@ Oe DUBAI GEM PRIVATE SCHOOL CHEMISTRY A2 LEVEL UNIT 6 a ctl wae mel CHEMISTRY LABORATORY SKILLSInorganic © Topics 4 and 15 include sections on reactions that may be used to test for the presence of cations and anions '* Most of these reactions may be carried out on a test tube scale + Students may be set these tests as part of an examination question on the analysis, of inorganic unknowns * A.useful source of these exercises is the activity (b) tasks set as part of the 6CHO3, and 6CHO6 internally assessed coursework in the 2008 Edexcel Chemistry Specification. * The tables that follow provide a reference for the observations made in the tests. blue copper(it), [Cu(Hz0)6}** green iron(ll), [Fe(Hs0)s]**; chromium(IIN), [Cr(H20)e]* brown / yellow iron(tt), [Fe(H20)6)>* red / pink cobalt(tt), (Co(Hs0)e)* yellow chromate(V1}, CrO.® orange dichromate(Vi}, Cr0;* purple | manganate(vit), mnos Flame tests Flame tests may be carried out by using a clean nichrome wire to mix a sample of a solid compound with a few drops of concentrated hydrochloric acid. The wire is then held at the edge of a hot Bunsen flame and the colour observed. io yellow sodium lilac potassium yellow-red calcium [pele green barium red lithiurn, strontium red-violet rubidium “Further tests are needed to identify these metal cations,Addition of sodium hydroxide solution When dilute, aqueous sodium hydroxide is added to an aqueous solution of a metal fon a Precipitate of the insoluble hydroxide may be formed e.g. Cr(OH)s. Some precipitates will dissolve in excess sodium hydroxide to give @ solution containing a complex ion e.g. [Cr(OH)6)*. When carrying out these tests students should be told to add aqueous sodium hydroxide, drop-by-drop, until th fa moet precipitate dissolves to a chromium(II1), [Cr(H20)6]* | green precipitate dark green solution ie 7 ‘green precipitate, turning | a ccitate ig ron(HH), {Fe(H20)s} brown on exposure to are, | Precipitate is insoluble lron(111), [Fe(H20}6]** red-brown precipitate precipitate is insoluble cobalt(l), (Co(Heo)6}2" blue precipitate, turning |» acinitate is insoluble pink on standing copper(ii), [CuH20}6I?* blue precipitate precipitate is insoluble Group 2 cations: . cite Ma?*(2q), C2?*(aq), Ba?(aq) | White Precipitat Preciptate Is Insoluble Group 1 cations: - _ Nat(aq), K'(ea) no precipitate Addition of ammonia solution When dilute, aqueous ammonia is added to an aqueous solution of a transition metal ion € precipitate of the insoluble hydroxide is formed. e.g. Cu(OH)z, Lo ‘Some precipitates will dissolve in excess ammonia to give a solution containing a complex ion e.g. [Cu(NHs)s(H20)2?* When carrying out these tests students should be told to add aqueous ammonia, drop- by-drop, until there is no further change. precipitate slowly dissolves chromium(I}, [Cr(H20)s]** | green precipitate fomviolensolntee iron), {Fe(H:0)2 green precipitate turing | crecipitate is insoluble iron(118), (Fe(HzO)e}* red-brown precipitate precipitate Is insoluble cobalt(II), [Co(H.0)5}%* blue precipitate preeipitats dissolves toe brown solution copper(II), [Cu(HaO}<]2* blue precipitate teeSilver nitrate solution Aqueous silver nitrate Is used to test for the presence of halide ons in solution. Anions such as carbonate that would form precipitates with silver nitrate are removed by adding dilute nitric acd before the silver nitrate, ‘The identity of the halide may be confirmed by adding aqueous ammonia to the silver halide. chloride, C1- soluble bromide, Br | cream AgBr insoluble soluble lodide, 1~ pale yellow | Agi Insoluble insoluble Barium chloride solution ‘Aqueous barium chloride forms precipitates with a number of anions but is usually used as the test for the sulfate(VI), SO. anion, When dilute hydrochloric acid is added to the anion solution before aqueous barium chloride only the sulfate anion will form as a precipitate. sulfate(vi), So? | white BaSOs precipitate is insoluble sulfate(IV), $0:- | white BaSos precipitate dissolves carbonate, COs _| white Bacoa precipitate dissolves Concentrated sulfuric acid ‘When a few drops of concentrated suifuric acid are added to a solid halide the observed products may be used to identify the halide ion. ‘The test must be carried out on a small scale and in a fume cupboard, ‘The gaseous products in brackets will not be observed since they are colourless, ‘No attempt should ever be made to smell the products of these reactions. chloride, cl- steamy fumes HCI bromide, Br steamy fumes, brown vapour HBr, Bra, (SO2) odds, steamy fumes, purple vapour, black solid, yellow solid HB 8 AHS)Displacement of halide ions When aqueous chlorine is added to a solution of a bromide or an iodide then bromine or iodine Is displaced When aqueous bromine is added to a solution of an iodide then iodine is displaced. ‘The formation of aqueous solutions of bromine or lodine may be used as a test for the bromide and iodide ions. JF an organic solvent such as hexane is added to the reaction mixture the bromine or lodine dissolves in the organic layer. No reaction No reaction or -brov (20) | ale green solution | Pale red-brown No rea Brown solution Red-brown solution | No reaction, Br(aq) | yet Pale red-b Ne reaction plonsacmge ale red-brown organic layer solution Briel seit Brown solution Brown solution. orveaction rtaq) | Black soa Black solid Brown solution Purple organic layer _| Purple organic layer compound. Group 2 carbonates OR lithium carbonate oxygen Group 1 nitrates (except lithium nitrate) Group 2 nitrates OR ‘oxygen and nitrogen dioxid ys 3 © lithium nitrateOrganic analysis * Topics 6, 17 and 18 include sections on reactions that may be used to test for the presence of organic functional groups * Most of these reactions may be carried out on a test tube scale * Students may be set these tests as part of an exercise to analyse organic unknowns + The exercise may include spectroscopic information from Topics 7 and 19 * Auseful source of these exercises is the activity (b) tasks set as part of the 6CHO3 and 6CHO6 internally assessed coursework in the 2008 Edexcel Chemistry ‘Specification, + The tables that follow provide a reference for the observations made in the tests. Ignition Igniting an organic compound on 2 crucible lid in a fume cupboard may provide evidence for the Identity of the compound. arene, unsaturated aliphatic burns with smoky flame avg. cyclohexene saturated low molar mass compound burns with a clean flame e.g. ethanol no residue ‘most lower molar mass compoundsChemical tests yellow solution is decolorised alkene iF white precipitate | eno also formed) warm with aqueous, acidified potassium dichramate(vi) orange to green solution primary or secondary alcohol, aldehyde warm with ethanol and aqueous silver nitrate white precipitate cream precipitate yellow precipitate chloroalkane bromoalkane lodoalkane phospharus(V) chloride steamy fumes that