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12ChF321 Bonding and Structure

Bonding and Structure


Candidates should be able to: (a) describe the term ionic bonding as electrostatic attraction between oppositely charged ions; (b) construct dot-and-cross diagrams to describe ionic bonding; (c) predict ionic charge from the position of an element in the Periodic Table; (d) state the formulae for the following ions: NO3, CO32, SO42 and NH4+; (e) describe the term covalent bond as a shared pair of electrons; (f) construct dot-and-cross diagrams to describe: (i) single covalent bonding, eg as in H2, Cl2, HCl, H2O, NH3, CH4, BF3 and SF6, (ii) multiple covalent bonding, eg as in O2,N2 and CO2, (iii) dative covalent (coordinate) bonding, eg as in NH4+, (iv) molecules and ions analogous to those specified in (i), (ii) and (iii); (g) explain that the shape of a simple molecule is determined by repulsion between electron pairs surrounding a central atom; (h) state that lone pairs of electrons repel more than bonded pairs; (i) explain the shapes of, and bond angles in, molecules and ions with up to six electron pairs (including lone pairs) surrounding a central atom, eg as in: (i) BF3 (trigonal planar), (ii) CH4 and NH4+ (tetrahedral), (iii) SF6 (octahedral), (iv) NH3 (pyramidal), (v) H2O (non-linear), (vi) CO2 (linear); (j) predict the shapes of, and bond angles in, molecules and ions analogous to these; (p) describe metallic bonding as the attraction of positive ions to delocalised electrons; (r) describe, interpret and/or predict physical properties, including melting and boiling points, electrical conductivity and solubility in terms of: (i) different structures of particles (atoms, molecules, ions and electrons) and the forces between them, (ii) different types of bonding (ionic bonding, covalent bonding, metallic bonding, hydrogen bonding, other intermolecular interactions); (s) deduce the type of structure and bonding present from given information.

Types of structure and associated properties Substances have one of four types of structure, each of which has characteristic sets of properties. We need to be able to identify the type of structure (and the type of bonding in it) the properties, and we also need to be able to explain why these properties arise.
Giant Ionic Lattice
Bonding How bond is formed Boiling and melting points Ionic Electrostatic attraction between oppositely charged ions High Reason: strong ionic bonds throughout the lattice have to be broken Solid: No Molten/solution: Yes Reason: Ions in solid are fixed in lattice, but ions in solution/liquid are mobile and can therefore act as charge carriers Often dissolve in polar solvents (e.g. water)

Simple Molecular
Covalent Positively charged nuclei attracted to shared pair of electrons Low Reason: only weak intermolecular forces need to be overcome Not in any state Reason: No ions or free electrons to act as charge carriers

Giant Covalent Lattice


Covalent Positively charged nuclei attracted to shared pair of electrons High Reason: strong covalent bonds throughout the lattice have to be broken Not in any state Reason: No ions or free electrons to act as charge carriers (EXCEPT Graphite) Insoluble

Giant Metallic Lattice


Metallic Electrostatic attraction between positive metal ions and negative delocalized electrons High Reason: strong metallic bonds throughout the lattice have to be broken. Yes Sea of delocalized electrons are mobile and act as charge carriers Insoluble

Electrical conductivity

Solubility

Often dissolve in nonpolar solvents (e.g. hydrocarbons)

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12ChF321 Bonding and Structure Ion Formation The charge on an ion is therefore usually related to the group it is in and reflected in the valency of the ion. e.g. valency ion Na 1 Na+ Mg Al 2 3 Mg2+ Al3+ Si 4 P 3 P3S 2 S2Cl 1 ClAr 0 -

Some elements, e.g. the transition metals, have more than one possible valency, e.g. iron(II) sulphate iron(III) sulphate Fe2+ Fe3+ SO42SO42Formula: Formula: FeSO4 Fe2(SO4)3

Definition: An ionic bond is the electrostatic attraction between oppositely charged ions Ionic Dot-and-Cross diagrams Use these to show bonds between metal and non-metal atoms (unless the properties indicate the substance has covalent bonding there are a few substances with metal to non-metal covalent bonds) show outer shell only unless asked otherwise draw each ion in square brackets, and add the charge to the bracket use the element symbol to represent the nucleus draw each ion individually either show empty outer shell or filled ex-inner shell e.g.

