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Part 1. Why do atoms bond together? - 'electron glue'!

Some atoms are very reluctant to combine with other atoms and exist in the air around us as single atoms. These are the Noble Gases and have very stable electron arrangements e.g. 2, 2,8 and 2,8,8 because their outer shells are full. The first three are shown in the diagrams below and explains why Noble Gases are so reluctant to form compounds with other elements.

(atomic number) electron arrangement All other atoms therefore, bond together to become electronically more stable, that is to become like Noble Gases in electron arrangement. Bonding produces new substances and usually involves only the 'outer shell' or 'valency' electrons and atoms can bond in two ways. The phrase CHEMICAL BOND refers to the strong electrical force of attraction between the atoms or ions in the structure. The combining power of an atom is sometimes referred to as its valency and its value is linked to the number of outer electrons of the original uncombined atom (see examples later).

(a) IONIC BONDING - By one atom transferring electrons to another atom to form oppositely charged particles called ions which attract each other - the ionic bond. An ion is an atom or group of atoms carrying an overall positive or negative charge + 2+ 2o e.g. Na , Cl , [Cu(H2O)] , SO4 etc. If a particle, as in a neutral atom, has equal numbers of protons (+) and electrons (-) the particle charge is zero i.e. no overall electric charge. The proton/atomic number in an atom does not change BUT the number of associated electrons can! If negative electrons are lost the excess charge from the protons produces an overall positive ion. If negative electrons are gained there is an excess of negative charge, so a negative ion is formed. The charge on the ion is numerically related to the number of electrons transferred i.e. electrons lost or gained. For any atom or group of atoms, for every electron gained you get a one unit increase in negative charge on the ion, for every electron lost you get a one unit increase in the positive charge on the ion. The atom losing electrons forms a positive ion (cation) and is usually a metal. The atom gaining electrons forms a negative ion (anion) and is usually a non-metallic element. The ionic bond then consists of the attractive force between the positive and negative ions in the structure. The ionic bonding forces act in all directions around a particular ion, it is not directional, as in the case of covalent bonding.

The sodium atom transfers an electron to the chlorine atom in forming sodium chloride For more detailed notes on this example and other examples see Ionic Bonding - compounds and properties

(b) COVALENT BONDING - sharing electrons to form molecules with covalent bonds, the bond is usually formed between two non-metallic elements in a molecule. The two positive nuclei (due to the positive protons in them) of both atoms are mutually attracted to the shared negative electrons between them forming the covalent bond. They share the electrons in a way that gives a stable Noble Gas electron arrangement like helium (2) or neon (2.8) etc.. This kind of bond or electronic linkage does act in a particular direction i.e. along the 'line' between the two nuclei of the atoms bonded together, this is why molecules have a particular shape.

Hydrogen and oxygen atoms share electrons to form covalent O-H bonds to form water

o o o

which has a 'bent' shape More detailed notes on this example and other examples see the Revision notes Covalent Bonding - small simple molecules and properties Covalently bonded structures can lead to the formation of some very BIG molecules See Covalent Bonding - macromolecules and giant covalent structures Advanced Level Chemistry notes on the shapes of molecules

(c) METALLIC BONDING isn't quite like ionic or covalent bonding, the metal atoms form positive ions, but no negative ion is formed from the same metal atoms, but the positive metal ions/atoms are attracted together by the free moving negative electrons between them.

Example of a metal bonding diagram More detailed notes on Metallic Bonding - structure and properties of metals

(d) As explained at the start of Part 1 NOBLE GASES are very reluctant to share, gain or lose electrons to form a chemical bond. They are already electronically very stable. For most other elements the types of bonding and the resulting properties of the elements or compounds are described in detail in Parts 2 to 5. In all the electronic diagrams ONLY the outer electrons are shown.

2. Ionic Bonding - electron transfer Ionic bonds are formed by one atom transferring electrons to another atom to form ions. Elements consist of neutral atoms or molecules, the electrical neutrality is because the number of positive protons equals the number of negative electrons.

Ions are atoms, or groups of atoms, which have lost or gained electrons to have a net electrical charge overall . The atom losing electrons forms a positive ion (a cation) and is usually a metal. The overall charge on the ion is positive due to excess positive nuclear charge (protons do NOT change in chemical reactions). The atom gaining electrons forms a negative ion (an anion) and is usually a non-metallic element. The overall charge on the ion is negative because of the gain, and therefore excess, of negative electrons. The examples below combining a metal from Groups 1 (Alkali Metals), 2 or 3, with a non-metal from Group 6 or Group 7 (The Halogens). The electron structures are shown in () or []. Only the outer electrons of the original atoms, and where they end up in the ions, are shown in the dot and cross (ox) diagrams Ionic bonding is not directional like covalent bonding, in the sense that the force of attraction between the positive ions and the negative ions act in every direction around the ions.

