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# a.

demonstrate an understanding of the use of electron-pair repulsion theory to interpret and predict the shapes of simple molecules and ions b. recall and explain the shapes of BeCl2, BCl3, CH4, NH3, NH4+, H2O, CO2, gaseous PCl5 and SF6 and the simple organic molecules listed in Units 1 and 2 c. apply the electron-pair repulsion theory to predict the shapes of molecules and ions analogous to those in 2.3b d. demonstrate an understanding of the terms bond length and bond angle and predict approximate bond angles in simple molecules and ions e. discuss the different structures formed by carbon atoms, including graphite, iamond, fullerenes and carbon nanotubes, and the applications of these, eg the potential to use nanotubes as vehicles to carry drugs into cells Shapes of Molecules The electron pair repulsion theory In 1940 Sidgwick and Powell pointed out that the shape of molecules could be explained in terms of electron pair repulsions. Electron pairs whether bonding or non-bonding repel each other and will arrange themselves in space to be as far apart as possible. Hence, the shape of a molecule is related to the number of outer electron pairs. Here are the different structures: No. of outer electrons pairs: 2

## Valence Shell Electron Pair Repulsion Theory:

1. Valence shell electron pairs are arranged to minimise repulsions between themselves. 2. Order of Repulsion Strength: Lone pair - lone pair lone pair - bonding pair bonding pair bonding pair 3. When there are 5 or more electrons pairs neglect repulsion between electron pairs at an angle greater than 900 4. Basic geometry is still determined by number of electron pairs. 5. Lone pair repulsion Double bond repulsion Bonding pair repulsion

How To Calculate The Shape Of A Molecule Example: CH4 1. 2. 3. 4. 5. 6. How many electrons around the central atom C = 4 How many valence electrons shared by H = 4 Number of bonding pairs = 4 + 4 / 2 = 4 Number of lone pairs = 0 Total number of electron pairs = 4 Arrangement = Tetrahedral

The same calculation can be used for all molecules with single bonds. Distorted shapes due the presence of lone pairs Ammonia: This molecule has three bonding pairs of electrons and one lone pair. Although, based on the tetrahedral shape, due to the extra repulsion from the presence of a lone pair, the 3 N-H bonds bend further away from the lone pair, in order to minimise the repulsion. The shape is described as pyramidal and has a bond angle of 1070. Water: This molecule consists of two lone pairs and two bonding pairs. Again, these repel each other towards the corners of the tetrahedron, due to the extra repulsion from the presence of two lone pairs. This shape is described as bent and has a bond angle of 1040.

H2S isn't 105 degrees. It's 92 degrees. Water is 105 degrees. I think you are asking why the H2S bond angle is smaller than the H2O bond angle, when they both have two lone pairs, yes? There are a number of ways of thinking about this, depending on the level you are studying at. But a simple explanation would be that 1) the H-S bond is longer than the H-O bond (so less repulsion between bond pairs) 2) the S lone pairs are larger than the O lone pairs (so more lone pair-bond pair replusion). Hence the H2S bond angle is less than the water one

Electron pair repulsion Like charges repel, negative charges repel other negative charges. The electrons are constrained around the nucleus in pairs. Each pair exerts a repulsion on other electron pairs. To ascertain the actual shape adopted by molecules we must consider these repulsions. The electrons in a charge region are also attracted to the nucleus. Thus any repulsion will cause the electron pairs to move as far apart as possible, while still remaining attached to the central nucleus. It is rather like having two magnetic north poles attached to two strings with the strings attached to a central pivot. The magnets will push as far away as possible while staying tied to the central pivot. The final electronic shape adopted depends on the number of regions of electronic charge around the nucleus.

top Two regions of electron density (charge) No. of outer electrons pairs: 2

## Bond angle: 1800 Example: BeCl2

The two regions move as far apart as possible while remaining fixed to the nucleus. They adopt an arrangement in which they are at 180 to one another. Here we can see the beryllium dichloride molecule that has only two pairs of electrons on the central atom. They move as far apart as possible and adopt an arrangement as shown.

