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

o

with two hydrogen - oxygen 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

o

with three nitrogen - 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

o

with four carbon - 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: O=O double covalent bond

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

Example 8: dioxide CO2. The molecule can be shown as

o

One atom of carbon (2.4) combines with two atoms of oxygen (2.6) to form the compound carbon with two carbon = oxygen double 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
o

(called a planar shape, its completely flat!, the H-C=C and H-C-H bond angles 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. 11ethane 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 o o 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 the oxygen. All the H-CH, H-C-O and C-O-H bond angles are approximately 109
o o 2+

The blue icon e.g. below, represents an octahedral shape (e.g. SF 6, complex transition metal ions like [Cu(H2O)6] angles are either 90 or 180 Simple molecules with a triple bond are often linear e.g. H-C C-H ethyne or H-C

and the bond

N hydrogen cyanide (methanenitrile)

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 I 2 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 o 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. 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 theEnergetics Notes. This contrasts with the high melting points of giant covalent structures with their strong 3D network.

Note: The weak electrical attractive forces between molecules, the so called intermolecular forces should be clearly distinguished between thestrong 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!

Introduction - electron pair repulsion theory and bond angle The shape of a molecule is determined by the number of groups of electrons around the central atom. The 'groups' might be a non-bonding single electron, a non-bonding or bonding pair of electrons, a double pair of bonding electrons or triple pair of bonding electrons etc. The electron 'groupings' repel to minimise the potential energy of the system i.e. to make the A-B-C angle as wide as possible.

The dot and cross diagrams (ox) are presented in 'Lewis style' In the diagrams the central atom is denoted by X and attached surrounding bonded atoms by Q. The bond angle is therefore based on angle between the atoms Q-X-Q. This is known as The VALENCE SHELL ELECTRON PAIR REPULSION THEORY MODEL (VSEPR theory, valence shell electron pair repulsion). It has an important 'sub-rule' which affects the precise bond angle. Any lone pairs of non-bonding electrons on the central atom X, are closer to X than bond pairs because there is no Q atom attracting/sharing the lone pair electron charge. This will increase the repulsion between a lone pair of electrons on X and any other bonding/non-bonding on X. The result is two-fold: In terms of electron pair repulsion: lone pair-lone pair > lone pair-bond pair > bond pair-bond pair. As the lone pair - 'other pair' repulsion increases, the angle between these pairs increases, so the Q-X-Q angle will be slightly reduced compared to what might be expected from the 'simple' geometry of the shape (this is best illustrated by the sequence H2O, NH3 and CH4, see below) underdeveloped test! on shapes and angles

Diatomic molecules These are not considered to have a 'shape', but useful dot and cross diagram revision based on the outer valence electrons e.g. hydrogen H2 H-H

e.g. hydrogen chloride HCl, HX in general where X = halogen

H-Cl

e.g. chlorine Cl2, iodine(I) chloride ICl (iodine monochloride)

Cl-Cl

Q and X are both halogen atoms from group 7

O=O oxygen molecule

Two groups of electrons around the central atom two bonding pairs of electrons or two double bond pairs - linear shape - bond angle 180 gaseous beryllium hydride BeH2 (Q = H, X = Be) gaseous beryllium halides BeCl2 (X = Be, Q = F, Cl, X = Be)
o

valence bond dot and cross diagrams O=C=O carbon dioxide CO2 transition metal complex of co-ordination number 2: e.g. the [H3N-Ag-NH3]
+

diamminesilver(I) ion, [Ag(NH3)2] , where the :NH3 ammonia molecule acts as an electron pair donor to form the bond. N-AgN bond angle 180 .
o

Three groups of electrons around the central atom electrons: two bond pairs, one lone pair shape BENT, bond angle approximately 120 Does anyone know of any example? electrons: two bond pairs, one lone pair shape BENT, bond angle approximately 120
o o

Does anyone know of an example? but for X=Q double bonds see sulphur dioxide electrons: 3 bond pairs shape TRIGONAL PLANAR: Q-X-Q bond angle exactly 120 : e.g. X = B and Q = H for gaseous boron hydride BH3 electrons: 3 bond pairs shape TRIGONAL PLANAR: bond angle, 120 : e.g. gaseous boron trifluoride BF3 (others in the gaseous state e.g. if Q = F or Cl then X = B or Al for F) but for X=Q double bonds see sulfur trioxide
o o

COCl2 (g) carbonyl dichloride (many other commonly used names! e.g. carbonyl chloride, carbon oxychloride, carbon dichloride oxide, phosgene-gas warfare agent). The dot and cross diagram shows this is another example of three groups of bonding electrons (two single C-Cl bonds and a C=O double bond) giving a trigonal planar structure with Cl-C-Cl and O=C-Cl bond angles of 120 .
o

Four groups of electrons around the central atom (see also sulfate and sulfite ions) electrons: two bond pairs and two lone pairs ANGULAR or BENT shape: e.g. hydrogen sulphide, H2S, or water H2O, i.e. H2X with H-X-H bond angle of approximately 109 (actually 104.5 in water) and similarly ions like NH2 . (Q = H, X = O, S etc. in group 6)
o o