Example 1: A Group 1 metal + a Group 7 non-metal e.g. sodium + chlorine ==> sodium chloride NaCl or ionic formula + Na Cl In terms of electron arrangement, the sodium donates its outer electron to a chlorine atom forming a single positive sodium ion and a single negative chloride ion. The atoms have become stable ions, because electronically, sodium becomes like neon and chlorine like argon. Na (2.8.1) + Cl (2.8.7) ==> Na (2.8) Cl (2.8.8) can be summarised electronically to give the stable 'noble gas' structures as [2,8,1] + [2,8,7] ==> [2,8] [2,8,8]
+ + -

ONE

combines with ONE

to form

The valencies of Na and Cl are both 1, that is, the numerical charge on the ions. sodium fluoride NaF, potassium bromide KBr and lithium iodide LiI etc. will all be electronically similar. Note:

would represent the full electronic structure of the sodium ion.

would represent the full electronic structure of the chloride ion and note that the 'blob' and 'x' electrons are identical, but their use is just a useful visual device to show how the ion is formed. Only the outer valency electrons of the chloride ion are shown, the 'blob' electron represents the electron from the sodium atom which is accepted by the chlorine atom to form the chloride ion. The charge on the sodium ion Na is +1 units (shown as just +) because there is one more positive proton than there are negative electrons in the sodium ion. The charge on the chloride ion Cl is -1 units (shown as just -) because there is one more negative electron than there are positive protons in the chloride ion. See Example 6. aluminium oxide for more highly charged ion analysis. Li is 2.1, K is 2.8.8.1, F is 2.7, rest of dot and cross diagram is up to you. Reminder: How to work out formula of ionic compounds without going through some demanding electronic thinking is described on the "Elements, Compounds and Mixtures" page and it is followed by a section on naming compounds.
+

Example 2: A Group 2 metal + a Group 7 non-metal e.g. magnesium + chlorine ==> magnesium chloride MgCl2 or 2+ ionic formula Mg (Cl )2 In terms of electron arrangement, the magnesium donates its two outer electrons to two chlorine atoms forming a double positive magnesium ion and two single negative chloride ions. The atoms have become stable ions, because electronically, magnesium becomes like neon and chlorine like argon. Mg (2.8.2) + 2Cl (2.8.7) ==> Mg
2+

(2.8) 2Cl (2.8.8)


2+

can be summarised electronically as [2,8,2] + 2[2,8,7] ==> [2,8]

[2,8,8] 2

ONE NOTE

combines with TWO

to form

see *

* you can draw two separate chloride ions, but in these examples square brackets and a number subscript have been used, as in ordinary chemical formula. The valency of Mg is 2 and chlorine 1, i.e. the numerical charges of the ions.

Beryllium fluoride BeF2, magnesium bromide MgBr2, calcium chloride CaCl2 or barium iodide BaI2 etc. will all be electronically similar.

represents the full electronic structure of the magnesium ion. Ca is 2.8.8.2, F is 2.7 rest of dot and cross diagrams are up to you.

Example 3: A Group 3 metal + a Group 7 non-metal e.g. aluminium + fluorine ==> aluminium fluoride AlF3 or ionic 3+ formula Al (F )3 In terms of electron arrangement, the aluminium donates its three outer electrons to three fluorine atoms forming a triple positive aluminium ion and three single negative fluoride ions. The atoms have become stable ions, because aluminium and fluorine becomes electronically like neon. Valency of Al is 3 and F is 1, i.e. equal to the charges on the ions. Al (2.8.3) + 3F (2.7) ==> Al
3+

(2.8) 3F (2.8)
3+

can be summarised electronically as [2,8,3] + 3[2,7] ==> [2,8]

[2,8] 3

ONE

combines with THREE

to form

Solid aluminium chloride/bromide/iodide have similar formula but are covalent when vapourised into Al 2X6 dimer molecules, but AlCl3 has an ionic lattice in the solid, not sure on solid AlBr 3 and AlI3, but these points are best left for an advanced AS-A2 chemistry discussion, not for GCSE students!

