Sei sulla pagina 1di 2267

chemguide: helping you to understand Chemistry - Main Menu

             
   

chemguide

   
 

Helping you to understand Chemistry

 

You can search Chemguide either using a keyword search (courtesy of Google) or the menu system.

See the bottom of this page for the latest additions and updates.

 
 

Keyword searching

           
     
   

Search www

Search chemguide

 
             

Notes: If you don't find what you want, use the BACK button on your browser to return to this page.

Remember that this is a UK site, so spellings will be English. Take care if you want to search for words like sulphur, sulphate, sulphuric acid or aluminium.

Searching using the menus

Atomic Structure and Bonding

Covers basic atomic properties (electronic structures, ionisation energies, electron affinities, atomic and ionic radii), bonding (including intermolecular bonding) and structures (ionic, molecular, giant covalent and metallic).

chemguide: helping you to understand Chemistry - Main Menu

Inorganic Chemistry

Physical Chemistry

Instrumental analysis

Basic Organic Chemistry

Properties of organic compounds

Organic Reaction Mechanisms

About this site

Chemistry Calculations

Includes essential ideas about redox reactions, and covers the trends in Groups 2, 4 and 7 of the Periodic Table. Plus: lengthy sections on the chemistry of some important complex ions, and of common transition metals.

Covers rates of reaction including catalysis, an introduction to chemical equilibria, redox equilibria, acid-base equilibria (pH, buffer solutions, indicators, etc) and phase equilibria (including Raoult's Law and the use

of various phase diagrams).

Explains how you can analyse substances using machines - mass spectrometry, infra-red spectroscopy and NMR.

Includes help on bonding, naming and isomerism, and a discussion of organic acids and bases.

Covers the physical and chemical properties of compounds on UK A level chemistry syllabuses.

Covers all the mechanisms required by the current UK A level chemistry syllabuses.

Includes a contact address if you have found any difficulties with the site.

A description of the author's book on

calculations at UK A level chemistry standard.

chemguide: helping you to understand Chemistry - Main Menu

Textbook suggestions

Download syllabuses

Suggestions for textbooks and revision guides covering the UK AS and A level chemistry syllabuses, with links to Amazon.co.uk if you want to follow them up.

For UK A level students. Download a copy of your current syllabus from your Exam Board.

A link to Dr Phil Brown's website

where UK GCSE, AS and A level chemistry students will find a wide and growing range of multiple

choice, short answer and structured questions.

A link to Rod Beavon's chemistry

pages. Rod Beavon is chief examiner for A level chemistry for the UK exam board Edexcel. A close look at what he has to offer is a must for Edexcel students, but there is a lot of good stuff whatever exam system you are working in.

Latest additions and important updates

5/12/2004

There is now the beginnings of a section on phase equilibria. I'm working on it at the moment and it is unlikely to be finished before the end of January. It currently deals with vapour pressure, phase diagrams for pure substances and for solutions of non-volatile solutes (including the effect of the solute on the boiling point and freezing point of the solvent).

18/12/2004

An introduction to phase diagrams involving eutectic mixtures is now available using the tin-lead system.

chemguide: helping you to understand Chemistry - Main Menu

© Jim Clark 2004

Understanding Chemistry - Atomic Structure and Bonding Menu

Understanding Chemistry

ATOMIC STRUCTURE AND BONDING MENU

Basic atomic properties

Includes a discussion of orbitals, electronic structures of atoms and ions, ionisation energies, electron affinities, atomic and ionic radii.

Bonding

Includes ionic, covalent, co-ordinate (dative covalent) and metallic bonding as well as intermolecular attractions like Van der Waals forces and hydrogen bonding. Also includes full discussions of electronegativity and shapes of molecules and ions.

Types of structure

Describes and explains how the various types of structure (ionic, giant covalent, metallic, and molecular) affect physical properties.

Go to Main Menu

© Jim Clark 2000

Atomic properties menu

Understanding Chemistry

ATOMIC PROPERTIES MENU

Simple background

Revises the simple knowledge you should already have about the structure of atoms from introductory courses (e.g. GCSE).

Atomic orbitals

Explains what atomic orbitals are and discusses their shapes and relative energies. This is essential pre-reading before you go on to any of the remaining topics in this section.

Electronic structures

How to work out and write the electronic structures for atoms and simple monatomic ions (containing only one atom - e.g. Cl - or Mg 2 + ) using s, p, d notation.

Ionisation energies

Explains what ionisation energies are and how and why they vary around the Periodic Table.

Electron affinities

Explains what electron affinities are and how and why they vary around the Periodic Table.

Atomic and ionic radii

Atomic properties menu

Looks at the various measures of atomic radius, and explains how and why atomic radii vary around the Periodic Table. Also considers how the radii of positive and negative ions differ from the atoms they come from.

Go to atomic structure and bonding menu

Go to Main Menu

© Jim Clark 2000

a simple view of atomic structure

A SIMPLE VIEW OF ATOMIC STRUCTURE

This page revises the simple ideas about atomic structure that you will have come across in an introductory chemistry course (for example, GCSE). You need to be confident about this before you go on to the more difficult ideas about the atom which under-pin A'level chemistry.

The sub-atomic particles

Protons, neutrons and electrons.

relative mass

relative charge

proton

1

+1

neutron

1

0

electron

1/1836

-1

Beyond A'level: Protons and neutrons don't in fact have exactly the same mass - neither of them has a mass of exactly 1 on the carbon-12 scale (the scale on which the relative masses of atoms are measured). On the carbon-12 scale, a proton has a mass of 1.0073, and a neutron a mass of 1.0087.

a simple view of atomic structure

The nucleus

The nucleus is at the centre of the atom and contains the protons and neutrons. Protons and neutrons are collectively known as nucleons.

Virtually all the mass of the atom is concentrated in the nucleus, because the electrons weigh so little.

Working out the numbers of protons and neutrons

No of protons = ATOMIC NUMBER of the atom

The atomic number is also given the more descriptive name of proton number.

No of protons + no of neutrons = MASS NUMBER of the atom

The mass number is also called the nucleon number.

This information can be given simply in the form:

number. This information can be given simply in the form: How many protons and neutrons has

How many protons and neutrons has this atom got?

The atomic number counts the number of protons (9); the mass number counts protons + neutrons (19). If there are 9 protons, there must be 10 neutrons for the total to add up to 19.

The atomic number is tied to the position of the element in the Periodic Table and therefore the number of protons defines what sort of element

a simple view of atomic structure

you are talking about. So if an atom has 8 protons (atomic number = 8), it must be oxygen. If an atom has 12 protons (atomic number = 12), it must be magnesium.

Similarly, every chlorine atom (atomic number = 17) has 17 protons; every uranium atom (atomic number = 92) has 92 protons.

Isotopes

The number of neutrons in an atom can vary within small limits. For example, there are three kinds of carbon atom 12 C, 13 C and 14 C. They all have the same number of protons, but the number of neutrons varies.

protons

neutrons

mass number

carbon-12

6

6

12

carbon-13

6

7

13

carbon-14

6

8

14

These different atoms of carbon are called isotopes. The fact that they have varying numbers of neutrons makes no difference whatsoever to the chemical reactions of the carbon.

Isotopes are atoms which have the same atomic number but different mass numbers. They have the same number of protons but different numbers of neutrons.

The electrons

Working out the number of electrons

Atoms are electrically neutral, and the positiveness of the protons is balanced by the negativeness of the electrons. It follows that in a neutral atom:

no of electrons = no of protons

a simple view of atomic structure

So, if an oxygen atom (atomic number = 8) has 8 protons, it must also have 8 electrons; if a chlorine atom (atomic number = 17) has 17 protons, it must also have 17 electrons.

The arrangement of the electrons

The electrons are found at considerable distances from the nucleus in a series of levels called energy levels. Each energy level can only hold a certain number of electrons. The first level (nearest the nucleus) will only hold 2 electrons, the second holds 8, and the third also seems to be full when it has 8 electrons. At GCSE you stop there because the pattern gets more complicated after that.

These levels can be thought of as getting progressively further from the nucleus. Electrons will always go into the lowest possible energy level (nearest the nucleus) - provided there is space.

To work out the electronic arrangement of an atom

Look up the atomic number in the Periodic Table - making sure that you choose the right number if two numbers are given. The atomic number will always be the smaller one.

This tells you the number of protons, and hence the number of electrons.

Arrange the electrons in levels, always filling up an inner level before you go to an outer one.

e.g. to find the electronic arrangement in chlorine

The Periodic Table gives you the atomic number of 17.

Therefore there are 17 protons and 17 electrons.

The arrangement of the electrons will be 2, 8, 7 (i.e. 2 in the first level, 8 in the second, and 7 in the third).

The electronic arrangements of the first 20 elements

a simple view of atomic structure

a simple view of atomic structure After this the pattern alters as you enter the transition

After this the pattern alters as you enter the transition series in the Periodic Table.

Two important generalisations

If you look at the patterns in this table:

The number of electrons in the outer level is the same as the group number. (Except with helium which has only 2 electrons. The noble gases are also usually called group 0 - not group 8.) This pattern extends throughout the Periodic Table for the main groups (i.e. not including the transition elements).

So if you know that barium is in group 2, it has 2 electrons in its outer level; iodine (group 7) has 7 electrons in its outer level; lead (group 4) has 4 electrons in its outer level.

Noble gases have full outer levels. This generalisation will need modifying for A'level purposes.

Dots-and-crosses diagrams

In any introductory chemistry course you will have come across the electronic structures of hydrogen and carbon, for example, drawn as:

structures of hydrogen and carbon, for example, drawn as: http://www.chemguide.co.uk/atoms/properties/gcse.html (5 of

a simple view of atomic structure

Note: There are many places where you could still make use of this model of the atom at A'level. It is, however, a simplification and can be misleading. It gives the impression that the electrons are circling the nucleus in orbits like planets around the sun. As you will find when you look at the A'level view of the atom, it is impossible to know exactly how they are actually moving.

The circles show energy levels - representing increasing distances from the nucleus. You could straighten the circles out and draw the electronic structure as a simple energy diagram.

Carbon, for example, would look like this:

energy diagram. Carbon, for example, would look like this: Thinking of the arrangement of the electrons

Thinking of the arrangement of the electrons in this way makes a useful bridge to the A'level view.

Note: If you have come to this page as a UK GCSE student (or a student on a similar introductory chemistry course elsewhere) and want some more help, you may be interested in my GCSE Chemistry book. This link will take you to a page describing it.

a simple view of atomic structure

Where would you like to go now?

To the atomic properties menu

To the atomic structure and bonding menu

To Main Menu

© Jim Clark 2000

GCSE chemistry

Understanding Chemistry

GCSE CHEMISTRY

This book covers the chemistry content of all the UK GCSE Chemistry syllabuses - whether as a part of dual award science, or as a separate science. It is aimed at students likely to achieve grades from A* to B.

