— = — Gosreo ve Ppodon aye Surry] | Preteen | pros snonsn | ouxpoy sOlX0re | 667 1st vie orot sco ero 81 vIT Koa8 90, | | pinbry auyuorg | OL x08’ 99€ £61 thee ort | sero viro 8s T- | atheton umorgt | euro), SOL X PET ler we poe o9zt oso 660°0 Lye T0I- se8 used oped | | lawson haan | 7% | sauionyy tel zs 8s1 8re- 0891 ero 100 881° ore: | se8 moyjok area SUP Tou | jour py | tom py | tom pay | 1our p/ wauy wuuy Def Del Dest (eH—H) | wsopreq | wy | Adyequua ‘kBx0u0 ‘ainssoid pure (9|77210W | aoauis jo. | Jo Sdyeynua | uonepossip | Arayye monestuor smypes smupes yuyod mod aanyesodwia, PYYSFO!P | Auanjos puog puog W099 ash oqmoy aro Bumog Bun | WoorzE ayes | HOW SIE |Trends in the Halogens Identify i js i alee explain the trends in each of the following physical properties of the 1. Melting and boiling points higher met / ber 2. Atomic radius 3. Ionic radius 4. Electron affinity 5. ElectronegativityBreas of metal ar ehh) Bee SAM SHS Cor It is advisable that aqueous halogens are stored in a fume cupboard. To describe and carry out oxidation reactions with metal and non- ‘metallic elements and ions such as iron(\l) and iron(l) ions in solution [27.26(i)] Background ‘The halogens are strong oxidising agents due to their electronic structure and position in the periodic table. They are able to increase the oxidation number of a variety of species e (reducing agents), whilst themselves decreasing in oxidation number i.e. they become reduced. An example would be the oxidation by Cl, of Fe* ions to Fe**. The two ionic half equations showing the redox reaction would be: Cl, + 2e 9 2Cr Fe?* > Feit + Combining the two half equations would give: Cl, + 2Fe?* > 2Cr + 2Fe#* [You will need: ) | + Eye protection + LM Sodium hydroxide CORROSIVE + Test tubes and test tube rack + Starch solution + 10 cm? measuring cylinder + 1M Iron(ll) chloride IRRITANT + Dropping pipettes + 1M Iron) sulfate IRRITANT (® + Aqueous saturated chlorine HARMFUL + 11M sodium thiosulfate + 0105 M aqueous bromine HARMFUL + (@clo}hexane HIGHLY FLAMMABLE, HARMFUL \ + 0(05 M aqueous iodine (stains skin and clothes) ~ z 2 A Method Experiment 1: The react h Fe2* ions A Place 2 cm? of a solution of Fe?* into a test tube and add the aqueous halogens until a change is observed. L pale greean seivtion in of the halogens B Record your observations. Experiment 2: The reaction of the halogens with alkalis A Place 2 cm? of each of the aqueous halogens and add a few drops at a time of NaOH. B Record your observations, Ch SES, Cac Br- went colowless \~ went colouctess [Bdexcel practi materi adapted from Nufield Advanced Chemistry materialSr dicptacemeO* Experiment 3: The reaction of the chlorine with potassium iodide (KI) A Place about 1 em? of KI into a test tubs and add a few drops of chlorine water. mer . B Add an equal volume of (cyclé)Rexane, cork and shake, - gerne PIAR Layer © Record your observations. _ieaing #8 atisplacedl colousers > yellous Experiment 4: The reaction of iodine with sodium thiosulfate (Na,S,05) A. Place 2 em? of iodine into a test tube and add a few drops ae ee Wwe B Add an equal quantity of sodiim thiosulfate solution. eres L goer colour! ugnen © Record your observations, on Todlide iors —fodine is ® + nck iodlina pt rer Results Premar Qreent Observations should be recorded in the form of inital and final observations. Questions 1 Construct ionic half equations for any reactions occurring and hence write the overall ionic equation (only do Cl, and NaOH for the reaction of the halogens with NaOH), [Edexcel praccal materials adapted from Nuffled Advanced Chemistry materialsrd ies i netal 2 ind non-metallic elements ueALG In experiment 2, disproportionation reactions occur. Use the equation for the reaction of Cl, with NaOH to explain the term disproportionation. In experiment 3, Cl, converts Iv to Izy what does tell you about the order of oxidising strength of the halogens? Starch iodide indicator paper can be used to test for C1, and will go black. Explain this. Edexcel practical materials adapted from Nuffield Advanced Chemisay materials R.0.4 M sodium hydroxide solution is irritant. To describe and carry out disproportionation (tos wana alkali [2.7.2b (i)] The reactions of halogens with alkalis — - > {You will need: Access to: : Eye protection + The following solutions, each with a dropping pipette: | 3 test tubes 0.4 M sodium