turn damp blue litmus paper blue OH group in alcohols and carboxylic acids 2, 4-dinitrophenylhydrazine solution orange precipitate C=0 group in aldehydes and ketones heat with Fehiing’s solution or Benedict's solution red precipitate aldehyde warm with Tollens’ reagent (ammoniacal silver nitrate) silver mirror aldehyde lodine in alkaline solution pale yellow precipitate methyl ketone or ethanal methyl secondary alcohol or ethanal | warm with ethanol and a few drops | of concentrated sulfuric acid and our reaction mixture into aquéous sodium carbanate ester smelt e.g. glue- like carboxylic acid |: Unit 6 ee Unit 6 Activity B: Qualitative observation Organic substances Introduction {tis important to read the student brief carefully. Hints may be given such as: ® each organic compound contains only one functional group ® the number of carbon atoms that molecules of each compound contains and whether itis a branched or a straight-chain compound « the fact that one unknown may be oxidised, reduced or hydrolysed to another of | the unknown or unknowns You will aways be given the quantities ofboth the unknown and the test reagent and | -e full details of how to carry out the test, so you do not need to learn these, imap ‘Make sure that you can Although the main part of the task will be about substances met in Unit 4, questions | interpret mass infrared will be asked about alkenes, alcohols or possibly halogenoatkanes, so these must and NMR spectra befare also be revised before the practical assessment, 1 you-do the assessment, ‘Make sure that you know the difference between displayed formulae (all the atoms and bonds must be shown), structural formulae (an unambiguous formula showing { each group separately) and skeletal formulae, ii fi ego, ° ghd XX Donn ard site Make sure that your deductions are logical. The deduction from a positive iodoform test is not that the unknown is one of ethanal, a methyl ketone or an alcohol with a CHsCH(OH) group if you have already shown that an unknown is a ketone. The unknowns that you could be asked to identify are alkenes * alcohols © halogenoalkanes (rot very likely) aldehydes and ketones arboxylic acids carboxylic acid derivatives (not very likely) Meke sure that you know F the test for aldehydes and Possible observations marks are shown with av. ketones, Unit 3 and 6 Chemistry Laboratory Skis Bals Content Guidance (eRe ‘Draw the skeletal formula cof methylpropanal £ Atypical mark scheme is Bor 9 marks 2or 3 marks :| 2 6r3 marks Vimar Possible tests Combustion Burn a few drops ona |« It burns with a clear non-smoky | ® Low carbon-to-hydrogen crucible lid flamey ratio ‘Ie burns with a smoky flame 7 | @ High éarbon-to-hydrogeh ratio Solubility in water and pH test ‘Add to water «© Either two layers form v | ® Either no.OH group; orf an alcohol or acid it hasa high molar mass (at least f6ur carbon atoms) © Or it dissolves fuly 7” | © Forms hydrogen bonds with ‘Add litmus or water, so has an OH group universal indicator (UI) | ® Litrus"paper (or UI” | @ Ieigan acid | solution) goes red V | | ® Utsolution goes green |@ Itisa neutral substance (not an acid) | Test for alkenes ‘Add some bromine water to | Brown bromine water goes | C=C group present the unknown — stopper the | colourless wand two layers test tube and shake carefully | are formed 7 Tests for talogenoalanes Tet) Shake afew drops ofthe ‘Two layers form 7 unknown with water Add a few drops of ethanol and | White precipitate ¥ | It contains a C-Cl group aqueous sliver nitrate and dilute |e Cream precipitate | ®t contains a C-Br group nitric acid — stand the test tube | © Yellow precipitate w | @ It contains a C-I group 1 [lina beaker of hot water ‘Add 4'drops of ethanol and [a White precipitate v | @ It contains a C-Cl group then 2em? of dilute sodium | Cream precipitate ¥ | @ It contains a C-Br group hydroxide — stand the test tube | @ Yellow precipitate # | @ It contains a C-I group ina beaker of hot water for § minutes; then add excess nitric acid followed by aqueous silver nitrate x Edexcel ASIA2 Chemistry |Test 5 hydroxide in ethanol —fitthe | colourless v test tube with a delivery tube and warm gently, passing any gas evolved through’a little bromine water ‘Add concentrated sodium ‘© Brown bromine goes © H-halogen eliminated forming an alkene confirmed by adding ammonia solution, ‘The identity of the halogen in the precipitate formed with silver nitrate can be eee inteenee uae Precipitate dissolves in dilute ammonia ¥ | The unknown is a chloroalkane Precipitate insoluble concentrated ammonia W tte but soluble in] The unknown is a bromoalkane ammonia V Precipitate insoluble in concentrated ‘The unknown is an iodoalkane Test for aldehydes and ketones ‘These contain the C=O group. ‘Add & few drops ‘of a solution of 2d-nitrophenylhydrezine A yellow or orange precipitate [Inference ia leis an aldehyde or a aaa es | Benedict’) solution and warm Aik fa drop of he © Either red precipitate 7 ‘unknown to some Fehling’s (or | @ Or the blue colour remains © leis an aldehyde Ieis aketone™ | (see Below) and warm ‘Add a few drops of the © Either silver mirror formed W | unknown to Tollens' reagent | © Or solution stays colourless 7 © Itisan aldehyde ® Ieisaketone® solution and wari ‘Adda few drops of the © Either orange solution goes | It is dn aldehyde* unknown to acidified green potassium dichromate() © Or solution stays orange | itis a ketone®™ solution ‘Add a few drops ofthe © Either purple solution © Itis an aldehyde ‘unknown to acidified decolourised ¥ potassium manganate() © Or solution stays purple | * leis aketone* “This inférence can only be made ifthe substance has already been shown to be a carbory| compound. Tollens’ reagent is made by adding aqueous sodium hydroxide drop by drop to aqueous silver nitrate until a grey precipitate is formed. The clear liguid above the precipitate (the supernatant liquid) is poured off and the precipitate dissolved in the minimum of dilute ammonia. Unit 3 and 6: Chemistry Laboratory Skils | The equations for the F action'of aquecus silver nitrate are; RCH H;O.5 ROH + HEE XC and X HAs AX Draw the structural | formula of the product of £ 2,4-dinitrophenylhydrazine and propanone. 