Lecture 3: Structure and Bonding

(Chemistry in Context 8.18.5 & 10.110.8 & ChemFactsheet 5)

The Chemical Bond -classification of bond type The Ionic Bond -formation of positive and negative ions -ionic bonding & lattices The Covalent Bond -dot and Cross Diagrams -simple & Giant covalent structures -dative Covalent Bonding The Metallic Bond -metallic lattices and electron delocalisation -alloys Intermediate Bond Types -electronegativity and polarized bonds -polarised ionic bonds and Fajans Rules

Periodicity (4.2-4.4)
-repeating chemical properties of the chemical elements that occurs when layed out in order of atomic number (Z) is called periodicity

-elements in same valence electron configuration similar chemistry s2

-blocks of periodic table are named after the orbitals housing valence electrons:
Mg Ca Sr

s2p5
Cl Br I

s-block f-block

d-block

p-block

Cation and Anion formation

first ionisation (endothermic)

first electron affinity (exothermic)

M+

second ionisation (endothermic)

second

M2+

X-

electron affinity (endothermic)

X2-

Ionic Bonding (8.2)

when K atom and Cl atom brought together it eventually becomes favourable for electron to jump from K to Cl:

(now both K+ and Cl- have stable octet (noble gas configuration)
heat evolved (lattice energy)

Cl

DH

K+

_ Cl

(Lewis formula of KCl)

Ionic Bonding (8.2)

-both metal and non-metal seek stable noble gas electron configuration
[Ar]4s1

Cl

[Ne]2s22p5
chlorine

Cl

Sylvite (KCl)

[Ar]
chloride ion

[Ar]

Ionic Bonding (8.2)

-both metal and non-metal seek stable noble gas electron configuration
[Ar]4s1

Cl

[Ne]2s22p5
chlorine

-MX ionic salts form favourably when M has a small ionisation energy and X has a large, exothermic electron affinity

Cl

[Ar]
chloride ion

Dot-Cross Diagrams (8.2)

dot/cross diagrams show: -compounds electronic structure -where the electrons originated

e.g. CaCl2:

[Ar] [Ar]

Dot-Cross Diagrams (8.2)

dot/cross diagrams show: -compounds electronic structure -where the electrons originated

e.g. CaCl2:

What salt is this?

[Ar] [Ar]

Dot-Cross Diagrams (8.2)

dot/cross diagrams show: -compounds electronic structure -where the electrons originated

e.g. CaCl2:
e.g. MgO:

[Ar] [Ar]

[Ne]

[Ne]

Ionic Lattices (10.7)

-salts are crystalline: ions are arranged regularly giving solids with flat faces and straight edges

Physical Properties of Salts (10.8)

-ionic bonds are strong! high melting points (750 C for KCl, 3000 C for MgO)
giant CaSO4 crystals, Mexico

small NaCl crystals

-ionic bonds are very polar dissolve well in polar solvents solid salt (fixed ions) electrical insulators aqueous salt solution or molten salt (ions free to move in liquid) conduct electricity

What is a chemical bond? (8.1)

-an attractive force holding together atom(s) or ions(s) that makes them function as a unit.

-bond forms if it makes the system is lower in energy than when atoms are apart. -energy input required to break bond = bond strength or bond energy
e.g. the ClCl bond has a strength of 243 kJ/mol the O=O bond has a strength of 499 kJ/mol the lattice energy of KCl is 715 kJ/mol the lattice energy of MgO is 3930 kJ/mol

Why Study Bonding?

