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4 Bonding and structure

4.1 Investigating structure and bonding
The regular shapes of crystals suggest an underlying arrangement of the atoms, ions and molecules in their structure. X-rays can be used to investigate crystal structures because their wavelengths are about the same as the distances between atoms in a crystal. A narrow beam of x-rays is directed at a crystal of the substance being studied The atoms of ions in the crystal scatter the X-rays producing a pattern of diffracted rays. The diffracted X-rays - photographed using X-ray > can be recorded electronically From the diffraction pattern it is possible to deduce the 3D crystal structure by studying the pattern If we know how the structure/bonding then we can explain the properties. e.g. copper Freely moving outer electrons can move when connected to battery good conductor Atoms closely packed can slide over each other drawn into wires

4.2 Two types of structure

Giant structures form crystals which all the atoms/ions are linked by a network of strong bonds extending throughout. These strong bonds result in high melting / boiling temperatures. e.g. metals, ionic solids, polymers, ceramics, glasses All of these are solids that depend on their properties by three types of strong bonding : metallic, ionic and covalent The strength of each bond depends on electrostatic attractions between positive and negative charges Simple molecular structure small groups of atoms bonds linking atoms are relatively strong, but the forces between molecules are weak. Such weak forces allow the molecule to be separated easily so they have low melting and boiling temperatures.

4.3 Metallic bonding and structures

X-rays atoms in most metals are packed closely together close packing One layer of a metal crystal each atom in the middle of the layer touches six other atoms in the same layer When a second layer is placed on top of the first, atoms in this layer sink into the dips between atoms in the first layer. This closely packing allows atoms in one layer to get as close as possible to those in the next layer, forming a giant lattice of closely packed atoms in a regular pattern, In this giant lattice, electrons in the outer shell of each metal atom are free to drift through the whole structure. These electrons dont have fixed positions they are described as delocalised.

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2 Metals giant lattice positive ions with electrons moving around and between them in a sea of delocalised negative charge. The strong electrostatic attractions between the positive metal ions and the sea of delocalised electrons result in strong forces between the metal atoms. Lattice- a regular arrangement of atoms or ions in a crystal The properties of metals high melting and boiling temperatures - metal atoms are closely packed with strong forces of attraction between the positive ions and delocalised electrons takes a lot of energy to move positive ions away from their positions in the giant lattice and move around each other allowing the metal to melt. It takes even more energy to separate individual atoms in the metal at the boiling temperature. high densities good conductors of heat/electricity When a metal is heated energy is transferred to the electrons as they are delocalised they move around faster and conduct heat energy rapidly to other parts of the metal malleable bent into shapes the bonds between metal atoms are strong but they are not directional because the delocalised electrons can drift throughout the lattice and attract any of the positive ions. When a force is applied to a metal, lines or layers of atoms can slide over each other. This is known as a slip. After slipping the atoms settle into close-packed positions again. Delocalised electrons bonding electrons which are not fixed between two atoms in a bond they are free to move and shared by many more atoms. Metallic bonding strong attraction between a lattice of positive metal ions and a sea of delocalised electrons.

4.4 Ionic bonding and structures

Atoms into ions Compounds of metals with non-metals such as sodium chloride and calcium oxide, are composed of ions. When compounds form between metals and non-metals, the metal atoms lose electrons and become positive ions (cations) The non-metal gains electrons and becomes an anion In many cases when atoms react to form ions they gain or lose electrons in such a way that the ions formed have the same electron configuration as a noble gas. The transfer of electrons involves redox Ionic bonding When metals react with non-metals the ions produced form ionic crystals which are giant lattices containing billions of positive and negative ions packed together in a regular pattern. Each ion is surrounding by other ions of the other element. Overall there are strong electrostatic attractions between ions in all directions throughout the lattice. These electrostatic attractions between oppositely charged ions are described as ionic bonding

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3 Properties of ionic compounds Strong ionic bonds hold the ions firmly together in ionic compounds hard crystalline substances high melting / boiling temperatures soluble in water/polar solvents but not non-polar solvents cant conduct electricity when solid as ions cant move from fixed positions in giant lattice conduct electricity when melted/dissolved charged ions are free to move Positive ions (cations) move towards the negative terminal (cathode) Negative ions (anions) move towards the positive terminal (anode) When the cations reach the cathode they gain electrons and return to atoms. When the anions reach the anode they lose electrons and become atoms. This process is described as electrolysis where it reverses the changes that happen when an ionic compound forms from its elements. Electrolysis decomposition of a compound by electricity the compound is usually decomposed into its constituent elements. The compound which is decomposed is called an electrolyte and we say that it has been electrolysed. Ionic radii X-ray diffraction methods are used to study ionic compounds and to measure the spacing between ions in crystals. The patterns allow the calculation of the radii of individual ions The radius of positive ion of an element is smaller that its atomic radius because it loses electrons from its outer shell when turning into an ion. The radius of a negative ion of an element is larger than its atomic radius because it gains electrons in its outer shell when turning into an ion.