If you are working in another system, GCSE in the UK is an exam taken at the end of a (usually) two year course at the age of 16. Anyone taking a similar introductory chemistry course may find the book helpful.

introductory chemistry course may find the book helpful. On this page you will find a description

On this page you will find a description of how the book is organised, together with a summary of the contents. You will also find direct links to the book on both the Longman and the Amazon.co.uk sites.

Education in Chemistry, May 2003

"I was impressed with this new book,

."

"The text is clearly laid out with excellent diagrams and illustrations."

"This is an excellent textbook."

School Science Review (issue 307)

will stretch and enthuse those with some ability in chemistry."

GCSE chemistry

"It would certainly help to bridge the gap between GCSE and AS level."

How to get hold of the book

Schools or colleges would probably find it best to go to the Longman GCSE Chemistry website, but this site isn't really set up for individual purchases.

You can, of course, buy the book through normal book sellers, but if you want to buy online, you will find a direct link to Amazon.co.uk coming up.

Non-UK students can also buy the book from Amazon.co.uk, but will obviously have to pay a slightly higher delivery charge.

Note: If your usual source of books is Amazon.com, you should compare the price for the book (including delivery) from Amazon.com with the price from Amazon.co.uk - even if you live in North America.

You may well find that it is significantly cheaper to buy from Amazon.co.uk and have it sent by air mail across the Atlantic, than to buy it in America!

GCSE chemistry

GCSE chemistry Have a look at the book on the Amazon site What the book covers

What the book covers

The book is organised into 6 sections plus an important appendix. Each section is made up of a number of related chapters.

There are questions at the end of each chapter to test understanding, and a set of GCSE-style exam questions at the end of each section. Answers to all the questions are provided on the supporting website - although these are password-protected so that only teachers can get at them!

Section A: Particles

This covers an introduction to atomic structure and bonding (including metallic bonding and intermolecular forces) and the relationship between the structures of elements and compounds and their physical properties.

There is also a chapter on how to write formulae and equations, and a final one on the factors affecting rates of reaction together with explanations.

Section B: Some essential background chemistry

This is a lengthy section which covers the important lab-based chemistry:

Reactivity series

Acids and their reactions

Salts

Simple analysis

Periodic Table: including some history, the structure of the table, the noble gases, Groups 1 and 7, and an introduction to transition

GCSE chemistry

metals

Electrolysis and electrochemical cells

Energy changes in reactions

Section C: Large scale chemistry

This covers the extraction of several metals, and the chemistry of salt and limestone. It introduces reversible reactions leading to the Haber and Contact Processes.

Section D: Air, water and earth

Discusses the atmosphere (including its evolution and some environmental problems), water (including hardness, water treatment, and an introduction to colloids) and types of rock.

Section E: Organic chemistry

An introductory look at the oil industry and some simple organic compounds (alkanes, alkenes, alcohols, carboxylic acids, and a brief look at esters). Structural isomerism is explained where it arises.

There are also chapters on food and drugs, and enzymes.

Section F: Sums

This section deals with all the calculations involving relative atomic masses and moles up to and including simple titration and electrolysis calculations.

Appendices

The most important appendix explains how to maximise your score when writing up coursework practical investigations to satisfy the requirements of UK GCSE examiners. The fully written out investigation is available from the website accompanying the book. (See below.)

The website

GCSE chemistry

There is a website to accompany the book which you can find by following this link. You may find this useful even if you don't end up buying the book!

You will find lots of links to other other useful chemistry web sites, a fully written up example of a coursework investigation, and a set of worksheets. Answers to all the questions in the book are available, but only to teachers who have purchased the book from Longman. The answers are password-protected for obvious reasons!

Go to Main Menu

© Jim Clark 2003

atomic orbitals

ATOMIC ORBITALS

This page explains what an atomic orbital is. 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.

What is an atomic orbital?

Orbitals and orbits

When the 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 (not required at A'level) says - loosely - that you can't know with certainty both where an electron is and where it's going next. 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.

Hydrogen's electron - the 1s orbital

atomic orbitals

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.

much larger than it really is. This is just for clarity. Suppose you had a single

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!

atomic orbitals

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.

of rather chunky material with the nucleus at its centre. The orbital on the left is

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

atomic orbitals

atomic orbitals electron. Not all electrons inhabit s orbitals (in fact, very few electrons live in

electron.

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 right 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

Beyond A'level:

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? For A'level chemistry you just have to accept that it does! If you want to find out more, read about the wave nature of electrons.

If you imagine a horizontal plane through

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 p x , p y and p z . 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.

atomic orbitals

atomic orbitals d and f orbitals The p orbitals at the second energy level are called

d and f orbitals

The p orbitals at the second energy level are called 2p x , 2p y and 2p z . There are similar orbitals at subsequent levels - 3p x , 3p y , 3p z , 4p x , 4p y , 4p z 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.

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 (3p x , 3p y , 3p z ). 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 A'level purposes, you have to be aware that there are sets of five d orbitals at levels from the third level upwards, but you will not be expected to draw them or name them. Apart from a passing reference, you won't come across f orbitals at all.

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, 2p x , 2p y and 2p z 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

atomic orbitals

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.

Beyond A'level: 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.

A 1s orbital holding 2 electrons would be drawn as shown

on the right, but it can be written even more quickly as 1s 2 . This is read as "one s two" - not as "one s squared".

as "one s two" - not as "one s squared". You mustn't confuse the two numbers

You mustn't confuse the two numbers in this notation:

You mustn't confuse the two numbers in this notation: The order of filling orbitals Electrons fill

The order of filling orbitals

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.

atomic orbitals

The diagram (not to scale) summarises the energies of the orbitals up to the 4p level.

summarises the energies of the orbitals up to the 4p level. Notice that the s orbital

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 A'level 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 A'level.

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.

Where would you like to go now?

To look at how to write electronic structures

To the atomic properties menu

atomic orbitals

To the atomic structure and bonding menu

To Main Menu

© Jim Clark 2000 (modified 2004)

electronic structures of atoms

ELECTRONIC STRUCTURES

This page explores how you write electronic structures for atoms using s, p, and d notation. It assumes that you know about simple atomic orbitals - at least as far as the way they are named, and their relative energies. If you want to look at the electronic structures of simple monatomic ions (such as Cl - , Ca 2+ and Cr 3+ ), you will find a link at the bottom of the page.

Important! If you haven't already read the page on atomic orbitals you should follow this link before you go any further.

The electronic structures of atoms

Relating orbital filling to the Periodic Table

of atoms Relating orbital filling to the Periodic Table Most A'level syllabuses stop at krypton when

Most A'level syllabuses 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 beyond A'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.

electronic structures of atoms

Important! You must have a copy of your syllabus and copies of recent exam papers. If you haven't got them, follow this link to find out how to get hold of them.

The first period

Hydrogen has its only electron in the 1s orbital - 1s 1 , and at helium the first level is completely full - 1s 2 .

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 1s 2 2s 1 . Beryllium adds a second electron to this same level - 1s 2 2s 2 .

Now the 2p levels start to fill. These levels all have the same energy, and so the electrons go in singly at first.

B

1s

2 2s 2 2p x 1

C

1s

2 2s 2 2p x 1 2p y 1

N

1s

2 2s 2 2p x 1 2p y 1 2p z 1

Note: The orbitals where something new is happening are shown in bold type. You wouldn't normally write them any differently from the other orbitals.

electronic structures of atoms

The next electrons to go in will have to pair up with those already there.

O

1s

F

1s

Ne

1s

2

2

2

2s

2s

2s

2

2

2

2p x 2 2p

2p

2p

x 2

x 2

y 1

2p z 1 2p z 1

z 2

2p y 2

2p y 2 2p

You can see that it is going to get progressively tedious to write the full electronic structures of atoms as the number of electrons increases. There are two ways around this, and you must be familiar with both.

Shortcut 1: All the various p electrons can be lumped together. For example, fluorine could be written as 1s 2 2s 2 2p 5 , and neon as 1s 2 2s 2 2p 6 .

This is what is normally done if the electrons are in an inner layer. If the electrons are in the bonding level (those on the outside of the atom), they are sometimes written in shorthand, sometimes in full. Don't worry about this. Be prepared to meet either version, but if you are asked for the electronic structure of something in an exam, write it out in full showing all the p x , p y and p z orbitals in the outer level separately.

For example, although we haven't yet met the electronic structure of chlorine, you could write it as 1s 2 2s 2 2p 6 3s 2 3p x 2 3p y 2 3p z 1 .

Notice that the 2p electrons are all lumped together whereas the 3p ones are shown in full. The logic is that the 3p electrons will be involved in bonding because they are on the outside of the atom, whereas the 2p electrons are buried deep in the atom and aren't really of any interest.

Shortcut 2: You can lump all the inner electrons together using, for example, the symbol [Ne]. In this context, [Ne] means the electronic structure of neon - in other words: 1s 2 2s 2 2p x 2 2p y 2 2p z 2 You wouldn't do

this with helium because it takes longer to write [He] than it does 1s 2 .

On this basis the structure of chlorine would be written [Ne] 3s 2 3p x 2 3p y 2 3p z 1 .

The third period

electronic structures of atoms

At neon, all the second level orbitals are full, and so after this we have to start the third period with sodium. The pattern of filling is now exactly the same as in the previous period, except that everything is now happening at the 3-level.

For example:

Mg

1s

2 2s 2

2p

S

1s

2 2s 2

2p

Ar

1s

2 2s 2

2p

6

6

6

3s

3s

3s

2

2

2

3p x 2

3p x 2

3p y 1 3p

3p y 2 3p

z 1

z 2

short version

[Ne]3s 2

[Ne]3s 2

[Ne]3s 2

3p

3p

x 2

x 2

3p y 1

3p y 2

3p

3p

z 1

z 2

Note: Check that you can do these. Cover the text and then work out these structures for yourself. Then do all the rest of this period. When you've finished, check your answers against the corresponding elements from the previous period. Your answers should be the same except a level further out.

The beginning of the fourth period

At this point the 3-level orbitals aren't all full - the 3d levels haven't been used yet. But if you refer back to the energies of the orbitals, you will see that the next lowest energy orbital is the 4s - so that fills next.

K

Ca

1s

1s

2

2

2s

2s

2

2

2p

2p

6

6

3s

3s

2

2

3p 6

3p 6

4s

4s

1

2

There is strong evidence for this in the similarities in the chemistry of elements like sodium (1s 2 2s 2 2p 6 3s 1 ) and potassium (1s 2 2s 2 2p 6 3s 2 3p 6 4s 1 )

The outer electron governs their properties and that electron is in the same sort of orbital in both of the elements. That wouldn't be true if the outer electron in potassium was 3d 1 .

s- and p-block elements

electronic structures of atoms

electronic structures of atoms The elements in group 1 of the Periodic Table all have an

The elements in group 1 of the Periodic Table all have an outer electronic structure of ns 1 (where n is a number between 2 and 7). All group 2 elements have an outer electronic structure of ns 2 . Elements in groups 1 and 2 are described as s-block elements.

