Topic 3: Bonding and Structure

Syllabus
2017
Topic
Level
AS

Learning objectives

3.1Interpret evidence for the existence of ionsKnow and be able to interpret evidence for the existence of ions, limited to physical properties of ionic compounds, electron density maps and the migration of ions3.2The formation of ions in terms of loss or gain of electronsBe able to describe the formation of ions in terms of loss or gain of electrons3.3Draw dot-and-cross diagrams to show electrons in cations and anionsBe able to draw dot-and-cross diagrams to show electrons in cations and anions3.4Ionic crystals as giant lattices of ionsBe able to describe ionic crystals as giant lattices of ions3.5Ionic bonding is the result of strong net electrostatic attraction between ionsKnow that ionic bonding is the result of strong net electrostatic attraction between ions3.6The effects of ionic radius and ionic charge on the strength of ionic bondingUnderstand the effects of ionic radius and ionic charge on the strength of ionic bonding3.7Reasons for the trends in ionic radii down a group in the Periodic Table, and for a set of isoelectronic ionsUnderstand reasons for the trends in ionic radii down a group in the Periodic Table, and for a set of isoelectronic ions, including N3− to Al3+3.8The meaning of the term ‘polarisation’ as applied to ionsUnderstand the meaning of the term ‘polarisation’ as applied to ions3.9The polarising power of a cation depends on its radius and charge, and the polarisability of an anion also depends on itsUnderstand that the polarising power of a cation depends on its radius and charge, and the polarisability of an anion also depends on its radius and charge3.10Covalent bonding is the strong electrostatic attraction between two nuclei and the shared pair of electrons between themUnderstand that covalent bonding is the strong electrostatic attraction between two nuclei and the shared pair of electrons between them, based on the evidence: i the physical properties of giant atomic structures ii electron density maps for simple molecules3.11Draw dot-and-cross diagrams to show electrons in covalent substancesBe able to draw dot-and-cross diagrams to show electrons in covalent substances, including: i molecules with single, double and triple bonds ii species with dative covalent (coordinate) bonds, including Al2Cl6 and the ammonium ion3.12The different structures formed by giant lattices of carbon atomsBe able to describe the different structures formed by giant lattices of carbon atoms, including graphite, diamond and graphene, and discuss the applications of each3.13The meaning of the term ‘electronegativity’ as applied to atoms in a covalent bondUnderstand the meaning of the term ‘electronegativity’ as applied to atoms in a covalent bond3.14Ionic and covalent bonding are the extremes of a continuum of bonding typeKnow that ionic and covalent bonding are the extremes of a continuum of bonding type and be able to explain this in terms of electronegativity differences, leading to bond polarity in bonds and molecules, and to ionic bonding if the electronegativity is large enough3.15Distinguish between polar bonds and polar molecules and predict whether or not a given molecule is likely to be polarBe able to distinguish between polar bonds and polar molecules and predict whether or not a given molecule is likely to be polar3.16The principles of the electron-pair repulsion theory, used to interpret and predict the shapes of simple molecules and ionsUnderstand the principles of the electron-pair repulsion theory, used to interpret and predict the shapes of simple molecules and ions3.17The terms ‘bond length’ and ‘bond angle’Understand the terms ‘bond length’ and ‘bond angle’3.18And explain the shapes of, and bond angles in, BeCl2, BCl3, CH4, NH3, NH4+, H2O, CO2, gaseous PCl5, SF6 and C2H4Know and explain the shapes of, and bond angles in, BeCl2, BCl3, CH4, NH3, NH4+, H2O, CO2, gaseous PCl5, SF6 and C2H4.3.19Apply the electron-pair repulsion theory to predict the shapes of, and bond angles in, molecules and ions analogous to thoseBe able to apply the electron-pair repulsion theory to predict the shapes of, and bond angles in, molecules and ions analogous to those in 3.18 3D: Metallic bonding Students will be assessed on their ability to:3.20Metals consist of giant lattices of metal ions in a sea of delocalised electronsUnderstand that metals consist of giant lattices of metal ions in a sea of delocalised electrons3.21Metallic bonding is the strong electrostatic attraction between metal ions and the delocalised electronsKnow that metallic bonding is the strong electrostatic attraction between metal ions and the delocalised electrons3.22The models in 3.20 and 3.21 to interpret simple properties of metalsBe able to use the models in 3.20 and 3.21 to interpret simple properties of metals, including electrical conductivity and high melting temperature

Three kinds of evidence reveal ions

Ions are charged particles. No single observation is the whole model: physical properties, electron-density evidence and migration together support the existence of oppositely charged particles in ionic substances.