Sodium chloride (NaCl)

Magnesium oxide (MgO)

Calcium chloride (CaCl2)

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12ChF321 Bonding and Structure Check your understanding: Draw dot-cross diagrams for i) lithium oxide ii) aluminium fluoride Ionic bonding in compound ions Ionic bonds may also be formed between ions which themselves contain more than one atom (called compound ions) e.g. SO42- bonds with Mg2+, to form magnesium sulphate; or NH4+ bonds with Cl- to form ammonium chloride. The bonding INSIDE these compound ions is covalent. You are expected to know the following compound ions: Sulphate Nitrate Carbonate Ammonium Hydroxide SO42NO3CO32NH4+ OHvalency = 2 valency = 1 valency = 2 valency = 1 valency = 1

Covalent dot-and-cross diagrams Definition: A covalent bond is shared pair of electrons Use to show bonds between two non-metal atoms. A single covalent bond is found, for example, in a chlorine molecule: Cl Cl

Atoms can also share two electrons each to form two covalent bonds between them (a double covalent bond), for example in an oxygen molecule:
X X

Cl
X

X X

Cl X

O=O

Rarely a triple covalent bond may be formed between two atoms (examples: H-CC-H and NN). A quadruple covalent bond would require too many negatively charged electrons in the same space between the two atoms, and does not occur instead atoms with valency of 4 often form giant covalent lattices.

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12ChF321 Bonding and Structure Expanded Octet: Although it is usual for bonding to result in an electron arrangement isoelectronic with a noble gas, there are a number of atoms that can accept more than a full shell as a result of covalent bond formation. While atoms of elements in the second period never have more than 8 electrons in their outer shell, those in period 3 and subsequent periods often do this is called having an expanded octet. Examples: SF6 sulphur hexafluoride XeF4 xenon tetrafluoride

Incomplete outer shells In other cases, covalent bond formation increases the number of electrons around an atom, but not all the way to a filled shell. Example: BH3 borine

Check your understanding: Draw dot-cross diagrams for iii) NH3, iv) CO2, v) BF3, vi) SCl2 Lone pairs The two unbonded atoms in the N atoms outer shell in ammonia are not just two random electrons, but a non-bonding pair of electrons called a LONE PAIR. Youll also find two lone pairs on each of the O-atoms of O2. These lone pairs are important they can get involved in reactions, and they help determine the shape of molecules. a lone pair

Dative covalent bonds In some situations, one atom may contribute both electrons to form the covalent bond. The bond formed is in all respects identical to a normal covalent bond, and is called a DATIVE covalent bond. A dative covalent bond can be formed where one atom has a lone pair of electrons available to donate, and another atom has a vacancy for two electrons in its outer shell.

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12ChF321 Bonding and Structure e.g. The ammonium ion, formed by the reaction of an ammonia molecule with an H+ ion (acid): NH3(g) + H+(aq) NH4+(aq)

dative covalent bond

This is possible because the N has a lone pair to donate and the H+ ion has an empty n=1 shell able to accept the two electrons. Check your understanding: Draw a dot-cross diagram for the ion H3O+ Dative bonds can also form part of a set of double or triple bonds. The bonding in CO is :

C=O
You will always be able to tell a dative covalent bond in a dot cross diagram because both electrons in the intersection of shells will have the same symbol (i.e. from the same atom). Check your understanding: Ozone and sulphur trioxide also have dative bonds. See if you can draw a dot-cross diagram for vii) O3 and viii) SO3. Note that sulphur in SO3 has an expanded octet. Metals forming covalent bonds to non-metals We dont just see pure ionic and pure covalent bonding there are degrees in between. Ionic and covalent are simply two extremes with all possibilities in between. Dont be thrown if you see a metal atom involved in covalent bonding especially metals like Al, Pb or Sn. This is the exception, however, and would be indicated by properties which would be inconsistent with ionic bonding e.g. SnCl4 is a red liquid at room temp (i.e. has a low melting and boiling point) so its bonding is not ionic.

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12ChF321 Bonding and Structure Metallic bonding diagrams A dot-and-cross diagram is not needed, but a labeled diagram of the kind shown on the right must be drawn. Note that the strength of the metallic bond (and hence how high the melting and boiling point is) depends on how highly charged the metal ion is, and how many electrons it has donated to the sea of delocalized electrons. e.g. Al has a higher melting point than Na. Shapes of Molecules Remember, molecules have simple molecular structure and therefore covalent bonding there are no molecules of metals or ionic substances ! There are a variety of basic shapes and bond angles:

The shapes of real molecules are determined by the outer shell electrons of the atoms which are bonded together. A dot-and-cross diagram is the essential starting point for working out shape. What we need to know is how many lone pairs and how many bonding pairs each atom has.