Elements from group 3 across to the noble gases all have their outer electrons in p orbitals. These are then described as p-block elements.

d-block elements

are then described as p-block elements. d-block elements Remember that the 4s orbital has a lower

Remember that the 4s orbital has a lower energy than the 3d orbitals and so fills first. Once the 3d orbitals have filled up, the next electrons go into the 4p orbitals as you would expect.

d-block elements are elements in which the last electron to be added to the atom is in a d orbital. The first series of these contains the elements from scandium to zinc, which at GCSE you probably called transition elements or transition metals. The terms "transition element" and "d-

electronic structures of atoms

block element" don't quite have the same meaning, but it doesn't matter in the present context.

If you are interested: A transition element is defined as one which has partially filled d orbitals either in the element or any of its compounds. Zinc (at the right-hand end of the d- block) always has a completely full 3d level (3d 10 ) and so doesn't count as a transition element.

d electrons are almost always described as, for example, d 5 or d 8 - and not written as separate orbitals. Remember that there are five d orbitals, and that the electrons will inhabit them singly as far as possible. Up to 5 electrons will occupy orbitals on their own. After that they will have to pair up.

d 5 means

d 8 means

that they will have to pair up. d 5 means d 8 means Notice in what
that they will have to pair up. d 5 means d 8 means Notice in what

Notice in what follows that all the 3-level orbitals are written together, even though the 3d electrons are added to the atom after the 4s.

Sc

Ti

V

Cr

1s

1s

1s

1s

2

2

2

2

2s

2s

2s

2s

2

2

2

2

2p

2p

2p

2p

6 3s 2 6 3s 2 6 3s 2 6 3s 2

3p 6

3p 6

3p 6

3p 6

3d 1 4s 3d 2 4s 3d 3 4s 3d 5 4s

2

2

2

1

Whoops! Chromium breaks the sequence. In chromium, the electrons in the 3d and 4s orbitals rearrange so that there is one electron in each orbital. It would be convenient if the sequence was tidy - but it's not!

Mn

1s

2 2s 2

2p

Fe

1s

2 2s 2

2p

6

6

3s

3s

2

2

3p 6

3p 6

3d

3d

5 4s

6 4s

2

2

(back to being tidy again)

electronic structures of atoms

Co

1s

2 2s 2

2p

Ni

1s

2 2s 2

2p

Cu

1s

2 2s 2

2p

Zn

1s

2 2s 2

2p

6

6

6

6

3s

3s

3s

3s

2

2

2

2

3p 6

3p 6

3p 6

3p 6

3d

3d

3d

3d

7 4s

8 4s

2

2

10 4s 1 10 4s 2

(another awkward one!)

And at zinc the process of filling the d orbitals is complete.

Filling the rest of period 4

The next orbitals to be used are the 4p, and these fill in exactly the same way as the 2p or 3p. We are back now with the p-block elements from gallium to krypton. Bromine, for example, is 1s 2 2s 2 2p 6 3s 2 3p 6 3d 10 4s 2 4p x 2 4p y 2 4p z 1 .

Useful exercise: Work out the electronic structures of all the elements from gallium to krypton. You can check your answers by comparing them with the elements directly above them in the Periodic Table. For example, gallium will have the same sort of arrangement of its outer level electrons as boron or aluminium - except that gallium's outer electrons will be in the 4-level.

Summary

Writing the electronic structure of an element from hydrogen to krypton

Use the Periodic Table to find the atomic number, and hence number of electrons.

Fill up orbitals in the order 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p - until you run out of electrons. The 3d is the awkward one - remember that specially. Fill p and d orbitals singly as far as possible before pairing electrons up.

Remember that chromium and copper have electronic structures which break the pattern in the first row of the d-block.

electronic structures of atoms

Writing the electronic structure of big s- or p-block elements

Note: We are deliberately excluding the d-block elements apart from the first row that we've already looked at in detail. The pattern of awkward structures isn't the same in the other rows. This isn't an A'level problem.

First work out the number of outer electrons. This is quite likely all you will be asked to do anyway.

The number of outer electrons is the same as the group number. (The noble gases are a bit of a problem here, because they are normally called group 0 rather then group 8. Helium has 2 outer electrons; the rest have 8.) All elements in group 3, for example, have 3 electrons in their outer level. Fit these electrons into s and p orbitals as necessary. Which level orbitals? Count the periods in the Periodic Table (not forgetting the one with H and He in it).

Iodine is in group 7 and so has 7 outer electrons. It is in the fifth period and so its electrons will be in 5s and 5p orbitals. Iodine has the outer structure 5s 2 5p x 2 5p y 2 5p z 1 .

What about the inner electrons if you need to work them out as well? The 1, 2 and 3 levels will all be full, and so will the 4s, 4p and 4d. The 4f levels don't fill until after anything you will be asked about at A'level. Just forget about them! That gives the full structure:

1s 2 2s 2 2p 6 3s 2 3p 6 3d 10 4s 2 4p 6 4d 10 5s 2 5p x 2 5p y 2 5p z 1 .

When you've finished, count all the electrons to make sure that they come to the same as the atomic number. Don't forget to make this check - it's easy to miss an orbital out when it gets this complicated.

Barium is in group 2 and so has 2 outer electrons. It is in the sixth period. Barium has the outer structure 6s 2 .

Including all the inner levels: 1s 2 2s 2 2p 6 3s 2 3p 6 3d 10 4s 2 4p 6 4d 10 5s 2 5p 6 6s 2 .

electronic structures of atoms

It would be easy to include 5d 10 as well by mistake, but the d level always fills after the next s level - so 5d fills after 6s just as 3d fills after 4s. As long as you counted the number of electrons you could easily spot this mistake because you would have 10 too many.

Note: Don't worry too much about these complicated structures. You need to know how to work them out in principle, but your examiners are much more likely to ask you for something simple like sulphur or iron.

Where would you like to go now?

To working out electronic structures for ions

To the atomic properties menu

To the atomic structure and bonding menu

To Main Menu

© Jim Clark 2000

Understanding Chemistry - A' level syllabuses

Understanding Chemistry

UK A and AS LEVEL CHEMISTRY SYLLABUSES

I assume that you want to get the best grade you possibly can with the minimum of effort! Getting a good A level grade is rather like playing a game with your examiners - in which they make up the rules (and occasionally change them). You aren't going to win unless you know those rules.

Before you do anything else:

Get a copy of your syllabus if you haven't already got one. Details of how to do this are given below.

Syllabuses are often quite difficult to interpret, so you need to know exactly what questions your examiners are asking, and how they are marking them.

Explore your Exam Board web site. They all offer free downloads of specimen papers (including mark schemes), but you might have to pay for recent exam papers and mark schemes, and other support material. If they don't offer these free, find out how to order them and invest a small amount of money in your future!

If you want the best possible grade, you should be working with exam papers all the way through your course. Leaving looking at exam papers until your last minute revision is too late.

Be careful, though! Syllabuses change and so do examiners. Make sure that the question papers and mark schemes you get relate to your current syllabus and are as recent as possible. A new chief examiner can make a lot of difference to the style of a question paper.

How to download a copy of your syllabus

Understanding Chemistry - A' level syllabuses

Finding your way to the right syllabus

The following links take you to the front pages of each of the Exam Board web sites and you will then have to find your own way to your syllabus. This is because these sites are liable to change.

Be aware that the syllabuses are known as specifications. You want GCE Advanced and Advanced Subsidiary (A and AS) Chemistry. Finding the syllabuses is very straightforward - finding other information may take you longer!

The Exam Boards:

OCR

This includes both the standard OCR syllabus and the Salters syllabus.

Edexcel

This includes both the standard Edexcel syllabus and the Nuffield syllabus.

AQA

AQA have free downloadable versions of all their recent exam papers and mark schemes. Once you get to the chemistry page, look for it under "Assessment Material". You can also get Examiners' Reports (another link from the chemistry page). These are essential if you want to avoid common mistakes.

WJEC

This link should take you directly to the correct chemistry page to download a syllabus. At the time of writing, you will have to pay if you want past papers or mark schemes.

Problems reading the downloaded syllabus?

The syllabuses are available only in pdf format. You need software such as Adobe Acrobat Reader to access it. You have almost certainly got this

Understanding Chemistry - A' level syllabuses

(or the equivalent) software on your computer, but if your computer is old, you may not have the latest version.

If your downloaded syllabus won't open, it may be that the syllabus was created in a newer version of the Reader than you've got. You will have to download a new version of Reader.

Each of the Exam Board web sites provides a link to Adobe, but these links are often easy to miss.

Use this link:

This will take you to Adobe's front page where you will find a link enabling you to download the Reader. Be warned that this is a seriously large bit of software and could take a long time to download on a dial-up connection.

Go to Main Menu

© Jim Clark 2000 (modified 2004)

electronic structures of ions

ELECTRONIC STRUCTURES OF IONS

This page explores how you write electronic structures for simple monatomic ions (ions containing only one atom) using s, p, and d notation. It assumes that you already understand how to write electronic structures for atoms.

Important! If you have come straight to this page via a search engine, you should read the page on electronic structures of atoms before you go any further.

Working out the electronic structures of ions

Ions are atoms (or groups of atoms) which carry an electric charge because they have either gained or lost one or more electrons. If an atom gains electrons it acquires a negative charge. If it loses electrons, it becomes positively charged.

The electronic structure of s- and p-block ions

Write the electronic structure for the neutral atom, and then add (for a negative ion) or subtract electrons (for a positive ion).

To write the electronic structure for Cl - :

Cl

1s

Cl -

1s

2

2

2s 2 2p

2s 2 2p

6 3s 2 3p

x 2 3p

y 2 3p

6 3s 2 3p

x 2 3p

y 2 3p

z 1

z 2

but Cl - has one more electron

To write the electronic structure for O 2- :

O 1s 2 2s 2 2p x 2 2p y 1 2p z 1

but O 2- has two more electrons

electronic structures of ions

O 2-

1s 2 2s 2 2p x 2 2p y 2 2p z 2

To write the electronic structure for Na + :

Na

Na +

1s

1s 2 2s

2 2s

2 2p

2 2p

6 3s 1

6

but Na + has one less electron

To write the electronic structure for Ca 2+ :

Ca

Ca 2+

1s

1s

2

2

2s

2 2p 6 3s 2

3p 6 4s 2

2s

2 2p 6 3s 2

3p 6

but Ca 2+ has two less electrons

The electronic structure of d-block ions

Here you are faced with one of the most irritating facts in A'level chemistry! You will recall that the first transition series (from scandium to zinc) is the result of the 3d orbitals being filled after the 4s orbital.