Evidence Observation Ionic interpretation
Physical properties Ionic solids usually have high melting temperatures, are brittle, do not conduct as solids, but conduct when molten or dissolved Strong attractions hold a lattice; charged ions become mobile only when the lattice is broken or the solid dissolves
Electron-density map Electron density is concentrated around separate positive and negative ion centres rather than shared evenly between adjacent atoms Electron transfer has produced distinguishable ions
Migration In an electric field, cations move to the negative electrode and anions to the positive electrode The particles carry opposite charges

For a coloured solution containing a blue cation and a yellow anion, movement of the two colours towards opposite electrodes is especially direct migration evidence. A complete circuit and an ion-conducting path are needed for the observation.

Conductivity alone does not prove that a solid contains mobile ions: metals conduct through delocalised electrons. Interpret the full pattern of evidence and the state of the substance.

Ions form when atoms lose or gain electrons

An atom becomes an ion by changing its number of electrons. Losing electrons leaves more protons than electrons and forms a cation; gaining electrons gives more electrons than protons and forms an anion.

Process Electron equation Check
sodium loses one electron NaNa++e\mathrm{Na \rightarrow Na^+ + e^-} charge changes from 0 to +1
magnesium loses two electrons MgMg2++2e\mathrm{Mg \rightarrow Mg^{2+} + 2e^-} charge changes from 0 to +2
chlorine gains one electron Cl+eCl\mathrm{Cl + e^- \rightarrow Cl^-} charge changes from 0 to −1
oxygen gains two electrons O+2eO2\mathrm{O + 2e^- \rightarrow O^{2-}} charge changes from 0 to −2

Balance both the number of atoms and the total charge. The electron is on the product side for electron loss and on the reactant side for electron gain.

Ion formation in chemical reactions changes electrons, not the number of protons. Changing proton number would change the element.

Dot-and-cross diagrams account for ionic electrons

A dot-and-cross diagram tracks the outer-shell electrons supplied by different atoms. Dots and crosses show electron origin; they do not represent different kinds of electron.

First determine the ions and their simplest whole-number ratio. Draw each ion in square brackets, show its outer shell after transfer, and write the charge outside the bracket. Repeat each ion the number of times required by the formula.

Compound Cations to draw Anions to draw Outer-shell result
NaCl\mathrm{NaCl} one [Na]+[\mathrm{Na}]^+ one [Cl][\mathrm{Cl}]^- Na+^+ has lost its outer electron; Cl^- has eight outer electrons
MgCl2\mathrm{MgCl_2} one [Mg]2+[\mathrm{Mg}]^{2+} two [Cl][\mathrm{Cl}]^- each chloride has one transferred electron
Al2O3\mathrm{Al_2O_3} two [Al]3+[\mathrm{Al}]^{3+} three [O]2[\mathrm{O}]^{2-} each oxide has eight outer electrons

Do not draw a shared pair or a line between ionic particles. The diagram shows electron transfer and ion charges, not a small covalent molecule.

An ionic crystal is a giant repeating lattice

An ionic crystal contains a three-dimensional, regularly repeating arrangement of cations and anions. Each ion is surrounded by ions of opposite charge in a pattern that extends throughout the crystal.

In a two-dimensional section, show alternating positive and negative ions in both row and column directions. A three-dimensional lattice continues the alternation through additional layers; the exact coordination depends on the compound.

The chemical formula gives the lowest whole-number ratio of ions needed for electrical neutrality. For example, NaCl means a 1:1 ratio and CaCl2_2 means a 1:2 ratio across the giant lattice.

An ionic formula such as NaCl does not identify one separate NaCl molecule. It states the ion ratio in the extended lattice.

Ionic bonding is net attraction through a lattice

Ionic bonding is the strong net electrostatic attraction between oppositely charged ions.

Every ion interacts with many surrounding ions. Opposite charges attract and like charges repel, but at the stable lattice spacing the overall arrangement has a strong net attraction and lower energy than widely separated ions.

The attraction acts in all directions through the giant lattice. This helps explain why separating ions requires substantial energy rather than breaking one isolated link.

Do not define an ionic bond as electron transfer. Transfer explains ion formation; the bond itself is electrostatic attraction between the ions after they form.

