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1 of 41 © Boardworks Ltd 2009 2 of 41 © Boardworks Ltd 2009 Physical properties The arrangement of the periodic table is such that trends can be analysed both across a period and down a group. Group 2 of the periodic table is shown here. Trends that can be analysed down the group include atomic radius, first ionization energy and melting point. Elements in the same group also undergo similar chemical reactions. 3 of 41 © Boardworks Ltd 2009 Trend in atomic radius 4 of 41 © Boardworks Ltd 2009 Explaining the trend in atomic radius The atomic radius of the elements increases down Element group 2 from beryllium to barium. The number of protons increases down the group; however, so does the number of shielding electrons. Effective nuclear charge therefore remains approximately constant. Atomic radius (nm) beryllium 0.112 magnesium 0.145 calcium 0.194 strontium 0.219 barium 0.253 The increase in radius is due to higher principle energy levels being filled, whose orbitals are located further from the nucleus. 5 of 41 © Boardworks Ltd 2009 Trend in first ionization energy 6 of 41 © Boardworks Ltd 2009 First ionization energies in group 2 7 of 41 © Boardworks Ltd 2009 Trend in melting points 8 of 41 © Boardworks Ltd 2009 Explaining the trend in melting points The melting points of the elements decrease down group 2, with the exception of magnesium to calcium. A metal’s melting point depends on the strength of its metallic bonds. This decreases down the group because the atomic radius increases, resulting in a weaker attraction between the nucleus and delocalized electrons. Element Melting point (K) beryllium 1560 magnesium 923 calcium 1115 strontium 1050 barium 1000 The melting point of magnesium is lower than expected due to variation in how its atoms pack in the metallic crystal. 9 of 41 © Boardworks Ltd 2009 Physical properties summary 10 of 41 © Boardworks Ltd 2009 First ionization energy of group 2 metals 11 of 41 © Boardworks Ltd 2009 12 of 41 © Boardworks Ltd 2009 Solubilities of group 2 hydroxides 13 of 41 © Boardworks Ltd 2009 Solubilities of group 2 hydroxides The solubility of the group 2 hydroxides increases down the group. Magnesium hydroxide is considered to be sparingly soluble and the hydroxides of the lower members of the groups are all considered to be soluble. Group 2 hydroxide Solubility Mg(OH)2 sparingly soluble Ca(OH)2 slightly soluble Sr(OH)2 soluble Ba(OH)2 soluble As the solubility of the group 2 hydroxides increases, so does the pH of the solutions formed. This is because the more of the hydroxide that dissolves, the greater the concentration of hydroxide ions (OH-) in the solution formed. 14 of 41 © Boardworks Ltd 2009 Applications of group 2 hydroxides A suspension of magnesium hydroxide is commonly called milk of magnesia. It is used in medicine as a laxative and to relieve acid indigestion. Calcium hydroxide, also called slaked lime, is used in agriculture to raise the pH of soils. Soil pH is an important factor in agriculture. 15 of 41 © Boardworks Ltd 2009 Solubilities of group 2 sulfates 16 of 41 © Boardworks Ltd 2009 Solubilities of group 2 sulfates The solubility of the group 2 sulfates decreases down the group. Magnesium and calcium sulfate are considered to be soluble, whereas strontium and barium sulfate are considered to be insoluble. Group 2 hydroxide Solubility MgSO4 soluble CaSO4 slightly soluble SrSO4 insoluble BaSO4 insoluble 17 of 41 Note that this decrease in solubility down the group is the opposite of the trend for the solubility of the group 2 hydroxides. © Boardworks Ltd 2009 Testing for sulfate ions 18 of 41 © Boardworks Ltd 2009 Applications of group 2 sulfates Barium sulfate is used as a radiocontrast agent to help take X-ray images of the digestive system. It is sometimes known as a ‘barium meal’. Barium sulfate is insoluble, so is not absorbed by the body when swallowed. However, barium is a very good absorber of X-rays and it helps to define structures of the digestive system to aid in diagnosis. 19 of 41 © Boardworks Ltd 2009 Applications of group 2 compounds 20 of 41 © Boardworks Ltd 2009 Chemical properties summary 21 of 41 © Boardworks Ltd 2009 22 of 41 © Boardworks Ltd 2009 Reaction with oxygen 23 of 41 © Boardworks Ltd 2009 Flame tests When group 2 metals are burned in oxygen, coloured flames are produced. This is due to the presence of metal ions. Flame tests exploit this fact. The presence of certain metal ions can be identified by noting the characteristic flame colour that results from burning. The colours for group 2 metal ions are: magnesium – bright white calcium – brick red/orange strontium – red/crimson barium – pale green/yellow-green 24 of 41 © Boardworks Ltd 2009 Explaining flame tests When heated, some electrons in an atom or ion are excited to higher energy levels. When they fall back to their initial levels, energy is emitted; sometimes seen as visible light. 