an atom gains one or
                                   charged ions in a crystal lattice is referred to as ionic bonding.
 -metal atoms usually gain electrons
  ns.                                           Dot-and-cross diagrams
  depends on the number ofPositive ions,        Youknown
                                                     will noticeasthat  in Figureare
                                                                    cations,            we used dots
                                                                                   4.2, formed       and electrons are removed from
                                                                                                  when
 d (see page 29).                               crosses to show the electronic configuration of the chloride
  ne with non-metals, the electrons
                                   atoms. They     are smaller than the original atom. The energy associated with the
                                                and sodium ions. This helps us keep track of where the
  e metal atoms are transferred    process
                                     to     is known       as the
                                                electrons have   come ionisation
                                                                         from. It doesenergy
                                                                                        not mean that the
 Each non-metal atom usually gains              electron transferred is any different from the others.
  l its outer shell. As a result ofNegative
                                     this,    ions,   known
                                                Diagrams          as are
                                                            like this  anions,     are larger than
                                                                           called dot-and-cross         the original atom. Energy is
                                                                                                 diagrams.
  tal atoms usually end up with       outer as the
                                   released        When   drawing apulls
                                                        nucleus        dot-and-cross    diagram forThis
                                                                               in an electron.      an ionic
                                                                                                         energy is the electron affinity.
  re complete – they have an electron           compound it is usually acceptable to draw the outer
                                                                                                                 2+               2–
ble gas.                                        electron shell of the metal ion without any electrons. This
n see that:                                     is because it has transferred these Oelectrons
                                                                                             1  to the negative
                                                                                                          Mg               O
                                                                     Mg
 he electronic structure [2,8]+, the            ion. Figure 4.4 shows the outer shell dot-and-cross               2+               2–
                                                diagram for sodium chloride.
                                                                                                              2+               2–
 the electronic structure [2,8,8]−, the            A dot-and-cross2,8,2
                                                                      diagram shows:
                                                                      Mg              2,6
                                                                                        O                [2,8]
                                                                                                           Mg            [2,8]
                                                                                                                           O
n.                                              • the outer electron shells only                                 MgO
                                                • that the charge of the ion is spread evenly, by using 2+
                                                              Figure2,8,2                                 [2,8] oxide. [2,8]2–
                                                                                      2,6diagram for magnesium
                                                                      4.5 Dot-and-cross
                                                  square brackets
                                                                                                                  MgO
                                                • the charge on each ion, written at the top right-hand
                                                  corner of the square brackets.
  a noble gas electron configuration                    Calcium
                                                        Figure 4.5 chloride
                                                                    Dot-and-cross diagram for magnesium oxide.
  the German physicist Walther Kossel                   Each calcium atom has two electrons in its outer shell and
 ar the American chemist Gilbert Lewis
 idea independently.                               ‘DOTthese  AND
                                                        Calciumcanchloride     CROSS’
                                                                    be transferred                DIAGRAMS
                                                                                      to two chlorine    atoms. By losing
                                                        two
                                                        Each calcium atom has two electrons in itsthe
                                                             electrons,    each calcium    atom   achieves      electron
                                                                                                             outer  shell and
                                                        confi
                                                        theseguration     [2,8,8] (Figure
                                                               can be transferred           4.6).
                                                                                       to two      The two
                                                                                                chlorine     chlorine
                                                                                                         atoms.   By losing
 tals of salt are made up of millions of sodium ions    atoms   each gaineach
                                                        two electrons,
                                                      NaCl
                                                                              onecalcium
                                                                                  electronatom
                                                                                             to achieve  thethe
                                                                                                   achieves
                                                                                                        MgO
                                                                                                             electron
                                                                                                                 electron
                                                        confi guration    [2,8,8].
                                                       +configuration [2,8,8]–
                                                                                    [2,8,8]  is the electron confi
                                                                                   (Figure 4.6). The two chlorine
                                                                                                          2+        guration2–
 tals of salt are made up of millions of sodium ions
                                                        of argon;   it is a ‘noble-gas   confi guration’.
                                                        atoms each gain one electron to achieve the electron
             Na                   Cl                      Na         Mg     Cl
                                                                     configuration  O
                                                                                   [2,8,8].             Mgelectron confiO
                                                                                            [2,8,8] is the              guration
               +                                 –                    of argon; it is a ‘noble-gas configuration’.                  –
            2,8,1               2,8,7                    [2,8]xx
                                                               +
                                                                            x [2,8,8] –                   [2,8]2+         [2,8]2–
                                                           x NaClx 2,8,2                  2,6
                                                         [ x Na x]+(Na [Cl )Cl ]–
                                                                      + –
                                                                                                Cl               CaCl2
                                                                                                                   MgO   Cl
 a             +                 Cl              –             xx
                                                                                                                2+                  –
 f a sodium ion and chloride ion by electron transfer.
                                                               Figure 4.5 Dot-and-cross diagram for magnesium oxide. [2,8,8] –
                                                                           Ca           2,8,7
                                                                                          Cl           Ca                Cl
 a                               Cl                                                                             2+                  –
 oss diagram for sodium chloride.                                                                                 [2,8,8]     –
                                                 Calcium chloride
                                                               Ca           2,8,7
                                                                             Cl                  Ca 2+
                                                                                             [2,8,8]
                                                                                                                    Cl
                                                            2,8,8,2                                                           –
                                                 Each calcium atom has two electrons in its outer shell and
  ross diagram for sodium chloride.              these can be transferred    Cl to2 two chlorine atoms.             By
                                                                           2,8,7                                     Cl – losing
                                                                                                                 [2,8,8]
sg of dot-and-cross diagrams                                 2,8,8,2                          [2,8,8]2+ CaCl2
                                                 two electrons, each calcium atom achieves the electron
e                                                confiFigure
                                                      guration      [2,8,8]2,8,7
                                                                             (Figure
                                                             4.6 Dot-and-cross          4.6).
                                                                                diagram for       Thchloride.
                                                                                            calcium   e two chlorine
                                                                                                                  [2,8,8] –
 es made
    of  dot-and-cross
           up of millions ofdiagrams
m   reacts   with oxygen tosodium
                               form ions         atoms each gain one electron to achieve the2 electron   CaCl