However, once the electrons are established in their orbitals, the energy order changes - and in all the chemistry of the transition elements, the 4s orbital behaves as the outermost, highest energy orbital. The reversed order of the 3d and 4s orbitals only applies to building the atom up in the first place. In all other respects, the 4s electrons are always the electrons you need to think about first.

You must remember this:

When d-block elements form ions, the 4s electrons are lost first.

Provided you remember that, working out the structure of a d-block ion is no different from working out the structure of, say, a sodium ion.

electronic structures of ions

To write the electronic structure for Cr 3+ :

Cr

1s

Cr 3+

1s

2

2

2s

2s

2

2

2p

2p

6

6

3s

3s

2 3p

2 3p

6

6

3d 5 4s 1 3d 3

The 4s electron is lost first followed by two of the 3d electrons.

To write the electronic structure for Zn 2+ :

Zn

1s 2 2s 2 2p 6 3s 2

3p

Zn 2+

1s 2 2s 2 2p 6 3s 2

3p

6 3d 10 4s 2

6 3d 10

This time there is no need to use any of the 3d electrons.

To write the electronic structure for Fe 3+ :

Fe

1s

2 2s 2 2p 6 3s 2

3p

6 3d 6 4s 2

Fe 3+

1s 2 2s 2 2p 6 3s 2

3p

6 3d 5

The 4s electrons are lost first followed by one of the 3d electrons.

The rule is quite simple. Take the 4s electrons off first, and then as many 3d electrons as necessary to produce the correct positive charge.

electronic structures of ions

Note: You may well have the impression from GCSE that ions have to have noble gas structures. It's not true! Most (but not all) ions formed by s- and p-block elements do have noble gas structures, but if you look at the d-block ions we've used as examples, not one of them has a noble gas structure - yet they are all perfectly valid ions. Getting away from a reliance on the concept of noble gas structures is one of the difficult mental leaps that you have to make at the beginning of A'level chemistry.

Where would you like to go now?

To the atomic properties menu

To the atomic structure and bonding menu

To Main Menu

© Jim Clark 2000

first ionisation energy

IONISATION ENERGY

This page explains what first ionisation energy is, and then looks at the way it varies around the Periodic Table - across periods and down groups. It assumes that you know about simple atomic orbitals, and can write electronic structures for simple atoms. You will find a link at the bottom of the page to a similar description of successive ionisation energies (second, third and so on).

Important! If you aren't reasonable happy about atomic orbitals and electronic structures you should follow these links before you go any further.

Defining first ionisation energy

Definition

The first ionisation energy is the energy required to remove the most loosely held electron from one mole of gaseous atoms to produce 1 mole of gaseous ions each with a charge of 1+.

This is more easily seen in symbol terms.

a charge of 1+. This is more easily seen in symbol terms. It is the energy

It is the energy needed to carry out this change per mole of X.

Worried about moles? Don't be! For now, just take it as a measure of a particular amount of a substance. It isn't worth worrying about at the moment.

first ionisation energy

Things to notice about the equation

The state symbols - (g) - are essential. When you are talking about ionisation energies, everything must be present in the gas state.

Ionisation energies are measured in kJ mol -1 (kilojoules per mole). They vary in size from 381 (which you would consider very low) up to 2370 (which is very high).

All elements have a first ionisation energy - even atoms which don't form positive ions in test tubes. The reason that helium (1st I.E. = 2370 kJ mol - 1 ) doesn't normally form a positive ion is because of the huge amount of energy that would be needed to remove one of its electrons.

Patterns of first ionisation energies in the Periodic Table

The first 20 elements

energies in the Periodic Table The first 20 elements First ionisation energy shows periodicity. That means

First ionisation energy shows periodicity. That means that it varies in a repetitive way as you move through the Periodic Table. For example, look at the pattern from Li to Ne, and then compare it with the identical pattern from Na to Ar.

These variations in first ionisation energy can all be explained in terms of the structures of the atoms involved.

Factors affecting the size of ionisation energy

first ionisation energy

Ionisation energy is a measure of the energy needed to pull a particular electron away from the attraction of the nucleus. A high value of ionisation energy shows a high attraction between the electron and the nucleus.

The size of that attraction will be governed by:

The charge on the nucleus.

The more protons there are in the nucleus, the more positively charged the nucleus is, and the more strongly electrons are attracted to it.

The distance of the electron from the nucleus.

Attraction falls off very rapidly with distance. An electron close to the nucleus will be much more strongly attracted than one further away.

The number of electrons between the outer electrons and the nucleus.

Consider a sodium atom, with the electronic structure 2,8,1. (There's no reason why you can't use this notation if it's useful!)

If the outer electron looks in towards the nucleus, it doesn't see the nucleus sharply. Between it and the nucleus there are the two layers of electrons in the first and second levels. The 11 protons in the sodium's nucleus have their effect cut down by the 10 inner electrons. The outer electron therefore only feels a net pull of approximately 1+ from the centre. This lessening of the pull of the nucleus by inner electrons is known as screening or shielding.

Warning! Electrons don't, of course, "look in" towards the nucleus - and they don't "see" anything either! But there's no reason why you can't imagine it in these terms if it helps you to visualise what's happening. Just don't use these terms in an exam! You may get an examiner who is upset by this sort of loose language.

first ionisation energy

Whether the electron is on its own in an orbital or paired with another electron.

Two electrons in the same orbital experience a bit of repulsion from each other. This offsets the attraction of the nucleus, so that paired electrons are removed rather more easily than you might expect.

Explaining the pattern in the first few elements

Hydrogen has an electronic structure of 1s 1 . It is a very small atom, and the single electron is close to the nucleus and therefore strongly attracted. There are no electrons screening it from the nucleus and so the ionisation energy is high (1310 kJ mol -1 ).

Helium has a structure 1s 2 . The electron is being removed from the same orbital as in hydrogen's case. It is close to the nucleus and unscreened. The value of the ionisation energy (2370 kJ mol -1 ) is much higher than hydrogen, because the nucleus now has 2 protons attracting the electrons instead of 1.

Lithium is 1s 2 2s 1 . Its outer electron is in the second energy level, much more distant from the nucleus. You might argue that that would be offset by the additional proton in the nucleus, but the electron doesn't feel the full pull of the nucleus - it is screened by the 1s 2 electrons.

first ionisation energy

first ionisation energy You can think of the electron as feeling a net 1+ pull from

You can think of the electron as feeling a net 1+ pull from the centre (3 protons offset by the two 1s 2 electrons).

If you compare lithium with hydrogen (instead of with helium), the hydrogen's electron also feels a 1+ pull from the nucleus, but the distance is much greater with lithium. Lithium's first ionisation energy drops to 519 kJ mol -1 whereas hydrogen's is 1310 kJ mol -1 .

The patterns in periods 2 and 3

Talking through the next 17 atoms one at a time would take ages. We can do it much more neatly by explaining the main trends in these periods, and then accounting for the exceptions to these trends.

The first thing to realise is that the patterns in the two periods are identical - the difference being that the ionisation energies in period 3 are all lower than those in period 2.

first ionisation energy

first ionisation energy Explaining the general trend across periods 2 and 3 The general trend is

Explaining the general trend across periods 2 and 3

The general trend is for ionisation energies to increase across a period.

In the whole of period 2, the outer electrons are in 2-level orbitals - 2s or 2p. These are all the same sort of distances from the nucleus, and are screened by the same 1s 2 electrons.

The major difference is the increasing number of protons in the nucleus as you go from lithium to neon. That causes greater attraction between the nucleus and the electrons and so increases the ionisation energies. In fact the increasing nuclear charge also drags the outer electrons in closer to the nucleus. That increases ionisation energies still more as you go across the period.

Note: Factors affecting atomic radius are covered on a separate page.

first ionisation energy

In period 3, the trend is exactly the same. This time, all the electrons being removed are in the third level and are screened by the 1s 2 2s 2 2p 6 electrons. They all have the same sort of environment, but there is an increasing nuclear charge.

Why the drop between groups 2 and 3 (Be-B and Mg-Al)?

The explanation lies with the structures of boron and aluminium. The outer electron is removed more easily from these atoms than the general trend in their period would suggest.

Be

1s 2 2s 2

1st I.E. = 900 kJ mol -1

B

1s

2 2s 2 2p x 1

1st I.E. = 799 kJ mol -1

You might expect the boron value to be more than the beryllium value because of the extra proton. Offsetting that is the fact that boron's outer electron is in a 2p orbital rather than a 2s. 2p orbitals have a slightly higher energy than the 2s orbital, and the electron is, on average, to be found further from the nucleus. This has two effects.

The increased distance results in a reduced attraction and so a reduced ionisation energy.

The 2p orbital is screened not only by the 1s 2 electrons but, to some extent, by the 2s 2 electrons as well. That also reduces the pull from the nucleus and so lowers the ionisation energy.

The explanation for the drop between magnesium and aluminium is the same, except that everything is happening at the 3-level rather than the 2- level.

Mg

1s

2 2s 2

2p

Al

1s

2 2s 2

2p

6

6

3s

3s

2

2 3p x 1

1st I.E. = 736 kJ mol -1

1st I.E. = 577 kJ mol -1

The 3p electron in aluminium is slightly more distant from the nucleus than the 3s, and partially screened by the 3s 2 electrons as well as the inner electrons. Both of these factors offset the effect of the extra proton.

first ionisation energy

Warning! You might possibly come across a text book which describes the drop between group 2 and group 3 by saying that a full s 2 orbital is in some way especially stable and that makes the electron more difficult to remove. In other words, that the fluctuation is because the group 2 value for ionisation energy is abnormally high. This is quite simply wrong! The reason for the fluctuation is because the group 3 value is lower than you might expect for the reasons we've looked at.

Why the drop between groups 5 and 6 (N-O and P-S)?

Once again, you might expect the ionisation energy of the group 6 element to be higher than that of group 5 because of the extra proton. What is offsetting it this time?

N

O

1s

1s

2

2

2s 2

2s 2

2p

2p

x 1

x 2

2p y 1 2p 2p y 1 2p

z 1

z 1

1st I.E. = 1400 kJ mol -1

1st I.E. = 1310 kJ mol -1

The screening is identical (from the 1s 2 and, to some extent, from the 2s 2 electrons), and the electron is being removed from an identical orbital.

The difference is that in the oxygen case the electron being removed is one of the 2p x 2 pair. The repulsion between the two electrons in the same orbital means that the electron is easier to remove than it would otherwise be.

The drop in ionisation energy at sulphur is accounted for in the same way.

Trends in ionisation energy down a group

As you go down a group in the Periodic Table ionisation energies generally fall. You have already seen evidence of this in the fact that the ionisation energies in period 3 are all less than those in period 2.