25 of 41 light heat energy Electrons may be excited by different amounts into different energy levels and drop back at different times. The colour of the flame is a combination of all these energy emissions. © Boardworks Ltd 2009 Flame test colours 26 of 41 © Boardworks Ltd 2009 Redox reaction with oxygen When group 2 metals react with oxygen, they form the metal oxide. For example: 2Mg(s) + O2(g) 2MgO(s) 0 0 +2 -2 oxidation states The oxidation state of magnesium has increased from 0 in its elemental form to +2 when it is in magnesium oxide. This means the magnesium has been oxidized. The oxidation state of oxygen has decreased from 0 in its elemental form to -2 when it is in magnesium oxide. This means the oxygen has been reduced. 27 of 41 © Boardworks Ltd 2009 Redox reaction with chlorine When group 2 metals react with chlorine, they form the metal chloride. For example: Ca(s) + Cl2(g) CaCl2(s) 0 0 +2 -1 oxidation states The oxidation state of calcium has increased from 0 in its elemental form to +2 when it is in calcium chloride. This means the calcium has been oxidized. The oxidation state of chlorine has decreased from 0 in its elemental form to -1 when it is in calcium chloride. This means the chlorine has been reduced. 28 of 41 © Boardworks Ltd 2009 Reaction with water 29 of 41 © Boardworks Ltd 2009 Redox reaction with water When group 2 metals react with water they form the metal hydroxide and hydrogen gas. For example: Sr(s) + 2H2O(l) → Sr(OH)2(aq) + H2(g) 0 +1 +2 0 oxidation states The oxidation state of strontium has increased from 0 in its elemental form to +2 when it is in strontium hydroxide. This means the strontium has been oxidized. The oxidation state of hydrogen has decreased from +1 in water to 0 when it is in its elemental form. The means the hydrogen has been reduced. 30 of 41 © Boardworks Ltd 2009 Explaining the trend in reactivity The reactivity of the elements down group 2 from beryllium to barium increases. Mg This is because it is successively easier to remove electrons to form the 2+ ion. Ca Although increased shielding cancels the increased nuclear charge down the group, the increase in atomic radius results in a decrease in the attractive force between the outer electrons and the nucleus. 31 of 41 Sr Ba © Boardworks Ltd 2009 Reaction of oxides with water When group 2 metal oxides react with water they form the metal hydroxide. For example: SrO(s) + H2O(l) Sr(OH)2(aq) Similar to the reaction between the metal and water, the resulting solution has high pH due to the hydroxide ions from the metal hydroxide. Reactivity is as follows: Oxide beryllium magnesium calcium Reaction does not react reacts slowly to form alkaline suspension reacts to form alkaline suspension strontium, barium react to form alkaline solutions 32 of 41 © Boardworks Ltd 2009 Decomposition of group 2 carbonates When heated, the group 2 metal carbonates decompose to form the metal oxide and carbon dioxide gas. Splitting compounds using heat is called thermal decomposition. MCO3(s) MO(s) + CO2(g) The group 2 carbonates become more stable to thermal decomposition going down the group: magnesium carbonate: MgCO3 increasing stability calcium carbonate: CaCO3 strontium carbonate: SrCO3 barium carbonate: BaCO3 33 of 41 © Boardworks Ltd 2009 Decomposition of group 2 nitrates Thermal decomposition of group 2 metal nitrates forms the metal oxide, nitrogen dioxide and oxygen. 2M(NO3)2(s) 2MO(s) + 4NO2(g) + O2(g) Like the group 2 metal carbonates, the nitrates become more stable to thermal decomposition down the group. magnesium nitrate: Mg(NO3)2 increasing stability calcium nitrate: Ca(NO3)2 strontium nitrate: Sr(NO3)2 barium nitrate: Ba(NO3)2 34 of 41 © Boardworks Ltd 2009 Explaining the trend in thermal stability Metal ions become larger down group 2 but have the same charge. This means their charge density is reduced. A metal ion with a high charge density has strong polarizing power. It can therefore polarize the carbonate ion, making it more likely to split into O2- and CO2 when heated. polarization A metal ion with a low charge density has weak polarizing power, meaning the carbonate ion is less polarized and therefore more thermally stable. 35 of 41 © Boardworks Ltd 2009 Equations for reactions 36 of 41 © Boardworks Ltd 2009 Stability of group 2 carbonates 37 of 41 © Boardworks Ltd 2009 38 of 41 © Boardworks Ltd 2009 Glossary 39 of 41 © Boardworks Ltd 2009 What’s the keyword? 