4 a Ls & si 4, sa Remember that primary alcohols can be oxidiséd to aldehydes and secondary alcohols to ketones. na Ba J “FeyContent Guidance The iodoform test This is a reaction between an organic alcohol or carbonyl compound and a solution of iodine and sodium hydroxide. The mixture is then allowed to stand, | Observation Previous tose 0° [inferences Pale yellow precipitate | © A precipitate with ® It contains a CH;C=O- (efiodoform!) v7 2A-dinitrophenylhydrazine— | group showing it to be a carbonyl compound © Ared precipitate with Fehling’s | © Its ethanal a (or Benedict's) solution or Lees 2 silver mirror with Tollens’ Which of the following reagent — showing it to be an «wil not givea precipitate aldehyde ofiodoform when alkaline © Steamy furnes with PCls or | @ It contains the jodie is added: ethanal, ‘other test — showing itto be | CHCH(OH) group, for propa propanol, an alcohol (see below) exemple propan-2-ol butan-2-one! *lodoform's systematic name is triiodomethane, CHb, Tests for OH group in alcohols and carboxylic acids Test Observations. ~ [inferences = ay Add a small piece of sodium | @ Bubbles evolved 7 © It contains an QH group to the unknown in an © Sodium disappears or a and so is an alcohol or a evaporating basin white solid forms 7 carboxylic acid ‘Add solid phosphorus(y) | Steamy fumes evolved ¥_| © le contains an OH group CAIEaS chloride and test any ges and s0 isan alcohol ora Remember that the evolved: either with a glass carboxylic acid observation is bubbles } | rod dipped in concentrated | ® White smoke formed (izzinglefervescencs), not | | ammonia; or with damp blue | Litmus goes red ‘that a gas is evolved. fiemus paper To distinguish an acid from an alcoho! Test ne Observations Inferences: ‘Add the unknown toa solution |e Fizzing V «© Ieisa carboxylic acid of sodium carbonate or sodium — | © Gas evolved turns hydrogencarbonate and test any | —imewater cloudy 7 2s evolved with imewater ‘Add blue litmus (or universal © Litmus goes red ¥ | It is a carboxylic acid indicator) to a solution of the unknown ‘Add some ethanol (or other alcohol) and a few drops of concentrated sulfuric acid to the unknown and warm ‘Then pour into a beaker containing | © Fizzing W | @ visa carboxylic acid (and some sodium carbonate solution | Smells of glueliruity | an ester is formed) and cautiously smell the product | smell ¥ | Edexcel ASIA2 CherristryTo distinguish an alcohol from a carboxylic acid Observations inferences Add some ethanoic acid and a few drops of concentrated sulfure acid to the unknown and warm. Pour into abeaker containing | @ Fiazing v © Itis an alcohol (and an some sodium carbonate solution | ¢ Smells of glue/fruity ester is formed) and cautiously smell the product _| smell v ‘Warm the unknown gently with | © Orange solution goes | © [eis a primary or acidified potassium dichromate() | green” secondary alcohol solution “This inference can only be made iit has been shown that the unknown contains an OH group. This is because aldehydes also turn acidified cichromate(w) green, | Tests for acid chlorides jae i Observations —_ Al | ‘Add the unknown to some water in a test tube © Sceamy fumes 7 Then add dilute nitric acid and aqueous silver nitrate | © White precipitate 7 ‘Add the unknown to some ethanol and then pour into | » Fruitylglue smell «beaker containing aqueous sodium carbonate Carefully smell che beaker's contents Spectra Mass spectra look for are: ‘molecular mass of the compound ® apeak at (M- 15) or at 15 due to the presence of a CH group in the molecule © apeak at (M — 29) or at 29 due to either a C,H or a CHO group in the molecule * apeak at (M— 43) or at 43 due to a C3H, group in the molecule © apeak at (M — 45) or at 45 due to.a COOH group in the molecule infrared spectra that it states that the C=0 absorption in ketones is in the range 1680-700 cm". This is wrong because only aromatic ketones fall in this range. Aliphatic ketones are in the range 1710-1720cm"? and aliphatic aldehydes in the range 1720-1730em~. Look out for absorptions in the range: © 1710-1730cm caused by the C=O group in aldehydes, ketones and carboxylic acids @ 1735-1750cm~ caused by the C=O group in esters © 3000-2400cm~' caused by (hydrogen-bonded) 0-H in alcohols | * 2800-3200cm™~ due to (aydrogen-bonded) O-# in carboxylic acids Unit 3 and 6: Chemistry Laboratory Skils ‘Assubstance that has an OH group, farms an ester E with ethanoic acid but does nat change the colour | ofaciified potassium FP dichromate(w), must be a tertiary alcohol. You may be given a mass spectrum to help identify the unknown. The m/ values to i © the largest value is due to the molecular fon, Mt, and corresponds to the relative = ‘You will be allowed to use the Edexcel data booklet during the assessment, but note | The hydrogen-bonded O-H absorption is very broad and itis difficult toassign a definite | wavenumberThe peak due to GH ig fat split, nor does it cause: spitting, Content Guidance NAR spectra You will be allowed to use the Edexcel data booklet during the assessment. The points to look for are: © The number of peaks — this gives the number of different environments of the hydrogen atoms. For example, propan-2-ol, CHsCH(OH)CHs, will have three peaks because the hydrogen atoms in both CH groups are in the same environment. Propan-1-ol, CH,CH,CH,OH, will have four peaks. © The splitting pattern —if a peak is not split either the group has no hydrogen atoms on adjacent carbon atoms (as in propanone) or it is an O-H group: ~ ifit is split into 2 there is one hydrogen atom on the adjacent carbon atom ~ ifit is split into 3 then there are two hydrogen atoms on adjacent carbon atoms ~ ifitis split into 4 then there are three hydrogen atoms on adjacent carbon atoms © The chemical shift, 6ppm (see the Edexcel data booklet for 6 values}: ~ the H of the O-H in alcohols has a ébetween 2 and 4 ppm | = the H of the O-H{in carboxylic acids between 11 and 12.ppm | the Hin CHs, CH, or CH between 0.5 and 3.5 ppm H Knowledge check 27. Compounds A and B both have molectles containing 3 carbon ators and | oxygen atom, ‘Assume that A is propantne and that B is propan'2-ol Write down the observations that {would be made in the following tests @) Some 2,4-cinitrophenylhydrazine was added to each. Write down your observations with A and with B 2 E (b) Some phosphorus(y) chloride was added to each. Write down your observations with A and with B Q £ (© Each was warmed with acicfied potassium dichromate(v) solution. Write down } your observations with A and with B. Q (@) How many peaks would there be in the NMR spectrum of compound A, and how would they be split? Q The molecules of compounds P and Q contain 4 carbon atoms, and molecules of compound Recontain 3 carbon atoms. Assume that P is butan-2-ol, Q is butanone and that R is propanoie acid, Write down the observations and deductions that would be made in the following tests | @ Assmallpiece of sodium was added to P in an evaporating basin. Write down your observations. Q (b) Pwas warmed with aciifed potassium dicrromate(y) solution, Write dowm your observations, 0} (© Pas warmed gently with @ micture of iodine and sodium hycroxide sokstion. Write down your observations, w (@) Use your answers to (2), (b), (0) and the information in the stem of the question to identify compound P by writing its name or formula, 0 [© The infrared spectrum of @ is shown below. Edexcel ASIA2 Chemistry4000 3000 2000 1500 000 ‘What does ths indicate about the nature of compound Q? @ (f) Qwas warmed with some acidified potassium dichromate(y) solution. Write