Example 4: A Group 1 metal + a Group 6 non-metal e.g. sodium/potassium + oxygen ==> sodium/potassium oxide + 2+ 2Na2O/K2O or ionic formula (Na )2O /(K )2O In terms of electron arrangement, the two sodium/potassium atoms donate their outer electron to one oxygen atom. This results in two single positive potassium ions to one double negative oxide ion. All the ions have the stable electronic structures 2.8.8 (argon like) or 2.8 (neon like). Valencies, K 1, oxygen 2. Lithium oxide, Li2O, sodium oxide Na2O, sodium sulphide Na2S and potassium K2S etc. will be similar. sodium oxide 2Na (2.8.1) + O (2.6) ==> 2Na (2.8.8) O (2.8) can be summarised electronically as 2[2,8,1] + [2,6] ==> [2,8]
+ 2 + 2-

[2,8]

2-

TWO

combine with ONE or

to form

==> potassium oxide

2K (2.8.8.1) + O (2.6) ==> 2K (2.8.8) O (2.8) can be summarised electronically as 2[2,8,8,1] + [2,6] ==> [2,8,8]
+ 2

2-

[2,8]

2-

TWO

combine with ONE

to form

The electronic similarities between the two examples are very obvious. Li is 2.1, Na is 2.8.1, S is 2.8.6 (for group 1 sulphide compound), rest of dots and crosses diagrams are up to you.

Example 5: A Group 2 metal + a Group 6 non-metal e.g. magnesium/calcium + oxygen ==> magnesium/calcium oxide 2+ 22+ 2MgO/CaO or ionic formula Mg O /Ca O In terms of electron arrangement, one magnesium/calcium atom donates its two outer electrons to one oxygen atom. This results in a double positive calcium ion to one double negative oxide ion. All the ions have the stable electronic structures 2.8.8 (argon like) or 2.8 (neon like). the valency of both calcium and oxygen is 2. magnesium oxide

ONE

combines with ONE

to form
2+

For magnesium oxide: Mg (2.8.2) + O (2.6) ==> Mg

(2.8) O (2.8)
2+

2-

the stable 'noble gas' structures can be summarised electronically as [2,8,2] + [2,6] ==> [2,8,8]

[2,8]

2-

calcium oxide Ca (2.8.8.2) + O (2.6) ==> Ca


2+

(2.8.8) O (2.8)
2+

2-

can be summarised electronically as [2,8,8,2] + [2,6] ==> [2,8,8]

[2,8]

2-

ONE

combines with ONE

to form

Magnesium oxide MgO, magnesium sulphide MgS and calcium sulphide CaS will be similar electronically and give identical giant ionic lattice structures. Group 2 metals lose the two outer electrons to give the stable 2+ positive ion (cation) and S and O, both non-metals in Group 6, have 6 outer electrons and gain 2 electrons to form 2- negative ion (anion). For magnesium sulphide: Mg (2.8.2) + S (2.8.6) ==> Mg For calcium sulphide: Ca (2.8.8.2) + S (2.8.6) ==> Ca
2+ 2+

(2.8) S (2.8.8)
2-

2-

(2.8.8) S (2.8.8)

The dot and cross (ox) diagrams will be identical to that for calcium oxide above, except Mg instead of Ca (same group) and S instead of O (same group of Periodic Table).

Example 6: A Group 3 metal + a Group 6 non-metal e.g. aluminium + oxygen ==> aluminium oxide Al2O3 or ionic 3+ 2formula (Al )2(O )3 In terms of electron arrangement, two aluminium atoms donate their three outer electrons to three oxygen atoms. This results in two triple positive aluminium ions to three double negative oxide ions. All the ions have the stable electronic structure of neon 2.8. Valencies, Al 3 and O 2. 2Al (2.8.3) + 3O (2.6) ==> 2Al
3+

(2.8) 3O (2.8)
3+ 2

2-

can be summarised electronically as 2[2,8,3] + 3[2,6] ==> [2,8]

[2,8]

23

TWO Note:

combine with THREE

to form

The charge on the aluminium ion Al is +3 units (shown as 3+) because there are three more positive protons than there are negative electrons in the aluminium ion. The charge on the oxide ion O is -2 units (shown as 2-) because there are two more negative electrons than there are positive protons in the oxide ion. on another web page is how to work out an ionic formula given the ionic charges (combining power)
2-