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12ChF321 Bonding and Structure Valence Shell Electron Pair Repulsion Theory (VSEPR) The shape of molecules results from bonding pairs and lone pairs around a central atom repelling one another as a result they want to get as far apart (as large an angle) from each other as possible. Lone pairs repel more than bonding pairs, so the order of repulsion is: lone pair - lone pair > lone pair bonding pair > bonding pair bonding pair As a result, each lone pair on the central atom reduces the bond angle by 2.5. It is actually quite straight forward well consider the shapes of a number of molecules and use VSEPR theory to explain why they have these shapes and bond angles. Well then be able to take any molecule and if we can draw a dot-and-cross diagram well be able to name its shape and predict its bond angles. BeCl2 Central Be atom: bonds = 2 lone pairs = 0

The two bonding pairs repel as far as possible from one another, giving a bond angle of 180. The lone pairs on Cl have no effect on the shape. The molecule is LINEAR. CO2 Central C atom: bonds 2 (doubles) lone pairs = 0

The fact that the bonds are double has no effect on shape the two double bonds repel each other as far as possible. The bond angle is 180and the molecule is LINEAR. For the purpose of working out shapes (only) we dont consider double or triple bonds any differently than single bonds. BF3 Central B atom: bonds = 3 lone pairs = 0

The CH4

There are 3 bonds arranging themselves as far away as possible. This leads to 120 bond angles in a planar molecule. shape is TRIGONAL PLANAR. Central C atom: bonds = 4 lone pairs = 0

There are 4 bonds arranging themselves as far away as possible. This leads to a 109.5 bond angle and a TETRAHEDAL shape.

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12ChF321 Bonding and Structure

PF5

Central P atom:

bonds = 5 lone pairs = 0

There are 5 bonds arranging themselves as far apart as possible. Three lie in a plane, with 120 bond angles and the other two are at 90 to this plane. The shape is TRIGONAL BIPYRAMIDAL

SF6

Central S atom:

bonds = 6 lone pairs = 0

There are 6 bonds arranging themselves as far apart as possible. Each lies at 90 to the others. The shape is OCTAHEDRAL.

NH3

Central N atom:

bonds = 3 lone pairs = 1

There are four bonds/lone pairs repelling each other, so the arrangement around the central N atom is based on a tetrahedral shape BUT the lone pair repels the bonding pairs more than the bonding pairs repel each other so the bond angle between the N-H bonds is reduced from 109.5 to 107 degrees. When we come to name the shape, we dont consider the lone pairs as part of the shape, so its PYRAMIDAL, not tetrahedral. H2O Central O atom: bonds = 2 lone pairs = 2

There are four bonds/lone pairs repelling each other, so the arrangement around the central O atom is based on a tetrathedral shape BUT the two lone pairs reduce the bond angle by 2.5 each, so the H-O bond angle is 104.5. When we come to name the shape we dont include the lone pairs, so its NON-LINEAR.

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12ChF321 Bonding and Structure NH4+ Central N atom: bonds = 4 lone pairs =0

It doesnt matter that it is an ion shapes work just the same. It doesnt matter that one bond is dative. Covalent and dative bonds are identical once they are formed. The central N has four bonds and no lone pairs, so the shape is TETRAHEDRAL and the bond angle 109.5. Check your understanding: Predict the shapes and bond angles in: ix) x) sulphur trioxide (SO3) xi) xii) silane (SiH4) xiii) ozone (O3) sulphur dichloride (SCl2) carbon disulphide (CS2)

Shapes of more complicated molecules Most molecules don't consist of one central atom with a few other atoms bonded to it. In a larger molecule, we need to consider each atom that has more than one other atom bonded to it. While we can't specify the overall shape of the molecule we can specify the shape around at each of these atoms but considering lone pairs and bonding pairs in the usual way. For example, consider the ethanal, an aldehyde with structural formula CH3CHO: We could draw a dot-cross diagram for this molecule, or just consider the valence shell electrons of the bonded atoms to determine that the C of the CH3 has four bonding pairs and no lone pairs. The shape around this carbon is therefore tetrahedral and the bond angle will be 109.5. The other carbon, in the CHO group, has three bonding pairs (one of which is a double bond, but for shapes we treat these the same as single bonds) and no lone pair. The shape around this carbon is therefore trigonal planar and the bond angles will be 120.

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12ChF321 Bonding and Structure Answers to 'Check your Understanding' questions: Draw dot-cross diagrams for i) lithium oxide ii) aluminium fluoride

Draw dot-cross diagrams for iii) PH3

iv) CS2

v) BF3

vi) SCl2

Dot-cross diagram for: vii) O3

viii) SO3

Predict the shapes of: ix) ozone (O3) x) sulphur trioxide (SO3) xi) sulphur dichloride (SCl2) xii) silane (SiH4) xiii) carbon disulphide (CS2)

non-linear trigonal planar non linear tetrahedral linear

117.5 120 104.5 109.5 180

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