AS Chemistry Revision Notes Unit 1 Structure, bonding and main group chemistry

Warren Rieutort-Louis Topic 1.4 The periodic table I

Elements in the periodic table are arranged in order of ascending atomic number.

H :- 1s1 He :- 1s2 Li :- 1s2 2s1 Be :- 1s2 2s2 B :- 1s2 2s2p1 Kr :- 1s2 2s22p6 3s23p63d10 4s24p6 Cu :- 1s2 2s2p6 3s23p63d10 4s14p

GROUP 3: o Melting and boiling temperature:

o Melting and boiling points rise across the three metals because of the increasing number of electrons and smaller cations, which each atom can contribute to the delocalised "sea of electrons" and the increased nuclear charge, therefore greater attraction in metallic bonding. o Silicon is giant molecular very strong covalent bonds, which require a lot of energy to break. It therefore has very high melting and boiling points. o Phosphorus, sulphur, chlorine and argon are simple molecular substances with only van der Waals attractions between the molecules. Their melting or boiling points are lower and depend on their size. The bigger, the more vdW, the higher the boiling point.

o Electrical conductivity: o Sodium, magnesium and aluminium all have metallic structures, which accounts for their electrical conductivity. This increases from Na to Al, because the number of delocalised electrons able to carry current increases. o Silicon is a semiconductor and conducts in a different way. o The elements P to Ar do not conduct, because they bond covalently, so the electrons are not free to conduct electricity. o Ionisation energy: o Nuclear charge is increasing by 1. The new electron is added to the same energy level. Outer electrons are held more firmly. Warren Rieutort-Louis 2004

o For aluminium electron is removed from 3p orbital leaving a complete 3s orbital. This requires less energy than the removal of the outer electron in magnesium, which comes from a complete 3s orbital. o For sulphur there is no increase because the electron is removed from a paired 3p orbital. The electron removed from phosphorus comes from a half filled 3p sub-shell, which is more stable and is energetically slightly more difficult.

Topic 1.5 Introduction to oxidation and reduction

An oxidation number is a number assigned to an atom or ion to describe its relative state of oxidation or reduction. Using oxidation numbers it is possible to decide whether redox has occurred. An atom is oxidised when its oxidation number increases and reduced when its oxidation number decreases. The oxidation state is the number of electrons that need to be added or removed in order to get a neutral atom.

An oxidising agent causes oxidation. Their strength varies. F2 > MnO4- > Cl2 > Cr2O72- > Br2 > I2 A reducing agent causes reduction. They have variable strengths. Na > Zn > H2

Oxidation is loss of electrons Reduction is gain of electrons An oxidising agent is itself reduced and therefore gains electrons A reducing agent is itself oxidised and therefore loses electrons.

Electron half-equations:

A redox reaction is made up of two half-equations. One shows oxidation, the other shows reduction. Working out electron-half-equations and using them to build ionic equations: Write down what you know for each half reaction. Balance the atoms apart from hydrogen and oxygen. Balance the oxygens by adding water molecules

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Balance the hydrogens by adding hydrogen ions Balance the charges by adding electrons. Make sure the two half equations have the same number of electrons. Combine the half equations to get the ionic full equation.

Working out oxidation states: o The oxidation state of all uncombined elements is 0. o The sum of oxidation states of each element in an ion equals the charge on the ion. o In neutral molecules, the algebraic sum of the oxidation numbers is 0. o The oxidation state of hydrogen is +1 (except when combined with group I and II metals as hydrides where it is -1). o The oxidation state of oxygen is -2 (except in compounds with O (peroxides) (-1) or F (+2) ). o Group 1 metals ~ +1 Group 2 metals ~ +2 Using oxidation states:

e.g. Here, O.N. of Mg increases oxidised. O.N. of H decreases reduced. A disproportionation reaction: one in which the same species has been both oxidised and reduced: the chlorine is both oxidised and reduced!