down your observations (@ Use your answers to (€),(0) and the information in the stern of the question to identify compound Q. (h) Some R was added to aqueous sodium carbonate and the gas tested with limewater, i Write down your observations. Q. () 2am? of Pand 2em? of R were mixed and 4 drops of concentrated sulfuric acid were ‘arelully added, The mixture was warmed in a beaker of hot water for S minutes. ‘The mixture was then poured into a beaker containing aqueous sodium carbonate and cautiously smelled, Write down your observations Y () Name the type of organic compound formed by the reaction of compound P with compound R. 0} (8) Use your answers to (h) @) and the information in the stem of the question to i identify compound R. 0 Inorganic substances Most of the marks are for observations. You will normally be expected to identify: each unknown, and you may also be required to write an equation — eg. for a ligand exchange reaction, a tedox reaction or for a precipitation reaction. A typical mark distribution is: Observations z 3 or 10 marks Identification of each unlinowa [2073 marks Equation and/or comment | | or 2 marks ‘You will be given two or three d-block compounds as solids or as their solutions, Cations The cations will be limited to Cr+, Mn+, Fe2+, Fe*, Co?*, Ni*, Cu and Zn?*; and possibly K’, Na* and NH,?. Unit 3 and 6: Chemistry Laboratory Skis ¥ies The ionic equation for the precipitation of barium sulfate is: Ba aq) + 50% eq) > BaSO,(s) Content Guidance Anions | The anions will be limited to SO,2, Cl, Br, 2 and MnO, {Oy- and COs"; plus Crog-, CxO? Possible tests : Appearance of solid ‘You may be asked to comment on the colour and whether the solid is crystalline or Pa powder, Colour | Possible ions Colourless | Zn? Green FE CP NBO Blue cu Pinke Co Mine Orange | COP Yellow [Cro Purple MnOe ~ | | Appearance of dilute solution Colour [Pos Colourless | Zn, M Green Fe, Ce", NB | Ble [cu Pink __[co® Orange | CrO> Yellow | CrO,™ Purple | MnO, : Test for a sulfate | AlTew drops of dilute hydrochloric acid are added to the unknown solution followed | by a few drops of barium chloride solution, Observations | Inferences Whice precipcate v* | leis sulfate | *Somatimes the barium chloride is added fist, followed bythe hydrochloric acd. The observations then are wie precipitate W which stays on addition of hydrochloric aid Test for a halide ‘A few drops of dilute nitric acid are added to the unknown solution, followed by a few drops of silver nitrate solution. The solubility of the precipitate forme ammonia then tested in dilute and concentrated Edexcel ASIA2 ChemistryUnit 6 ee Tet [Observations inferences ‘Add dilute nitric acid to» | © White precipitate V turning | Itisa chlor solution of the unknown | purple on standing W; soluble in and then silver nitrate* dilute ammonia ¥ Test the precipitate: ‘© Cream precipitate V insoluble in | Its a bromides first with dilice ammonia | — qiute but soluble in concentrated “The tonic equation for the and then (no change) ammonia v precipitation ofa siver with concentrated © Yellow precipitate 7 insoluble in | ¢ It is an iodide | halide (where X stand: ee [gence vl rl a *Somatiies the siver nitrate is added frst, folowed by the nitric acid. The observations fora Agteq) +X Gd) > chioride then are white precipitate W which stays on addition tric acid v, 0) Tests for a carbonate Test =| Observations inferences, Heat the solid — cest | A gas is produced which eurns imewater | It is earbonate any gas evolved with | cloudy limewater Acid + solid —test | Bubbles ¥ (or fizing or effervescence) | Its carbonate any g35 evolved with | Limewater turns milkylcloudy limewater Test for a nitrate Tete chen ace ‘Observations — “inferences ‘Add Devarde's alloy (or aluminium | Bubbles (effervescence) powder) and dilute sodium v hydroxide and warm — test any gas evolved: either witha gass rod dipped in concentrated hydrochloric | © White smoke w” ® Itisa nfrate acid or with damp red lizmus © Litmus goes blue 7 Addition of sodium hydroxide until in excess ton. | Observations after a little NaOH added | Observations after exces | GQEMERTD Fe | Green precipitate v which goes brown on | Precipitate stays 7 gy Cesaibesec oor exits iting?” | precipitate and whether or = at - ot It dssolves in excess Green precipitate” | Forms green solution 7 eat there Green precipitate v Precipitave stays V : Cu?” | Blue precipitate 7 Precipicate stays 7 L Knowledge check 29 Ma | Oftavhite (butf or sandy) 7 precipitate which | Precipitate stays 7 ues dakeawon ear? Write the ionic equations To = fer adding 2 small amount Co | Blue precipitate 7 which goes pink on Precipitate stays 7 fer acing esa aon cule | ofaqueous sodium F = hydroxide to [Cr(Hy0)* Zot | White precipicato ¥ Forms colourless solution ¥ _ ions followed by excess 3 and 6:Chemistry Laboratory Skils 4Miiereeesen Write the ionic equations for adding a small amount of aqueous ammonia to [CulH,0)-P* ions, followed by excess Record the colour after adding potassium iodide and after adding starch, Content Guidance Addition of ammonia until in excess Ton_| Observations after a little NH, added Observations after excess Fe | Green precipitate ¥ which goes brown on Precipitate stays W standing C+* | Green precipitate W Precipitate slowly dissolves in concentrated ammonia to form green solution 7 N#* | Green precipitate W Forms blue solution v7 Cu | Pale blue precipitate 7 Forms dark blue solution 7 Mn?* | Off-whice (buff or sandy) # precipitate which Precipitate stays ¥ darkens on standing ¥ Co | Blue precipitate ¥ which goes pink on standing ¥ | Slowly forms brown solution Zn** | White precipitate ¥ Forms colourless solution 7 : Ligand exchange with hydrochloric acid | Hydrated copper(t) and cobalt(n) ions undergo ligand exchange when a few drops of E concentrated hydrochtoric acid are added, Ton Observations (CuHO}g* | Salucion goes green {ColH;0)-F* [Solution goes blue v7 The equation for the reaction of hydrated copperin) ions is: [Cu(H,O)g?