 e the  two   electrons  in the  outer  shell of
  atom    arewith
              transferred
                                                 configuration      [2,8,8]. [2,8,8]
                                                       Figure 4.6 Dot-and-cross diagram is
                                                                                         for the   electron
                                                                                             calcium   chloride.configuration
m    reacts        oxygento tothe
                                formincompletely          Check-up
                                                 of argon; it is a ‘noble-gas configuration’.
enthe
    oxygen    atom. Byin
         two electrons    losing  two electrons,
                            the outer   shell of
 atom              CEDAR
  atom achieves  the electron
                        to theconfi  guration
                              COLLEGE                                     1 Draw dot-and-cross diagrams for the      BONDING: OTHER
        are transferred         incompletely                              Check-up
 .nBy  gaining
    oxygen     twoBy
            atom.   electrons,  eachelectrons,
                       losing– two                                          following ionic compounds. Show only the
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  eves the electron configuration [2,8].                                                                             –
                                                                            outer electron shells.
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                                 SKILL CHECK
    (a) Define ionic bonding.
    (b) Explain in terms of electrons, how an ionic bond forms between
    atoms of calcium and atoms of fluorine.
    (c) Draw electron configuration diagrams for a calcium ion and for a
    fluoride ion, showing their charges and outer electrons.

                                           3

                                 SKILL CHECK
    Draw ‘dot-and-cross’ diagrams for:
    (a) lithium fluoride
    (b) magnesium chloride

    (c) lithium oxide
    (d) calcium oxide

                                           4

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                               SKILL CHECK
    In a historically famous experiment Wohler heated “inorganic” ammonium
    cyanate in the absence of air. The only product of the reaction was
    “organic” urea, CO(NH2)2. No other products were formed in the reaction.
     What is the formula of the cyanate ion present in ammonium cyanate?

    A CNO-        B CNO2-        C CO-        D NO-

                                         5

                         IONIC COMPOUNDS
    The compounds formed by ionic bonds do not contain individual
    molecules, but are formed of an infinite assembly of ions.
    The ions due to their mutual attraction arrange themselves in a regular
    pattern. Thus they are always crystalline solids at room temperature.

