The structure of metals The arrangement of the atoms

below. The right hand diagram shows the 8 atoms (4 above and 4 below) touching the darker coloured one. Crystal grains

Metals are giant structures of atoms held together by metallic bonds. "Giant" implies that large but variable numbers of atoms are involved - depending on the size of the bit of metal. 12-co-ordination Most metals are close packed - that is, they fit as many atoms as possible into the available volume. Each atom in the structure has 12 touching neighbours. Such a metal is described as 12-co-ordinated. Each atom has 6 other atoms touching it in each layer.

It would be misleading to suppose that all the atoms in a piece of metal are arranged in a regular way. Any piece of metal is made up of a large number of "crystal grains", which are regions of regularity. At the grain boundaries atoms have become misaligned.

There are also 3 atoms touching any particular atom in the layer above and another 3 in the layer underneath.

Note: Within a crystal grain you get rather subtle irregularities known as dislocations. It isn't important to know about these for UK A level Chemistry (or equivalent) purposes, although they turn out to be essential in discussing the workability of metals at a higher level. I haven't included a description of them here because it is quite difficult to visualise how they work, and I don't want to add unnecessary complications.

The physical properties of metals Melting points and boiling points This second diagram shows the layer immediately above the first layer. There will be a corresponding layer underneath. (There are actually two different ways of placing the third layer in a close packed structure, but that goes beyond the requirements of current A'level syllabuses.) 8-co-ordination Some metals (notably those in Group 1 of the Periodic Table) are packed less efficiently, having only 8 touching neighbours. These are 8-co-ordinated. Metals tend to have high melting and boiling points because of the strength of the metallic bond. The strength of the bond varies from metal to metal and depends on the number of electrons which each atom delocalises into the sea of electrons, and on the packing. Group 1 metals like sodium and potassium have relatively low melting and boiling points mainly because each atom only has one electron to contribute to the bond - but there are other problems as well:

Group 1 elements are also inefficiently packed (8-co-ordinated), so that they aren't forming as many bonds as most metals. They have relatively large atoms (meaning that the nuclei are some distance from the delocalised electrons) which also weakens the bond.

The left hand diagram shows that no atoms are touching each other within a particular layer . They are only touched by the atoms in the layers above and

Electrical conductivity

Metals conduct electricity. The delocalised electrons are free to move throughout the structure in 3dimensions. They can cross grain boundaries. Even though the pattern may be disrupted at the boundary, as long as atoms are touching each other, the metallic bond is still present. Liquid metals also conduct electricity, showing that although the metal atoms may be free to move, the delocalisation remains in force until the metal boils.

The hardness of metals This rolling of layers of atoms over each other is hindered by grain boundaries because the rows of atoms don't line up properly. It follows that the more grain boundaries there are (the smaller the individual crystal grains), the harder the metal becomes. Offsetting this, because the grain boundaries are areas where the atoms aren't in such good contact with each other, metals tend to fracture at grain boundaries. Increasing the number of grain boundaries not only makes the metal harder, but also makes it more brittle. Controlling the size of the crystal grains

Thermal conductivity Metals are good conductors of heat. Heat energy is picked up by the electrons as additional kinetic energy (it makes them move faster). The energy is transferred throughout the rest of the metal by the moving electrons.

If you have a pure piece of metal, you can control the size of the grains by heat treatment or by working the metal. Heating a metal tends to shake the atoms into a more regular arrangement - decreasing the number of grain boundaries, and so making the metal softer. Banging the metal around when it is cold tends to produce lots of small grains. Cold working therefore makes a metal harder. To restore its workability, you would need to reheat it. You can also break up the regular arrangement of the atoms by inserting atoms of a slightly different size into the structure. Alloys such as brass (a mixture of copper and zinc) are harder than the original metals because the irregularity in the structure helps to stop rows of atoms from slipping over each other.

Strength and workability Malleability and ductility Metals are described as malleable (can be beaten into sheets) and ductile (can be pulled out into wires). This is because of the ability of the atoms to roll over each other into new positions without breaking the metallic bond. If a small stress is put onto the metal, the layers of atoms will start to roll over each other. If the stress is released again, they will fall back to their original positions. Under these circumstances, the metal is said to be elastic.