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Topic 1.6 Group 1 (lithium to caesium) and Group 2 (Beryllium to Barium)

Physical properties of Group 1 and Group 2 elements: o All solids because of strong metallic bonding. o The solids are silvery and shiny. o The metallic bonding involves delocalised electrons: - good electrical conductors. o Group 1 metals are very soft and can be cut with a knife. o Group 1 metals are softer and have lower b.p. and m.p. because they have less delocalised electrons and bigger atoms cationelectron attraction is weaker. o They have low melting points, boiling points and densities. o Density increases down a group because the nuclear mass increases faster than the atomic radius (i.e. volume of the atom) o The Atomic radius increases down groups 1 and 2 because more electron shells are being added, with the same constant net pull from the nucleus because of increased shielding. G1 G2 Decreases Increasing nuclear charge Increases More shells- bigger atom Atomic radii G1 G2 Decreases Increasing nuclear charge Increases More shells- bigger atom Ionic radii

Flame colours: o The elements in Group 1 and 2 do not produced coloured compounds but they do produce colours when passed through a flame. o This is because outer electrons are excited to higher energy levels, when they absorb energy from the source of heat. The falling back of the electrons causes light emission, which for groups I and II is in the visible region. The energy emitted is only of certain allowed quantities which correspond to certain electronic transitions

Lithium- scarlet(red) Calcium- brick red Strontium- crimson(red) Potassium- lilac Barium- apple green Sodium - yellow
Ionisation Energies:

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o The I.E. decrease down both groups because electrons are removed from shells further from the nucleus, and electrons experience less attraction (shielding). o The 2nd ionisation energy of group I elements is much higher than the first. The second electron is removed from an already positive ion and from a stable full energy level closer to the nucleus

Reactions of Group 1 (O.N. +1) with Oxygen, Chlorine and water: o Reactions with oxygen: All Group 1 react with Oxygen to form oxides O2-

4X + O2 2X 2O 2X + O2 X 2O2 X + O2 XO2

All Group 1 except Lithium react to form peroxides (O2)2All Group 1 except Li and Na form superoxides (O2)- (a radical anion). Li and Na are too polarising and anion decomposes.

o Reactions with chlorine: Group 1 metals reduce chlorine to form a chloride (not 100% ionic):

2X + Cl2 2XCl

o Reactions with water: Group 1 react with water to form hydrogen + the metal hydroxide, which in turn gives an alkaline solution. Reactivity decreases down Group 1.

2X + 2H 2O 2XOH + H 2

Reactions of Group 2 (O.N. +2) with Oxygen, Chlorine and water: o Reactions with oxygen: All Group 2 react with Oxygen to form oxides O2-

2X + O2 2XO X + O2 XO2

All Group 1 except Be, Mg and Ca react to form peroxides (O2)2-

Group 2 do not form superoxides (O2)- because cations are too polarising. o Reactions with chlorine: Warren Rieutort-Louis 2004

Group 2 metals reduce chlorine to form a chloride (covalent or covalent character):

X + Cl2 XCl2

o Reactions with water: Calcium, Strontium and Barium react with water to form their metal hydroxides + hydrogen.

X + 2H 2O X (OH )2 + H 2

Magnesium reacts with steam forming its oxide + Hydrogen

Mg + H 2O( g) MgO + H 2

Be does not react.

Reactions of Group 1+2 Oxides with water and dilute acid: o Reactions with water: Oxides act as strong bases, removing a proton from water. OXIDES: PEROXIDES: PEROXIDES:

O 2 + 2H 2O 2OH

(O2 )2 + 2H 2O(cold ) 2OH + H 2O2

(O2 )2 + 2H 2O(warm) 2OH + 1 O2 2

(O2 ) + 2H 2O 2OH + H 2O2 + O2

SUPEROXIDES:

Group I oxides are all soluble and form hydroxides. A similar reaction is seen for group II but low solubility at the top of the group means MgO forms very little hydroxide. BeO does not react as due to its covalent character O2- is not fully formed. o Reactions with acid: All of the oxides react with acids although sulphuric acid does not always react completely because it forms insoluble sulphates with Ca, Sr and Ba. 2+ OXIDES: O + 2H ---> H2O