    The electrical force binding them being very strong, they are non–volatile
    with high melting and boiling points. Every bond in the lattice needs to be
    broken down to melt the ionic compound.

                                         6

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                                                 IONIC COMPOUNDS
                   Because they comprised of ions they conduct electricity in the molten or
                   aqueous state, once the ions are made mobile.
                   In the solid state they do not conduct electricity. Generally ionic
                   compounds are soluble in polar solvents likeRelate
                                                                  water.trends in the properties
                                                                             of the chlorides of period 3
                                                                             elements to their structure and
 hows some data for some of the chlorides of period 3 elements.              bonding
 d magnesium chloride are both high-melting-point ionic                      Describe the reactions of period
y consist of a giant lattice of positive and negative ions (Figure           3 chlorides with water
 oppositely charged ions attract each with strong electrostatic
 therefore a lot of energy is required to separate the ions. The
  these compounds is considered on pages 84–90.
NaCl or MgCl2 are melted, the ions become free to move
                                                                   7
d so the molten salts conduct electricity.

                                                             *                          **

                                                      IONIC LATTICE
                   Oppositely charged ions held in a regular 3-dimensional lattice by
                   electrostatic attraction

 bonding in the solid state is more ionic with six coordinate Al
 valent molecular (Al2Cl6) is present in liquid and gaseous states.
 ists as [PCl6]−[PCl4]+ in the solid state but is covalent
 n the liquid state.

 ding in aluminium chloride is complicated, and it undergoes
  structure and bonding as it changes state. For simplicity, we
  that the bonding is covalent molecular in all states. The Lewis
 r AlCl3 shows that the Al only has six electrons in its outer shell. 8

 to generate an octet, two AlCl3 molecules come together to
 er. A dative covalent bond is formed from a lone pair on a Cl
            CEDAR
ne AlCl3 unit        COLLEGE
               to an Al on the other AlCl3 unit.                                                    BONDING: OTHER
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                                  IONIC LATTICE

            Each Na+ is surrounded by 6 Cl¯        Each Cl¯ is surrounded by 6 Na+

                     Na+ Sodium ion                         Cl   Chloride ion

                                              9

                        BRITTLE IONIC LATTICES
    Ionic compounds are hard. However they are brittle. With a slight
    deforming force it is possible to slightly displace one layer of ions relative
    to the next and thereby bring ions of similar charge next to each other.
    Similar ions repel each other forcing apart the two portions of the crystal.

                    −    +    −    +                        −    +   −    +

                    +    −    +    −                   +    −    +   −

    If you move a layer of ions, you get ions of the same charge next to each
    other. The laters repel each other and the crystal breaks up
                                              10

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                                       SKILL CHECK
    Magnesium oxide may be used for the lining of an electric furnace for
    making crockery. Which properties of magnesium oxide help to explain
    this use?
           strong forces between                   electrical
                                   ionic bonding
                 particles                         conductor

       A           yes                 yes            no

       B           yes                  no            yes

       C            no                 yes            no

       D            no                  no            yes

                                                     11

                               METALLIC BONDING
    Involves a lattice of positive ions surrounded by delocalised electrons

    Metal atoms achieve stability by “off-loading” outer shell electrons to
    attain the electronic structure of the nearest noble gas. These electrons
    join up to form a mobile cloud which prevents the newly-formed positive
    ions from flying apart due to repulsion between similar charges.
    Metals are excellent conductors of
    electricity because the ELECTRON CLOUD
    IS MOBILE, electrons are free to move
    throughout its structure. Electrons attracted
    to the positive end are replaced by those
    entering from the negative end.
                                                    12

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tallic bond is thus electrostatic in nature, resulting from
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ween the positive metal ions and the negatively charged
                                                            17
ons. Each electron is attracted by all the positive ions in
s the whole lattice is held together.                                     The structure of a metal is shown in Figure 3.111.