3+

The properties of Ionic Compounds

The diagram on the right is typical of the giant ionic crystal structure of ionic compounds like sodium chloride and magnesium oxide. The alternate positive and negative ions in an ionic solid are arranged in an orderly way in a giant ionic lattice structure shown on the left. The ionic bond is the strong electrical attraction between the positive and negative ions next to each other in the lattice. The bonding extends throughout the crystal in all directions. Salts and metal oxides are typical ionic compounds. This strong bonding force makes the structure hard (if brittle) and have high melting and boiling points, so they are not very volatile! A relatively large amount of energy is needed to melt or boil ionic compounds. Energy changes for the physical changes of state of melting and boiling for a range of differently bonded substances are compared in a section of the Energetics Notes. The bigger the charges on the ions the stronger the 2+ 2bonding attraction e.g. magnesium oxide Mg O has a higher + melting point than sodium chloride Na Cl . Unlike covalent molecules, ALL ionic compounds are crystalline solids at room temperature. They are hard but brittle, when stressed the bonds are broken along planes of ions which shear away. They are NOT malleable like metals (see below). Many ionic compounds are soluble in water, but not all, so don't make assumptions. Salts can dissolve in water because the ions can separate and become surrounded by water molecules which weakly bond to the ions. This reduces the attractive forces between the ions, preventing the crystal structure to exist. Evaporating the water from a salt solution will eventually allow the ionic crystal lattice to reform. The solid crystals DO NOT conduct electricity because the ions are not free to move to carry an electric current. However, if the ionic compound is melted or dissolved in water, the liquid will now conduct electricity, as the ion particles are now free.

3. Covalent Bonding - electron sharing in big or small molecules! Covalent bonds are formed by atoms sharing electrons to form molecules. This type of bond usually formed between two non-metallic elements. The molecules might be that of an element i.e. one type of atom only OR from different elements chemically combined to form a compound. The covalent bonding is caused by the mutual electrical attraction between the two positive nuclei of the two atoms of the bond, and the negative electrons between them. One single covalent bond is a sharing of 1 pair of electrons, two pairs of shared electrons between the same two atoms gives a double bond and it is possible for two atoms to share 3 pairs of electrons and give a triple bond. Note: In the examples it is assumed you can work out the electron configuration (arrangement in shells or energy levels) given the atomic number from the Periodic Table. This kind of bond or electronic linkage does act in a particular direction i.e. along the 'line' between the two nuclei of the atoms bonded together, this is why molecules have a particular shape. In the case of ionic or metallic bonding, the electrical attractive forces act in all directions around the particles involved.

The bonding in Small Covalent Molecules The simplest molecules are formed from two atoms and examples of their formation are shown below. The electrons are shown as dots and crosses to indicate which atom the electrons come from, though all electrons are the same. The diagrams may only show the outer electron arrangements for atoms that use two or more electron shells. The electron structures are given in (). Examples of simple covalent molecules are

Example 1: two hydrogen atoms (1) form the molecule of the element hydrogen H2

and combine to form where both atoms have a pseudo helium structure of 2 outer electrons around each atom's nucleus. Any covalent bond is formed from the mutual attraction of two positive nuclei and negative electrons between them. The nuclei would be a tiny dot in the middle of where the H symbols are drawn! H valency is 1.

Example 2: two chlorine atoms (2.8.7) form the molecule of the element chlorine Cl2

and combine to form where both atoms have a pseudo argon structure of 8 outer electrons around each atom. All the other halogens would be similar e.g. F2, Br2 and I2 etc. Valency of halogens like chlorine is 1 here.

Example 3: one atom of hydrogen (1) combines with one atom of chlorine (2.8.7) to form the molecule of the compound hydrogen chloride HCl

and combine to form where hydrogen is electronically like helium and chlorine like argon. All the other hydrogen halides will be similar e.g. hydrogen fluoride HF, hydrogen bromide HBr and hydrogen iodide HI. Note: Hydrogen chloride gas is a true covalent substance consisting of small HCl molecules. If the gas is dissolved in a hydrocarbon solvent like hexane or methylbenzene it remains as HCl molecules and because there are no ions present, the solution does not conduct electricity. However, if hydrogen chloride gas is dissolved in water, things are very different + and the HCl molecules split into ions. Hydrochloric acid is formed which consists of a solution of hydrogen ions (H ) and chloride ions (Cl ). The solution then conducts electricity and passage of a d.c. current causes electrolysis to take place forming hydrogen and chlorine. Reminder: How to work out formula of covalent compounds without going through some demanding electronic thinking is described on the "Elements, Compounds and Mixtures" page and it is followed by a section on naming compounds.