Taking Group 1 as a typical example:

first ionisation energy

first ionisation energy Why is the sodium value less than that of lithium? There are 11

Why is the sodium value less than that of lithium?

There are 11 protons in a sodium atom but only 3 in a lithium atom, so the nuclear charge is much greater. You might have expected a much larger ionisation energy in sodium, but offsetting the nuclear charge is a greater distance from the nucleus and more screening.

Li

1s 2 2s 1

1st I.E. = 519 kJ mol -1

Na

1s

2 2s 2 2p 6 3s 1

1st I.E. = 494 kJ mol -1

Lithium's outer electron is in the second level, and only has the 1s 2 electrons to screen it. The 2s 1 electron feels the pull of 3 protons screened by 2 electrons - a net pull from the centre of 1+.

The sodium's outer electron is in the third level, and is screened from the 11 protons in the nucleus by a total of 10 inner electrons. The 3s 1 electron also feels a net pull of 1+ from the centre of the atom. In other words, the effect of the extra protons is compensated for by the effect of the extra screening electrons. The only factor left is the extra distance between the outer electron and the nucleus in sodium's case. That lowers the ionisation energy.

Similar explanations hold as you go down the rest of this group - or, indeed, any other group.

Trends in ionisation energy in a transition series

first ionisation energy

first ionisation energy Apart from zinc at the end, the other ionisation energies are all much

Apart from zinc at the end, the other ionisation energies are all much the same.

All of these elements have an electronic structure [Ar]3d n 4s 2 (or 4s 1 in the cases of chromium and copper). The electron being lost always comes from the 4s orbital.

Note: Confusingly, once the orbitals have electrons in them, the 4s orbital has a higher energy than the 3d - quite the opposite of their order when the atoms are being filled with electrons. That means that it is a 4s electron which is lost from the atom when it forms an ion. It also means that the 3d orbitals are slightly closer to the nucleus than the 4s - and so offer some screening.

You will find this commented on in the page about electronic structures of ions.

As you go from one atom to the next in the series, the number of protons in the nucleus increases, but so also does the number of 3d electrons. The 3d electrons have some screening effect, and the extra proton and the extra 3d electron more or less cancel each other out as far as attraction from the centre of the atom is concerned.

The rise at zinc is easy to explain.

Cu

[Ar]3d 10

4s

Zn

[Ar]3d 10

4s

1

2

1st I.E. = 745 kJ mol -1

1st I.E. = 908 kJ mol -1

In each case, the electron is coming from the same orbital, with identical

first ionisation energy

screening, but the zinc has one extra proton in the nucleus and so the attraction is greater.

Ionisation energies and reactivity

The lower the ionisation energy, the more easily this change happens:

the ionisation energy, the more easily this change happens: You can explain the increase in reactivity

You can explain the increase in reactivity of the Group 1 metals (Li, Na, K, Rb, Cs) as you go down the group in terms of the fall in ionisation energy. Whatever these metals react with, they have to form positive ions in the process, and so the lower the ionisation energy, the more easily those ions will form.

The danger with this approach is that the formation of the positive ion is only one stage in a multi-step process.

For example, you wouldn't be starting with gaseous atoms; nor would you end up with gaseous positive ions - you would end up with ions in a solid or in solution. The energy changes in these processes also vary from element to element. Ideally you need to consider the whole picture and not just one small part of it.

However, the ionisation energies of the elements are going to be major contributing factors towards the activation energy of the reactions. Remember that activation energy is the minimum energy needed before a reaction will take place. The lower the activation energy, the faster the reaction will be - irrespective of what the overall energy changes in the reaction are.

The fall in ionisation energy as you go down a group will lead to lower activation energies and therefore faster reactions.

first ionisation energy

Note: You will find a page discussing this in more detail in the inorganic section of this site dealing with the reactions of Group 2 metals with water.

Where would you like to go now?

To look at second (and successive) ionisation energies

To the atomic properties menu

To the atomic structure and bonding menu

To Main Menu

© Jim Clark 2000

atomic and ionic radius

ATOMIC AND IONIC RADIUS

This page explains the various measures of atomic radius, and then looks at the way it varies around the Periodic Table - across periods and down groups. It assumes that you understand electronic structures for simple atoms written in s, p, d notation.

Important! If you aren't reasonable happy about electronic structures you should follow this link before you go any further.

ATOMIC RADIUS

Measures of atomic radius

Unlike a ball, an atom doesn't have a fixed radius. The radius of an atom can only be found by measuring the distance between the nuclei of two touching atoms, and then halving that distance.

of two touching atoms, and then halving that distance. As you can see from the diagrams,

As you can see from the diagrams, the same atom could be found to have a different radius depending on what was around it.

The left hand diagram shows bonded atoms. The atoms are pulled closely together and so the measured radius is less than if they are just touching. This is what you would get if you had metal atoms in a metallic structure, or atoms covalently bonded to each other. The type of atomic radius being measured here is called the metallic radius or the covalent radius depending on the bonding.

atomic and ionic radius

The right hand diagram shows what happens if the atoms are just touching. The attractive forces are much less, and the atoms are essentially "unsquashed". This measure of atomic radius is called the van der Waals radius after the weak attractions present in this situation.

Note: If you want to explore these various types of bonding this link will take you to the bonding menu.

Trends in atomic radius in the Periodic Table

The exact pattern you get depends on which measure of atomic radius you use - but the trends are still valid.

The following diagram uses metallic radii for metallic elements, covalent radii for elements that form covalent bonds, and van der Waals radii for those (like the noble gases) which don't form bonds.

Trends in atomic radius in Periods 2 and 3

form bonds. Trends in atomic radius in Periods 2 and 3 Trends in atomic radius down

Trends in atomic radius down a group

It is fairly obvious that the atoms get bigger as you go down groups. The reason is equally obvious - you are adding extra layers of electrons.

Trends in atomic radius across periods

You have to ignore the noble gas at the end of each period. Because neon and argon don't form bonds, you can only measure their van der Waals radius - a case where the atom is pretty well "unsquashed". All the other atoms are being measured where their atomic radius is being lessened by strong attractions. You aren't comparing like with like if you

atomic and ionic radius

include the noble gases.

Leaving the noble gases out, atoms get smaller as you go across a period.

If you think about it, the metallic or covalent radius is going to be a measure of the distance from the nucleus to the electrons which make up the bond. (Look back to the left-hand side of the first diagram on this page if you aren't sure, and picture the bonding electrons as being half way between the two nuclei.)

From lithium to fluorine, those electrons are all in the 2-level, being screened by the 1s 2 electrons. The increasing number of protons in the nucleus as you go across the period pulls the electrons in more tightly. The amount of screening is constant for all of these elements.

Note: You might possibly wonder why you don't get extra screening from the 2s 2 electrons in the cases of the elements from boron to fluorine where the bonding involves the p electrons.

In each of these cases, before bonding happens, the existing s and p orbitals are reorganised (hybridised) into new orbitals of equal energy. When these atoms are bonded, there aren't any 2s electrons as such.

If you don't know about hybridisation, just ignore this comment - you won't need it for UK A level purposes anyway.

atomic and ionic radius

In the period from sodium to chlorine, the same thing happens. The size of the atom is controlled by the 3-level bonding electrons being pulled closer to the nucleus by increasing numbers of protons - in each case, screened by the 1- and 2-level electrons.

Trends in the transition elements

1- and 2-level electrons. Trends in the transition elements Although there is a slight contraction at

Although there is a slight contraction at the beginning of the series, the atoms are all much the same size.

The size is determined by the 4s electrons. The pull of the increasing number of protons in the nucleus is more or less offset by the extra screening due to the increasing number of 3d electrons.

Note: Confusingly, once the orbitals have electrons in them, the 4s orbital has a higher energy than the 3d - quite the opposite of their order when the atoms are being filled with electrons. That means that it is the 4s electrons which can be thought of as being on the outside of the atom, and so determine its size. It also means that the 3d orbitals are slightly closer to the nucleus than the 4s - and so offer some screening.

You will find this commented on in the page about electronic structures of ions.

atomic and ionic radius

IONIC RADIUS

Ions aren't the same size as the atoms they come from. Compare the sizes of sodium and chloride ions with the sizes of sodium and chlorine atoms.

chloride ions with the sizes of sodium and chlorine atoms. Positive ions Positive ions are smaller

Positive ions

Positive ions are smaller than the atoms they come from. Sodium is 2,8,1; Na + is 2,8. You've lost a whole layer of electrons, and the remaining 10 electrons are being pulled in by the full force of 11 protons.

Negative ions

Negative ions are bigger than the atoms they come from. Chlorine is 2,8,7; Cl - is 2,8,8. Although the electrons are still all in the 3-level, the extra repulsion produced by the incoming electron causes the atom to expand. There are still only 17 protons, but they are now having to hold 18 electrons.

Where would you like to go now?

To the atomic properties menu

To the atomic structure and bonding menu

To Main Menu

atomic and ionic radius

© Jim Clark 2000 (modified 2004)

Bonding menu

Understanding Chemistry

BONDING MENU

Ionic bonding

Includes a simple view of ionic bonding and the way you need to modify this for A'level purposes.

Covalent bonding

Includes a simple view of covalent bonding (single and double) and the modifications needed for A'level purposes.

Co-ordinate (dative covalent) bonding

Explains what co-ordinate (dative covalent) bonding is, and looks at a wide range of examples.

Electronegativity

Explains what electronegativity is and how it varies around the Periodic Table. Describes and explains how electronegativity differences determine the type of bond formed. Looks at polar bonds and molecules.

Shapes of simple molecules and ions

Explains how to work out the shapes of a wide range of simple molecules and ions.

Metallic bonding

A simple explanation of the forces holding metals together.

Bonding menu

van der Waals forces

A description of van der Waals forces (temporary fluctuating dipole and dipole-dipole interactions) causing attractions between individual molecules.

Hydrogen bonding

An explanation of how hydrogen bonding arises and its effect on boiling points.

Bonding in organic compounds

This leads you to the bonding menu in the organic section of this site in case you are only interested in bonding in organic compounds.

Go to atomic structure and bonding menu

Go to Main Menu

© Jim Clark 2000

ionic (electrovalent) bonding

IONIC (ELECTROVALENT) BONDING

This page explains what ionic (electrovalent) bonding is. It starts with a simple picture of the formation of ions, and then modifies it slightly for A'level purposes.

A simple view of ionic bonding

The importance of noble gas structures

At a simple level (like GCSE) a lot of importance is attached to the electronic structures of noble gases like neon or argon which have eight electrons in their outer energy levels (or two in the case of helium). These noble gas structures are thought of as being in some way a "desirable" thing for an atom to have.

You may well have been left with the strong impression that when other atoms react, they try to organise things such that their outer levels are either completely full or completely empty.