oints of sodium and magnesium are compared below:
                                                   METALLIC BOND STRENGTH
                The strength of the metallic bonding in sodium is relatively weak
                                                                     Metallic bonding is the
                because each atom donates one electron to the cloud. The
                                                                     electrostatic attraction between                 M
                metallic bonding in potassium is weaker than in sodium because                         Figure
                                                                     the positive ions in the lattice and     5.9  Youar
                                                                                                                      io
                the resulting ion is larger and the electron cloud has a bigger
                                                                     the delocalised  electrons.       this metal plate
                                                                                                                      de

                      Figure 5.7 Sapphires sparkle in the light           when polished.    They
 reasons why magnesium
                volume has  a higher
                        to cover  so ismelting   pointatthan
                                        less effective    holding the ions together.
                        are cut by exerting a force on the cleavage planes between                                                               M
of these is that magnesium forms a 2+ ion compared                                                                                               lo

                        layers  of ions in   the  crystal.                                                                                       p
ch forms a 1+ ion.The  metallic
                    This meansbonding
                                 that theinelectrostatic
                                             magnesium is
                                                                                                                        Alloys                andn

n the ions and thestronger thanelectrons
                   delocalised   in sodium is because
                                              stronger each
                                                       in
                                                                                                                                An alloy is a m
                                                                       The electrons are described as delocalised, because they do not belong

                                 Metallic lattices
                  atom has donated two electrons to the                     to any one metal atom, but rather are able to move throughout the

                                                                            the attraction between the positive metal ions andwith            a charged
                                                                                                                                                   non-me
                                                                            structure. The metallic bond is thus electrostatic in nature, resulting from

ason why magnesiumcloud.
                      hasThe  greater
                          a higher    the electron
                                    melting  point density
                                                    than                                                                          the negatively

                        In
                        theChapter     4, weinlearnt  that a metallic latticetheThestructure;
                                                                                 consists               oflattice is held together.becomes part o
                                                                            delocalised electrons. Each electron is attracted by all the positive ions in

ere are two delocalised
                  holdselectrons  per atom
                            ions together  more magnesium;
                                                 strongly.                                    thus the whole
                                                                                       melting points of sodium and magnesium are compared below:

 ill be a greater number ions  surrounded
                         of electrostatic       by a sea of electrons. The ions are often
                                          attractions                                                                                       Brass is anM
                         packed in hexagonal layers or in
  and the delocalised electrons.
                                                                13
                                                                   a cubic arrangement.                                            It is stronger th           el
                                                                                                                                                               th
                   2+                                     +
on is that the Mg ion When
                         (65 pm) aisforce
                                     smalleristhan
                                               applied,
                                                   the Nathe layers can slideThere
                                                                               over          each
                                                                                      are several
                                                                                                                                   reasons
                                                                                                  reasons why magnesium has a higher melting point than
                                                                                                                                                        it is
                                                                                                                                                               th
                                                                                                                                                              us
                                                                              sodium. The first of these is that magnesium forms a 2+ ion compared
therefore the delocalisedother.
                           electrons
                                 Butare
                                      incloser   to the bond, the attractive with
                                          a metallic                          forces            between                            household                item
                                                                                    sodium, which forms a 1+ ion. This means that the electrostatic
                                                                              attraction  between   the ions and the delocalised electrons is stronger in
 sitive ion in magnesium and more strongly attracted.                         magnesium.
                               the metal ions and the delocalised electronssodium,     act
                                                                                       The secondinreason
                                                                                                        allwhy magnesium has a higher meltingBut            why is
                                                                                                                                                    point than
                                                                                              is that there are two delocalised electrons per atom in magnesium;
                               directions. So when the layers slide, new metallic                    bonds                                        Zinc ions a
                                                                                     therefore there will be a greater number of electrostatic attractions
                                                                                     between the ions and the delocalised electrons.