*(aq) + 4CI-(aq) + [CuCl,)*taq) + 64,00) Redox tests Addition of potassium iodide ‘Aqueous potassium iodide is added to a solution containing the unknown ions, which oxidise the iodide ions to iodine. Starch solution is then added. Ton Observations Starchadded Fe Red—brown solution Blue-black colour v cu | Red-brown colour ¥ (with | Blue-black colour 7” precipitate) F [€rO)¥ or CrO,*inacid | Brown colour ¥ Blue-black colour ¥ Addition of aqueous chiorine (chlorine water) This is a redox reaction in which chlorine oxidises the unknown ion, Jon. | Observations Bro | Red colour ¥ 1 | Red-brown solution 73 goes blue-black ¥ when starch added Fe | Goes slightly brown 7; the Fe ions can then be tested using NaOH(aq) Edexcel ASIA2 Chemistry‘The ionic half-equation for the reduction of chlorine is: Ch{ag) + 2e- 20 aq) ' Addition of other oxidising agents lon to which an | Observations with hydrogen vations with lead(iv) oxidising agent is | peroxide asthe oxidising as the oxidising agent adde Bey agent followed by filtration Cin alkaline Yellow solution ¥ (of CrO?") _ | Yellow solution ¥ (of CrO?") solution Fe® in acid solution | Goes slightly brown V; Goes slightly brown ‘the Fe fons can then be tested | the Fe" ions can then be - using NaOH (aq) tested using NaOH(aq) eed ‘Assume that you have been given some sold hydrated copper() nitrate ‘Write down the observations that you would expect to make, The answers are on p. 72. (9) Note the appearance of the soli (De (0) Heat a smal sample ofthe slid, Write down your observations ai {© Dissolve some ofthe sold in water and then add aqueous ammonia, with shaking, Lntiin excess, Write down your observations. Qi {@) Dissolve the remainder ofthe solid in water and add potassium iodide solution. Then add 5 drops of starch solution, Write down your observations @ (© White an ionic equation, with state symbols, forthe reaction that took place when potassium iodide was added, “) (ees ‘Assure that you have been given some solid iron(i) sulfate ‘Write down the observations that you would expect to make. The answers are on p73. @) Note the colour afthe solid 0 (0) Dissolve the solid in water in a bolng tube. To one portion, add aqueous sodium hydroxide and allow to stand for a few minutes, Write down your observations. @ (9 To another portion, add dikite hydrochloric acid folowed by barium chloride solution, Write down your observations 0) (@ Toa third portion, add some solid lead(v) oxide and some dilute sulfuric acid, Warm gently for 3 minutes and fiter. Test the filtrate with aqueous sodium hydroxide, Write ‘down your observations we (eRe eee Assume that you have been given a solution of zinc bromide. ite down the observations that you would expect to make. The answers are on p. 73, @) Note the appearance of the solution. my (B To one portion, add aqueous sodium hydroxide unti in excess. Write down your observations. Q Unit 3 and 6 Chemistry Laboratory Skillsaaa Content Guidance 1 @ To another portion, add aqueous ammonia until in excess. Write down your ‘observations, Q (@) To a third portion, add dilute nitric acid followed by aqueous silver nitrate. Write down your observations. : (” (© Toa fourth portion, add aqueous chlorine. Write down your observations. “0 BYE) You must record: © Use spectra, information in the question and Ef) © the colourbefore and after the test your observations to work out the identity of an BIE @ the colour of any precipitate unknown © whether or not a precpitate dissolves in excess Teanslinertetedsio: & @ aldehydes, ketones, carboxylic acids, alechols and sodium hydroxide or excess ammonia. ae ‘You must be able to: © write equations or ligand exchange, redox and precipitation reactions _ Activity C: Quantitative measurement Full details of all the experiments assessing this activity will bé given to you just before starting the assessment. It is essential that you read them carefully before | starting any practical work. Redox titrations You will be required to titrate a solution of potassium manganate(w), which is in a burette, with 25.0cm? of a solution of a reducing agent to which acid kas been added. No indicator is needed because the titration is stopped when you see the "3 PP x | first permanent pink colour. This is due to a slight excess of the intensely coloured P g ly ‘You. must stop when MnO¢ ions. one drop of potassitm mangenate(vi) turns the |The reducing agent will be supplied as a solid and it must be weighed and made up solution pale pin, Eto 250cm? in a volumettic flask Possible errors © Not recording all masses to 2 decimal places. © Not rinsing all the reducing agent solution from the beaker into the volumetric flask. © Not shaking the volumetric flask sufficiently. Not rinsing out the burette with the potassium manganate(va) solution and the pipette with the reducing agent solution, « Not making sure that the part below the tap ofthe burett i filled before doing the You must record ai Volumes t0.0.05¢r¥, Thus a volume recorded as first titration, 23.6cm? would lose a mark | © Not obtaining two or more concordant titres — the difference between the largest st should be recorded and the smallest titres you use to caiculate the mean titre must not be greater than as 2360eW. P 02cm, 4 Edexcel ASIA2 Chemistry_ . E Knowledge check 34 * Manganate(wi) ions oxidise Se?* ions to Sot ions and Calculations You will be given the equation. The two most likely reactions are: © with iron(i) compounds as the reducing agents a Se? (aq) + MnO (ag) > SFe*faq) + Min? are reduced to Mn?* ions. “e*(aq) + MnOg (aq) + 8H*(aq) > 5Fe*+(aq) + Mn?*(aq) + 4H,0() 1 rut bthe'raenateett ‘where the number of moles of Fe’*= 5 x the males no,- toMn0,? «with ethanedioic acid, H,C,0,, or its salts as reducing agents 5,04? (aq) + 2MnOs-(aq) + 16H*(@q) > 10CO4(g) + 2Mn2*(aq) + BHZO()) where the number of moles of C,0,- Se the moles MnO, Note that the reaction between ethanedioate ions and manganate(vs) ions is very slow at room temperature, so the acidified ethanedioate solution must be heated belore being titrated. | Atypical mark scheme is: Table of masses and titrés | 2 marks 1 Calculation of mean titre | | mark ‘Accuracy of titration Tmarks Calculation 2or 3 marks Comments Tor 2 marks (CRM aee ‘951 g of an iron(i) compound, Z, was weighed out, dissolved in water and made up to 250cm% 25.0cm? portions were pipetted into a conical flask and some dilute sulfuric acid added. This solution was then titrated with 0.0202moldm”? potassium manganate(vt) Sf (aq) + MnO, eq) + BH (aq) —> SFe?* (aq) + Mn?*(aq) + 4H,0(0) and the mean titre was 24.05 cm, (@) Cakulate the mass of Fet* in 250m? of solution. @: (@) Cakulate the percentage ofiron in the sold Z, We {9 What would be the effect on the mean titre and the % of iron fsome of the compound Z had not been washed into the volumetric flask? Justify your answer, 2) ieee 159g ofa group | ethanedioste sat, M,C; was weighed out, dissolved in water and made upto 280cm?, 25.0cmn* aliquots were acidified and heated to 60°C. The hat solution was ‘ityated with 0.0202molden3 potassium manganate(a) solution. The mean titre was 23.65em 5C,0¢ (aq) + 2MnO,"(aq) + 16H" (aq) -> 10CO2(g) + 2Mn?