Example 4: two atoms of hydrogen (1) combine with one atom of oxygen (2.6) to form the molecule of the compound water H2O

and

and

combine to form

so that the hydrogen atoms are electronically like

helium and the oxygen atom becomes like neon. The molecule can be shown as with two hydrogen - oxygen o single covalent bonds (AS note: called a V or bent shape, the H-O-H bond angle is 105 ). Hydrogen sulphide will be similar, since sulphur (2.8.6) is in the same Group 6 as oxygen. Valency of oxygen and sulphur is 2 here.

Example 5: three atoms of hydrogen (1) combine with one atom of nitrogen (2.5) to form the molecule of the compound ammonia NH3

three of

and one

combine to form

so that the hydrogen atoms are electronically like

helium and the nitrogen atom becomes like neon. The molecule can be shown as with three nitrogen o hydrogen single covalent bonds (AS note: called a trigonal pyramid shape, the H-N-H bond angle is 107 ). PH3 will be similar since phosphorus (2.8.5) is in the same Group 5 as nitrogen. Valency of nitrogen or phosphorus is 3 here.

Example 6: four atoms of hydrogen (1) combine with one atom of carbon (2.4) to form the molecule of the compound methane CH4

four of

and one of

combine to form

so that the hydrogen atoms are electronically

like helium and the nitrogen atom becomes like neon. The molecule can be shown as with four carbon o hydrogen single covalent bonds (AS note: called a tetrahedral shape, the H-C-H bond angle is 109 ). SiH4 will be similar because silicon (2.8.4) is in the same group as carbon. All the bonds in the above examples are single covalent bonds. Below are three examples 7-9, where there is a double bond in the molecule, in order that the atoms have stable Noble Gas outer electron arrangements around each atom. Carbon and silicon have a valency of 4. More complex examples can be worked out e.g. involving C, H and O. In each case link in the atoms so that there are 2 around a H (electronically like He), or 8 around the C or O (electronically like Ne).

Example 7:

Two atoms of oxygen (2.6) combine to form the molecules of the element oxygen O2. The molecule has one O=O double covalent bond . Oxygen valency 2.

Example 8:

One atom of carbon (2.4) combines with two atoms of oxygen (2.6) to form

the compound carbon dioxide CO2. The molecule can be shown as with two carbon = oxygen double o covalent bonds (AS note: called a linear shape, the O=C=O bond angle is 180 ). Valencies of C and O are 4 and 2 respectively.

Example 9:

Two atoms of carbon (2.4) combine with four atoms of hydrogen (1) to form

ethene C2H4. The molecule can be shown as with one carbon = carbon double bond and four carbon - hydrogen single covalent bonds (called a planar shape, its completely flat!, the H-C=C and H-C-H bond angles o are 120 ). The valency of carbon is still 4.

Examples 10-13: The scribbles below illustrate some more complex examples. Can you deduce them for yourself? Ex. 10 nitrogen N2; Ex. 11 ethane C2H6; Ex. 12 chloromethane CH3Cl and Ex. 13 methanol CH3OH. Electronic origin of the diagrams showing the outer electrons of N, C, Cl and O: N at. no. 7 (2.5), H at. no. (1), C at. no. 6 (2.4), Cl at. no. 17 (2.8.7) and O at. no. 8 (2.6) plus a variety of crosses and blobs! The valencies or combining power in theses examples are N 3, H 1, C 4, Cl 1 and O 2. From these you can work out others e.g. Ex. 12 can be used to derive the ox diagram for tetrachloromethane CCl4.

AS advanced level notes on shapes and bond angles: o o Ex. 11 Ethane has a linked double tetrahedral shape, all H-C-H and H-C-C bond angles are 109 o o Ex. 12 chloromethane has tetrahedral shape with H-C-H and H-C-Cl bond angles of approximately 109 o Ex. 13 methanol, the four bonds around the central carbon are tetrahedrally arranged with a H 'wiggle' on o the oxygen. All the H-C-H, H-C-O and C-O-H bond angles are approximately 109 o The blue icon e.g. below, represents an octahedral shape (e.g. SF 6, complex transition metal ions like 2+ o o [Cu(H2O)6] and the bond angles are either 90 or 180 o Simple molecules with a triple bond are often linear e.g. H-C C-H ethyne or H-C N hydrogen cyanide (methanenitrile) o The theory of shapes and bond angles with more examples and diagrams is on another page for AS-A2 students and with an extra section on bond angles in organic molecules.

on another web page is how to work out a covalent formula given the element valencies (combining power)