METALLIC BONDING

This page introduces the bonding in metals. It explains how the metallic bond arises and why its strength varies from metal to metal.

What is a metallic bond? If a larger stress is put on, the atoms roll over each other into a new position, and the metal is permanently changed. Metallic bonding in sodium Metals tend to have high melting points and boiling points suggesting strong bonds between the atoms. Even a metal like sodium (melting point 97.8C) melts

at a considerably higher temperature than the element (neon) which precedes it in the Periodic Table. Sodium has the electronic structure 1s22s22p63s1. When sodium atoms come together, the electron in the 3s atomic orbital of one sodium atom shares space with the corresponding electron on a neighbouring atom to form a molecular orbital - in much the same sort of way that a covalent bond is formed. The difference, however, is that each sodium atom is being touched by eight other sodium atoms - and the sharing occurs between the central atom and the 3s orbitals on all of the eight other atoms. And each of these eight is in turn being touched by eight sodium atoms, which in turn are touched by eight atoms - and so on and so on, until you have taken in all the atoms in that lump of sodium. All of the 3s orbitals on all of the atoms overlap to give a vast number of molecular orbitals which extend over the whole piece of metal. There have to be huge numbers of molecular orbitals, of course, because any orbital can only hold two electrons. The electrons can move freely within these molecular orbitals, and so each electron becomes detached from its parent atom. The electrons are said to be delocalised. The metal is held together by the strong forces of attraction between the positive nuclei and the delocalised electrons.

If you work through the same argument with magnesium, you end up with stronger bonds and so a higher melting point. Magnesium has the outer electronic structure 3s2. Both of these electrons become delocalised, so the "sea" has twice the electron density as it does in sodium. The remaining "ions" also have twice the charge (if you are going to use this particular view of the metal bond) and so there will be more attraction between "ions" and "sea". More realistically, each magnesium atom has one more proton in the nucleus than a sodium atom has, and so not only will there be a greater number of delocalised electrons, but there will also be a greater attraction for them. Magnesium atoms have a slightly smaller radius than sodium atoms, and so the delocalised electrons are closer to the nuclei. Each magnesium atom also has twelve near neighbours rather than sodium's eight. Both of these factors increase the strength of the bond still further. Metallic bonding in transition elements Transition metals tend to have particularly high melting points and boiling points. The reason is that they can involve the 3d electrons in the delocalisation as well as the 4s. The more electrons you can involve, the stronger the attractions tend to be. Note: If you aren't happy about the electronic structure of transition metals, then you might like to follow this link to revise it.

The metallic bond in molten metals In a molten metal, the metallic bond is still present, although the ordered structure has been broken down. The metallic bond isn't fully broken until the metal boils. That means that boiling point is actually a better guide to the strength of the metallic bond than melting point is. On melting, the bond is loosened, not broken. The electronic structures of atoms Relating orbital filling to the Periodic Table

This is sometimes described as "an array of positive ions in a sea of electrons". If you are going to use this view, beware! Is a metal made up of atoms or ions? It is made of atoms. Each positive centre in the diagram represents all the rest of the atom apart from the outer electron, but that electron hasn't been lost - it may no longer have an attachment to a particular atom, but it's still there in the structure. Sodium metal is therefore written as Na - not Na+. Metallic bonding in magnesium

UK syllabuses for 16 - 18 year olds tend to stop at krypton when it comes to writing electronic structures, but it is possible that you could be asked for structures for elements up as far as barium. After barium you have to worry about f orbitals as well as s, p and d orbitals and that's a problem for chemistry at a higher level. It is important that you look through past exam papers as well as your syllabus so that you can judge how hard the questions are likely to get. This page looks in detail at the elements in the shortened version of the Periodic Table above, and then shows how you could work out the structures of some bigger atoms. Important! You must have a copy of your syllabus and copies of recent exam papers. If you are studying a UKbased syllabus and haven't got them, follow this link to find out how to get hold of them.