*eq) + 8H,0() (@) Calculate the number of moles of ethanedioate ions in 2S0cm? of the solution. Qe (0) Use your answer to @) to calculate the molar mass of MC). and hence the identity ‘ofthe group | metal M. Q [Relative atomic masses: Li = 69; Na = 23.0; K = 39, Rb = 85.5) {© State and explain the effect onthe fist tite ifthe burette had been wet with and not rinsed out with some potassium manganate(\t) solution, w Unit 3 and 6: Chemistry Laboratory Skils 5Make sure that you record all volumes to 0.05 cm? andall pH values to | or 2 decimal places. Content Guidance pH titrations You will be asked to measure out, using a pipette, 25,0cm? of a solution of a weak acid and measure its pH using a probe and pH meter. A strong alkali, such as sodium hydroxide, of knownsconcentration is then added, initially in small amounts of between | and2cm*to get arough idea of the equivalence point. This is then repeated but adding the alkali in targer amounts until close to the equivalence point, when it is then added in 0.5 or 1.0cm? portions. After each addition, the pH of the solution is measured. The addition is continued until an excess of alkali has been added. You will be required to plot a graph of pH against volume of alkali, and then perform some calculations and make comments about accuracy. Errors in technique ‘© Aswith all titrations, make sure that you rinse out the pipette and burette with the appropriate solutions. © Make sure that the part of the burette below the tap is filled before starting the pH titration, © Make sure that you add the alkali in small amounts to start with and close to the end point. In between these it can be added in 6 or 10cm portions. Make sure that you stir the solution thoroughly with the pH probe after each addition of alkali, Failure to do this properly is a common error, Graph plotting © Make sure that you use at least half the graph paper—do not draw a tiny graph at the bottom left of the graph paper. ® Make sure that you label the y-axis (pH) and the x-axis (volume of alkali /cmn. © ‘The pH value before any alkali is added should be about pH = 3. It should rise sharply over the next 2 to 3cm? and then flatten off, slowly increasing before rising almost vertically as the equivalence point is reached (when the acid and the alkali are ina |! ratio by moles). It then flattens off again after about Scmn? of excess alkali has been added. To see what this looks like, look at the graph of the answer to Knowledge check 37 on page 73. ‘The buffer region runs from after the initial rise in pH (after about Scm? alkali has been added) to about 5cm* before the almost vertical part. This is when the ratio of [weak acid] : [salt] varies from about 5:1 to 1:6. A typical mark scheme i Table of readings - | 4 or 5 marks Graph 3s 2or3 marks Accuracy’ Zor 3 marks Calculations from graph —| 3 marks Comiients Vor 2 marks Edexcel ASIA2 Chemistry25.0crn ofa solution of a weak acid HX was measured into @ beaker andits pH measured. A | bourette was filed with 0.125 mold sodium hycroxide solution, This was added 2 lite ata time, with stirring, measuring the pH after each addition, The resus are shown below. Volume: of alkalilem?-| pH=|~>|-Volume of allealilem? |: pH>- = 0 29 19.00 57 100 38 19.50 59. 2.55 43 20.00 88 5.05 Hb] 21.05 Te mo —ja7_| | 23.00 uz 12.50 5.0 25.00 120 15.05 52 30.05 23 17.50 55 40.00 27 @ Plot graph of pH on the y-axis against volume of sodium hydroxide on the xaxis. (6) (b) Use your graph to find the volume of alkali needed to react with the 25.0cm? of the acid, HX (3) and the pH at the equivalence paint (1) (© Use your answer to (b) and the concentration of the sodium hydroxide solution given to calalate the concentration of the acd, HX. Q (@) Measure the pH at the point when half the acid has been neutralised, and hence i cakulate the value of pK, of the acid HX. Q {@) Use your answer to (d) to calculate the value of K, of the acid (Om (f) Over what pH range would the solution in the pH titration be able to act as a buffer? (1) (@ Comment on the accuracy ofthis method for finding the concentration of the acid compared with a normal acid/base tration. 0 Grime You must read the instructions completely before starting the experiment because, once you have started, there will E not be time to work out | what to do next Kinetic experiments Following a reaction at constant temperature This type of experiment is performed to find the order of reaction of one of the reactants Full details will be given and care must be taken to follow these instructions carefully ‘The procedure will be: (1) Measure out the reagents and catalyst solutions in two separate beakers, (2) Prepare the quenching reagent in a conical flask. (3) Fill a burette with a solution that will react rapidly with one reagent (or product) (4) Mix the contents of the two beakers and start a clock, (8) After § minutes remove a 10cm? sample, quench the reaction and titrate against the solution in the burette (6) Remove further samples every 5 minutes and quench and titrate. Unit 3 and 6: Chemistry Laboratory Skils aContent Guidance (es This method can be used to find the order of the reaction between propanone and Why must the J fodine in the presence of an acid catalyst: concentrations of propanone and acid be much larger than that of the iodine solution? CHACOCHG() + In(aq) Healalyst . cyscocu,taq) + Htaq) ‘The iodine in the samples removed is titrated against sodium thiosulfate solution A typical mark scheme is: [ Table of volumes of reagents, titres and times [3 or4marke Plotting of graph d Dor 3 marks Interpretation of graph 2or3 marks | Accuracy of experiment ‘marks Comments on experiment [Bor 4 marks (EE Using a measuring cylinder, 25 cm? of a solution af propanone was mixed with 25 cm? of dilute sulfuric acid in a beaker: 25 cm? ofa dilute iodine solution was measured out in another measuring cylinder Using a third measuring cylinder, 20cm? por put into conical asks, cf sodium hydrogencarbonate solution were A burette was filled with 0,0500moldm”3 sodium thiosulfate solution, The iodine solution was poured into the beaker containing the propanone and acd, stirred and a dock started. After 5 minutes, |Ocm? of the reaction mixture was removed and run into the sodium hydrogencarbonate to quench the reaction. This was then immediately {titrated with the sodium thiosulfate solution. 4 Another |Ocm} portion was then removed, quenched and titrated, until five portions had been removed, The results are shown below. Volume of [Volume of Volume of. [Volume of sodium | Propanone solution! | sulfuric acid! ~ | iodine solutioni' hydrogencarbonate em? cm? Lem? solutionlem3 5 25 [ss 20 Timemmin [5 [10 [15 [20 [25 | Titrefem? [10 [isa [108 [76 [40 | @ Plot a graph of ttre on the y-axs against time on the x-axis ®@ (©) Calcuate the slope (gradient) ofthis graph, 0 (© What does the slope of the graph measure? ”) {@) Use your answer to (€) to find the order ofthe reaction with respect to iodine, Jtstify your answer ® (@) Inthis experiment, the concentration of propanone was much larger than that of the iodine. Why is this necessary? 0 (f) Why isitnot necessary to use a pipette to measure the volume of propanone, sulfuric acid and iodine solutions? 0 (@) Why's itrecessary to add the reaction micture to aqueous sodium hydrogencarbonate? @ #8 Edexcel ASIA2 ChemistryUnit 6 Ea! (®) What would be produced ifsodium hydroxide and not sodium hydrogencarbonate had been used to quench the reaction? 