Typical properties of simple covalent substances - small molecules! The electrical forces of attraction, that is the chemical bond, between atoms in a molecule are usually very strong, so, most covalent molecules do not change chemically on moderate heating. o e.g. although a covalent molecule like iodine, I2, is readily vapourised on heating, it does NOT break up into iodine atoms I. The I-I covalent bond is strong enough to withstand the heating and the purple vapour still consists of the same I2 molecules as the dark coloured solid is made up of. So why the ease of vaporisation on heating? o The electrical attractive forces between individual molecules are weak, so the bulk material is not very strong physically and there are also consequences for the melting and boiling points. These weak electrical attractions are known as intermolecular forces and are readily weakened further on heating. The effect of absorbing heat energy results in increased the thermal vibration of the molecules which weakens the intermolecular forces. In liquids the increase in the average particle kinetic energy makes it easier for molecules to overcome the intermolecular forces and change into a gas or vapour. Consequently, small covalent molecules tend to be volatile liquids with low boiling points, so easily vapourised, or low melting point solids. o On heating the inter-molecular forces are easily overcome with the increased kinetic energy of the particles giving the material a low melting or boiling point and a relatively small amount of energy is needed to effect these state changes. o Energy changes for the physical changes of state of melting and boiling for a range of differently bonded substances are compared in a section of the Energetics Notes. o This contrasts with the high melting points of giant covalent structures with their strong 3D network. o Note: The weak electrical attractive forces between molecules, the so called intermolecular forces should be clearly distinguished between the strong covalent bonding between atoms in molecules (small or giant), and these are sometimes referred to as intramolecular forces (i.e. internal to the molecule). Covalent structures are usually poor conductors of electricity because there are no free electrons or ions in any state to carry electric charge. Most small molecules will dissolve in some solvent to form a solution. o This again contrasts with giant covalent structures where the strong bond network stops solvent molecules interacting with the particles making up the material. The properties of these simple small molecules should be compared and contrasted with those molecules of a giant covalent nature (next section). o Apart from points on the strong bonds between the atoms in the molecule and the lack of electrical conduction, all the other properties are significantly different!

4. Large Covalent Molecules and their Properties macromolecules - giant covalent networks and polymers What is the bonding, structure and properties of the carbon allotropes diamond, graphite & buckminsterfullerenes (fullerenes), silica (silicon dioxide), thermosets, thermoplastics? Because covalent bonds act in a particular direction i.e. along the 'line' between the two nuclei of the atoms bonded together in an individual bond, strong structures can be formed, especially if the covalent bonds are arranged in a strong three dimensional giant covalent lattice. The structure of the three allotropes of carbon (diamond, graphite and fullerenes), DIAGRAMS

silicon and silicon dioxide (silica) It is possible for many atoms to link up to form a giant covalent structure or lattice. The atoms are usually non-metals. This produces a very strong 3-dimensional covalent bond network or lattice. This gives them significantly different properties from the small simple covalent molecules mentioned above. This is illustrated by carbon in the form of diamond (an allotrope of carbon). Carbon has four outer electrons that form four single bonds, so each carbon bonds to four others by electron pairing/sharing. Pure silicon, another element in Group 4, has a similar structure. o NOTE: Allotropes are different forms of the same element in the same physical state. They occur due to different bonding arrangements and so diamond, graphite (below) and fullerenes (below) are the three solid allotropes of the element carbon. Oxygen (dioxygen), O2, and ozone (trioxygen), O3, are the two small gaseous allotrope molecules of the element oxygen. Sulphur has three solid allotropes, two different crystalline forms based on small S8 molecules called rhombic and monoclinic sulphur and a 3rd form of long chain ( -S-S-S- etc.) molecules called plastic sulphur. TYPICAL PROPERTIES of GIANT COVALENT STRUCTURES This type of giant covalent structure is thermally very stable and has a very high melting and boiling points because of the strong covalent bond network (3D or 2D in the case of graphite below). A relatively large amount of energy is needed to melt or boil giant covalent structures. Energy changes for the physical changes of state of melting and boiling for a range of differently bonded substances are compared in a section of the Energetics Notes. They are usually poor conductors of electricity because the electrons are not usually free to move as they can in metallic structures. Also because of the strength of the bonding in all directions in the structure, they are often very hard, strong and will not dissolve in solvents like water. The bonding network is too strong to allow the atoms to become surrounded by solvent molecules Silicon dioxide (silica, SiO2) has a similar 3D structure and properties to carbon (diamond) shown below. The hardness of diamond enables it to be used as the 'leading edge' on cutting tools. Energy changes for the physical changes of state of melting and boiling for a range of differently bonded substances is given in a section of the Energetics Notes. Many naturally occurring minerals are based on -O-X-O- linked 3D structures where X is often silicon (Si) and aluminium (Al), three of the most abundant elements in the earth's crust. o Silicon dioxide is found as quartz in granite (igneous rock) and is the main component in sandstone - which is a sedimentary rock formed the compressed erosion products of igneous rocks. o Many some minerals that are hard wearing, rare and attractive when polished, hold great value as gemstones. Carbon also occurs in the form of graphite. The carbon atoms form joined hexagonal rings forming layers 1 atom thick. There are three strong covalent bonds per carbon (3 C-C bonds in a planar arrangement from 3 of its 4 outer electrons), BUT, the fourth outer electron is 'delocalised' or shared between the carbon atoms to form the equivalent of a 4th bond per carbon atom (this situation requires advanced level concepts to fully explain, and this bonding situation also occurs in fullerenes described below, and in aromatic compounds you deal with at advanced level). The layers are only held together by weak intermolecular forces shown by the dotted lines NOT by strong covalent bonds. Like diamond and silica (above) the large molecules of the layer ensure graphite has typically very high melting point because of the strong 2D bonding network (note: NOT 3D network).. Graphite will not dissolve in solvents because of the strong bonding