hydroxide, 1 cm? IRRITANT | | and rack ‘Aqueous chlorine, saturated solution, 2. cm? HARMFUL 0.05 M aqueous bromine, 2. cm? HARMFUL 0.05 M aqueous iodine, 2 cm? Fume cupboard (for the aqueous chlorine and bromine) Procedure ‘Take 2 cm? samples of solutions of each of the halogens in water and add a few drops at a time of 0.4 M sodium hydroxide solution. It should be easy to see what happens to the bromine and iodine because the solutions are coloured; the chlorine is less easy to observe. Observations Record your observations as follows. errr Pocrcu etn Cee og An interpretation of the reactions of the halogens with alkalis Halogens react with cold sodium hydroxide solution according to the pattern set by chlorine: Clg) + 2NaOH(aq) > NaCl(aq) + NaClO(aq) + HO) ‘The compound with formula NaCIO is called sodium chlorate(1) or sodium hypochlorite. Edexcel praccal materials adapted from Nuffield Advanced Chemistry materials 6Questions | 1 Turn the equation into an ionic equation, leaving out the sodium ions since these are spectator ions. 2 What changes of oxidation number does the chlorine undergo? | A reaction in which the same element both increases and decreases in oxidation number is called a disproportionation reaction — we say that chlorine “disproportionates’ when it reacts with alkalis. ‘When the solution is hot, chlorate(I) ions themselves disproportionate so that the Ax overall reaction between chlorine and hot sodium hydroxide is: | : 3Cl,(aq) + 6NaOH(aq) > SNaCl(aq) + NaClO3(aq) + 3H,0() or ionically: 3Cl,(aq) + 6OH-(aq) > SCI‘(aq) + ClO3"(aq) + 3HZ0M | 3 What changes of oxidation number does the chlorine now undergo? 4 What is the equation for the reaction between iodine and hot potassium hydroxide solution? (® ba pce mc tp Med Atmaed Coney macesPractica reactions of the halides Lrg (iy) | You will need: + Eye protection + 12 test tubes To describe and carty out the reaction of potassium halides ‘with concentrated sulfuric acid, halogens and silver ritrate solution [2.7.2d (i)] Te describe and cary out reactions of silver halides with Sunlight and their solubilities To describe and carry out reactions of hydrogen halides ‘with ammonia and water (to produce acids) [2.724 (i 2.9 Reactions between halogens and Palen Sa Handle the solutions with care; aqueous chlorine and bromine are harmful. Avoid inhaling any vapours, and do not allow the solutions to come into contact with your skin or clothing. Fluorine is too hazardous for use under ordinary laboratory conditions. Remember to wear eye protection. sin aqueous ammonia [2.7.24 The reactions between halogens and halide ions . Lime golulcie in hydrocerben Selyent This experiment investigates the relative reactivity of the"haloges elements towards the thon halide anions, safer bromine and iodine in solution: chlorine and bromine dissolved in aqueous potassium iodide, as the solubility ‘Use the halogen elements chlorine, are dissolved in water, and iodine is Of iodine in water is low, Handle the solutions with care: aqueous chlorine and bromine are harmful. Avoid inhaling any vapours, and do not allow the solutions to come into contact with your Skin or clothing, Fluorine is too hazardous for use under ordinary laboratory conditions. Remember to wear eye protection, > The following reagents, each with a dropping pipette for dispensing: ‘Aqueous chlorine, saturated solution, $ cm? HARMFUL Access to: and ack 005 Msqto omie en? HARMUL ® Bungs to fit 0.05 M aqueous iodine, § em? test tubes 0.1 M potassium bromide, § cm? 0.1 M potassium chloride, 5 cm? 10.1 M potassium iodide, 5 cm? “Petroleum spit, biting range 120-160 °C, 10 emi labelled "Hydrocarbon solvent’ HIGHLY FLAMMABLE, HARMFUL * Fume cupboard (For the aqueous chlorine and bromine) ) no reaction Vs Edexcel prctical materi adapted from Nuffield Advanced Chemistry materials Chlovine VS chloricte . Ns bromide Rocher yellow iodide. Grange 8 eeProcedure 1. Set up four test tubes containing about 1 cm? each of solutions of potassium chloride, Potassium bromide and potassium iodide, and 1 cm? of water as a control. @ Add two or three drops of chlorine solution to each. Cork and shake. Observations and interpretations ‘Have reactions taken place? What are the products? Use the colour changes as @ guide. ‘Write equations for any reactions you see. a a pee Se fe Ae i a eee ‘Would the addition of a hydrocarbon solvent help you in reaching a decision? Ee ca ere vans Ne ® Add an equal volume of hydrocarbon solvent (€.g. hexane) to each test tube, stopper the test tubes and shake. Observations and interpretations Record the colours of each layer. Why do you think the halogens are more soluble in hydrocarbon solvent than in water? Edexcel praca! materiPractical 2.9 (cont) Reactions between halogens and halide ions/some reactions of the halides _ ae ‘Now repeat the experiment, using in turn bromine solution and iodine solution. 