What is an atomic orbital? Orbitals and orbits When a planet moves around the sun, you can plot a definite path for it which is called an orbit. A simple view of the atom looks similar and you may have pictured the electrons as orbiting around the nucleus. The truth is different, and electrons in fact inhabit regions of space known as orbitals. Orbits and orbitals sound similar, but they have quite different meanings. It is essential that you understand the difference between them. The impossibility of drawing orbits for electrons To plot a path for something you need to know exactly where the object is and be able to work out exactly where it's going to be an instant later. You can't do this for electrons. The Heisenberg Uncertainty Principle says - loosely that you can't know with certainty both where an electron is and where it's going next. (What it actually says is that it is impossible to define with absolute precision, at the same time, both the position and the momentum of an electron.) That makes it impossible to plot an orbit for an electron around a nucleus. Is this a big problem? No. If something is impossible, you have to accept it and find a way around it. Note: Over the years I have had a steady drip of questions from students in which it is obvious that they still think of electrons as orbiting around a nucleus which is completely wrong! I have added a page about why the idea of orbits is wrong to try to avoid having to say the same thing over and over again!

The first period Hydrogen has its only electron in the 1s orbital - 1s1, and at helium the first level is completely full - 1s2. The second period Now we need to start filling the second level, and hence start the second period. Lithium's electron goes into the 2s orbital because that has a lower energy than the 2p orbitals. Lithium has an electronic structure of 1s22s1. Beryllium adds a second electron to this same level 1s22s2. Now the 2p levels start to fill. These levels all have the same energy, and so the electrons go in singly at first. B C N 1s22s22px1 1s22s22px12py1 1s22s22px12py12pz1

Hydrogen's electron - the 1s orbital Note: In this diagram (and the orbital diagrams that follow), the nucleus is shown very much larger than it really is. This is just for clarity.

ATOMIC ORBITALS

This page explains what atomic orbitals are in a way that makes them understandable for introductory courses such as UK A level and its equivalents. It explores s and p orbitals in some detail, including their shapes and energies. d orbitals are described only in terms of their energy, and f orbitals only get a passing mention.

Suppose you had a single hydrogen atom and at a particular instant plotted the position of the one electron. Soon afterwards, you do the same thing, and find that it is in a new position. You have no idea how it got from the first place to the second. You keep on doing this over and over again, and gradually build up a sort of 3D map of the places that the electron is likely to be found.

In the hydrogen case, the electron can be found anywhere within a spherical space surrounding the nucleus. The diagram shows a cross-section through this spherical space. 95% of the time (or any other percentage you choose), the electron will be found within a fairly easily defined region of space quite close to the nucleus. Such a region of space is called an orbital. You can think of an orbital as being the region of space in which the electron lives. Note: If you wanted to be absolutely 100% sure of where the electron is, you would have to draw an orbital the size of the Universe!

Not all electrons inhabit s orbitals (in fact, very few electrons live in s orbitals). At the first energy level, the only orbital available to electrons is the 1s orbital, but at the second level, as well as a 2s orbital, there are also orbitals called 2p orbitals. A p orbital is rather like 2 identical balloons tied together at the nucleus. The diagram on the left is a cross-section through that 3-dimensional region of space. Once again, the orbital shows where there is a 95% chance of finding a particular electron. Taking chemistry further: If you imagine a horizontal plane through the nucleus, with one lobe of the orbital above the plane and the other beneath it, there is a zero probability of finding the electron on that plane. So how does the electron get from one lobe to the other if it can never pass through the plane of the nucleus? At this introductory level you just have to accept that it does! If you want to find out more, read about the wave nature of electrons.

What is the electron doing in the orbital? We don't know, we can't know, and so we just ignore the problem! All you can say is that if an electron is in a particular orbital it will have a particular definable energy. Each orbital has a name. The orbital occupied by the hydrogen electron is called a 1s orbital. The "1" represents the fact that the orbital is in the energy level closest to the nucleus. The "s" tells you about the shape of the orbital. s orbitals are spherically symmetric around the nucleus - in each case, like a hollow ball made of rather chunky material with the nucleus at its centre. The orbital on the left is a 2s orbital. This is similar to a 1s orbital except that the region where there is the greatest chance of finding the electron is further from the nucleus - this is an orbital at the second energy level. If you look carefully, you will notice that there is another region of slightly higher electron density (where the dots are thicker) nearer the nucleus. ("Electron density" is another way of talking about how likely you are to find an electron at a particular place.) 2s (and 3s, 4s, etc) electrons spend some of their time closer to the nucleus than you might expect. The effect of this is to slightly reduce the energy of electrons in s orbitals. The nearer the nucleus the electrons get, the lower their energy. 3s, 4s (etc) orbitals get progressively further from the nucleus. p orbitals