DIAMOND

SILICA silicon dioxide

GRAPHITE

BUT there are two crucial differences compared to diamond ... o Electrons, from the 'shared bond', can move freely through each layer, so graphite is a conductor like a metal (diamond is an electrical insulator and a poor heat conductor). Graphite is used in electrical contacts e.g. electrodes in electrolysis. o The weak forces enable the layers to slip over each other so where as diamond is hard material graphite is a 'soft' crystal, it feels slippery. Graphite is used as a lubricant. These two different characteristics described above are put to a common use with the electrical contacts in electric motors and dynamos. These contacts (called brushes) are made of graphite sprung onto the spinning brass contacts of the armature. The graphite brushes provide good electrical contact and are self-lubricating as the carbon layers slide over each other. A 3rd form of carbon are fullerenes or 'bucky balls'! It consists of hexagonal rings like graphite and alternating pentagonal rings to allow curvature of the surface. Buckminster Fullerene C60 is shown and the bonds form a pattern like a soccer ball. Others are oval shaped like a rugby ball. It is a black solid insoluble in water. They are NOT considered giant covalent structures and are classed as simple molecules. They do dissolve in organic solvents giving coloured solutions (e.g. deep red in petrol hydrocarbons, and although solid, their melting points are not that high. They are mentioned here to illustrate the different forms of carbon AND they can be made into continuous tubes to form very strong fibres of 'pipe like' molecules called 'nanotubes'. These 'molecular size' particles behave quite differently to a bulk carbon material like graphite. Uses of Nanotubes - carbon nanotechnology - examples of nanochemistry o They can be used as semiconductors in electrical circuits. o They act as a component of industrial catalysts for certain reactions whose economic efficiency is of great importance (time = money in business!). The catalyst can be attached to the nanotubes which have a huge surface are per mass of catalyst 'bed'. They large surface combined with the catalyst ensure two rates of reaction factors work in harmony to increase the speed of an industrial reaction so making the process more efficient and more economic. o Nanotube fibres are very strong and so they are used in 'composite materials' e.g. reinforcing graphite in carbon fibre tennis rackets. o Nanotubes can 'cage' other molecules and can be used as a means of delivering drugs in controlled way to the body because the thin carbon nanotubes can penetrate cell walls. I've written NEW pages with more examples and details on o General introduction to nanoscience and commonly used terms explained o NANOCHEMISTRY - an introduction and potential applications o NANOCHEMISTRY including fullerenes and CARBON NANOTUBES o SMART MATERIALS SCIENCE (alphabetical index at top of page)

FULLERENES

Bonding in polymers and 1-3 'dimension' concepts in macromolecules The bonding in polymers or plastics is no different in principle to the examples described above, but there is quite a range of properties and the difference between simple covalent and giant covalent molecules can get a bit 'blurred'. o Bonds between atoms in molecules, e.g. C-C, are called intra-molecular bonds. o The much weaker electrical attractions between individual molecules are called inter-molecular forces. In thermosoftening plastics like poly(ethene) the bonding is like ethane except there are lots of carbon atoms linked together to form long chains. They are moderately strong materials but tend to soften on heating and are not usually very soluble in solvents. The structure is basically a linear 1 dimensional strong bonding networks. The polymer molecules are held together by weak intermolecular forces and NOT strong chemical bonds. The long polymer molecules mean the intermolecular forces are appreciable but the material is flexible and softens on heating.