7 ain Is a definite wend in reactivity observable in the experiment? Can you explain it using ideas about electronic structure? ee ee eo oe ‘Write an ionic equation for each reaction that took place. Results Record your results below. Solution added] water potassium chore | potassium bromide | potassium iodide solution solution solution I dere praca mater sdped fom Nudd Advaned Chensey mnerits 1)Some reactions of the halides ions/some . ™M ae 's corrosive. Concentrated sulfuric acid and solid phosphoric acid are corrosive. se solid potassium (or sodium) chloride, bromide and iodide in part 2. You MUST wear Soggles. Do part 3 ina fume cupboard as toxic and corrosive gases are formed. Procedure 1 The silver halides \ white how Use 0.1 € 0.1 M solutions of potassium (or sodium) chloride, bromide and iodide. Where you can, attempt to estimate roughly the proportions of the solutions needed for complete reaction, a To 1 cm portions of each of the halide solutions, add a few drops of 0.1 M silver nitrate solution followed by some dilute HNO3. : ssoles b To the precipitates obtained in part a add 8 M concentrated ammonia solution. ~, ee Obtain a second set of silver halide precipitates and leave them exposed to the light for a few minutes. Results © Record your results in a table, noting similarities and differences between the reactions. ‘The photochemical change which occurs when silver bromide is exposed to sunlight Is used in black-and-white photography. The silver ions are converted to silver metal which remains a5 2n ‘opaque image on the photographic film. Edexcel praca materials adapted from Nuffield Advanced Chemistry marr 11HALIDE.ION TESTs oo Reason 1) Ad itre aca (ag tothe solution being tested “This removes any atheros that could give a pret wth saver trate 2a), 9, carbonate ions! CO: + 2H" > CO2+ HO | 2) _ Add siver nitrate (a) tothe solution being tested “This produces a precitatefor CF, Br and ons 9) Ac ammonia (ag) (ute & cone) othe precipitate “This use to see he precipitates re-cissove to help conti theridentty T4 ing out Complete the tae to ive (a) obseraons and (b) equations for any reactions that take place (se ioc equations) ‘Aton of AgNOaq) ‘Aton of te NH) ‘Aadhton of concentrated NHs(aq) Fea) crte0) Br(aq) Nea) "ART 2 - Testing for halide ions T Sample u | v w x ‘Aaaion of AgNOsleq) ‘Adon of due NHy ‘Addition of cone NHs Halide ion contained (or #) ‘dentty o aide on © www.CHEMSHEETS.co.uk 3-July-2015 Chemsheets AS 1068 \2020T Sy syeayswIEYyD © 9toz-uer-8z 3n"02'S1a3HSWAHO"MMM @ ssexeenn G ») ypa6u0ns ©) ‘WoReUeyaxT TSMOd BUDNPSE oa l ® [ = oh vorpe=at wonenas40 ap DIe eH StH © '0S*H Aen Senco asa tos © 10st 1-10 “SAGQKIWH 40°WaMOd-SNIONGIN | —— ates on eg2.9 (cont.) Reactions between halogens and halide fons/some Teactions of the halides _ a Put about 0.1 g of the solid salt into a test tube (about enough to fil the rounded end of the tube if it is 100 x 16 mm) and add about 10 drops of concentrated sulfuric acid (TAKE CARE). Warm the reaction mixture gently ig necessary. Observations and interpretations Identify as many products as you can (test with strips of filter paper moistened with lead(ID ethanoate (TOXIC), acidified potassium dichromate(VI) (VERY TOXIC AND IRRITANT) and ammonia solution (CORROSIVE). Do not hhandle the papers with bare fingers ~ use forceps or wear gloves. Note the similarities and differences between the reactions. Record and explain your ‘observations as fully as you can ® Repeat part a, using phosphoric cid (CORROSIVE TAKE CARE) in place of sulfuric acid. Note any difference oo ee ee aaa ae ee 3 The properties of the hydrogen seared halides ‘Wearing goggles use the reactions in 2 to prepare and collect samples of hydrogen chloride, hydrogen bromide, and hydrogen iodide in a fume cupboard (toxic and/or corrosive). The