Why isn't the H-O-H angle 109 ? The exact H-O-H angle in H2O is 104.5 due to the extra repulsion of two lone pairs, the H-N-H is 107.5 in NH3 (one lone pair) and H-C-H is 109 (no lone pairs) because of the 'repulsion order' lone pair-lone pair > lone pairbond pair > bond pair-bond pair. electrons: two bond pairs and two lone pairs BENT shape: e.g. fluorine oxide (oxygen(II) fluoride) X = O, Q = F F2O with bond F-O-F bond angle of approximately 109 electrons: three bond pairs and one lone pair PYRAMIDAL or TRIGONAL PYRAMID shape: e.g. ammonia NH3 with bond angle of approximately 109 . Why isn't the H-N-H angle 109 ? The exact H-N-H angle is 107 due to the extra repulsion of one lone pair (see below).
o o o o o o o

Note: the exact H-O-H angle in H2O is 104.5 due to the extra repulsion of two lone pairs, the H-N-H is 107.5 in NH3 (one lone pair) and H-C-H is 109 (no lone pairs) because of the 'repulsion order' lone pair-lone pair > lone pair-bond pair > bond pair-bond pair. electrons: three bond pairs and one lone pair PYRAMIDAL or TRIGONAL PYRAMID shape. e.g. nitrogen trifluoride/trichloride, NCl3, orphosphorus(III) fluoride/chloride (phosphorus trifluoride/trichloride), PF3/PCl3, with bond angles Q-X-Q of approximately 109 and similarly with ions like the oxonium ion H3O
+ o o o

(Q = F, Cl etc. X = N, P etc.) electrons: 4 bond pairs TETRAHEDRAL shape: e.g. methane CH4, silicon hydride SiH4 with H-X-H bond angle of 109 and similarly ions like the ammonium ion NH4 . Note: No lone pair, no extra repulsion, no reduction in angle,
+ o

therefore perfect tetrahedral angle (for H-X-H angles: CH4 > NH3 > H2O, see below).

(Q = H, X = C, Si, Ge etc. in group 4) Note: the exact H-O-H angle in H2O is 104.5 due to the extra repulsion of two lone pairs, the H-N-H is 107.5 in NH3 (one lone pair) and H-C-H is 109 (no lone pairs) because of the 'repulsion order' lone pair-lone pair > lone pair-bond pair > bond pair-bond pair. electrons: 4 bond pairs TETRAHEDRAL shape: e.g. tetrachloromethane CCl4 or [PCl4] with exact Cl-C-Cl and Cl-P-Cl bond angles of 109
o + o o o

Five groups of electrons around the central atom

electrons: 5 bond pairs TRIGONAL BIPYRAMID shape: e.g. phosphorus(V) fluoride (phosphorus pentafluoride) PF5, gaseous phosphorus(V) chloride, PCl5, with bond angles 90 and 180 based on the vertical Q-X-Q bond and 120 based on the central trigonal planar arrangement. valence bond dot and cross diagram Note that solid PCl5 has an ionic structure and is not a trigonal bipyramidal (bypyramid) molecule - a tetrahedral [PCl4] ion and an octahedral [PCl6] ion.
+ o o o

Six groups of electrons around the central atom electrons: 6 bond pairs OCTAHEDRAL SHAPE: e.g. sulfur(VI) fluoride (sulphur hexafluoride molecule) SF6 or the [PCl6] ion and many transition metal complexes (see below), with Q-X-Q bond angles of 90 and 180 .
o o -

More complex inorganic molecules/ions and organic molecules

These often are not given a particular shape name, but never-the-less, an appreciation of the 3D spatial arrangement is expected e.g. Ethane consists of two joined 'tetrahedral halves', with all C-C-H and H-C-H bond angles of 109 . See other page for more on shape and bond angle analysis of organic molecules
o

Boron trifluoride (3 bonding pairs, 6 outer electrons) acts as a lone pair acceptor (Lewis acid) and ammonia (3 bond pairs) and lone pair which H3N:=>BF3 enables it to act as a Lewis base - a an electron pair donor. It donates the lone pair to the 4th 'vacant' boron orbital to form a sort of 'adduct' compound.
would be like ethane above

Its shape is essentially the same as ethane, a sort of double tetrahedral with HN-H, N-B-F and F-B-F bond angles of ~109 .
o

Benzene is a completely planar molecule, with all C-C-C or C-C-H bond angles of 120 . or valence bond dot and cross diagrams
o

TRANSITION METAL COMPLEX IONS

COMPLEXES The three examples below show cis/trans isomerism

cis/trans octahedral

cis/trans octahedral

cis/trans square planar more details and examples on "Transition Metals" pages All the bonds shown, or , are dative covalent, with lone electron pair donation by the ligand L, to the central metal ion i.e. L: M
n+ __ ....

etc.