4.5 Energy changes and ionic bonding

When sodium reacts with chlorine sodium starts as a giant structure of atoms energy is required to separate the sodium atoms (enthalpy change of atomisation) energy is required to remove electrons (first ionisation energy) to form sodium ions chlorine consists of molecules energy is required to separate the chlorine atoms (the enthalpy change of atomisation) energy is involved (the electron affinity) in adding one electron to each chlorine atom to form a chloride ions. Ionic crystals are stable because of the release of energy when oppositely charged ions come together forming a crystal lattice. This is called the lattice energy of the ionic compound. Na+ + Cl- NaCl

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The strength of ionic bonds, measured as lattice energies in kJ mol arises from the energy given out as millions of positive and negative ions come together to form a crystal lattice. The energy released is greater and the force of attraction between the ions is stronger if: the charges on the ions are large the ions are small allowing them to get closer to each other It is important to distinguish between the lattice energy of a compound and its standard enthalpy change of formation, which involves the formation of a compound from its elements.

First electron affinity energy change when each atom in mole of gaseous atoms gains one electron to form one mole of gaseous ions with a single negative charge. The gain of the first electron is exothermic, but adding the second electron to a negatively charged ion is endothermic. Lattice energy standard enthalpy change when one mole of the compound forms from free gaseous ions.

4.6 Born-Haber cycles

These are an application of Hesss Law which enable chemists to calculate lattice energies which cant be measured directly. It identifies all the enthalpy changes which contribute to the standard enthalpy change of formation of a compound. Such changes involve: the energy required to create free gaseous ions by atomising and then ionising the elements. the energy given out (the lattice energy) when the ions come together to form a crystal. A Born-Haber cycle is usually set out as an enthalpy level diagram where everything can be measured experimentally apart from the lattice energy so this can be calculated using Hesss law. Exothermic change in one direction becomes an endothermic change in the reverse direction

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4.7 Testing the ionic model covalent or ionic

Born-Haber cycles help as they enable chemists to test the ionic model and check whether the bonding in a compound is truly ionic. The experimental lattice energy calculated from a cycle can be compared with the theoretical value calculated using the laws of electrostatics and assuming that the only bonding in the crystal is ionic. Using the law of electrostatics, it is possible to calculate a theoretical value for the lattice energy of an ionic compound by summing the effects of all the attractions and repulsions between the ions in the crystal lattice. Pure ionic bonding arises solely from the electrostatic forces between the ions in a crystal. Where the experimental values are larger than the theoretical values for lattice energy, it is assumed that covalent bonding is also included with the substances. Polarisation distortion of the electron cloud in a molecule/ion by a nearby charge.

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6 Polarisation of ions. In ionic compounds positive metal ions will attract the outermost electrons of negative ions, pulling electrons into the space between the ions. This distortion of the electron clouds around anions by positively charged cations is an example of polarisation. Polarisation of negative anions by positive metal ions gives rise to some electron sharing that is to a degree of covalent bonding. The polarising power of a cation depends on its charge and its radius. The polarisability of an anion depends on its size. The larger the negative ion and the larger its charge the more polarisable it becomes. The stability of ionic compounds Almost all the compounds of metals with non-metals are ionic these have standard enthalpy changes of formation which are exothermic. This means that the compounds are at a lower energy lower and therefore more stable than their constituent elements. An ionic compound will have an exothermic standard enthalpy of formation if its negative lattice energy can outweigh the total energy needed to produce gaseous ions from the elements.

4.8 Covalent bonding and structures

Simple molecular structures Non-metals atom join together as molecules Non-metals with other non-metals usually have simple molecular structures e.g. H2O The covalent bonds holding atoms together within these simple molecular structures are strong, so the molecules do not break up into atoms easily. However, the forces between the individual molecules (intermolecular forces are weak so it is quite easy to separate them). This means that molecular substances are often liquids or gases at room temperature and that molecular solids are usually easy to melt and evaporate. Properties of simple molecular Usually gases, liquids or soft solids at room temperature Have relatively low melting and boiling temperatures Do not conduct electricity as solids, liquids or gases because they contain neither ions nor free electrons to carry the electric charge Are usually more soluble in non-polar solvents such as hexane than in water, and the solutions do not conduct electricity.

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Giant covalent structures A few non-metal elements including diamond, graphite and silicon consist of giant structures of atoms held together by covalent bonding. The covalent bonds in diamond are strong and point in a definite direction so diamonds are very hard and have very high melting temperatures. Diamond does not conduct electricity because the electrons in its covalent bonds are fixed localised between pairs of atoms. Some compounds of non-metals, such as silicon dioxide and boron nitride also have giant structures with covalent bonding. These compounds are also hard non-conductors

4.9 Covalent bonding

Strong covalent bonding holds the atoms of non-metals together in molecules and giant structures Covalent bonds form when atoms share electrons a single covalent bond consists of a shared pair of electrons The atoms are held together by the electrostatic attraction between the positive charges on their nuclei and the negative charge on the shared electrons. The electron configuration of fluorine is 2,7 when two fluorine atoms combine to form a molecule they share two electrons the electron configuration of each atom is then like that of neon, the nearest noble gas. Multiple bonds One shared pair of electrons makes a single bond Double bonds and triple bonds are also possible with two or three shared pairs There are two covalent bonds between both the oxygen atoms and the carbon atom in carbon dioxide. With two electron pairs involved in the bonding there is a region of high electron density between the two atoms joined by a double bond. Lone pairs of electrons In many molecules there are atoms with pairs of electrons in their outer shells not involved in the bonding between atoms in the molecule. These affect the shapes of molecules / form dative covalent bonds / are important in the reactions of some compounds (water and ammonia) [draw electron diagrams count no of paired electrons] Dative covalent bond bond in which two atoms share a pair of electrons, both the electrons being donated by one atom. In a covalent bond two atoms share a pair of electrons usually each atom supplies one electron to make up the pair. (once formed there is no different between a dative covalent bond any other covalent bond)

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