Charge and distance control ionic attraction

Ionic attraction becomes stronger when the charges are larger and when the distance between ion centres is smaller. Ionic radius affects that separation: smaller ions can approach more closely.

Change, with other factors comparable Effect on attraction Reason
+1+1 cation replaced by +2+2 cation stronger larger charge product
large cation replaced by smaller cation stronger smaller centre-to-centre distance
1-1 anion replaced by 2-2 anion stronger larger charge product

BaCl2_2 has stronger ionic attraction than CsCl because Ba2+^{2+} has a higher charge and is smaller than Cs+^+. More energy is therefore needed to separate its ions, consistent with its higher melting temperature.

When comparing real melting temperatures, control both charge and radius and remember that lattice structure can also matter. Do not use charge alone if ion sizes differ.

Ionic-radius trends follow shells and nuclear charge

For ions with the same charge down a group, ionic radius increases. Each step adds an occupied electron shell; the greater distance and shielding outweigh the increased nuclear charge.

Ion Protons Electrons Relative position in the sequence
N3\mathrm{N^{3-}} 7 10 largest
O2\mathrm{O^{2-}} 8 10 smaller
F\mathrm{F^-} 9 10 smaller
Na+\mathrm{Na^+} 11 10 smaller
Mg2+\mathrm{Mg^{2+}} 12 10 smaller
Al3+\mathrm{Al^{3+}} 13 10 smallest

All ions from N3^{3-} to Al3+^{3+} are isoelectronic: they have ten electrons and the same occupied-shell pattern. As proton number increases, the same electron cloud experiences stronger nuclear attraction, so radius decreases.

Do not explain the isoelectronic sequence by changing electron-shell number: it is constant across this set. The changing variable is nuclear charge.

Polarisation is distortion of an ion's electron cloud

Polarisation occurs when a cation attracts and distorts the electron cloud of a neighbouring anion.

The anion's electrons are drawn towards the cation, so the electron distribution is no longer symmetrical. Greater distortion increases electron density between the nuclei and gives the bonding more covalent character.

The cation has polarising power; the anion is polarisable. These terms describe the ability to cause distortion and the ease of being distorted, respectively.

Polarisation of an ion is electron-cloud distortion. It is not the same as making an entire molecule polar, which depends on bond dipoles and molecular shape.

Ion size and charge govern polarisation

Particle property Consequence Explanation
small cation greater polarising power its positive charge is concentrated close to the anion
cation with higher positive charge greater polarising power it attracts the anion's electrons more strongly
large anion greater polarisability outer electrons are farther from their nucleus and more shielded
anion with greater negative charge, for a sensible comparison usually greater polarisability the larger, more electron-rich cloud is more readily distorted

The greatest distortion is expected when a small, highly charged cation is next to a large, highly charged anion. The bonding then shows more covalent character than a simple ionic model predicts.

F^- is difficult to polarise because it is small and carries only a single negative charge. Al3+^{3+} has much greater polarising power than Na+^+ because it is smaller and has a higher charge.

State whether you are discussing polarising power of a cation or polarisability of an anion; they are related but not interchangeable properties.

A shared electron pair attracts two nuclei

A covalent bond is the strong electrostatic attraction between two nuclei and a shared pair of electrons between them.

Evidence Observation Covalent interpretation
Electron-density map of a simple molecule increased electron density lies between bonded nuclei the bonding pair is shared between the atoms
Giant atomic structure very high melting temperature and hardness are common; most do not conduct many strong covalent bonds extend through a giant network and require much energy to break

Both nuclei attract the negatively charged shared pair. A stable bond length is reached where the attractions lower the energy while nucleus–nucleus and electron–electron repulsions prevent collapse.

Covalent bonding is not simply 'atoms sharing electrons'. The defining force is electrostatic attraction between the shared pair and both nuclei.

Dot-and-cross diagrams show shared and donated pairs

Show outer-shell electrons only, using one symbol for electrons from each starting atom. A single, double or triple bond contains one, two or three shared pairs. Add every lone pair needed to complete the outer-shell accounting.

Species What the diagram must show
H2_2, O2_2, N2_2 one, two and three shared pairs respectively
NH4+_4^+ NH3_3 donates its nitrogen lone pair to H+^+; enclose the resulting ion in brackets with an overall + charge
Al2_2Cl6_6 two bridging chlorines; for each bridge, a chlorine lone pair is donated to an electron-deficient aluminium centre

In a dative covalent bond, both electrons in the shared pair originally come from the same donor atom. Once formed, the pair is attracted to both nuclei like any other covalent bond.