The molecule is linear with bond angles of 180 Three regions of electronic charge

Three regions move as far apart as possible while remaining attached to the central atom. They adopt a trigonal planar arrangement in which the angle formed between the electron pairs is 120. Boron Trifluoride- Here we can see the boron trichloride molecule. It has three pairs of electrons on the central atom. They move as far apart as possible and adopt an arrangement as shown: The bond angle subtended by the Cl-B-Cl atoms is 120 in all cases.

## Bond angle: 1090 and 270 Example: CH4

Four regions of charge adopt a tetrahedral arrangement. This is a three dimensional shape that can be considered formed from the peaks of a regular pyramid (tetrahedron) with the central atom in the very centre of the pyramid. The molecule methane has four regions of electronic charge around the central atom, which adopt a tetrahedral arrangement. Methane has a tetrahedral 3-D arrangement

Electronic shape and molecular shape The shape of a molecule is given by the relative positions of its constituent atoms. This may, or may not, be the same as the electronic shape of the molecule. If all of the electrons around the central atom are involved in bonding, then the molecular shape equals the electronic orientation. However, if there is one, or more, lone pairs (non-bonding pairs) of electrons, then the molecular shape will be different from the electronic orientation. If, for example, the central atom has three regions of electron density (three charge centres), but is attached to only two atoms then the electronic shape is trigonal planar, but the molecular shape is angular (bent). Trigonal planar electronic shape - three charge centres Angular molecular shape - 2 out of 3 charge centres used for bonding.

The shape adopted by electron pairs around a central atom depends on the number of regions of electrical charge. Each region will move so as to minimise the repulsive forces experienced. The molecular shape is not necessarily the same as the electronic shape, as only the positions of the atoms themselves are used to describe the molecular shape. To determine the molecular shape it is necessary to first determine the shape adopted by the electrons, and only then can the positions of the atoms be known. The electronic shape is tetrahedral, but the shape of the water molecule considers only the H-O-H. It is angular, or bent.

top Unequal repulsion - VSEPR One of the successes of the Valence Shell Electron Pair Repulsion theory lies in its ability to predict, or explain, the bond angles of molecules. To do this, it considers that electron pairs that are shared by two atoms (bonding pairs) experience less repulsion than lone, or non-bonding pairs, of electrons. The logic of this assumption comes from the idea that shared pairs have their electron density relatively displaced away from the central atom by the bonded atom, when compared to a lone (non-bonding) pair. This idea gives rise to an order or repulsive force experienced by electron pairs, in which lone pair lone pair repulsion is greater than lone pair - bonding pair repulsion, which in turn is greater than bonding pair - bonding pair repulsion. These different forces of repulsion distort the perfectly symmetrical shapes that would be adopted by the electron pairs under ideal conditions. We can appreciate this by studying examples such as the ammonia molecule, NH3.

top Ammonia The ammonia molecule has a central nitrogen atom with four pairs of electrons. These electrons tend to adopt a tetrahedral orientation. A perfect tetrahedron has a bond angle of 109 28'. However, there is a greater repulsion between the lone pair (non-bonding pair) of electrons and the bonding pairs, than there is between the bonding pairs themselves. This greater repulsive force has the effect of 'squeezing' the hydrogen atoms closer together, creating smaller H-N-H bond angles of 107. The ammonia molecule The ammonia molecule - VSEPR

1 The four electron pairs adopt a tetrahedral arrangement. 2 Only three pairs of electrons are actually used for bonding. 3 The lone pair of electrons, shown in red, repel the bonding pairs more than the bonding pairs repel each other. 4 The final bond angle is 107.

top Water The water molecule has four pairs of electrons on the central oxygen atom. These electron pairs, or regions of electron density, adopt a tetrahedral arrangement. The theoretical bond angle of the electron pairs would be 109 28'. However, only two of the electron pairs are actually used in bonding and the other electrons are lone (non-bonding) pairs. The lone pairs of electrons repel the bonding pairs more than the bonding pairs repel each other. This has the effect of closing the 109 28' bond angle down to 104 30'. The water molecule The water molecule - VSEPR