40 of 41 © Boardworks Ltd 2009 Multiple-choice quiz 41 of 41 © Boardworks Ltd 2009 42 of 43 © Boardworks Ltd 2009 43 of 43 © Boardworks Ltd 2009 What are the halogens? The halogens are the elements in Group 7 of the periodic table. The name halogen comes from the Greek words for salt-making. 44 of 43 © Boardworks Ltd 2009 Physical properties of halogens 45 of 43 © Boardworks Ltd 2009 Trends in boiling point Halogen molecules increase in size down the group. This leads to greater van der Waals forces between molecules, increasing the energy needed to separate the molecules and therefore higher melting and boiling points. van der Waals forces fluorine atomic radius = 42 × 10-12 m boiling point = -118 °C 46 of 43 iodine atomic radius = 115 × 10-12 m boiling point = 184 °C © Boardworks Ltd 2009 Trends in electronegativity Electronegativity of the halogens decreases down the group due to an increase in atomic radius. Increased nuclear charge has no significant effect because there are more electron shells and more shielding. Iodine atoms therefore attract electron density in a covalent bond less strongly than fluorine. fluorine atomic radius = 42 × 10-12 m electronegativity = 4.0 47 of 43 iodine atomic radius = 115 × 10-12 m electronegativity = 2.5 © Boardworks Ltd 2009 Astatine The name astatine comes from the Greek word for unstable. Astatine exists in nature in only very tiny amounts. It is estimated that only 30 grams of astatine exist on Earth at any one time. This is because it is radioactive, and its most stable isotope (210At) has a half-life of only 8 hours. It was first made artificially in 1940, by bombarding 209Bi with a-radiation. What do you predict for these properties of astatine? colour state at room temperature electronegativity. 48 of 43 © Boardworks Ltd 2009 Halogens: true or false? 49 of 43 © Boardworks Ltd 2009 50 of 43 © Boardworks Ltd 2009 Reactions of the halogens Halogens react with metals such as sodium and iron: halogen + sodium sodium halide They also react with non-metals such as hydrogen: halogen + hydrogen hydrogen halide They also take part in displacement reactions with halide ions, such as the reaction that is used to make bromine from potassium bromide in seawater: potassium potassium chlorine + bromine + bromide chloride 51 of 43 © Boardworks Ltd 2009 Reaction with iron 52 of 43 © Boardworks Ltd 2009 Reactions with hydrogen The halogens react with hydrogen gas to product hydrogen halides. For example: Cl2(g) + H2(g) 2HCl(g) Chlorine and hydrogen explode in bright sunlight but react slowly in the dark. Bromine and hydrogen react slowly on heating with a platinum catalyst. Iodine combines partially and very slowly with hydrogen, even on heating. 53 of 43 © Boardworks Ltd 2009 Redox reactions of halogens 54 of 43 © Boardworks Ltd 2009 What is the reactivity of the halogens? The reactions of the halogens with iron and hydrogen show that their reactivity decreases down the group. Halogen Reaction with iron wool chlorine Iron wool burns and glows brightly. Reaction with hydrogen Explodes in sunlight, reacts slowly in the dark. bromine Iron wool glows but less Reacts slowly on brightly than with chlorine. heating with catalyst. iodine Iron wool has a very slight glow. Reacts partially and very slowly. How do you think fluorine and astatine would react with iron wool and hydrogen? 55 of 43 © Boardworks Ltd 2009 Electron structure and reactivity 56 of 43 © Boardworks Ltd 2009 Halogen displacement reactions 57 of 43 © Boardworks Ltd 2009 Halogen displacement reactions 58 of 43 © Boardworks Ltd 2009 Halogen displacement reactions Halogen displacement reactions are redox reactions. Cl2 + 2KBr 2KCl + Br2 To look at the transfer of electrons in this reaction, the following two half equations can be written: Cl2 + 2e- 2Cl- 2Br- Br2 + 2e- What has been oxidized and what has been reduced? Chlorine has gained electrons, so it is reduced to Cl- ions. Bromide ions have lost electrons, so they have been oxidized to bromine. 59 of 43 © Boardworks Ltd 2009 In displacement reactions between halogens and halides, the halogen acts as an oxidizing agent. This means that the halogen: oxidizes the halide ion to the halogen gains electrons is reduced to form the halide ion. What is the order of oxidizing ability of the halogens? increasing oxidizing ability Oxidizing ability of halogens fluorine chlorine bromine iodine 60 of 43 © Boardworks Ltd 2009 Oxidizing ability of halogens 61 of 43 © Boardworks Ltd 2009 Chlorine and disproportionation 62 of 43 © Boardworks Ltd 2009 Reaction of chlorine with water Chlorine is used to purify water supplies because it is toxic to bacteria, some of which can cause disease. Adding it to water supplies is therefore beneficial for the