Quick Revision/Bonding and Structure/P.

Physical Chemistry: Bonding and Structure

I. Ionic Bonds A. Definition The formation of ionic bond in terms of electrostatic attraction between ions of opposite charge. These ions are formed by complete transfer of electrons between atoms. B. Energetics of Formation of Ionic Compounds a. Lattice energy of an ionic compound is the standard heat of formation one mole of the crystal lattice from its constituent ions in the gaseous state. M+(g) + X-(g) M+X-(s)

H 298 = lattice energy

b. Taking the formation of NaCl(s) as an example,

Na(s) + 1/2 Cl2(g)

Hf[NaCl(s)]

NaCl(s)

Hatom[Na(s)]

Hatom[Cl2(g)]

Na(g)

Cl(g)

Hlattice

HIE

HEA

Na+(g)

Cl-(g)

By Hesss Law, Hlattice = Hf[NaCl(s)] {Hatom[Na(s)] + Hatom[Cl2(g)] + HIE + HEA } c. Theoretical lattice energy of ionic compounds could be found by calculation, basing of some assumptions: (i) ions are spherical, separate entities; (ii) charges are distributed uniformly around ions; (iii) transfer of electrons is complete. d. Comparison between the experimental lattice energy and theoretical lattice energy can illustrate the degree of ionic character of the ionic bond. Large difference between the experimental lattice energy and theoretical lattice energy shows that the bond is not purely ionic. C. Ionic crystals A unit cell is the smallest basic portion of the space lattice that, when repeatedly stacked together at various directions, can reproduce the entire crystal structure. a. NaCl lattice

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two interpenetrating face centred cubic lattices of Na+ and Cl-.

Number of Na+ = (1/4)12 + 1 = 4 Number of Cl- = (1/8)8 + (1/2)6 = 4 Co-ordination number of Na+ (and Cl-) = 6 [Co-ordination number is the number of nearest neighbours.] b. CsCl lattice two interpenetrating simple cubic lattices of caesium and chloride ions.

Number of Cs+ = 1 Number of Cl- = (1/8)8 = 1 Co-ordination number of Cs+ (and Cl-) = 8

c. CaF2 lattice Calcium fluoride has the fluorite structure, which is based on the

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(i) (ii)

face-centred cubic lattice of calcium ions. fluoride ions are located at the tetrahedral holes of the lattice and each fluoride ion is tetrahedrally surrounded by four calcium ions.

Number of Ca2+ = (1/8)8 + (1/2)6 = 4 Number of F- = 1(8) = 8 Co-ordination number of Ca2+ = 8; co-orindation number of F- = 4 D. Ionic Radii a. Cations are smaller than the atom from which they are formed, while anions are larger. 1. Cation has a smaller radius than the corresponding atom because (i) (ii) after losing the outermost shell electron(s) in forming the positive ion, the number of electron shells decreases. the number of protons is greater than the number of electrons in a cation, the attraction of the nucleus for the remaining electrons (effective nuclear charge) must be stronger than that in the atom. 2. (i) (ii) An anion has a larger radius than the corresponding atom because the repulsion between the newly added electron(s) and the electrons already present. the number of protons is smaller than the number of electrons in an anion, the effective nuclear attraction for the electron cloud becomes weaker.

b.

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For a series of ions with the same arrangement of electrons as in neon, e.g. F -, Na+, Mg2+, Al3+, the size of the ion decreases as the atomic number increases. Increasing atomic number means increasing nuclear charge and a correspondingly greater inwards attraction on the electrons. II. Covalent bonds Atoms may also achieve the noble gas electronic structures by sharing of electrons (overlapping of orbitals) to form covalent bonds. A. Dative covalent bond When one atom provides both of the electrons necessary for the formation of a single covalent bond. Once the dative bond is formed it is indistinguishable from other covalent bonds of the same type. e.g. H F | | H N B F | | H F H H | | H + : N H [ H N H ]+ | | H H
+

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B. Bond energy Bond energy is the enthalpy change when one mole of a particular bond is broken under standard conditions, producing free atoms or radicals. e.g. H2(g) 2H(g) a. Example Find the heat of reaction of the following reactions CH2=CH2(g) + H2(g) CH3CH3(g) Solution

CH2=CH2(g) + H2(g) H1

CH3CH3(g) H2

2C(g) + 6H(g)