1 The oxygen atom has four pairs of electrons. They are arranged in a tetrahedral arrangement.

2 Only two of the pairs of electrons are used in bonding 3 The lone pairs repel the bonding pairs more than the bonding pairs repel one another. 4 The final H-O-H bond angle is 104.5

top Electron-Pair Repulsion Theory With Ions Ions are atoms or groups of atoms that have lost or gained electrons to attain a stable electronic configuration. In the case of ions involving more than one atom the atoms always have an octet of electrons. When counting up the total number of electrons available, it is important to remember that a positive ion has lost an electron and a negative ion has gained one or more electrons with respect to the constituent atoms. For example, the ammonium ion has the formula NH4+. It is comprised of one N atom (group V) and four hydrogen atoms. The total valence electrons from the atoms = 5 + 4 = 9. However, the ion has a positive charge, so it has lost a valence electron. It therefore has only 8 valence electrons. The central nitrogen atom is attached to four hydrogen atoms by four shared pairs of electrons = 8 electrons. Thus, there are no electrons left over.

Chemical Bonding Ionic and covalent bonding Theories of chemical bonding are based on the knowledge that: 1. Metallic elements from Groups I, II, III tend to lose electrons and form positive ions that have a noble gas configuration.

2. Non-metallic elements in Groups VI and VII gain electrons top form negative ions with a noble gas configuration. 3. Elements in groups IV and V do not form charged ions. 4. Noble gases do not form chemical bonds. A full outer shell of electrons has extra stability. Ionic bonding

This involves the transfer of electrons from metal atoms to a non-metal atom to form charged ions. The oppositely charged ions are held together by electrostatic attractions. Formation of cations is governed by ionisation energies, with Group I elements forming ions most readily and Group III elements forming ions with difficulty. Group IV elements never form ions because the ionisation energy is too great. Formation of anions is governed by electron affinities. This is the energy change involved when a mole of uni-negative ions from a mole of gaseous atoms. Group VII and Group VI both form negative ions. Group VII form ions more readily due to greater electron affinity. Covalent bonding A covalent bond is made when atoms share one or more electrons to form a molecule. A single covalent bond is made when each atom donates one electron to the bond, It is also possible to form double and triple bonds where two and three electrons are donated. The two atoms come close together so that their outer orbitals overlap. Both nuclei are attracted to the shared pair of electrons and this attraction binds the atoms together. Each atom has been stabilised as it gains a full outer shell (2, 8, 8). Co-ordinate or dative covalent bonding: In a normal covalent bond, each atom donates one electron to the shared pair. In a co-ordinate bond electrons come from the same atom.

Ionisation Energy

Atomic Structure Revise quicker now! Ionisation energy as evidence for sub-shells Ionisation energy is a measure of the ease in which atoms lose electrons and become positive ions. The first ionisation energy is the energy required to remove one electron from each atom of a mole of gaseous atoms. M(g) - e- M+(g) Further electrons may be removed giving successive i.e.: M+(g) - e- M2+(g) This energy is usually quoted in units of kilojoules per mole (kJ mol-1). Energy is required to remove an electron from any atom because there is an attractive force between the nucleus and the electron being removed which has to be overcome. The value of the first ionisation energy depends upon: 1. The effective nuclear charge 2. The distance between the electron and the nucleus 3. The 'shielding' produced by lower energy levels Shielding involves the repulsion between electrons in inner, filled orbitals and electron being removed from the outer orbital. The graphs of atomic number against first ionisation number show that across each period there is an increase in ionisation energy.