PEROXIDES: O22- + 2H+ ---> H2O2 SUPEROXIDES: 2O2- + 2H+ ---> H2O2 + O2
Trends in solubility of sulphates and hydroxides of Group 2 elements: o The solubility of the sulphates decreases down the group. Magnesium sulphate is very soluble; barium sulphate is insoluble and is part of the test for sulphates. o The solubility of the hydroxides increases down the group. Calcium hydroxide is only slightly soluble in limewater but barium hydroxide is a very soluble alkali which can be used in titrations. o The carbonates tend to become less soluble as you go down the Group. Trends in thermal stability of nitrates and carbonates of Group 1 + 2 elements:

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o As polarising power of the cation increases, compounds become more covalent in character and less stable to heat. o Group I metal ions have low charges and large sizes so low polarising power, group I nitrates and carbonates are more stable to heat than Group II compounds. o Carbonates and nitrates of both groups become more thermally stable as we go down the group as cationic size increases, and polarising power decreases (i.e. less distortion of anion). o ALL GROUP I Nitrates (except lithium nitrate) decompose on strong heating to form nitrites and oxygen 2XNO3(s) ------> 2XNO2(s) +O2(g) o Lithium nitrate and all group II nitrates decompose to form a thermally stable oxide, Nitrogen Dioxide and oxygen 4LiNO3(s) -----> 2Li2O(s) + 4NO2(g) + O2(g) 2Y(NO3)2(s) -----> 2YO(s) + 4NO2(g) + O2(g) o Group II carbonates + lithium decompose to form an oxide + Carbon dioxide. o Na, K and Rb carbonates do not decompose. Beryllium chloride: the odd one out o BeCl2 is covalent. o This is because Be is small and more electronegative than the rest of the group i.e. more polarising. In the solid, BeCl2 molecules polymerise. They do this by forming dative covalent bonds between lone pairs on chlorine atoms and adjacent beryllium atoms. This is called a dimer.

Electrondeficient BeCl2 gas

o BeCl2 also reacts with water releasing HCl gas (white fumes). It also forms hydrated Beryllium ions, by getting water to form four dative covalent bonds with hybridised p-sub-shells of the Be atom.

o The same happens with magnesium except it forms 6 dative covalent bonds (it also uses d sub-shells).

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Topic 1.7 Group 7 (chlorine to iodine)

Physical properties of Group 7 elements:

Chlorine
Colour Colour in water Colour in organic Physical state Solubility in water yellow / green yellow / green gas high Trends in Group 7: Colour

Bromine
red / brown orange / brown red liquid medium Colour Colour in water Colour in organic Physical state Solubility in water

Iodine
black brown purple solid low Colour in water Colour in organic Physical state Solubility in water

Atomic radii increase down the group because decreases because the larger Electronegativity of more electron shells for thethe atom, the further the outer electron pair same net pull. hence less attraction- less electronegative

Electron affinity becomes moreB.E. lower downgroup because of larger atoms, negative up the group because the distance to outer electron decreases. In F, between nuclei (longer hence longer distance high electron density. adding an electron causesthe distance is so short that lone bond) weaker. extra repulsion going against attraction repel,nucleus. this distance longer, hence a pairs from making lower BE. Warren Rieutort-Louis 2004

All of the halogens exist as diatomic molecules - F2, Cl2, etc. The intermolecular attractions between one molecule and its neighbours are van der Waals dispersion forces. As the molecules (atoms) get bigger, there are more electrons and therefore the dispersion forces become greater.

Chemical tests for Group 7:

o Chlorine turns blue litmus red then bleaches it. o Chlorine displaces bromine and iodine from bromide or iodide solutions. Cl2(aq) + 2KBr(aq) ---> 2KCl(aq) + Br2(aq) Cl2(aq) + 2KI(aq) ---> 2KCl(aq) + I2(aq) o Bromine is red if dissolved in an organic solvent. o Bromine displaces iodine from an iodide solution. Br2(aq) + 2KI(aq) ---> 2KI(aq) + I2(aq) o Iodine turns starch black, is decolourised by thiosulphate solution and is brown in water but purple in organic solvents. The hydrogen halides and their acidity in solution: o Physical properties: The hydrogen halides are colourless gases at room temperature, producing steamy fumes. HF has a high boiling point because of hydrogen bonding. The others do not have H-bonding because the halides are less electronegative and the bond is less polar.