                               are easily re-formed between ions in new lattice      ion (98 pm),positions
                                                                                                                               2+                       +
                                                                                       The third reason is that the Mg ion (65 pm) is smaller than the Na
                                                                                                                                         ofare closer
                                                                                                   and therefore the delocalised electrons      different-siz
                                                                                                                                                      to the
                                                                                     nucleus of the positive ion in magnesium and more strongly attracted.
                               and the delocalised electrons (Figure 5.8). The delocalised                                               the lattice less
                               electrons continue to hold the ions in the lattice together.                                              sliding over ea
                                                    METALLIC BONDING
                               The metal now has a different shape. This explains why                                                    (Figure 5.10).
                               metals
                            When   forceare  malleable
                                          is applied,      (they
                                                       layers    can
                                                               can    be over
                                                                   slide  hammered       into different
                                                                               one another,            since attractive
                               shapes)
                            forces       and metal
                                   between     ductileions
                                                         (they
                                                             andcan
                                                                 seabeof drawn  into
                                                                         electrons     wires).direction,
                                                                                   in every               The new                                force
                               high bonds
                            metallic tensileare
                                              strength     and hardness
                                                  easily re-formed,         of most
                                                                      attaining      metalsshape.
                                                                                a different             is alsoThis
                               due metals
                            makes   to the strong   attractive
                                             malleable            forces between the metal ions
                                                          and ductile.
                               and the delocalised electrons.
                                                     –       –                               –               –
                                                   + + + + + +                                 +
                                                                                               + + + + +                                      force
                                                –   –  – –  ––                           –   –  –   –       ––
                                    force         + + + + + +                              + + + + + +
                                    applied +         +     + + + +                    –          –       –
                                                                                     + + + + + +
                                                  –       – – –  –                    – – –           –
                                                  +       + +  + +                      + + + + +
                                                           – –     –                  – –       –       –
                                                                                                                                         Figure 5.10 Th
                                 Figure 5.8 When a force is applied14 to a metallic structure,                                           than in a pure m
                                 the layers slide over each other and re-form in new lattice                                             less regular.
                                 positions.
                                                                                                        Pure aluminiu
                                                                                                        thermal condu
                                                                                                        aluminium is
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                                                                                                        can be increas
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                                                                                                        copper, magne
the strength of the intermolecular bonding. The same is true
 ble 4.2).
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                                                                             18
                                                        solid argon – weak
                                                        instantaneous
                                                        dipole forces
                                          SIMPLE MOLECULAR LATTICE

                                                                                       Iodine also forms crystals with
                       +                  +
                                                                                       weak van der Waals’ forces
 –                            –               –
                                  +
                                      –
                                                        solid iodine – strong
                                                                                       between molecules.
                       +                  +             instantaneous
                           –                  –
                                                        dipole forces                  This lattice is easily broken
                                                                                       down when iodine is heated.

ula           Main type of intermolecular                Melting point/∞C
              attraction
                                                                             15
              weak instantaneous dipole                  −189
              dipole–dipole                              −115
              hydrogen bonding                              0
              strong instantaneous dipole                 114
2O11          strong hydrogen bonding                     185

are in several ways rather different from those of other
nces. Unlike the molecules of other compounds capable of
 , water has two lone pairs of electrons together with two
                                          GIANT (MACRO) MOLECULES
  means that it can form two hydrogen bonds per molecule
ohols, ammonia and hydrogen fluoride can only form one
                 Many atoms joined together in a regular array by a large number of
                 covalent bonds, e.g. diamond, graphite, silicon (iv) oxide.

                     MELTING POINT                ‣   Very high
                                                  ‣   structure is made up of a large number of covalent bonds, all of
                                                      which need to be broken if atoms are to be separated
                                                                            06/11/14 3:00 PM
                      ELECTRICAL                  ‣ Don’t conduct electricity - have no mobile ions or electrons
                     CONDUCTIVITY                 ‣ but... Graphite conducts electricity

                        STRENGTH                  ‣ Hard - exists in a rigid tetrahedral structure, Diamond and silica
                                                    (SiO2)...
                                                  ‣ but Graphite is soft

                                                                             16

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                                                                                       DIAMOND
                                     MELTING POINT                 ‣   VERY HIGH
                                                                   ‣   many covalent bonds must be broken to separate atoms

                                      ELECTRICAL                   ‣   NON-CONDUCTOR
                                     CONDUCTIVITY                  ‣   No free electrons - all 4 carbon electrons used for bonding
                                        STRENGTH                   ‣   STRONG
                                                                   ‣   each carbon is joined to four others in a rigid structure
naturally
lso has
ductivity
  than five
th these
 le for use
ncrusted
l through