Note: The central role given to noble gas structures is very much an over-simplification. We shall have to spend some time later on demolishing the concept!

ionic (electrovalent) bonding

Ionic bonding in sodium chloride

Sodium (2,8,1) has 1 electron more than a stable noble gas structure (2,8). If it gave away that electron it would become more stable.

Chlorine (2,8,7) has 1 electron short of a stable noble gas structure (2,8,8). If it could gain an electron from somewhere it too would become more stable.

The answer is obvious. If a sodium atom gives an electron to a chlorine atom, both become more stable.

an electron to a chlorine atom, both become more stable. The sodium has lost an electron,

The sodium has lost an electron, so it no longer has equal numbers of electrons and protons. Because it has one more proton than electron, it has a charge of 1+. If electrons are lost from an atom, positive ions are formed.

Positive ions are sometimes called cations.

The chlorine has gained an electron, so it now has one more electron than proton. It therefore has a charge of 1-. If electrons are gained by an atom, negative ions are formed.

A negative ion is sometimes called an anion.

The nature of the bond

The sodium ions and chloride ions are held together by the strong electrostatic attractions between the positive and negative charges.

The formula of sodium chloride

You need one sodium atom to provide the extra electron for one chlorine atom, so they combine together 1:1. The formula is therefore NaCl.

ionic (electrovalent) bonding

Some other examples of ionic bonding

magnesium oxide

bonding Some other examples of ionic bonding magnesium oxide Again, noble gas structures are formed, and

Again, noble gas structures are formed, and the magnesium oxide is held together by very strong attractions between the ions. The ionic bonding is stronger than in sodium chloride because this time you have 2+ ions attracting 2- ions. The greater the charge, the greater the attraction.

The formula of magnesium oxide is MgO.

calcium chloride

The formula of magnesium oxide is MgO. calcium chloride This time you need two chlorines to

This time you need two chlorines to use up the two outer electrons in the calcium. The formula of calcium chloride is therefore CaCl 2 .

potassium oxide

calcium chloride is therefore CaCl 2 . potassium oxide Again, noble gas structures are formed. It

Again, noble gas structures are formed. It takes two potassiums to supply the electrons the oxygen needs. The formula of potassium oxide is K 2 O.

ionic (electrovalent) bonding

THE A'LEVEL VIEW OF IONIC BONDING

Electrons are transferred from one atom to another resulting in the formation of positive and negative ions.

The electrostatic attractions between the positive and negative ions hold the compound together.

So what's new? At heart - nothing. What needs modifying is the view that there is something magic about noble gas structures. There are far more ions which don't have noble gas structures than there are which do.

Some common ions which don't have noble gas structures

You may have come across some of the following ions in a basic course like GCSE. They are all perfectly stable , but not one of them has a noble gas structure.

Fe 3+

[Ar]3d 5

Cu 2+

[Ar]3d 9

Zn

2+

[Ar]3d 10

Ag

+

[Kr]4d 10

Pb

2+

[Xe]4f 14 5d 10 6s 2

Noble gases (apart from helium) have an outer electronic structure ns 2 np 6 .

Note: If you aren't happy about writing electronic structures using of s, p and d notation, follow this link before you go on.

Return to this page via the menus or by using the BACK button on your browser.

ionic (electrovalent) bonding

Apart from some elements at the beginning of a transition series (scandium forming Sc 3+ with an argon structure, for example), all transition elements and any metals following a transition series (like tin and lead in Group 4, for example) will have structures like those above.

That means that the only elements to form positive ions with noble gas structures (apart from odd ones like scandium) are those in groups 1 and 2 of the Periodic Table and aluminium in group 3 (boron in group 3 doesn't form ions).

Negative ions are tidier! Those elements in Groups 5, 6 and 7 which form simple negative ions all have noble gas structures.

If elements aren't aiming for noble gas structures when they form ions, what decides how many electrons are transferred? The answer lies in the energetics of the process by which the compound is made.

Warning! From here to the bottom of this page goes beyond anything you are likely to need for A'level purposes. It is included for interest only.

What determines what the charge is on an ion?

Elements combine to make the compound which is as stable as possible - the one in which the greatest amount of energy is evolved in its making. The more charges a positive ion has, the greater the attraction towards its accompanying negative ion. The greater the attraction, the more energy is released when the ions come together.

That means that elements forming positive ions will tend to give away as many electrons as possible. But there's a down-side to this.

Energy is needed to remove electrons from atoms. This is called ionisation energy. The more electrons you remove, the greater the total ionisation energy becomes. Eventually the total ionisation energy needed becomes so great that the energy released when the attractions are set up between positive and negative ions isn't large enough to cover it.

ionic (electrovalent) bonding

The element forms the ion which makes the compound most stable - the one in which most energy is released over-all.

For example, why is calcium chloride CaCl 2 rather than CaCl or CaCl 3 ?

If one mole of CaCl (containing Ca + ions) is made from its elements, it is possible to estimate that about 171 kJ of heat is evolved.

However, making CaCl 2 (containing Ca 2+ ions) releases more heat. You get 795 kJ. That extra amount of heat evolved makes the compound more stable, which is why you get CaCl 2 rather than CaCl.

What about CaCl 3 (containing Ca 3+ ions)? To make one mole of this, you can estimate that you would have to put in 1341 kJ. This makes this compound completely non-viable. Why is so much heat needed to make CaCl 3 ? It is because the third ionisation energy (the energy needed to

remove the third electron) is extremely high (4940 kJ mol -1 ) because the electron is being removed from the 3-level rather than the 4-level. Because it is much closer to the nucleus than the first two electrons removed, it is going to be held much more strongly.

Note: It would pay you to read about ionisation energies if you really want to understand this.

You could also go to a standard text book and investigate Born-Haber Cycles.

ionic (electrovalent) bonding

A similar sort of argument applies to the negative ion. For example, oxygen forms an O 2- ion rather than an O - ion or an O 3- ion, because compounds containing the O 2- ion turn out to be the most energetically stable.

Where would you like to go now?

To explore the physical properties of ionic compounds

To the bonding menu

To the atomic structure and bonding menu

To Main Menu

© Jim Clark 2000

ionic structures

IONIC STRUCTURES

This page explains the relationship between the arrangement of the ions

in a typical ionic solid like sodium chloride and its physical properties -

melting point, boiling point, brittleness, solubility and electrical behaviour.

Note: If you need to revise how ionic bonding arises, then you might like to follow this link. It isn't important for understanding this page, however.

The structure of a typical ionic solid - sodium chloride

How the ions are arranged in sodium chloride

Sodium chloride is taken as a typical ionic compound. Compounds like this consist of a giant (endlessly repeating) lattice of ions. So sodium chloride (and any other ionic compound) is described as having a giant ionic structure.

You should be clear that giant in this context doesn't just mean very large. It means that you can't state exactly how many ions there are.

There could be billions of sodium ions and chloride ions packed together, or trillions, or whatever - it simply depends how big the crystal is. That is different from, say, a water molecule which always contains exactly 2 hydrogen atoms and one oxygen atom - never more and never less.

A small representative bit of a sodium chloride lattice looks like this:

ionic structures

ionic structures If you look at the diagram carefully, you will see that the sodium ions

If you look at the diagram carefully, you will see that the sodium ions and chloride ions alternate with each other in each of the three dimensions.

This diagram is easy enough to draw with a computer, but extremely difficult to draw convincingly by hand. We normally draw an "exploded" version which looks like this:

draw an "exploded" version which looks like this: Only those ions joined by lines are actually

Only those ions joined by lines are actually touching each other. The sodium ion in the centre is being touched by 6 chloride ions. By chance we might just as well have centred the diagram around a chloride ion - that, of course, would be touched by 6 sodium ions. Sodium chloride is described as being 6:6-co-ordinated.

You must remember that this diagram represents only a tiny part of the whole sodium chloride crystal. The pattern repeats in this way over countless ions.

How to draw this structure

Draw a perfect square:

ionic structures

ionic structures Now draw an identical square behind this one and offset a bit. You might

Now draw an identical square behind this one and offset a bit. You might have to practice a bit to get the placement of the two squares right. If you get it wrong, the ions get all tangled up with each other in your final diagram.

get all tangled up with each other in your final diagram. Turn this into a perfect

Turn this into a perfect cube by joining the squares together:

this into a perfect cube by joining the squares together: Now the tricky bit! Subdivide this

Now the tricky bit! Subdivide this big cube into 8 small cubes by joining the mid point of each edge to the mid point of the edge opposite it. To complete the process you will also have to join the mid point of each face (easily found once you've joined the edges) to the mid point of the opposite face.

joined the edges) to the mid point of the opposite face. Now all you have to

Now all you have to do is put the ions in. Use different colours or different sizes for the two different ions, and don't forget a key. It doesn't matter whether you end up with a sodium ion or a chloride ion in the centre of

ionic structures

the cube - all that matters is that they alternate in all three dimensions.

that matters is that they alternate in all three dimensions. You should be able to draw

You should be able to draw a perfectly adequate free-hand sketch of this in under two minutes - less than one minute if you're not too fussy!

Why is sodium chloride 6:6-co-ordinated?

The more attraction there is between the positive and negative ions, the more energy is released. The more energy that is released, the more energetically stable the structure becomes.

That means that to gain maximum stability, you need the maximum number of attractions. So why does each ion surround itself with 6 ions of the opposite charge?

That represents the maximum number of chloride ions that you can fit around a central sodium ion before the chloride ions start touching each other. If they start touching, you introduce repulsions into the crystal which makes it less stable.

Note: If the positive ion is big enough, you can fit 8 chloride ions around it. For example, caesium ions are significantly bigger than sodium ions, and so caesium chloride is 8:8-co- ordinated. It can gain stability from the extra attractions without any problems because of repulsion due to ions with the same charge touching each other.

The structure of caesium chloride isn't on any current A'level syllabuses.

ionic structures

The physical properties of sodium chloride

Sodium chloride has a high melting and boiling point

There are strong electrostatic attractions between the positive and negative ions, and it takes a lot of heat energy to overcome them. Ionic substances all have high melting and boiling points. Differences between ionic substances will depend on things like:

The number of charges on the ions

Magnesium oxide has exactly the same structure as sodium chloride, but a much higher melting and boiling point. The 2+ and 2- ions attract each other more strongly than 1+ attracts 1-.

The sizes of the ions

If the ions are smaller they get closer together and so the electrostatic attractions are greater. Rubidium iodide, for example, melts and boils at slightly lower temperatures than sodium chloride, because both rubidium and iodide ions are bigger than sodium and chloride ions. The attractions are less between the bigger ions and so less heat energy is needed to separate them.