apparatus aoe feel ad shown is convenient for this purpose. A good yield of gas is obtained if solid 100% phosphoric acid is used, but you tase, must use dry test tubes to collect your fea samples of gas pats fr mating ge bales excl pracl mats adaped fom Nofeld Advanced Chemis materials Ih EEere fo of halide with an equal quantity of solid phosphoric acid (TAKE in the side-arm test tbe. Stopper it securely. Puta day test tube round the delivery tube and warm the mixture gently until gas is evolved. Collect at Jeast three tubes of gas, sealing them with a dry stopper when full. Clouds of misty, white fumes will ist form at the mouth of the test tube when iti less than half full of hydrogen halide gas. Let the fumes form for at least 10 seconds before sealing with a dr stopper. ‘Use the tubes of gas to investigate: The solubility ofthe gas in water Invert a tube of gas in a beaker of water and remove the stopper. IF the water rises rapidly the gas i ead soubl, Is there a residue of undissolved ex and, if so, what do you suppose it is? see ee Coot ee ee AHS ‘The reaction of the gas with ammonia gas. Hold a drop of fairly concentrated ammonia solution in the mouth of an open test tube, using a glass tube or rod. ‘What do you observe, and what do you suppose is formed? The stability of the gas towards heat. Heat the end of a length of nichrome wire or a glass rod to dull red heat, and plunge it into a tube of gas; if no change occurs in the #35, try again with the wire hotter. What do you observe? Record the properties of these hydrogen halides in table, and write equations for the reactions you have seen. ‘lesa praca materi adapted from Nuffield Advancns Chemiry materi 15> Chemistry at work: Chlo: Making chlorine e and its compounds ye ; sioring = etogen Ghlotine, sodium hydroxide and hydrogen are made we |_ mpm by the electrolysis of brine (sodium chive eolution) * This is done in a diaphragm cell Look at the diagram opposite: brine += The Fill uses titanium anodes and steel cathodes, Chen ote Surrounded by a porous asbestos diaphragm. hlorine is given off at the anode iy postive anode (+) reaction: 2CI-(aq) —+ Cig) +20e- om Repacs | Ee ° through the The chlorine rises up through the brine and is piped away. __‘meibrene Sointhodes are hollow steel gauze fingers coated in asbestos. ‘odium hydroxide and hydrogen formed inside them are led away separately: cathode (—) reaction: 2H*(aq) + 2e- —+ H,g) % Removal of Ht ions during electrolysis leaves an excess of OH” (hydroxide) ions around the cathode. The brine is kept at a higher level in the anode compartment compared with the cathode compartment. This lets it Percolate through the diaphragm from anode to cathode. The design keeps the chlorine and hydrogen gas separate and keeps the sodium hydroxide solution in the cathode compartment. ‘The drawback of the diaphragm cell is that the solution produced contains only 10% sodium hydroxide. We find that there is about 15% sodium chloride mixed in the solution. The solution has to be evaporated to remove the less soluble sodium chloride, The final solution contains 50% sodium hydroxide and less than 1% sodium chloride Whiter than wl 1 Ofall the chlorine manufactured, about 20 per cent is used to make disinfectants and bleaches. Chlorine is a cheap industrial oxidising agent. It is used to bleach paper, although it is not used directly as itself. When we dissolve it in water we get chlorie() acid (HOCI). Chg) + H,O(1) == HOCI(aq) + HCl(aq) Itis the chloric(1) acid that acts as the oxidant. It can oxidise the complex organic molecules that make up coloured dyes, and turn them into colourless products. HOCI+ dye —» HCI+ oxidised dye (cotourec) (colouress) However, people are getting worried about the harmful products Chlorine bleaches paper in rivers near paper-mills, probably formed by reactions involving chlorine.Water without bugs Have you ever smelled chlorine from your water at home when you turn the taps on full? Chlorine is used in the water industry to sterilise our water supplies. The chloric(t) acid (HOC!) formed in the water acts as a bactericide {tis lethal to bacteria, and so rids our drinking water of harmful micro-organisms. We first used chlorine to sterilise water in 1905. u It was introduced to combat an epidemic of typhoid fever in Lincoln. There are stil many people who have to Modern water