                                                                                              17

                 Diamond has a very high melting point and boiling point (about
ctures are    4000 °C) because covalent bonds must be broken when diamond is
 solids.      melted/boiled. Diamond is very hard for the same reason.
                 Diamond does not conduct electricity, because all the electrons are held
              strongly in covalent bonds and are therefore not free to move around in
              the structure.
                 Diamond is not soluble in water or organic solvents, as the forces
              between the atoms are too strong. The energy to break these covalent
              bonds would not be paid back when the C atoms were solvated.

              Like diamond, graphite has a giant covalent structure. Unlike diamond,
              however, it has a layer structure (Figure 3.109). Each C is covalently
                                                                                            SILICA
              bonded to three others in a trigonal planar array.

                                  MELTING POINT               ‣   VERY HIGH
                                                              ‣   many covalent bonds must be broken
                                                                  to separate atoms

                                   ELECTRICAL                 ‣   NON-CONDUCTOR
                                  CONDUCTIVITY                ‣   No free electrons

                                      STRENGTH                ‣   STRONG
                                                              ‣   each silicon atom is joined to four
                                                                  oxygens
                                                              ‣   each oxygen atom are joined to two
                                                                  silicons

                                                                                              18

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                                                                       GRAPHITE
                     MELTING POINT               ‣   VERY HIGH
naturally                                        ‣   many covalent bonds must be broken to separate atoms
 so has
ductivity                                        ‣
                      ELECTRICAL                     CONDUCTOR
 than five
                     CONDUCTIVITY                ‣   Only three carbon electrons are used for bonding which leaves the
 h these
 e for use
                                                     fourth to move freely along layers
ncrusted                                         ‣
                        STRENGTH                   SOFT
  through
                                                 ‣ each carbon is joined to three others in a layered structure
                                                 ‣ layers are held by weak van der Waals’ forces
                                                 ‣ can slide over each other

                                     Layers can slide over each other
                                     Used as a lubricant and in pencils
                   Diamond has a very high melting point and boiling point (about
ctures are      4000 °C) because covalent bonds must be broken when     19
                                                                             diamond is
 solids.        melted/boiled. Diamond is very hard for the same reason.
                   Diamond does not conduct electricity, because all the electrons are held
                strongly in covalent bonds and are therefore not free to move around in
                the structure.
                   Diamond is not soluble in water or organic solvents, as the forces There are covalent bonds between the C atoms within a layer but only
                between the atoms are too strong. The energy to break these covalentvan der Waals’ forces between the layers (some of these are shown in blue
                                                                                                                                                                                 The lubricant propertie
                                                                                    in Figure 3.109). The presence of weak forces between the layers is usually
                bonds would not be paid back when the C atoms were solvated. given as the explanation that graphite is a good lubricant (used in pencils,                        are usually explained as
                                                                                                                                                                                 to the weak forces betw
                                                                                     for example) – not much force is required to separate the layers. However,
                                                                                                                                                                                 of carbon atoms. Howev
                                                                                     it has a very high melting/boiling point, because covalent bonds within
                                                                                                                                                                                 is a poor lubricant in a v
                Like diamond, graphite has a giant covalent structure. Unlike diamond,
                                                                                     the layers must be broken when it is melted/boiled.
                                                                                                                                                                                 it is now believed that t
                                                                                        Because of the strong covalent bonds between atoms, graphite is not                      properties come from ad
                however, it has a layer structure (Figure 3.109). Each C is covalently
                bonded to three others in a trigonal planar array.
                                                                       GRAPHITE      soluble in water or non-polar solvents.
                                                                                        Graphite conducts electricity because each C atom forms only three
                                                                                                                                                                                 molecules.