Unlike an s orbital, a p orbital points in a particular direction - the one drawn points up and down the page. At any one energy level it is possible to have three absolutely equivalent p orbitals pointing mutually at right angles to each other. These are arbitrarily given the symbols px, py and pz. This is simply for convenience - what you might think of as the x, y or z direction changes constantly as the atom tumbles in space. The p orbitals at the second energy level are called 2p x, 2py and 2pz. There are similar orbitals at subsequent levels - 3px, 3py, 3pz, 4px, 4py, 4pz and so on. All levels except for the first level have p orbitals. At the higher levels the lobes get more elongated, with the most likely place to find the electron more distant from the nucleus.

d and f orbitals In addition to s and p orbitals, there are two other sets of orbitals which become available for electrons to inhabit at higher energy levels. At the third level, there is a set of five d orbitals (with complicated shapes and names) as well as the 3s and 3p orbitals (3px, 3py, 3pz). At the third level there are a total of nine orbitals altogether. At the fourth level, as well the 4s and 4p and 4d orbitals there are an additional seven f orbitals - 16 orbitals in all. s, p, d and f orbitals are then available at all higher energy levels as well.

For the moment, you need to be aware that there are sets of five d orbitals at levels from the third level upwards, but you probably won't be expected to draw them or name them. Apart from a passing reference, you won't come across f orbitals at all. The order of filling orbitals Note: Some UK-based syllabuses will eventually want you to be able to draw, or at least recognise, the shapes of d orbitals. I am not including them now because I don't want to add confusion to what is already a difficult introductory topic. Check your syllabus and past papers to find out what you need to know. If you are a studying a UK-based syllabus and haven't got these, follow this link to find out how to get hold of them. Electrons fill low energy orbitals (closer to the nucleus) before they fill higher energy ones. Where there is a choice between orbitals of equal energy, they fill the orbitals singly as far as possible. This filling of orbitals singly where possible is known as Hund's rule. It only applies where the orbitals have exactly the same energies (as with p orbitals, for example), and helps to minimise the repulsions between electrons and so makes the atom more stable. The diagram (not to scale) summarises the energies of the orbitals up to the 4p level.

Fitting electrons into orbitals You can think of an atom as a very bizarre house (like an inverted pyramid!) - with the nucleus living on the ground floor, and then various rooms (orbitals) on the higher floors occupied by the electrons. On the first floor there is only 1 room (the 1s orbital); on the second floor there are 4 rooms (the 2s, 2px, 2py and 2pz orbitals); on the third floor there are 9 rooms (one 3s orbital, three 3p orbitals and five 3d orbitals); and so on. But the rooms aren't very big . . . Each orbital can only hold 2 electrons. A convenient way of showing the orbitals that the electrons live in is to draw "electrons-in-boxes". "Electrons-in-boxes" Orbitals can be represented as boxes with the electrons in them shown as arrows. Often an up-arrow and a down-arrow are used to show that the electrons are in some way different. Taking chemistry further: The need to have all electrons in an atom different comes out of quantum theory. If they live in different orbitals, that's fine - but if they are both in the same orbital there has to be some subtle distinction between them. Quantum theory allocates them a property known as "spin" - which is what the arrows are intended to suggest.

Notice that the s orbital always has a slightly lower energy than the p orbitals at the same energy level, so the s orbital always fills with electrons before the corresponding p orbitals. The real oddity is the position of the 3d orbitals. They are at a slightly higher level than the 4s - and so it is the 4s orbital which will fill first, followed by all the 3d orbitals and then the 4p orbitals. Similar confusion occurs at higher levels, with so much overlap between the energy levels that the 4f orbitals don't fill until after the 6s, for example. For UK-based exam purposes, you simply have to remember that the 4s orbital fills before the 3d orbitals. The same thing happens at the next level as well - the 5s orbital fills before the 4d orbitals. All the other complications are beyond the scope of this site. Knowing the order of filling is central to understanding how to write electronic structures. Follow the link below to find out how to do this.

A 1s orbital holding 2 electrons would be drawn as shown on the right, but it can be written even more quickly as 1s2. This is read as "one s two" - not as "one s squared". You mustn't confuse the two numbers in this notation: