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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! 8.1 Phase equilibria - vapour pressure - boiling point

e.g. liquid water

water vapour or H2O(l)

H2O(g)

The co-existence of water in two different phases is a clear example of a phase equilibrium. o o o If water (or an aqueous solution) is poured into a dry bottle of 'dry' air and then stoppered, some of the water will then evaporate to create a vapour pressure, so water vapour and liquid water co-exist. However, some of the water vapour may condense if the gas molecules hit the liquid surface but others can escape the intermolecular forces at the surface (which are imbalanced and incidentally cause the net inward pull of surface tension). When the rate of evaporation = rate of condensation, a dynamic physical equilibrium exists between liquid water and water vapour.

Note, that at a certain temperature and pressure (called the triple point), liquid water, water vapour and ice can all co-exist!

The saturated vapour pressure is the maximum pressure the vapour from a liquid (or solid/solution) can exert at a given temperature if the substance alone occupied a container in which the liquid/solution/solid is in equilibrium with the vapour. The maximum or saturated vapour pressure that liquid water exerts at a particular temperature can be measured and it increases exponentially with increase in temperature, i.e. the equilibrium is shifted more to the right, see graph below. The same shaped graph line (examples below for pure liquids) is obtained with any liquid, though the relative position of the curve depends on the volatility of the liquid, which in turn depends on the strength of the inter-molecular attractive forces (see later paragraph). Liquids containing dissolved substances i.e. mixtures of miscible liquids or solutions of solids, will show a reduced vapour pressure compared to the pure liquid (not covered here).

Typical saturated vapour pressure curves (max. pvap versus temperature). The vapour pressure curves are shown in the graph above for ... tetrachloromethane CCl4, ethanol C2H5OH, benzene C6H6, water H2O and ethanoic acid CH3COOH

The increase in vapour pressure of any liquid with rise in temperature is due to the increasing average kinetic energy of the liquid molecules, so more molecules with sufficient KE can 'escape' the intermolecular attractive forces of the liquid molecules,

increasing the rate of evaporation until it matches the rate of condensation i.e. a dynamic equilibrium point is reached and the liquid exerts its maximum or saturated vapour pressure. When the vapour pressure of a liquid matches the ambient pressure, the liquid boils as bubbles of vapour can now form in the bulk liquid. o o At 100 C, water vapour pressure = normal atmospheric pressure, and so water boils at normal atmospheric pressure (1 atm/760 mmHg, see dotted lines on diagram above). This has consequences for brewing a cup of tea as you climb a high mountain. It gets more and more difficult to brew a good pot of tea because the boiling temperature gets lower and lower as the pressure falls with increasing height! o Note on some applications of vapour pressure data: A knowledge of vapour pressures from data tables is important is understanding and using the
o

technique known as steam distillation, described in section 8.5, which is a method of extracting thermally unstable compounds from a mixture by a distillation process operating at a far lower temperature than its boiling point. You can also distil thermally unstable compounds at a more lower temperature than its normal boiling point at normal atmospheric pressure by means of reduced pressure distillation ('vacuum distillation') . If you reduce the pressure in the flask and condenser system, you then reduce the vapour pressure needed for the liquid to boil i.e. lower vapour pressure means a lower boiling-distillation temperature. This is actually a much cleaner and efficient process than steam distillation. The greater the intermolecular forces between molecules, the lower the saturated (maximum pvap) vapour pressure at a given temperature, given in Pa/mm Hg 20 C (sat'd pvap) in section 8.2. o o Collectively 'intermolecular forces' are also referred to as 'Van der Waals Forces' and you must be able to clearly distinguish these forces from ionic or covalent bonds, even for the unfortunately misnamed 'hydrogen bond'. All intermolecular forces are essentially electrostatic in origin arising from 'Coulombic' attraction between positive and negative 'centres' in the atoms or molecules. A 'centre' might quite simply be a region more positive or more negative than another due to asymmetry in the distribution of the electron charge (clouds).
o

Details of these intermolecular forces are further discussed later in the context of comparative studies of particular series of molecules. 8.2.1 A summary of Van der Waals forces and an introduction to intermolecular forces

o o o o

The greater the intermolecular forces the lower the vapour pressure, the higher the boiling point of the liquid and to some extent enthalpies of vaporisation, the latter does not give as clearer a pattern as you might expect. You also see, not surprisingly, higher enthalpies of vaporisation (H vap/kJ mol ) BUT not a good trend if you study the summary tables. However you get a more clearer trend with increasingly higher boiling point (bpt at 101325Pa / 1atm / 760mmHg) as more kinetic energy is needed by the molecules to overcome the increase in intermolecular attractive forces. These intermolecular forces are strongly influenced by the structure of the molecule and the extent of bond polarity can have a major effect on the boiling point of an organic liquid, but most of the attractive force for most molecules originates from transient (temporary) dipole - induced dipole interactions (explained further in the ALKANE section). 8.2.1 Introduction to intermolecular forces - Van der Waals forces also referred to as 'intermolecular bonding' (do NOT confuse with chemical bonding between atoms or ions i.e. so-called ionic, covalent or metallic bonds)
-1

The origin of each source of intermolecular force is summarised below and discussed further for particular molecules. In the context of this page, the word dipole means an asymmetric distribution of electron electrical charge to give partially positive and partially negative regions in the same molecule. In a simple sense its a molecule with a partially positive end and a partial negative charge at the other end. Electric dipoles may be permanent or transient (temporary) and the molecules discussed here are electrically neutral overall.

These attractive forces can operate between ANY particles whatever their constitution including free atoms in a gas or ions in a crystal etc. Total intermolecular force is quoted as a summation of the various possible dipoles interaction and the principal attractive forces are shown in bold for selected molecules. Wherever possible, albeit just for a few cases, I've quoted % contributions from the three types of intermolecular attractive force that I've been able to obtain from internet searches or textbooks and if I couldn't match the molecule then I may quote percentages for a similar molecule. One source used by writers of research papers is A. L. McClellan, Tables of Experimental Dipole Moments.

In pre-university advanced chemistry exams I suggest you use the terms in bold to describe the intermolecular force component Summary of Van Waals intermolecular forces or intermolecular bonds

1.

Instantaneous dipole - induced dipole interaction Also called London forces or dispersive/dispersion forces. The electrons of an atom behave in a random way within the spatial region they occupy for their specific quantum level e.g. in 3s, 2p, 3d atomic orbitals or a bonding molecular orbital. At any given instant in time the electron cloud will randomly distorted, giving rise to a dipole of partial charges which then induces a dipole in a neighbouring molecule. The partial positive charge of one dipole will attract the partial negative in the neighbouring molecule or vice versa

So even with a completely non-polar hydrocarbon molecule (i.e. a molecule with no significant polar bonds like alkanes and alkenes) there are still intermolecular attractive forces. Even in the case of helium, lowest boiling point of any substance, you still can get transient dipoles

because of the random behaviour of the electrons ...

attractions Instantaneous dipole - induced dipole interaction increase the more electrons in the molecule. The bigger the molecule, with more electrons in it, the more polarizable it is in terms of dipole creation. A good example is illustrated by the boiling point plots for various organic homologous series in section 8.3 where the addition of every nonpolar -CH2- unit in the carbon chain produces a corresponding incremental rise in the boiling point due to the incremental rise in intermolecular forces (instantaneous dipole - induced dipole).

For most molecules, this is the dominating contribution to the total intermolecular force, but the presence of polar bonds can add a significant contribution to this and the consequential affects on the properties of the molecule.

Comparing the boiling points and intermolecular forces operating between molecules with a similar number of electrons does provide important insights into their molecular behaviour. However, you should be aware that the way the electrons are distributed, both in terms of their electronc energy levels, and their spatial distribution, can have significant effects on the strength of instantaneous dipole - induced dipole forces. You will see this particularly in the case studies ofsection 8.4.

Note: You come across other words instead of instantaneous e.g. 'temporary', 'transient' or even 'induced' - induced dipole attractions.

2.

Permanent dipole - permanent dipole interactions Also called Keesom forces or orientation forces. If two atoms constituting a bond have significantly different electronegativities, the bond will be permanently polar and produce a permanently polar molecule. Such molecules posses what is known as dipole moment.

Dipole moments are quoted in D, debye units, 1D = 3.34 x 10 Cm This is a non-SI unit. C = coulomb, m = metre. Its unlikely you need to know about this unit, but some advanced pre-university courses do mention dipole moments.

-30

Therefore, as result of this permanent dipole, these permanently polarised molecules will attract neighbouring molecules because of this dipole moment as well as the attraction due to instantaneous dipole - induced dipole. e.g.

or in carbonyl compounds HYDROGEN BONDING


+ + -

attractions seem to make little difference to the bpt! C=O .... C=O in carbonyl compounds.

There is special sub-category of permanent dipole - permanent dipole interactions called hydrogen bonding. Hydrogen bonding only usually occurs when the three most electronegative elements (N, O and F) are bonded to a hydrogen atom (more on hydrogen bonding in section 8.6). In these molecules you get one of the following three very polar bonds:+ + + -

N-H

O-H

H-F

and via these highly polar bonds you get molecule to molecule attraction via so called hydrogen bonding. These are the strongest permanent dipole permanent dipole intermolecular forces e.g. using llll to indicate a hydrogen bond
+ + + +

O-H

llll O-H
+

llll O-H
+ -

llll O-H
+

llll in water

or llll N-H
+ -

llll N-H llll N-H


-

in amines and in the case of carboxylic acids the dominant interaction is the hydrogen

bonding via C=O llll


+

H-O from molecule to molecule.

3.

Permanent dipole - induced dipole interactions

Also called Debye forces or induction forces. The permanently polar bond in one molecule can induce a dipole in a neighbouring molecule, whether the other molecule is polar or non-polar.

e.g.

attractions

The discussions below primarily focus on intermolecular forces 1. and 2. and 3. is usually less significant and gets a brief mention. Data abbreviations used: Mpt = melting point, Bpt = boiling point (given in Kelvin and Celsius/centigrade) Here in section 8.2 examples are chosen from the eight homologous series listed below and all the molecules have 32-34 electrons and four larger C, N or O atoms plus hydrogen (except chloroethane C + C + Cl, but still has 34 electrons). The survey and a preliminary summary table - hopefully justified by the arguments outlined after the table and in on a separate page insection 8.2.2

Ins = instantaneous (temporary) dipole - induced dipole attraction (a sort of baseline force since it applies to all molecules) WP = weaker permanent dipole - permanent dipole attraction (doesn't seem to have much effect on the boiling point) SP stronger permanent dipole - permanent dipole attraction (NOT H bonding, but has a definite effect on the boiling point) HB = hydrogen bonding attraction (the strongest permanent dipole - permanent dipole attractive force, i.e. the strongest SP and has the largest effect on the boiling point) MHB multiple hydrogen bonding attraction sites on the molecule (i.e. where there are two 'functional' groups capable of two permanent dipole - permanent dipole interactions including hydrogen bonding, hence producing an even bigger effect on raising the boiling point) Note that permanent dipole - induced dipole attractive forces are not mentioned much and generally only contribute a small portion of the total intermolecular force.

Also, where I can obtain data, I've indicated the percentage contribution of the three types of intermolecular attraction which contribute to the total intermolecular force i.e. the % contributions to Van der Waals force.

8.4 Table 1a. Comparing 32-34 electron species - linear organic molecules (4 C/O/N atoms) 1.to 8. discussed below in detail MOLECULE 1. butane 2. methoxyethane 3. chloroethane 4. propylamine 5. propanone 6. propan-1-ol 7. ethanoic acid 8. ethanamide formula CH3CH2CH2CH3 CH3OCH2CH3 CH3CH2Cl CH3CH2CH2NH2 CH3COCH3 CH3CH2CH2OH CH3COOH CH3CONH2 Mr 58 60 64.5 59 58 60 60 59 electrons bpt 34 34 34 34 32 34 32 32 272.5K/-0.5 C 280K/7 C 285.5K/12.5 C 321K/48 C 329K/56 C 370K/97 C 391K/118 C 494K/221 C
o o o o o o o o

Hvap/kJmol 22 21 25 30 29 45 58 46

-1

Dipole moment/D 0.00 1.23 2.06 1.17 2.88 1.69 1.74 3.60

Intermolecular forces Ins Ins, WP Ins, WP Ins, HB Ins, SP Ins, HB Ins, SP, MHB Ins, SP, MHB

As you go down the table the boiling point increases clearly reflecting the increasingly strong intermolecular forces operating, all of which have been individually discussed above. The table shows that increasingly polar bonds will increase the intermolecular forces between polar molecules and raise the boiling point compared to a non-polar molecule of similar size and number of electrons and in particular where hydrogen bonding occurs - the strongest of the permanent dipole - permanent dipole interactions.

It should however, be pointed out, that in most cases, most of the intermolecular attractive force originates from the transient dipole induced dipole interactions, but the extra effect of polar bonds is significant in discussing and accounting for differences in physical properties such as melting points and boiling points, and also solubility ( see section 8.7 on solubility)

The enthalpies of vaporisation do not show as clearer a pattern, though the higher values are in bottom half of the table.

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