population. However, chlorine is also toxic to humans, so there are risks associated with gas leaks during the chlorination process. There is also a risk of the formation of chlorinated hydrocarbons, which are also toxic. Chlorination of drinking water raises questions about individual freedom because it makes it difficult for individuals to opt out. 63 of 43 © Boardworks Ltd 2009 Bleach and the chlorate(I) ion Household bleach commonly contains the chlorate(I) ion, ClO-, in the form of sodium chlorate(I), NaOCl. The chlorate(I) ion behaves as an oxidizing agent. It oxidizes the organic compounds in food stains, bacteria and dyes. ClO- + H2O + 2e- Cl- + 2OHHow many electrons are needed to balance this equation? Has the chlorine been oxidized or reduced in the reaction? The chlorine has been reduced because it has gained electrons. Its oxidation state has decreased from +1 in ClO- to –1 in Cl-. 64 of 43 © Boardworks Ltd 2009 Redox reactions of chlorate ions 65 of 43 © Boardworks Ltd 2009 66 of 43 © Boardworks Ltd 2009 Halides When halogens react with metals, they form compounds called halides. Many naturally-occurring halides have industrial, household and medical applications. Halide Formula Uses caesium chloride CsCl Extraction and separation of DNA sodium hexafluoroaluminate NaAlF6 Electrolysis of aluminium oxide titanium(IV) chloride TiCl4 Extraction of titanium lithium iodide LiI Electrolyte in batteries potassium bromide KBr Epilepsy treatment in animals 67 of 43 © Boardworks Ltd 2009 Identifying halide ions Halides can be identified by their reaction with acidified silver nitrate solution to form silver halide precipitates. potassium chloride + silver nitrate potassium nitrate + silver chloride KCl(aq) + AgNO3(aq) KNO3(aq) + AgCl(s) Silver chloride has a low solubility in water, so it forms a white precipitate: the positive result in the test for chloride ions. 68 of 43 © Boardworks Ltd 2009 Identifying halide ions 69 of 43 © Boardworks Ltd 2009 Identifying halide ions 70 of 43 © Boardworks Ltd 2009 Uses of halides in photography Silver halides are used in photography. Photographic film coated with a silver halide is exposed to light, causing the halide to decompose to form silver. This appears as a black precipitate on the photographic film. Ag+ + e- Ag light mask paper coated in silver halide 71 of 43 silver precipitate white paper under mask © Boardworks Ltd 2009 William Fox Talbot William Fox Talbot (1800–1877) was a British scientist and mathematician. He was one of the key figures in the development of the use of silver halides in photography. A French scientist called Louis Daguerre developed the use of silver halides on copper plates. These were effective at producing prints, but could only be used once. Fox Talbot adapted the process by removing any unreacted silver halide by washing with sodium thiosulfate solution. This meant that the print could be used repeatedly in the way that photographic negatives can be today. 72 of 43 © Boardworks Ltd 2009 Hydrogen halides The hydrogen halides are colourless gases at room temperature. Hydrogen halide Boiling point (°C) HF 20 HCl -85 HBr -67 HI -35 Hydrogen fluoride has an unexpectedly high boiling point compared to the other hydrogen halides. This is due to hydrogen bonding between the H–F molecules. 73 of 43 © Boardworks Ltd 2009 A substance that donates electrons in a reaction (i.e. is oxidized) is a reducing agent because it reduces the other reactant. The larger the halide ion, the easier it is for it to donate electrons and therefore the more reactive it is. This is because its outermost electrons are further from the attraction of the nucleus and more shielded from it by other electrons. The attraction for the outermost electrons is therefore weaker. increasing reducing ability Halides as reducing agents fluoride chloride bromide iodide 74 of 43 © Boardworks Ltd 2009 Halides: true or false? 75 of 43 © Boardworks Ltd 2009 Sodium halides and sulfuric acid The sodium halides react with concentrated sulfuric acid. During this reaction two things can happen to the sulfuric acid. It can be reduced act as an acid. The reactions of sodium halides with concentrated sulfuric acid demonstrate the relative strengths of the halide ions as reducing agents. 76 of 43 © Boardworks Ltd 2009 Sodium halides and sulfuric acid 77 of 43 © Boardworks Ltd 2009 Sodium halides and sulfuric acid 78 of 43 © Boardworks Ltd 2009 Oxidation states 79 of 43 © Boardworks Ltd 2009 Sodium halides and sulfuric acid 80 of 43 © Boardworks Ltd 2009 81 of 43 © Boardworks Ltd 2009 Glossary 82 of 43 © Boardworks Ltd 2009 What’s the keyword? 83 of 43 © Boardworks Ltd 2009 Multiple-choice quiz 84 of 43 © Boardworks Ltd 2009