H1 = E(C=C) + 4E(C-H) + E(H-H) = +611 + 4(413) + 435=+2698 H2 = E(C-C) + 6E(C-H) = +346 + 6(413) = +2824 H = H1 - H2 = +2698 2824 = -126 kJmol-1 b. Breakdown the Additive Rule of Bond Energies on Calculating Heats of Reaction Some compounds containing conjugated double bonds such as benzene, cannot be represented by simple structures. The additive rule of bond energies will be broken down when it is used to calculate the enthalpies of some reactions involving these compounds. C. The Shapes of Covalent Molecules and Polyatomic ions
No. of electron pairs 2 Basic arrangement of the electron pairs Linear Type and no. of electron pairs 2 bond pairs BeCl2, CO2, [Ag(CN)2]
-

Examples

Shape

Linear
180o B A B

180o B
3

A
Trigonal planar

B
3 bond pairs BF3, BCl3, BI3, SO3

Trigonal Planar

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B 120o B
2 bond pairs 1 lone pair SO2, SeO2, PbCl2

B 120o B

A B

A B

V-shaped
xx A B
less than 120o

No. of electron pairs 4

Basic arrangement of the electron pairs Tetrahedral

Type and no. of electron pairs 4 bond pairs

Examples

Shape

CH4, CHCl3, CCl4, SiCl4, NH4 ,

+

Tetrahedral
B 109.5o B

B B B A B B
3 bond pairs 1 lond pair

PCl5

A B

NH3, PCl3, NF3, H3O

Pyramidal
xx xx

A B
104.5o

2 bond pairs 2 lone pairs

H2O, H2S, H2Se Se: Selenium, Gp.6

V-shaped
xx xx

A B
104.5o
B

Trigonal Bipyramidal

5 bond pairs

PCl5, SbCl5 Sb: Antimony, Gp.5

Trigonal Bipyramidal

B B B A B
4 bond pairs ICl4
+

B B A B B

Distorted tetrahedral
B B A B B

1 lone pair
x x

3 bond pairs 2 lone pair

ClF3, BrF3

T-shaped
B
xx xx

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x x

I3-, Icl2-

Linear
B
xx xx

No. of electron pairs 6

Basic arrangement of the electron pairs Octahedral

Type and no. of electron pairs 6 bond pairs

Examples

Shape

SF6, PCl6-

Octahedral

B B A B B
5 bond pairs 1 lone pair SbF52-

B B B A B B B
Square pyramidal

B B A B xx
Square Planar

4 bond pairs 2 lone pairs

XeF4, SeBr42-

B B

xx A xx

D. Sigma () and Pi () Bonds (i) (ii) Sigma () bond For all single covalent bonds, orbitals overlap directly so as to form sigma () bonds. Pi () bond The lateral overlap of two parallel p orbitals of adjacent atoms results in the formation of an entirely different type of covalent bond, which is called a Pi () bond. E. Hybridization Theory Rules for hybridization: (1) Hybridization is a process of mixing atomic orbitals on a single atom (ion). (2) Only orbitals of similar energies can be mixed to form hybrids. (3) The number of orbitals mixed equals the number of hybrids obtained.

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(4) All hybrids are similar, but differ from one another in orientation in space.

a. sp hybridization Example BeF2 1s 1s 1s 2s 2p ground state of Be 2p excited state of Be sp 2p sp hybridization The molecule is considered to be formed by overlapping of each of two hybrid orbitals of Be atom with the singly occupied orbital of each of two chlorine atoms, 3p orbital. Two bonds results. Hence it is predicted that BeCl2 has a linear structure.

2s

b. sp2 hybridization e.g. BF3 1s 1s 1s 2s 2p ground state of B 2p excited state of B 2p sp2 sp2 hybridization

2s

Each sp2 hybrid orbitals of boron overlaps with the 2p orbital from each of three F atoms. 3 bonds give a planar trigonal molecule. c. sp3 hybridization

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e.g. CH4

1s 1s 1s

2s

2p ground state of C 2p excited state of C

2s

sp3 3 hybridization sp

Overlapping of sp3 hybrids of C with four 1s orbitals of four H atoms give rise to four equivalent bonds. The molecule takes a shape of a tetrahedron. Each bond angle is 109.5o. d. sp3d hybridization e.g. phosphorus pentachloride PCl5 1s 1s 1s 2s 2p ground state of P 2s 2p excited state of P 2s 2p 3s 3s 3p 3d