The way atoms are bonded together shapes physical and chemical properties of a compound. e.g. graphite is grey, soft, conductor of electricity diamond is a transparent insulator, the hardest substance known e.g. C and Si have similar chemistry but: SiO2 is a brittle unreactive crystalline solid CO2 is a gas Types of Chemical Bond

-atoms can bond to each other in three main ways:

Ionic bonding (e.g. NaCl, CaCO3) Covalent bonding (e.g. H2O, PCl5) Metallic bonding (e.g. Fe, K, Hg)

Covalent Bonding
-a covalent bond forms when partially filled orbitals overlap:

-electrons are shared so that each contributing atom can experience a full outer shell of electrons (noble gas configuration)

-each H obtains full valence shell (n = 1) and the same electron configuration as He H2 is stable

-other homonuclear diatomic molecules form by making similar covalent bond

e.g. F has seven valence electrons so shares one electron:

F

++
F
++

+ +

dot-cross structure of F2

++

++

F
++

each F obtains octet of electrons and electron configuration [Ne] note each F has three non-bonded or lone pairs of electrons in the valence shell (n = 2)
Octet rule: atoms proceed as far as possible toward completing their octets by sharing electron pairs in covalent bonds

++

++

-in some diatomic molecules electrons are not distributed evenly e.g. HF
electron-poor
electron-rich

dot-cross diagram -covalent HF bond allows both atoms to have full outer shell (H obtains full n = 1 shell, F obtains full n = 2 shell)

F is much more electronegative than H HF is a polar covalent bond

What is Electronegativity? (8.2) Electronegativity: the tendency of an atom to attract electron density towards itself in a chemical bond
increasing electronegativity

F is the most electronegative, Cs the least

The greater the difference in electronegativity between two elements, the greater the polarity of the bond

If electronegativity difference >1.8 compound is mostly ionic:

P2O5 (difference = 1.4) completely covalent LiI (difference = 1.5) partly ionic, partly covalent Al2O3 (difference = 2.0) mostly ionic, slightly covalent CsF (difference = 3.3) completely ionic

Polar Covalent Bonds

non-polar covalent: homonuclear diatomic molecules e.g. H2, Cl2, both atoms identical so electron density is arranged symmetrically

polar covalent: electrons not transferred between atoms but is unequally shared due to slightly different electronegativity

ionic bond other extreme very different atoms so electrons completely transferred very different electronegativity

-polar bonds can give polarity to the overall molecule e.g.

Cl
non polar C Cl CCl4 Cl Cl
-importantly for life, water is a polar molecule:

H C Cl Cl Cl
polar CHCl3

polar molecules spontaneously align themselves in an electric or magnetic field:

statically-charged plastic rod

non-polar liquids unpeturbed

e.g. Hg, Br2, hydrocarbons

polar liquids deflected e.g. H2O, alcohols, acetone

Dot-cross diagrams of polyatomic molecules (8.4)

-octet rule is obeyed for all atoms, even in larger molecules e.g.

ammonia (NH3)
N (1s22s22p3) is in group 5 must share 3 electrons to gain full octet structure features three bonding pairs and one lone (non-bonded) pair

carbon dioxide (CO2) O (1s22s22p4) is in group 6 must share 2 electrons to gain full octet

structure features four bonding pairs (two double bonds) and four lone (non-bonded) pairs

CO2 Lewis structure

Dative Bonding (8.5)

-sometimes both electron pairs from a covalent bond are provided by one atom e.g. formation of ammonium ion:

BF3
-boron trifluoride is electron-deficient compound (incomplete octet; only 6 electrons in outer shell) forms dative bond with electron donors e.g. H2O, NH3

Metallic Bonding (10.5)

- close packing of metals has important

consequences: -atoms outer (valence) electrons are delocalised (can move freely throughout lattice) -metal structure is array of positive ions immersed in a sea of electrons

delocalised sea of electrons

-delocalised electrons:

-bind atoms strongly - strong high melting points (e.g. Fe 1530 C, W 3500 C)
-allow conduction of heat and electricity throughout solid (especially Ag, Cu)

Metallic Bonding (10.5)

-bonding between atoms is not directional so metals are bendy and:

i) malleable - can be beaten into thin sheets without fracturing

ii) ductile - can be drawn into fine wires without fracturing -close-packing of atoms explains metals high density: as high as: 8 gcm-3 for Cu and Fe 22 gcm-3 for Os, Au & Ir