                                                                                     covalent bonds, and the extra electrons not used in these bonds (carbon
                                                                                     has four outer shell electrons) are able to move within the layers.
                                                                                        As only three covalent bonds are formed by each carbon atom in the
                                                                                     layers, each C atom possesses one p orbital, containing one electron,
                                                                                     perpendicular to the plane of the layers. These p orbitals can overlap
                                                                                     side on to give a delocalised system extending over the whole layer.
                                                                                     Movement of electrons within this system allows conduction of electricity
                                                                                     within layers. Graphite is, however, an electrical insulator perpendicular to
                                                                                     the plane of the layers.

                                                                                                  The third allotrope of carbon that will be considered here is a molecular
                                                                                                  rather than a giant structure. It consists of individual C60 molecules, with
                                                                                                  covalent bonds within the molecule and van der Waals’ forces between the
                                                                                                  molecules (Figure 3.110).
                                                                                                                                                                                    Diamond and graph
                                                                                    20                                                                                              structures but fullere
                                                                                                                                                                                    molecular structure
                                                                                                                                                                                    points of diamond a
                                                                                                                                                                                    therefore substantiall
                                                                                                                                                                                    that of fullerene, as c
                                                                                                                                                                                    must be broken whe
                                                                                                                                                                                    and graphite are me
                                                                                                                                                                                    intermolecular force
                                                                                                                                                                                    Waals’ forces) when
                                                                                                                                                                                    (it actually undergoe
                                                                                                                                                                                    at about 530 °C).

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                             CARBON NANOPARTICLES
     Cambridge  International AS Level Chemistry
            Allotropes of carbon, known as fullerenes, have been recently
                discovered and possess unique and exciting properties.
                They are based on rings of carbon, in hexagonal arrangement, similar to
     colourless crystals with high melting and boiling points
                the structure of graphite.                        Fullerenes
     and it does not conduct electricity.                         Fullerenes are allotropes of carbon in t
        Sand is They
                 largelyhave
                         silicon(IV)oxide.
                              dimensions between 0.1 to 100 nanometers.
                                                                  spheres or tubes. They are similar in st
                                                                    in that each carbon atom is bonded to
       QUESTIONS                                                    atoms. They contain rings of carbon at
                                                                    in hexagons and in addition many con
       11 Explain the following properties of silicon(IV) oxide by  carbon atoms arranged in pentagons. Th
          referring to its structure and bonding.                   discovered was called buckminsterful
          a It has a high melting point.                   21
                                                                    5.16). The C60 molecule has the shape o
          b It does not conduct electricity.                        ball). The carbon atoms are arranged a
          c It is a crystalline solid.                              20 hexagons and 12 pentagons. The bo
          d It is hard.                                             hexagons join are shorter than the bon
       12 Copy and complete the table below to compare              hexagons and the pentagons. As in gra
          the properties of giant ionic, giant molecular, giant     electrons in C60 are delocalised, but to
          metallic and simple molecular structures.                 in graphite. Since the discovery of the
                                                                    types of buckminsterfullerene have be
                         Giant Giant         Metallic   Simple
                                                FULLERENES are ball-shaped molecules that are mul
                         ionic molecular                molecular
                                                                    C120. Other fullerene molecules includ
        Two The firsts fullerene discovered was the buckminsterfullerene, C60, which has the
        examples
            shape of a football.                                     a                                b
         Particles
              Properties:
         present
         Forces
              Relatively low sublimation point (weak van der
         keeping
82            Waals between each molecule).
         particles
         together
              Poor conductor of electricity (extent of electron
         Physical
         statedelocalisation
              at room        is lower).
         temperature
              More reactive compared to graphite. Reacts with
         Melting
              hydrogen,
         points and     fluorine, chlorine, bromine and
         boiling points                                            Figure Buckminsterfullerene
                                                                            5.16 The shape of a buckminster
              oxygen.                                              C60, a is similar to that of a football b.
         Hardness
                                                     22

         Electrical
         conductivity                                              The properties of buckminsterfulleren
         Solubility in                                             different from those of graphite and di
         water                                                 It has a relatively low sublimation poin
                                                                   ■
                                                               from the solid to the vapour state whe
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                                                                                        turns from the s
                                                               state at about 3700 °C). This is because
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                                                                 high electron density in certain parts of the molecule (see      Graphene
                                                                 electrophilic addition on page 209).
                                                                                                                                  Graphene is a single iso
                                                             A second type of fullerene is a class of molecules described         The hexagonally arrang