Graphite structure is a layered 2 dimensional strong bond network made of layers of joined hexagonal rings of carbon atoms with weak inter-molecular forces between the layers. (more details on graphite) Thermosetting plastic structures like melamine have a 3 dimensional cross-linked giant covalent structure network similar to diamond or silica in principle, but rather more complex and chaotic! Because of the strong 3D covalent bond network they do not dissolve in any solvents and do not soften and melt on heating and are much stronger than thermoplastics. More on polymers in Oil Notes and Extra Organic Chemistry Notes.

BONDING IN METALS To explain the properties of metals like iron or sodium we need a more sophisticated picture than a simple particle model of atoms all lined up in close packed rows and layers. A giant metallic lattice. The crystal lattice of metals consists of ions (NOT atoms) surrounded by a 'sea of electrons' forming another type of giant lattice. The outer electrons (-) from the original metal atoms are free to move around between the positive metal ions formed (+). These free or 'delocalised' electrons are the 'electronic glue' holding the particles together. There is a strong electrical force of attraction between these free and mobile electrons (-) and the 'immobile' positive metal ions (+) and this is the metallic bond. Metallic bonding is not directional like covalent bonding, it is like ionic bonding in the sense that the force of attraction between the positive metal ions and the mobile electrons acts in every direction about the fixed (immobile) metal ions. Metals can become weakened when repeatedly stressed and strained. This can lead to faults developing in the metal structure called 'metal fatigue' or 'stress fractures'. If the metal fatigue is significant it can lead to the collapse of a metal structure. So it is important develop alloys which are well designed, well tested and will last the expected lifetime of the structure whether it be part of an aircraft (eg titanium aircraft frame) or a part of a bridge (eg steel suspension cables).

Explaining the physical properties of metals This strong bonding generally results in dense, strong materials with high melting and boiling points. o Usually a relatively large amount of energy is needed to melt or boil metals. Energy changes for the physical changes of state of melting and boiling for a range of differently bonded substances are compared in a section of the Energetics Notes. Metals are good conductors of electricity because these 'free' electrons carry the charge of an electric current when a potential difference (voltage!) is applied across a piece of metal eg copper wire in household wiring or electrical appliances. Metals are also good conductors of heat. This is also due to the free moving electrons. Non-metallic solids conduct heat energy by hotter more strongly vibrating atoms, knocking against cooler less strongly vibrating atoms to pass the particle kinetic energy on. In metals, as well as this effect, the 'hot' high kinetic energy electrons move around freely to transfer the particle kinetic energy more efficiently to 'cooler' atoms. Typical metals also have a silvery surface but remember this may be easily tarnished by corrosive oxidation in air and water. Unlike ionic solids, metals are very malleable, they can be readily bent, pressed or hammered into shape. The layers of atoms can slide over each other without fracturing the structure (see below). The reason for this is the mobility of the electrons. When planes of metal atoms are 'bent' or slide the electrons can run in between the atoms and maintain a strong bonding situation. This can't happen in ionic solids. For more on the properties and uses of metals see Transition Metals and Extra Industrial Chemistry pages and the note and diagram below. Note on Alloy Structure

1. Shows the regular arrangement of the atoms in a pure metal crystal and the white spaces show
where the free electrons are (yellow circles actually positive metal ions).

2. Shows what happens when the metal is stressed by a strong force. The layers of atoms can slide 3.
over each other and the bonding is maintained as the mobile electrons keep in contact with atoms, so the metal remains intact BUT a different shape. Shows an alloy mixture. It is NOT a compound but a physical mixing of a metal plus at least one other material (shown by red circle), it can be another metal e.g. Ni, a non-metal e.g. C or a compound of carbon or manganese, and it can be bigger or smaller than iron atoms. Many alloys are produced to give a stronger metal. The presence of the other atoms (smaller or bigger) disrupts the symmetry of the layers and reduces the 'slip ability' of one layer next to another. The result is a stronger harder less malleable metal. The main point about using alloys is that you can make up, and try out, all sorts of different compositions until you find the one that best suits the required purpose in terms of tensile/compression strength, malleability, electrical conductivity or corrosion resistance etc.

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