Alloys (10.5)

bronze statue

-man-made mixture of metals -made by mixing molten metals in desired proportions -metallic bonding but altered properties e.g. bronze (10% Sn in Cu) stronger than Cu iron
strengthens and

stainless steel

weak (layers slide)

solder (Pb-Sn) very low melt point)

makes corrosion resistant

Cr

Cr

Cu-Be alloys are strong and spark resistant (used on oil rigs)

Network Solids (Giant Covalent Lattices) (10.6)

-bonding is covalent and in an infinite lattice one giant molecule -e.g. diamond, quartz, ruby, sapphire brittle but very hard
amethyst

Quartz (SiO2) a three-dimensional infinite lattice of tetrahedral Si atoms linked by O atoms -sand is mostly made of silica (10.10)

Network Solids (Giant Covalent Lattices)

-bonding is covalent and in an infinite lattice one giant molecule -e.g. diamond, quartz, ruby, sapphire brittle but very hard

diamond a three-dimensional lattice of tetrahedral carbon atoms -lattice very rigid: the hardest substance known used in drill-bits and (powdered) as an abrasive good thermal conductor (rigidity transfers atomic vibrations) but electrical insulator (no delocalised electrons)

graphite - a two-dimensional array of trigonal carbon atoms

-hexagonal rings - strong bonding within the layers but weak bonding between them

graphite is soft (used in pencils and as lubricant).

non-bonded electrons are delocalised throughout plane graphite conducts electricity

Summary: Bonding in Solids

-bonding in solids can be grouped into four categories
:

Al
CaCO3

metallic, ionic, giant covalent and simple covalent

examples metals Cu, Al, Os, Hg, brass, solder bonding and structure metallic lattice positive metal ions held together by delocalised electrons ionic lattice conductivity good m.p./ b.p. high strength malleable, ductile, bendy

ionic solids

NaCl, CaCO3 graphite diamond, SiO2, BN ice, sugar, wax, I2, PCl5, S8.

network solids

covalent lattice

molecular solids

covalent molecules held by lattice of weak forces

very low (except in solution) very low (except graphite) very low

high

hard, rigid, brittle very hard, rigid, brittle soft, brittle

very high low

What kind of bonding is holding together the following?

Hg ice brass
SA GA

candle wax

limestone cliff

Classifying Bonding
bonding is general term referring to forces that hold together any type of chemical species: molecules, groups of molecules, atoms or ions Intramolecular bonding holds together atoms e.g. -ionic bonding -metallic bonding -covalent bonding -strong (150-500 kJ/mol)

Intermolecular bonding acts between molecules e.g. -van der Waals forces -dipole-dipole forces -ion dipole forces -hydrogen bonding
-weak (2-25 kJ/mol) but often responsible for bulk, physical properties of matter

Functional Groups and Physical Properties

molecules functional groups

determine
strength of intermolecular forces present

determines

compounds

physical properties
e.g.

INTERMOLECULAR FORCES SUMMARY

(non-covalent interactions)
van der Waals force (1-5 kJ/mol)
H3C CH3 H3C C H3

weakest force (lowest boiling point)

dipole-dipole interaction (5-10 kJ/mol)

H3C

d+

dCl

Cl C H3

d-

d+

hydrogen bonding interaction (10-30 kJ/mol) H3C

stronger force dO d+ (higher boiling H CH3 H point) d+ O d-

Functional Groups and Intermolecular Forces: Solubility -what determines if one compound is soluble in another?

Functional Groups and Intermolecular Forces: Solubility -polarity of a molecules bonds determine in which solvents it is soluble like dissolves like i.e. compound likely to be soluble in particular solvent if the intermolecular forces are similar in compound itself and the solvent: e.g.

C 2H5 H H O H H O
water and short-chain alcohols are miscible

methanol and acetone are miscible

C H3 C O H

H5C 2 O

H3C

H3C