                                     NANOTUBES               as nanotubes. Nanotubes are fullerenes of hexagonally
                                                             arranged carbon atoms like a single layer of graphite
                                                                                                                                  completely rigid and it

                                                             bent into the form of a cylinder (Figure 5.17). The first            a
                                                             nanotubes to be made were one layer of carbon atoms in
  Nanotubes are fullerenes hexagonally arranged carbon atoms like a single
                                                             thickness. More recently nanotubes have behave been made
                                                             with thicker walls with several tubes inside one another.
  layer of graphite bent into a cylinder.                    Although the diameter of a nanotube is very small, it
                                                             can be made relatively long. The length of the nanotube
                                                             cylinder can be a million times greater than its diameter.
  Properties:

  High electrical conductivity along axis of cylinder.                                                                            Figure 5.18 a Part of a
                                                                                                                                  of graphene.

  High tensile strength.                                                                                                          Graphene has some of t
                                                                                                                                  are more exaggerated. F
  Very high melting points ( 3500°C).                                                                                             ■   Graphene is the most
                                                                                                                                      Single sheets of graph
                                                                                                                                      and are much more re
  Used in tiny electrical circuits as wires, as electrodes                                                                        ■   Graphene is extremel
                                                                                                                                  ■   For a given amount of
  in paper thin batteries, treatment of certain types of     Figure 5.17 Part of the structure of a nanotube. The ends of
                                                                                                                                      electricity and heat m

                                                             the cylinder are often closed.                                       It has been said that ‘a o
  cancer in drug delivery and to strengthen clothing.                                                                             of graphene could supp
                                                             Nanotubes have characteristic properties:                            only as much as the cat
                                               23                                                                                 of graphene include use
                                                             ■   They have high electrical conductivity along the long axis
                                                                                                                                  tiny transistors, touchsc
                                                                 of the cylinder. This is because, like graphite, some of the
                                                                 electrons are delocalised and are able to move along the
                                                                                                                                  storage devices.
                                                                 cylinder when a voltage is applied.
                                                             ■   They have a very high tensile strength when a force is               QUESTION
                                                                 applied along the long axis of the cylinder. They can be up to
                                                                 100 times stronger than steel of the same thickness.                 13 Suggest, using ide
                                                             ■   They have very high melting points (typically about 3500 °C).           a buckminsterfu
                                                                 This is because there is strong covalent bonding throughout               solid to a gas a
                                                                 the structure.
                                                                                                                                         b graphene is a g
                                                             Fullerenes have a large range of potential uses.                            c   nanotubes con
                                                             Reactive groups can be attached to their surfaces and                           long axis of the
                                                             metal complexes (see page 371) can also be formed.                          d buckminsterfu
                                                             Small molecules or atoms can be trapped in the cage
                                                             of buckminsterfullerenes. Possible medical uses
                                      GRAPHENE               include delivering drugs to specific places in the body.
                                                                                                                                  Conserving m
                                                             Nanotubes are used in tiny electrical circuits as ‘wires’
                                                             and as electrodes in paper-thin batteries. They can be               Why conserve m
     Single isolated layer of graphite.                      incorporated into clothing and sports equipment for added            There is only a limited s
                                                             strength. They have also been used in the treatment of               If we use them all up, th
                                                             certain types of cancer.                                             we make from metals a
     Not completely rigid and shape can be distorted.
     Most reactive form of carbon (low melting point).

     Extremely strong.

     Conducts electricity.

                                               24

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                                      STRUCTURES
                       M.P. /
    TYPE                                                      REASON
                       B.P.
    ionic lattice       high    A large amount of energy must be put in to overcome the strong
                                electrostatic attractions and separate the giant lattice of ions

    simple covalent     low     Van der Waal’s forces holding the simple molecules together are weak
    molecules                   and can be overcome easily with low amounts of energy

    macromolecules      high    Many covalent bonds must be broken to separate atoms

    metallic lattice    high    A large amount of energy must be put in to overcome the strong
                                electrostatic attractions between the lattice of cations and the
                                delocalised electrons surrounding them

                                                   25

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