Sodium chloride crystals are brittle

Brittleness is again typical of ionic substances. Imagine what happens to the crystal if a stress is applied which shifts the ion layers slightly.

if a stress is applied which shifts the ion layers slightly. Ions of the same charge

Ions of the same charge are brought side-by-side and so the crystal

ionic structures

repels itself to pieces!

Sodium chloride is soluble in water

Many ionic solids are soluble in water - although not all. It depends on whether there are big enough attractions between the water molecules and the ions to overcome the attractions between the ions themselves. Positive ions are attracted to the lone pairs on water molecules and co- ordinate (dative covalent) bonds may form. Water molecules form hydrogen bonds with negative ions.

Note: The bonding in hydrated metal ions is covered in the page on co-ordinate bonding. The bonding between negative ions like chloride ions and water molecules is covered in the page on hydrogen bonding.

Sodium chloride is insoluble in organic solvents

This is also typical of ionic solids. The attractions between the solvent molecules and the ions aren't big enough to overcome the attractions holding the crystal together.

The electrical behaviour of sodium chloride

Solid sodium chloride doesn't conduct electricity, because there are no electrons which are free to move. Molten sodium chloride undergoes electrolysis, which involves conduction of electricity because of the movement of the ions. In the process, sodium and chlorine are produced. This is a chemical change rather than a physical process.

ionic structures

Where would you like to go now?

To the structures menu

To the atomic structure and bonding menu

To Main Menu

© Jim Clark 2000

co-ordinate (dative covalent) bonding

CO-ORDINATE (DATIVE COVALENT) BONDING

This page explains what co-ordinate (also called dative covalent) bonding is. You need to have a reasonable understanding of simple covalent bonding before you start.

Important! If you are uncertain about covalent bonding follow this link before you go on with this page.

Co-ordinate (dative covalent) bonding

A covalent bond is formed by two atoms sharing a pair of electrons. The

atoms are held together because the electron pair is attracted by both of

the nuclei.

In the formation of a simple covalent bond, each atom supplies one

electron to the bond - but that doesn't have to be the case. A co-ordinate

bond (also called a dative covalent bond) is a covalent bond (a shared pair of electrons) in which both electrons come from the same atom.

For the rest of this page, we shall use the term co-ordinate bond - but if you prefer to call it a dative covalent bond, that's not a problem!

The reaction between ammonia and hydrogen chloride

If these colourless gases are allowed to mix, a thick white smoke of solid ammonium chloride is formed.

a thick white smoke of solid ammonium chloride is formed. Ammonium ions, NH 4 + ,

Ammonium ions, NH 4 + , are formed by the transfer of a hydrogen ion from the hydrogen chloride to the lone pair of electrons on the ammonia molecule.

co-ordinate (dative covalent) bonding

co-ordinate (dative covalent) bonding When the ammonium ion, NH 4 + , is formed, the fourth

When the ammonium ion, NH 4 + , is formed, the fourth hydrogen is attached by a dative covalent bond, because only the hydrogen's nucleus is transferred from the chlorine to the nitrogen. The hydrogen's electron is left behind on the chlorine to form a negative chloride ion.

Once the ammonium ion has been formed it is impossible to tell any difference between the dative covalent and the ordinary covalent bonds. Although the electrons are shown differently in the diagram, there is no difference between them in reality.

Representing co-ordinate bonds

In simple diagrams, a co-ordinate bond is shown by an arrow. The arrow points from the atom donating the lone pair to the atom accepting it.

the atom donating the lone pair to the atom accepting it. Dissolving hydrogen chloride in water

Dissolving hydrogen chloride in water to make hydrochloric acid

Something similar happens. A hydrogen ion (H + ) is transferred from the chlorine to one of the lone pairs on the oxygen atom.

co-ordinate (dative covalent) bonding

co-ordinate (dative covalent) bonding The H 3 O + ion is variously called the hydroxonium ion,
co-ordinate (dative covalent) bonding The H 3 O + ion is variously called the hydroxonium ion,

The H 3 O + ion is variously called the hydroxonium ion, the hydronium ion or the oxonium ion.

In an introductory chemistry course (such as GCSE), whenever you have talked about hydrogen ions (for example in acids), you have actually been talking about the hydroxonium ion. A raw hydrogen ion is simply a proton, and is far too reactive to exist on its own in a test tube.

If you write the hydrogen ion as H + (aq) , the " (aq) " represents the water molecule that the hydrogen ion is attached to. When it reacts with something (an alkali, for example), the hydrogen ion simply becomes detached from the water molecule again.

Note that once the co-ordinate bond has been set up, all the hydrogens attached to the oxygen are exactly equivalent. When a hydrogen ion breaks away again, it could be any of the three.

The reaction between ammonia and boron trifluoride, BF 3

If you have recently read the page on covalent bonding, you may remember boron trifluoride as a compound which doesn't have a noble gas structure around the boron atom. The boron only has 3 pairs of electrons in its bonding level, whereas there would be room for 4 pairs. BF 3 is described as being electron deficient.

The lone pair on the nitrogen of an ammonia molecule can be used to overcome that deficiency, and a compound is formed involving a co- ordinate bond.

co-ordinate (dative covalent) bonding

co-ordinate (dative covalent) bonding Using lines to represent the bonds, this could be drawn more simply

Using lines to represent the bonds, this could be drawn more simply as:

to represent the bonds, this could be drawn more simply as: The second diagram shows another

The second diagram shows another way that you might find co-ordinate bonds drawn. The nitrogen end of the bond has become positive because the electron pair has moved away from the nitrogen towards the boron - which has therefore become negative. We shan't use this method again - it's more confusing than just using an arrow.

The structure of aluminium chloride

Aluminium chloride sublimes (turns straight from a solid to a gas) at 178°C. If it contained ions it would have a very high melting and boiling point because of the strong attractions between the positive and negative ions. The implication is that it must be covalent. The dots-and-crosses diagram shows only the outer electrons.

The dots-and-crosses diagram shows only the outer electrons. AlCl 3 , like BF 3 , is

AlCl 3 , like BF 3 , is electron deficient. There is likely to be a similarity, because aluminium and boron are in the same group of the Periodic Table, as are fluorine and chlorine.

co-ordinate (dative covalent) bonding

Measurements of the relative formula mass of aluminium chloride show that its formula in the solid is not AlCl 3 , but Al 2 Cl 6 . It exists as a dimer (two molecules joined together). The bonding between the two molecules is co-ordinate, using lone pairs on the chlorine atoms. Each chlorine atom has 3 lone pairs, but only the two important ones are shown in the line diagram.

only the two important ones are shown in the line diagram. Note: The uninteresting electrons on

Note: The uninteresting electrons on the chlorines have been faded in colour to make the co-ordinate bonds show up better. There's nothing special about those two particular lone pairs - they just happen to be the ones pointing in the right direction.

Energy is released when the two co-ordinate bonds are formed, and so the dimer is more stable than two separate AlCl 3 molecules.

The bonding in hydrated metal ions

Water molecules are strongly attracted to ions in solution - the water molecules clustering around the positive or negative ions. In many cases, the attractions are so great that formal bonds are made, and this is true of almost all positive metal ions. Ions with water molecules attached are described as hydrated ions.

co-ordinate (dative covalent) bonding

Although aluminium chloride is covalent, when it dissolves in water, ions are produced. Six water molecules bond to the aluminium to give an ion with the formula Al(H 2 O) 6 3+ . It's called the hexaaquaaluminium ion - which translates as six ("hexa") water molecules ("aqua") wrapped around an aluminium ion.

The bonding in this (and the similar ions formed by the great majority of other metals) is co-ordinate (dative covalent) using lone pairs on the water molecules.

(dative covalent) using lone pairs on the water molecules. Aluminium is 1s 2 2s 2 2p

Aluminium is 1s 2 2s 2 2p 6 3s 2 3p x 1 . When it forms an Al 3+ ion it loses the 3-

level electrons to leave 1s 2 2s 2 2p 6 .

That means that all the 3-level orbitals are now empty. The aluminium re- organises (hybridises) six of these (the 3s, three 3p, and two 3d) to produce six new orbitals all with the same energy. These six hybrid orbitals accept lone pairs from six water molecules.

You might wonder why it chooses to use six orbitals rather than four or eight or whatever. Six is the maximum number of water molecules it is possible to fit around an aluminium ion (and most other metal ions). By making the maximum number of bonds, it releases most energy and so becomes most energetically stable.

most energy and so becomes most energetically stable. Only one lone pair is shown on each

Only one lone pair is shown on each water molecule. The other lone pair is pointing away from the aluminium and so isn't involved in the bonding. The resulting ion looks like this:

co-ordinate (dative covalent) bonding

co-ordinate (dative covalent) bonding Because of the movement of electrons towards the centre of the ion,

Because of the movement of electrons towards the centre of the ion, the 3+ charge is no longer located entirely on the aluminium, but is now spread over the whole of the ion.

Note: Dotted arrows represent lone pairs coming from water molecules behind the plane of the screen or paper. Wedge shaped arrows represent bonds from water molecules in front of the plane of the screen or paper.

Two more molecules

Note: Only one current A'level syllabus wants these two. Check yours! If you haven't got a copy of your syllabus, follow this link to find out how to get one.

co-ordinate (dative covalent) bonding

Carbon monoxide, CO

Carbon monoxide can be thought of as having two ordinary covalent bonds between the carbon and the oxygen plus a co-ordinate bond using a lone pair on the oxygen atom.

Nitric acid, HNO 3

using a lone pair on the oxygen atom. Nitric acid, HNO 3 In this case, one

In this case, one of the oxygen atoms can be thought of as attaching to the nitrogen via a co-ordinate bond using the lone pair on the nitrogen atom.

a co-ordinate bond using the lone pair on the nitrogen atom. In fact this structure is

In fact this structure is misleading because it suggests that the two oxygen atoms on the right-hand side of the diagram are joined to the nitrogen in different ways. Both bonds are actually identical in length and strength, and so the arrangement of the electrons must be identical. There is no way of showing this using a dots-and-crosses picture. The bonding involves delocalisation.

co-ordinate (dative covalent) bonding

If you are interested: The bonding is rather similar to the bonding in the ethanoate ion (although without the negative charge). You will find thisdescribed on a page about the acidity of organic acids.

Where would you like to go now?

To the bonding menu

To the atomic structure and bonding menu

To Main Menu

© Jim Clark 2000

covalent bonding - single bonds

COVALENT BONDING - SINGLE BONDS

This page explains what covalent bonding is. It starts with a simple picture of the single covalent bond, and then modifies it slightly for A'level purposes. It also takes a more sophisticated view (beyond A'level) if you are interested. You will find a link to a page on double covalent bonds at the bottom of the page.

A simple view of covalent bonding

The importance of noble gas structures

At a simple level (like GCSE) a lot of importance is attached to the electronic structures of noble gases like neon or argon which have eight electrons in their outer energy levels (or two in the case of helium). These noble gas structures are thought of as being in some way a "desirable" thing for an atom to have.