3p

3d

sp3d

3d

sp3d hybridization Shape of the sp3d hybrids: trigonal bipyramidal

e. sp3d2 hybridization e.g. SF6 molecules 1s 2s 2p ground state of S 3s 3p 3d

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1s 1s

2s 2p excited state of S 2s 2p sp3d2 hybridization

3s

3p

3d

sp3d2

3d

Shape of sp3d2 hybridized orbitals - octahedral (all bond angles = 90o)

F. Covalent crystals a. Diamond

all the carbon atoms are sp3 hybridized, joining into a three dimensional network by strong, rigid and directional C-C covalent bonds. Each carbon is tetrahedrally bonded to four neighbours by strong covalent bonds. b. Graphite

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carbon atoms are all sp2 hybridized, so that each is bonded planar trigonally to three other carbon atoms by single, rigid covalent bonds, forming a hexagonal layer lattice. The unhybridized p electrons in the bonding carbon atoms overlap with each other, and are delocalized above and below the layer lattice, thus holding the lattices together by weak van der Waals' forces. c. Quartz (Silicon(IV) oxide, SiO2)

In silicon(IV) oxide structure, each silicon atom is covalently bonded to 4 oxygen atoms tetrahedrally. Each oxygen atom is bonded to 2 silicon atoms.

III. Intermediate Bonding Between Ionic and Covalent

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A. Polarization Of Ionic Bonds/Ions (i.e. ionic bond with covalent character) Factors affecting the polarization of ions a. Size Cation the smaller the cation the greater is the distortion of electron clouds of the neighbour anions Anion - the larger the anion the easier it will be distorted. b. Charge The larger the charge of the cation the better is the effective it will be in causing distortion. Conclusion, cations of small size and high charge (i.e. higher charge density) will cause the polarization of ionic bonds easily. e.g. AlCl3, FeCl3, ZnS are the common examples of ionic compounds with covalent character. B. Polarization of covalent bonds (i.e, covalent bond with ionic character) Polarization of covalent bond is due to the large difference in electronegativity of the bonding atoms. e.g. HCl Cl is very electronegative, hence the bonding electrons are attracted to the side of the Cl atom and then the Cl carries partial negative charge while the H carries partial positive charge. IV. Metallic Bond A. Atoms/ions in metals are attracted by the delocalized electrons in the metallic structure. B. Metallic structure a. Close packed structure (i) hexagonal close packed structure (hcp); with ababab. structure

Co-ordination number = 12 Packing efficiency = 74% (ii) cubic close packed structure (ccp) or face-centred cubic (fcc); with abcabc. structure

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Co-ordination number = 12 Packing efficiency = 74% b. open structure / Body centred cubic strucuture (b.c.c.)

Co-ordination number = 8 Packing efficiency = 68% c. Hexagonal close packed (h.c.p.): Cubic close packed (c.c.p.): Body centred cubic (b.c.c.): Be, Mg, Sc, Ti, Co and Zn Ca, Fe, Cu and Pb alkali metals

C. Alloys a. When compared with pure metals (i) (ii) is stronger and harder is less malleable and ductile

(iii) has a lower electrical and thermal conductivity and (iv) has a lower melting point

b. Alloy Composition In compare with pure metal Uses (in making)

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cheaper than copper, golden Brass 70% copper 30% zinc appearance, malleable, harder and more corrosion resistant more expensive than brass, yellowish Bronze 90-95% copper 5-10% tin Silver coin: 75% copper Coinage Metal 25% nickel Copper coin: 97% copper 2.5% nickel Duralumin 0.5% tin 95% aluminium 3% copper 1% magnesium Mild steel 1% manganese 99.5-99.9% iron 0.1-0.5% carbon 73% iron Stainless steel Solder N-carat gold 18% chromium 8% nickel 1% carbon 33-50% tin n/24 gold (24-n)/24 silver or copper harder than pure gold, lustrous hard and strong, very corrosion resistant melts at a temperature lower than the pure metals more corrosion resistant than aluminium, has strength similar to steel, but lower density than steel, expensive strong, malleable, cheap harder than copper, malleable and corrosion resistant brown appearance, malleable, stronger and more resistant to wear than brass

musical instrument, ornament, electrical fitting, buttons, screw, door knobs ancient weapons, ornaments, statues, church bell, ship propellers

coins

aircraft, spacecraft

thin sheets, car bodies. cans cutlery, surgical instruments, cooking utensils, bearing, razor blades welding jewellery, gold coins (since pure fold is too soft in many cases)