Dots and crosses record electron origin, not charge. Do not omit lone pairs or overall brackets and charge when drawing an ion such as NH4+_4^+.

Carbon lattices link structure to application

Allotrope Structure and bonding Key properties Example applications
diamond each C forms four covalent bonds in a rigid 3D tetrahedral lattice very hard, high melting temperature, no mobile electrons cutting and abrasive tools
graphite each C forms three bonds in planar hexagonal layers; one electron per C is delocalised; weak forces act between layers conducts along layers; layers slide; high melting temperature electrodes, lubricants
graphene one atom-thick hexagonal sheet; each C forms three bonds with delocalised electrons across the sheet strong, light and electrically conducting conductive electronics and reinforcing composites

Applications follow from structure: continuous strong bonds resist deformation, delocalised electrons carry charge, and weak attractions between graphite layers allow sliding.

Graphite is not soft because its covalent bonds are weak. Strong bonds hold each layer; softness comes from weak attractions between layers.

Electronegativity measures attraction for a bonding pair

Electronegativity is the ability of an atom in a covalent bond to attract the shared pair of electrons towards itself.

If two bonded atoms have different electronegativities, the more electronegative atom attracts the pair more strongly and becomes partially negative, δ\delta-; the other becomes partially positive, δ+\delta+.

Electronegativity is used comparatively. The difference between the two bonded atoms, rather than either value by itself, helps predict how unevenly the pair is shared.

Electronegativity is not an atom's charge and it is not the same as electron affinity. It describes an atom while it is covalently bonded.

Bonding lies on an ionic–covalent continuum

Covalent and ionic bonding are limiting models on a continuum. As the electronegativity difference between bonded atoms increases, electron sharing becomes more unequal: bond polarity and ionic character increase.

Electronegativity difference Useful description Electron distribution
zero or very small non-polar covalent shared nearly equally
intermediate polar covalent shifted towards the more electronegative atom, producing partial charges
very large predominantly ionic described mainly as oppositely charged ions

Using Ba 0.9, Be 1.5 and Cl 3.0, ΔEN\Delta EN is 2.1 for Ba–Cl but 1.5 for Be–Cl. BaCl2_2 therefore has more ionic character, while BeCl2_2 has more covalent character.

Do not treat one numerical cut-off as a universal switch. Electronegativity difference supports a continuum comparison; polarisation and structure also refine the model.

Polar bonds do not always make a polar molecule

A polar bond has unequal electron sharing and a bond dipole. A polar molecule has a non-zero resultant dipole after all bond dipoles are combined as vectors.

Step Question to ask
1 Which bonds are polar, and towards which atom does each dipole point?
2 What is the molecule's three-dimensional shape?
3 Do equal dipoles cancel by symmetry, or is there a non-zero resultant?

CO2_2 has two polar C=O bonds but is linear, so equal opposing dipoles cancel and the molecule is non-polar. H2_2O is bent, so its O–H dipoles do not cancel and the molecule is polar. Symmetrical BF3_3 and CCl4_4 are also non-polar despite polar bonds.

A molecule is not automatically polar because it contains polar bonds. Shape and symmetry decide whether the vector sum is zero.

Electron regions arrange for maximum separation

Electron pairs around a central atom repel one another and adopt an arrangement that keeps them as far apart as possible. Both bonding pairs and lone pairs must be counted.

Step Action
1 draw or infer the central atom's bonding and lone pairs
2 count regions of electron density; a single, double or triple bond counts as one region
3 arrange all regions for maximum separation
4 name the molecular shape from atom positions, then adjust angles for lone-pair repulsion

Repulsion strength follows lone pair–lone pair > lone pair–bond pair > bond pair–bond pair because a lone pair is held by only one nucleus and occupies more space near the central atom.

Electron-region geometry includes lone pairs, but the named molecular shape uses only atom positions. Do not count a double bond as two separate directions.

Bond length is a distance; bond angle is an angle

Bond length is the equilibrium distance between the nuclei of two bonded atoms. It is commonly measured in picometres or nanometres.

Bond angle is the angle between two bonds that meet at the same central atom. The three atoms defining it must be identified; for H–O–H, oxygen is the vertex.

A bond length is an equilibrium value because attraction and repulsion balance at the minimum-energy separation. Bond angles describe the spatial arrangement produced by electron-region repulsions.