You may well have been left with the strong impression that when other atoms react, they try to achieve noble gas structures.

As well as achieving noble gas structures by transferring electrons from one atom to another as in ionic bonding, it is also possible for atoms to reach these stable structures by sharing electrons to give covalent bonds.

Some very simple covalent molecules

Chlorine

For example, two chlorine atoms could both achieve stable structures by sharing their single unpaired electron as in the diagram.

covalent bonding - single bonds

covalent bonding - single bonds The fact that one chlorine has been drawn with electrons marked

The fact that one chlorine has been drawn with electrons marked as crosses and the other as dots is simply to show where all the electrons come from. In reality there is no difference between them.

The two chlorine atoms are said to be joined by a covalent bond. The reason that the two chlorine atoms stick together is that the shared pair of electrons is attracted to the nucleus of both chlorine atoms.

Hydrogen

is attracted to the nucleus of both chlorine atoms. Hydrogen Hydrogen atoms only need two electrons

Hydrogen atoms only need two electrons in their outer level to reach the noble gas structure of helium. Once again, the covalent bond holds the two atoms together because the pair of electrons is attracted to both nuclei.

Hydrogen chloride

of electrons is attracted to both nuclei. Hydrogen chloride The hydrogen has a helium structure, and

The hydrogen has a helium structure, and the chlorine an argon structure.

Covalent bonding at A'level

Cases where there isn't any difference from the simple view

If you stick closely to modern A'level syllabuses, there is little need to

covalent bonding - single bonds

move far from the simple (GCSE) view. The only thing which must be changed is the over-reliance on the concept of noble gas structures. Most of the simple molecules you draw do in fact have all their atoms with noble gas structures.

For example:

have all their atoms with noble gas structures. For example: Even with a more complicated molecule

Even with a more complicated molecule like PCl 3 , there's no problem. In this case, only the outer electrons are shown for simplicity. Each atom in this structure has inner layers of electrons of 2,8. Again, everything present has a noble gas structure.

of 2,8. Again, everything present has a noble gas structure. Cases where the simple view throws

Cases where the simple view throws up problems

Boron trifluoride, BF 3

the simple view throws up problems Boron trifluoride, BF 3 http://www.chemguide.co.uk/atoms/bonding/covalent.html (3 of

covalent bonding - single bonds

A boron atom only has 3 electrons in its outer level, and there is no

possibility of it reaching a noble gas structure by simple sharing of electrons. Is this a problem? No. The boron has formed the maximum number of bonds that it can in the circumstances, and this is a perfectly valid structure.

Energy is released whenever a covalent bond is formed. Because energy

is being lost from the system, it becomes more stable after every

covalent bond is made. It follows, therefore, that an atom will tend to make as many covalent bonds as possible. In the case of boron in BF 3 ,

three bonds is the maximum possible because boron only has 3 electrons to share.

Note: You might perhaps wonder why boron doesn't form ionic bonds with fluorine instead. Boron doesn't form ions because the total energy needed to remove three electrons to form a B 3+ ion is simply too great to be recoverable when attractions are set up between the boron and fluoride ions.

Phosphorus(V) chloride, PCl 5

In the case of phosphorus 5 covalent bonds are possible - as in PCl 5 .

Phosphorus forms two chlorides - PCl 3 and PCl 5 . When phosphorus burns in chlorine both are formed - the majority product depending on how much chlorine is available. We've already looked at the structure of PCl 3 .

The diagram of PCl 5 (like the previous diagram of PCl 3 ) shows only the outer electrons.

covalent bonding - single bonds

covalent bonding - single bonds Notice that the phosphorus now has 5 pairs of electrons in

Notice that the phosphorus now has 5 pairs of electrons in the outer level - certainly not a noble gas structure. You would have been content to draw PCl 3 at GCSE, but PCl 5 would have looked very worrying.

Why does phosphorus sometimes break away from a noble gas structure and form five bonds? In order to answer that question, we need to explore territory beyond the limits of current A'level syllabuses. Don't be put off by this! It isn't particularly difficult, and is extremely useful if you are going to understand the bonding in some important organic compounds.

A more sophisticated view of covalent bonding

The bonding in methane, CH 4

Warning! If you aren't happy with describing electron arrangements in s and p notation, and with the shapes of s and p orbitals, you need to read about orbitals before you go on.

Use the BACK button on your browser to return quickly to this point.

covalent bonding - single bonds

What is wrong with the dots-and-crosses picture of bonding in methane?

We are starting with methane because it is the simplest case which illustrates the sort of processes involved. You will remember that the dots- and-crossed picture of methane looks like this.

the dots- and-crossed picture of methane looks like this. There is a serious mis-match between this

There is a serious mis-match between this structure and the modern electronic structure of carbon, 1s 2 2s 2 2p x 1 2p y 1 . The modern structure shows that there are only 2 unpaired electrons for hydrogens to share with, instead of the 4 which the simple view requires.

You can see this more readily using the electrons-in-boxes notation. Only the 2- level electrons are shown. The 1s 2 electrons are too deep inside the atom to be involved in bonding. The only electrons directly available for sharing are the 2p electrons. Why then isn't methane CH 2 ?

are the 2p electrons. Why then isn't methane CH 2 ? Promotion of an electron

Promotion of an electron

covalent bonding - single bonds

covalent bonding - single bonds When bonds are formed, energy is released and the system becomes

When bonds are formed, energy is released and the system becomes more stable. If carbon forms 4 bonds rather than 2, twice as much energy is released and so the resulting molecule becomes even more stable.

There is only a small energy gap between the 2s and 2p orbitals, and so it pays the carbon to provide a small amount of energy to promote an electron from the 2s to the empty 2p to give 4 unpaired electrons. The extra energy released when the bonds form more than compensates for the initial input.

Note: People sometimes worry that the promoted electron is drawn as an up-arrow, whereas it started as a down-arrow. It simply makes the diagram look tidier - nothing very sophisticated is going on!

Now that we've got 4 unpaired electrons ready for bonding, another problem arises. In methane all the carbon-hydrogen bonds are identical, but our electrons are in two different kinds of orbitals. You aren't going to get four identical bonds unless you start from four identical orbitals.

Hybridisation

unless you start from four identical orbitals. Hybridisation The electrons rearrange themselves again in a process

The electrons rearrange themselves again in a process called hybridisation. This reorganises the electrons into four identical hybrid orbitals called sp 3 hybrids (because they are made from one s orbital and three p orbitals). You should read "sp 3 " as "s p three" - not as "s p cubed".

covalent bonding - single bonds

sp 3 hybrid orbitals look a bit like half a p orbital, and they arrange themselves in space so that they are as far apart as possible. You can picture the nucleus as being at the centre of a tetrahedron (a triangularly based pyramid) with the orbitals pointing to the corners. For clarity, the nucleus is drawn far larger than it really is.

clarity, the nucleus is drawn far larger than it really is. What happens when the bonds

What happens when the bonds are formed?

Remember that hydrogen's electron is in a 1s orbital - a spherically symmetric region of space surrounding the nucleus where there is some fixed chance (say 95%) of finding the electron. When a covalent bond is formed, the atomic orbitals (the orbitals in the individual atoms) merge to produce a new molecular orbital which contains the electron pair which creates the bond.

which contains the electron pair which creates the bond. Four molecular orbitals are formed, looking rather

Four molecular orbitals are formed, looking rather like the original sp 3 hybrids, but with a hydrogen nucleus embedded in each lobe. Each orbital holds the 2 electrons that we've previously drawn as a dot and a cross.

The principles involved - promotion of electrons if necessary, then hybridisation, followed by the formation of molecular orbitals - can be applied to any covalently-bound molecule.

covalent bonding - single bonds

Note: You will find this bit on methane repeated in the organic section of this site. That article on methane goes on to look at the formation of carbon-carbon single bonds in ethane.

The bonding in the phosphorus chlorides, PCl 3 and PCl 5

What's wrong with the simple view of PCl 3 ?

This diagram only shows the outer (bonding) electrons.

? This diagram only shows the outer (bonding) electrons. Nothing is wrong with this! (Although it

Nothing is wrong with this! (Although it doesn't account for the shape of the molecule properly.) If you were going to take a more modern look at it, the argument would go like this:

Phosphorus has the electronic structure 1s 2 2s 2 2p 6 3s 2 3p x 1 3p y 1 3p z 1 . If we look only at the outer electrons as "electrons-in-boxes":

only at the outer electrons as "electrons-in-boxes": There are 3 unpaired electrons that can be used

There are 3 unpaired electrons that can be used to form bonds with 3 chlorine atoms. The four 3-level orbitals hybridise to produce 4 equivalent sp 3 hybrids just like in carbon - except that one of these hybrid

covalent bonding - single bonds

orbitals contains a lone pair of electrons.

- single bonds orbitals contains a lone pair of electrons. Each of the 3 chlorines then

Each of the 3 chlorines then forms a covalent bond by merging the atomic orbital containing its unpaired electron with one of the phosphorus unpaired electrons to make 3 molecular orbitals.

You might wonder whether all this is worth the bother! Probably not! It is worth it with PCl 5 , though.

What's wrong with the simple view of PCl 5 ?

You will remember that the dots-and-crosses picture of PCl 5 looks awkward because the phosphorus doesn't end up with a noble gas structure. This diagram also shows only the outer electrons.

structure. This diagram also shows only the outer electrons. In this case, a more modern view

In this case, a more modern view makes things look better by abandoning any pretence of worrying about noble gas structures.

If the phosphorus is going to form PCl 5 it has first to generate 5 unpaired electrons. It does this by promoting one of the electrons in the 3s orbital to the next available higher energy orbital.

Which higher energy orbital? It uses one of the 3d orbitals. You might

covalent bonding - single bonds

have expected it to use the 4s orbital because this is the orbital that fills before the 3d when atoms are being built from scratch. Not so! Apart from when you are building the atoms in the first place, the 3d always counts as the lower energy orbital.

place, the 3d always counts as the lower energy orbital. This leaves the phosphorus with this

This leaves the phosphorus with this arrangement of its electrons:

the phosphorus with this arrangement of its electrons: The 3-level electrons now rearrange (hybridise) themselves

The 3-level electrons now rearrange (hybridise) themselves to give 5 hybrid orbitals, all of equal energy. They would be called sp 3 d hybrids because that's what they are made from.

3 d hybrids because that's what they are made from. The electrons in each of these

The electrons in each of these orbitals would then share space with electrons from five chlorines to make five new molecular orbitals - and hence five covalent bonds.

Why does phosphorus form these extra two bonds? It puts in an amount of energy to promote an electron, which is more than paid back when the new bonds form. Put simply, it is energetically profitable for the phosphorus to form the extra bonds.

The advantage of thinking of it in this way is that it completely ignores the