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o Manufacture of hydrogen halides by reaction of salt with an acid: Add concentrated sulphuric acid to a solid chloride like sodium chloride in the cold Hydrogen fluoride & hydrogen chloride can be made using concentrated sulphuric acid, but hydrogen bromide and hydrogen iodide can't because they are easily oxidised to Bromine + iodine by the H2SO4 which is a strong oxidising agent. OR Add concentrated phosphoric (V) acid to a solid chloride like sodium chloride This problem above doesn't happen with phosphoric(V) acid because it isn't an oxidising agent o Hydrogen halides in water acid: Hydrogen chloride is an acid because it gives protons (hydrogen ions) to other things Hydrogen chloride gas is very soluble in water, reacting with it to produce hydrochloric acid. Steamy fumes are caused by reaction with moisture in air. What happens is that the HCl donates a proton (H+) to a lone pair on a water molecule forming a dative covalent bond:

The H3O+ ion is the hydroxonium ion. In an equation it is H+(aq) All the HCl reacts in this way so the ions are fully dissociated HCl is a strong acid. Hydrogen bromide and hydrogen iodide react in the same way: they are also strong acids. HI is the strongest Although hydrogen fluoride dissolves freely in water, hydrofluoric acid is only a weak acid because of very strong hydrogen bonding between the un-ionised hydrogen fluoride molecules and water molecules

Testing for halide ions Dissolve the solid in pure water. Add dilute nitric acid (removes other ions) Add silver nitrate

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Bromide: cream Iodide: yellow Fluoride: AgF is soluble. To confirm the precipitate: Add ammonia solution AgCl dissolves in dilute ammonia AgBr dissolves in concentrated ammonia AgI does not dissolve.

Chloride: white

o The reducing power of halides When conc. H2SO4 is added to an ionic halide, the gaseous hydrogen halide is produced. This can then be oxidised to the halogen by the conc. sulphuric acid, depending on the reducing power of the hydrogen halide. Increasing reducing power.

Cl- with H2SO4, steamy HCl fumes are produced. HCl is a too weak
reducing agent to be oxidised by the H2SO4.

Br- with H2SO4, misty HBr fumes are produced and some are
oxidised further to brown-orange bromine vapour. SO2 is also produced from the reduction of the H2SO4.

I- with H2SO4, steamy HI fumes are produced. HI is a strong reducing

agent and is quickly oxidised to violet iodine. The H2SO4 is reduced to H2S and S.

o Oxidation states and the oxo-anions of chlorine All the halogens (except for F) have several positive oxidation states. These are caused by the promotion of electrons from p orbitals into empty d orbitals. Chloric (I) acid (HClO) forms salts called chlorate(I) e.g. NaClO. which contain the ion ClO-. Chloric acid (V) (HClO3) forms a series of salts called chlorate(V). e.g. NaClO3 containing the ion ClO3-. These salts and acids are all good oxidising agents. o Disproportionation of chlorine and chlorate (I) ion Disproportionation is the oxidation and reduction of atoms of the same element in the same reaction. Chlorine (ON = 0) disproportionates in water or alkali to form chloride (ON =-1) and chlorate(I) ions (ON = +1). (1) Cl2(g) + 2H2O(l) ----> Cl-(aq) + H3O+(aq) + HClO(aq) or (2) Cl2(g) + 2OH-(aq) -----> Cl-(aq) + ClO-(aq) + H2O(l). This can then be disproportionated further into chlorate (V) ions. 3ClO-(aq) -----> 2Cl-(aq) + ClO3-(aq) o Halogens as oxidising agents Oxidising power decreases down the group Fluorine is the strongest and Iodine the weakest. Bromide ions are present in seawater Chlorine gas is passed through the water and bromide ions are oxidised to bromine. Warren Rieutort-Louis 2004

Adding acid prevents reactions of Cl2 and Br2 with H2O. Air is blasted into the solution causing a stream of bromine in moist air. Bromine is reduced with SO2 to form a solution of hydrobromic acid It is treated with Cl2 again to convert Br- to Br2, separated by distillation.

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