Bond length is not the distance between electron pairs, and a bond angle cannot be assigned without specifying the central atom and the two bond directions.

Required molecules follow electron-pair geometry

Species Central electron regions Shape Bond angle(s)
BeCl2_2 2 bonding, 0 lone linear 180°
BCl3_3 3 bonding, 0 lone trigonal planar 120°
CH4_4 4 bonding, 0 lone tetrahedral 109.5°
NH3_3 3 bonding, 1 lone trigonal pyramidal 107°
NH4+_4^+ 4 bonding, 0 lone tetrahedral 109.5°
H2_2O 2 bonding, 2 lone bent 104.5°
CO2_2 2 bonding, 0 lone linear 180°
PCl5_5(g) 5 bonding, 0 lone trigonal bipyramidal 90°, 120°, 180°
SF6_6 6 bonding, 0 lone octahedral 90°, 180°
C2_2H4_4 3 regions at each C trigonal planar around each C; molecule planar about 120°

For two to six regions with no lone pairs, maximum separation gives linear, trigonal planar, tetrahedral, trigonal bipyramidal and octahedral arrangements. Lone pairs compress bond angles: CH4_4 109.5° becomes NH3_3 107° and H2_2O 104.5° as lone pairs are added.

The C=C double bond in ethene is one electron region around each carbon. Do not count it twice when predicting the trigonal-planar arrangement.

Apply the same repulsion method to analogous species

For an unfamiliar molecule or ion, determine the central atom's bonding pairs, lone pairs and overall charge, then use the same electron-region patterns as the required examples. Analogy means the same relevant region count, not merely a similar formula.

Unfamiliar species Electron-region analogy Prediction
CS2_2 CO2_2: two bonding regions linear, 180°
BF4_4^- CH4_4/NH4+_4^+: four bonding regions tetrahedral, 109.5°
PH3_3 NH3_3: three bonding regions and one lone pair trigonal pyramidal; angle less than 109.5°
SO2_2 three regions, one of them a lone pair bent; angle less than 120°

Include the ion's charge when counting electrons. After arranging all electron regions, ignore lone-pair positions when naming the molecular shape.

Do not copy an exact bond angle from an analogy when different atoms or multiple bonds alter repulsion. Use ideal angles where appropriate and state a justified 'less than' prediction when lone pairs compress them.

A metal is an ion lattice in delocalised electrons

A metal consists of a giant, regular lattice of positive metal ions surrounded by a sea of delocalised electrons.

Outer electrons are no longer attached to one particular atom or one ion–ion pair. They move throughout the lattice, while the total negative charge of the electrons balances the total positive charge of the ions.

In a particle diagram, show closely packed positive ions in repeating layers and many electrons distributed between them. The diagram represents a continuous giant structure, not separate molecules.

The lattice positions are occupied by positive metal ions, not neutral atoms. The delocalised electrons remain part of the metal and preserve overall electrical neutrality.

Metallic bonding is non-directional electrostatic attraction

Metallic bonding is the strong electrostatic attraction between positive metal ions and delocalised electrons.

Each ion is attracted to the shared electron sea around many ions. The attraction is non-directional and extends throughout the giant lattice.

More delocalised electrons per ion and a higher ion charge can strengthen the attraction; smaller metal ions also bring charge centres closer, when other structural factors are comparable.

Metallic bonding is not attraction between positive ions, which would repel. The delocalised electrons provide the negative charge attracted to the ions.

The metallic model explains conductivity and melting

Property Model-based explanation
electrical conductivity delocalised electrons are mobile and carry charge through the lattice when a potential difference is applied
high melting temperature much energy is needed to weaken the strong attraction between positive ions and delocalised electrons throughout the giant lattice
malleability layers of ions can shift while remaining attracted to the non-directional electron sea, so the structure can change shape without immediately shattering

Magnesium usually has stronger metallic bonding than sodium because each Mg atom contributes two delocalised electrons and forms Mg2+^{2+}, whereas sodium contributes one and forms Na+^+; Mg2+^{2+} is also smaller. The attraction is therefore stronger and more energy is required to overcome it.

Metals conduct as solids and when molten because their charge carriers are electrons, which remain mobile in both states. This contrasts with an ionic solid, whose ions are fixed until it melts or dissolves.

Do not say that heating 'breaks metal ions'. Melting weakens enough metallic attraction for the ordered lattice to lose its fixed structure; the ions themselves remain ions.