0 () How would you modify the procedure to enable the order with respect to : propanone be found? Q Finding the activation energy of a reaction This method requires the time, for a particular stage in the reaction to be measured ata certain temperature, 7: The experiment is then repeated at different temperatures. The Arthenius equation connects the activation energy to the rate constant of the reaction: . logiok aR where Ris the gas constant and Tis the temperature in kelvin ‘A graph of logiok against + will give a straight line of slope a However, the rate constant is difficult to measure and a graph of logtrate), or the | log of anything proportional to the rate such as 1/t, will also give a straight line £ of slope ~Es : 23k 1 “fa 1a graph flog is potted against, the slope is ¢ 23R (See the answer to Knowledge check 40 on page 74) Atypical mark scheme is: 5 or 6 marks dinterprecatio 3 or 4 marks 4 marks | or 2 marks Activation energy of the reaction between sodium thiosulfate and acid Sodium thiosulfate reacts with nitric acid to produce a precipitate of sulfur: 8,03 (aq) + 2H*(aq) > 5(s) + SO,(aq) + H20(l) ‘The experiment is designed to time how long it takes for enough sulfur to be produced to hide a cross on the reaction vessel when looked at through the reaction mixture. ‘The experiment is repeated at different temperatures. Cee ee A.cross was marked on the outside ofa boiling tube with a biack waterproof marker. |Ocrn? of a solution of sodium thiosulfzte was putin the boling tube and its temperature measured. 10cm? of dilute nitric acid was putin atest tube. This was then poured into the boiling tube and the solution stirred with a thermometer. The time taken forthe crass to become invisble was recorded and the temperature of the solution retaken, More sodium thiosulfate and nitric add were then warmed separately in a beaker of water and the experiment repeated. Unit 3 and 6: Chemistry Laboratory Skils _ 8‘The graph should have ~LO atthe top of the yraxis going down to ~2.2 and 0.00300 on the left going up to 0.00340 on the | (© Use your graph to calculate the slape af the line yrs have drawn, righl on Use x-axis, Content Guidance ‘The results are shown below. Time, ts | Initial temperaturel°C | Final _ Mean temperature!"C temperature!"C 120 20 2 2 54 35 35 6 2% 50 8 0 | 5 a 58 © | Het’ Hogi | Mean ‘temperature, 71K | Lc! t t i 00883 | -2.08 24 0.00340 oars | -173 | 308, 0.00325 oss | -142 mm 0.00311 00667 | -118 333 0.00300 \ \ (9 Pata gah of I — sn 8 (©) What does the shape ofthe graph tell you about the relationship between the rate of reaction and the temperature? ”) !) | @ Calculate the activation energy of the reaction. Give a sgn and urits with your answer: (3) £ © Why cid the temperature rise slightly in 3¢ first experiment? a _ Activation energy of the reaction between magnesium and acid | This is another experiment that is suitable for measuring the time taken for a certain point to be reached and for repeating at different temperatures. Ifa large excess of acid is used, the rate of reaction will he approximately constant | because the surface area of the magnesium ribbon does not alter significantly. Thus ! the rate is proportional to 1/time, where the time is that for the magnesium ribbon to | disappear (see Test question 6 on p. 68) Read and record © all massesto O0Ig Dos and don'ts; solution © all volumes in titrations to 0.05 cr? © con't leave the funnel in the top of the burette © all pH values to at least one decimal place © read the question carefully before starting akinetic © make sure that you stirthe solution with the pH probe before taking reading © shake the flask thoroughly when making up a © only use concordant titres (+0.2cm?) when calculating the mean titre ‘experiment to make sure that you know what to do . Edexcel ASIA ChemistryUnit 6 ee Activity D: Preparation inall preparations, you will be asked to wark out the percentage yield, This will score 3 oof the 12 marks in the assessment. ‘The method is: (1) Work out the molar masses of both the reactant that you measured out and the product. (2)Use the expression number of moles = moles of reactant, @)ifthereactant and productare ina 1: | ratio in the balanced equation for the reaction, mass SSS _ to calculate the number of molar mass the theoretical number of moles of product = he number of moles of reactant. "The percentage yield fs hot (4) The theoretical mass ofthe product = moles x molar mass 5 mass of product x 190 | mass of reactant (6) yiekd -Sctual mass of product __ 993 | theoretical mass of product Organic preparations You will be asked to prepare an organic compound and then purify it. Finally its | melting or boiling point will be measured. Full details of the procedure will be given and you shiould follow them carefully. Technique ‘© You must know how to set up apparatus for simple distillation (see p. 32) and for: heating under reflux, as shown below. > Water out Condenser -Round-bostomed fask All masses must be recorded to 2 decimal places and volumes to | cm, Melting and boiling * Make sure that the water flows into the condenser atthe bottom and out at the top. © Check that all the joints are firm and that they will not leak * When carrying out distillation, check thatthe thermometer is opposite the entrance of the condenser. * You must know how to recrystallise a solid, 2 temperatures should be # You must know how to measure the melting point of a solid } recorded to I°C Unit 3 and 6 Chemistry Laboratory Skls Ii _ Methods of measuring melting temperatures There are two common procedures, () This method is only to be used if you have sufficient amounts of the solid. Some £ ofthe purified solid is placed in a boiling or test tube. ‘The water or oil is heated until the solid begins to melt. Note this temperature Now remove the tube from the beaker and allow it to cool while: ‘stirring the molten Solid with the thermometer. Note the temperature at which solid first begins to form. The melting temperature is the mean of these two values, (2)This method should be used when small amounts of solid are available. Take a capillary tube that has been sealed at one end and fill it toa depth of 05cm with your purified solid. Attach it, using @ rubber band, to a thermometer and inserl the thermometer in a water or an oil bath, Surrer ‘Thermometer Rabber band: }—Oi or water bath 2 Edexcel ASIA? ChemistryHeat the bath quickly until its temperature reaches about 20°C below the expected melting point. Then gradually increase the temperature until the solid melts. Note this approximate melting temperature, Let the oil or water bath coot slightly, and repeat with another sample of the solid n another capillary tube. Heat gery up to lose to the approximate melting. _ Moke suresraty "you str temperature of the solid, as found earlier. Record the temperature at which | thoroughly