Beryllium (Group II) has an extra electron and proton compared with lithium. The extra electron goes into the same 2s orbital. The increase in ionisation energy (I.E.) can be attributed to the increased nuclear charge. The ionisation energy of Boron is less than that of Beryllium because in Boron there is a complete 2s orbital. The increased shielding of the 2s orbital reduces the ionisation energy. Similarly, the I.E. of Oxygen is less than that of Nitrogen because the extra electron is shielded by the half-filled 2p orbital. The break in the graph between N-O can be explained by the increased repulsion produced when two electrons are in the same orbital. The latter seems to be preferred by examiners! Within a group the first I.E. decreases down the group as the outer electron becomes progressively further from the nucleus. Also there is more shielding because of the extra filled orbitals. The graph below shows the successive I.E. for sodium:

The electronic structure for sodium is 1s2 2s2 2p6 3s1. The energy required to remove the first electron is relatively low. This corresponds to the loss of one 3s electron. To remove the second electron needs a much greater energy because this electron is closer to the nucleus in a 2p orbital. There is a steady increase in energy required as electrons are removed from 2p and then 2s orbitals. The removal of the tenth and eleventh electrons requires much greater amounts of energy, because these electrons are closer to the nucleus in the 1s orbital. Finally an alternative way of expressing electron configuration as s, p,d, and f is to use box notation as shown below for silicon:

## Atomic Structure Revise quicker now! The nucleus

The protons and neutrons in each atom are tightly packed in a positively charged nucleus. Negatively charged electrons move around the nucleus. The number of protons in a nucleus defines the type of atom and is the same asthe atomic number. The number of neutrons is found by subtracting the atomic number from the mass number. In an atom because there is no overall charge the number of electrons equals the number of protons. In chemical reactions the nucleus remains unchanged. Geiger and Marsden bombarded a thin gold foil with a beam of alpha particles. Most of the particles passed through the foil without deflection and were detected by a flash of light when the alpha particle struck a zinc sulphide screen, surrounding the gold foil. A few were deflected and some of these were deflected at angles greater than 900, suggesting they had been repelled by large positive charges within the foil - nuclei of atoms of gold. Arrangement of electrons around the nucleus From GCSE you should be familiar with the Bohr model of electrons arranged around a nucleus. The electrons are in certain energy levels and each energy level can hold only up to a maximum number of electrons. This is summarised in the table below: Energy level or 'shell' 1st 2nd Max no of electrons 2 8

## 3rd 4th 5th

18 32 50

A sodium atom containing 11 electrons has an electron arrangement of 2,8,1. Two electrons filling the first shell, eight electrons filling the second shell and one electron in the outer third shell.

However, these models of electron arrangement are simple and a more advance done can now be used. It is possible to break these energy levels into sub-shells. Electrons are impossible to locate exactly at any one time. It is however, possible to indicate a region or volume where the electron is most likely to be found. This region is called an Orbital. Each orbital is capable of holding a maximum of 2 electrons. Orbitals can be divided into s, p, d, and f types. Each type has its own characteristic shape. The shape of s and p orbitals are shown below:

The first energy level holds a maximum of 2 electrons in one s type orbital called 1s. There are no p, d, or f orbitals available at this energy level. The second energy level consists of one s type orbital and three p type orbitals: 2s, 2px, 2py, 2pz. Note: there are 3 p orbitals of identical energy, one along the x axis, one along the y-axis and one along the z-axis. These four orbitals can hold a total of 8 electrons (i.e. 2 electrons each). There are no 2d or 2f orbitals. The third energy level consists of: one s type orbital, three p type orbitals and 5 d type orbitals. These nine orbitals can hold a maximum of 18 electrons altogether (i.e. two electrons each). Note: there are seven f type orbitals holding a maximum of 14 electrons in total. When filling the available orbitals with electrons two important principles should be followed: 1. Electrons fill the lowest energy orbitals first and the other orbitals in order of ascending energy. It is incorrect to assume that an energy level is always completely filled before electrons enter the next energy level. The order of filling orbitals as shown below is 1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p. 2. Where there are several orbitals of exactly the same energy e.g. three 2p orbitals, electrons will occupy different orbitals whenever possible. For example: nitrogen is 1s2 2s2 2px1 2py1 2pz1 and not 1s2 2s2 2px2 2py1. This principle is Hund's rule. When an orbital only contains 1 electron then this electron is said to be unpaired. a) The small number above the orbital refers to the number of electrons in the orbital: 1s2 means 2 electrons in a 1s orbital.

b) The electron arrangements are sometimes abbreviated. For example: the electron arrangement for calcium may be written as 1s2 2s2 2p6 3s2 3p6 4s2.