treatment involves the processes shown below: drink untreated water +. coagulation adding sats mates sit, organic etter end microorganisms cump 2. sedimentation together removing them from solution Pardes sete out Once the water is free from any solids, chlorine is added to kill off any bacterial micro-organisms. ‘The water in a treatment works is adjusted to a pH of 73, although more HOCI(aq) would be present at lower pH’s. HOCl(aq) = H*(aq) + OCI-(aq) EOI, 4. hl Se” If H* ions are removed by raising the pH, more HOCI paticles “sinects . r splits up to replace them. However, more acidic conditions would dissolve harmful substances from the pipes. (Equilibrium reactions are discussed in detail in Chapter 29) Most chlorine is rernoved chemically, but some is left in the water. Why do you think that is? The water companies have to take care that the water is kept free from bacteria during its journey to homes and industry. HOClis a bactericide The amount of dissolved chlorine has to be carefully monitored. .emists can use the redox reaction with iodine jork this out. We described the method on page 123. Look at the example below: ‘An analyst from a water company collected a 500 cm? sample of water. She added excess potassium iodide to the sample. The iodide ions (I-) react with any chlorine molecules 21-(aq) + Cl(aq) —+ 2CI-(aq) + Ipaq) The iodine is then titrated against sodium thiosulphate, using starch as an indicator of the end point. Can you remember how we can tell when we've reached the end point? She found that it took 7.0 cm? of 0.00100 mol dm sodium thiosulphate 1 mole of iodine was formed, solution, from 1 mole of Clz fae The reaction between iodine and thiosulphate can be shown by ©. concentration of Cl = this ionic equation: 35x 2x 10-6 Iplaa) + 25,0.2-(aq) — 2I-(aq) + $402" (@s we used a 500.cm? sample) bs 20:2" (aq) (aq) + S,02"(aq) los wo used a 500 ery Her calculation is shown opposite:* Chemistry at work: Bromine and iodine Bromine from the sea oe Page 42 we saw how much sodium chloride is dissolved in seawater ut there are lots of other salts dissolved in the seas, especially the Dead Sea in Israel waters contain relatively large: i a! ters. ttge amounts of magnesium bromi Bromine is extracted from this and Israel isthe biggest Serprter of bromine and its compounds in the world. ‘© how do they get the bromine from the seawater? Once again, redox reactior ns are important in halogen chemistry. Li all, though, we have to get rid of most of the other salts Hssolved in the water. You can do this by evaporating off ‘The less soluble salts crysiallise out, a solutic i i Turing bromide (Br-}ione inlo bowie Tech clonal is where the redox reaction comes in! Chlorine is bubbled through the concentrated solution of bromide ions. © Saw on page 122 that chlorine will displace bromide ions from solution: Ch{aq) + 2Br-(aq) —- 2CI+(aq) + Bra(aq) © Which substan ions. The Dead Sea is rich in dissolved saits, ) ions into bromine (Br,) molecules including magnesium bromice acting as an oxidising agent? The bromine produced is not very soluble in water, and soon forms @ separate layer beneath the water. The bromine can then be tapped off. ‘The chlorine for the reaction is made by electrolysing seawater. The bromine formed has to be distilled to purify it, making it ready to be made into compounds. Its compounds are used to make pesticides, flame retardants and dru Iodine and health We all need a small amount of iodine in a healthy diet. Insufficient can result in people getting goitre, This is a condition in which the thyroid gland in the neck swells up. Iodide ions are converted into hormones in the thyroid gland. An underactive gland in children can result in slow mental and physical development. The child is treated with the iodine-containing hormones. Radioactive iodine-131 was released at Have you heard of the town Chernobyl? Chemoby! In 1986 there was a terrible accident at its nuclear power plant. Radioactive iodine-131 was one of the isotopes released into the People had to take tablets of non-radioactive iodine-127 to ensure that their bodies had enough iodine. This meant that they would not need to absorb any of the radioactive iodine. However, many people did get cancer as a result of the accident. lodine is a mild oxidising agent. 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