V. Intermolecular forces 2 types of intermolecular forces, namely a. van der Waals forces b. hydrogen bonding. A. van der Waals forces

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a. Dipole Dipole Interactions for polar molecules e.g. HCl, CHCl3 etc
+ H Cl + H Cl + H Cl

b Dipole Induced Dipole Interactions For a mixture of a polar substance and a non-polar substance e.g. mixture of CH3COCH3 and CCl4

+ CCl4

CH3COCH3 permanent dipole

induced dipole

c. Instantaneous Dipole Induced Dipole Interactions (i) the momentary dipoles arise because the electrons in a molecule are in a continual motion and at some moment that more electronic charge is one side of the molecule than the other, and then a momentary dipole is set up. This dipole induces a dipole in neighbouring molecules, and attractive forces result.

+ + + Ne + ++ - -

+ + + Ne + ++ - -

instantaneous dipole

induced dipole

(ii) the greater the molecular mass of the the molecules, the more the number of electrons and hence the stronger is the instantaneous dipole induced dipole interactions

d. van der Waals' radii and covalent radii

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Iodine molecules

covalent radius 0.128 nm

van der Waals' radius 0.215 nm

The covalent radius of an atom is half the distance between the nuclei in a homonuclear diatomic molecule of the element (bond length). The van der Waals' radius is one half of the distance between the nuclei of two atoms in adjacent molecules. Molecules H2 N2 Covalent radius (nm) 0.037 0.074 van der Waals' radius (nm) 0.120 0.150

The van der Waals radius is significantly greater than the corresponding covalent radius. It is due to the fact that van der Waals forces are much weaker than covalent bonds. B. Hydrogen bonds a. It is therefore a special kind of intermolecular forces in which the link is due to a proton lying between two very electronegative elements. X-H ........ :X' X or X' is the electronegative atoms (N, O or F) ........ is hydrogen bond : is lone pair from electronegative atom

where

b. Hydrogen bond is much stronger than van der Waals forces

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c. Intermolecular and intramolecular hydrogen bonding

2-nitrophenol boils at 489K whereas the 4-nitrophenol, which is hydrogen bonded to other molecules, boils at 532K.

d. Hydrogen bonds in water

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Each water molecule can donate and accept 2 protons. In the ice lattice, each oxygen atom is tetrahedrally surrounded by four other hydrogen atoms. The result is an open, cage like lattice with very inefficient packing of molecules, thus accounting for the low density of ice. Therefore ice floats on water

C.Phase diagram (i) Phase diagram of carbon dioxide

(i) (ii)

The line TA is called the sublimation curve. Solid carbon dioxide and carbon dioxide vapour are in equilibrium at any point of this curve. The line TB is the melting point curve for solid carbon dioxide Solid carbon dioxide and liquid carbon dioxide are in equilibrium at any point of this curve.

(iii) The line TC is the vaporization curve Liquid carbon dioxide and carbon dioxide vapour are in equilibrium at any point of this curve. (iv) (v) At point T is called the triple point at which solid carbon dioxide, liquid carbon dioxide and carbon dioxide vapour are in equilibrium. Point C is the critical point. When the temperature of the system is higher than the critical temperature, the vapour cannot be changed into liquid by increasing pressure alone. Two important characteristics: a. The triple point is above atmospheric pressure

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Solid carbon dioxide will pass directly into carbon dioxide gas without ever becoming liquid, i.e. it sublimes b. The second characteristics is about the fusion curve, which slopes from left to right in an upward direction (i.e. the slope is positive). This is typical behaviour and means that an increase in pressure raises the melting-point of solid carbon dioxide. (ii) Phase diagram of water

Two differences when compared with the pressure-temperature diagram of carbon dioxide: a. The line TB is the melting point curve (often called the fusion curve). This line represents the effect of pressure on the melting point of ice. It slopes slightly from right to left in an upward direction(i.e. the slope is negative), indicating that the melting-point of ice is lowered by an increase in pressure. b. The triple point is lower than 1 atm, therefore, ice will melt instead of sublime when heated.

D. Molecular crystals Molecular crystals consists of discrete molecules which are held in lattice sites by weak intermolecular forces such as van der Waals forces or hydrogen bonds.

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Buckminsterfullerene (C60)