al the time that it melts. {you heat the liquid. Marking ‘The mark scheme for organic preparations will be similar to the following: i] 2 marks 3 marks 50% for 2 marks 10% but <50% for | mark I mark “42° = 2 marks 5° I mark #|2 marks Preparation of aspirin Aspirin is a solid phenolic ester made by the reaction of 2-hydroxybenzoic acid (salicylic acid) and ethanoic anhydride in the presence of phosphoric acid catalyst: A? HO, oO A NF OH oO + (CHCO,O ——> (ence) ° — cH, + CHCOOH Salle sed Aspirin Some 2-iydroxybenzoic acid is weighed out and put in a distillation flask together with excess ethanoic anhytlride. Then § drops of phosphoric acid are added and a reflux condenser is ilted. The mixture is heated on a boiling water bath for § minutes and then some water is carefully added down the reflux condenser. This hydrolyses the excess ethanoic anhydride Your mass of purified aspirin should be similar to the mass of ‘The pure, dry aspirin is weighed, and finally the melting temperature of the aspirin is | 2shydroxybeneoie ackd measured. This should be between 134 and 135°C. originally taken. The mixture is poured into a beaker of cold water and stood in an ice bath, The mixture is filtered using suction filtration, and the solid obtained is recrystallised using hot water. Unit 3 and 6 Chemistry Laboratory Skils 3Content Guidance AL Knowledge check 41 The folowing questions are about the preparation of asprin, (0) What type of impurity is removed in the second fitration during recrystalisation? © (I) | {@) Describe the appearance of your sample of aspirin, “ | (b) Calculate the theoretical yield of aspirin starting with 4.00g of 2-hydroxybenzoic acid, (2) (© Why is the actual yield less than 100%? 0) E @) Why isitrnecessary to heat the sample slowly (at about 2°C per minute close to ‘the metting point) when measuring the melting temperature? (I) I {€) What type of impurity is removed in the frst filtration during reerystalistion? (i) | ‘of aspirin had been made from |.0g of salicylic acid? (@) What would be formed if?-hycroxybenzoic acid was warmed with methanol in the presence of concentrated sulfuric acid? (i) ‘What is the % yield if 0.95 Preparation of methyl 3-nitrobenzoate Methyl 3-nitrobenzoate is a solid ester made by the nitration of methyl benzoate. it Ox, OH, On -0 tH, j = i ) HS0, OC} ve 22 GO] oe q oe ee NO, A known volume of methyl benzoate is carefully mixed with some concentrated i sulfuric acid in a flask. A nitrating mixture of cooled concentrated sulfuric and nitric || Make sure that you use acid is then added in small portions and the temperature maintained between 5 and the minimum amount 15°C, The flask is allowed to warm up to room temperature and left to stand for 15. ‘1 ofhot ethanol when minutes. The contents are then poured onio some ice and stirred, The mixture is recrystalliing the product. filtered using suction, and the solid washed with a litle ice-cold ethanol ‘The solid is then recrystallised using ethanol as the solvent and is allowed to dry. | When dry, it is weighed and its melting point is determined in the usual way. The | melting point should be between 78 and 80°C. (eRe The following questions are about the preparation of methy! 3-itrobenzoate | @ Describe the appearance of your product. a © Calculate the theo yield of methy| 2-nitrobercoate starting methyl benzoate (density = LO ger) 8 @ Ifthe mass of your product was 5.05g, what was your % yield? Q | (© Why must the temperature during the nitration be kept at or below room | temperature! wy || Mekeswe thatyouryied | (© Ment the electrophie in tis reaction “ |) isateastOBgper len? of | () Why the recrystalzed sold washed wth ate ice-cold etal before being alowed i methyl benzoate to dry? W Edexcel ASIA2 ChemistryUnit 6 ae Inorganic preparation ‘You willbe given full instructions which must be followed carefully, You will be required to prepare a solid containing a complex transition metal ion, £ such as [Cu(NH3)4]"*SO_> or chromium(i) ethanoate, [Cry(CHsCOO}4(H20)) Preparation of tetraamminecopper(ti) sulfate ‘Some solid coppertt) sulfate, CuSO, 51,0, is weighed outand dissolvedin the minimum of water. Aqueous ammonia solution is added steadily, with stirring, until in excess. Ethanol is added to this solution and a precipitate of the copperti) complex salt; [Cu(NH;)4]SO, is formed. This is separated from the aqueous layer by suction filtration and the solid washed with ethanol and allowed to dry. Finally itis weighed Alypical mark scheme for an inorganic preparation is of ics [ or 3 marks Lor 2 marks Lor 2 marks 2or 3 marks | Errors in technique © Dissalving the solid in too much water. © Leaving behind some of the solid product before suction filtration, ‘© Washing the filtered solid with too much solvent. Errors in recording © Not making sure that all masses are recorded to 2 decimal places — a mass written a5 12.6 will lose a mark i © Not checking all subtractions when working out the mass of solid taken and the; mass of product, eae The following questions assume tht [Cu(NHh).JSO, has been prepared (@ What would you observe as the ammonia solution was added to the copper(t) sulfate solution? (8) Deserve the appearance of your product. {© Assuming that you took 600g of sold hydrated copper( sulfate, CuSO,5H,O, calculate the theoretical yield of the complex salt, [Cu(NH4},]SOy. @ @) Assuming that you made 468g of product, what is your yield? ( (@) Name the type of reaction between hydrated copper) ions and excess ammonia. (I) (Suggest a reason wi the yield i ess than 100% 0 () What was the purpose of adding ethanol to the reaction mixture! W (P) Why was the product washed with ethanol after suction fitration? We Unit 3 and & Chemistry Laboratory Skis_ Preparation of a chromium(t)) ethanoate complex i ‘Weigh some sodium dichromate(w), dissolve it in water and pour the solution into a round-bottomed flask, Add a mixture of powdered and granulated zinc. Pour some saturated sodium ethanoate solution into a boiling tube and assemble the apparalus as in the diagram below. Carefully add a mixture of concentrated hydrochloric acid | and water made up in 2:1 ratio. Make sure that the screw cap is loose, Sodium élehromate(y), hydrochloric acid and ine The dichromate(v) ions are first reduced to green Cr** ions, and then to blue Cr? ions. 1 When the solution is blue, screw the cap shut, The solution of Cr* ions is forced out into the sodium ethanoate solution by the pressure of the hydrogen being produced Ared precipitate of the neutral chromiumi(t) complex (Cra(CHyCOO},(11,0}p] is formed, | Filter this precipitate under suction, wash it with a trace of ice-cold propanone and ‘weigh it Eee ‘The following questions are about the preparation of a chromium(i) ethanoate complex, £ @) Calculate the theoretical yield of the chromiumn(i) ethanoate complex — assume that you took 2.22¢ of sodium dichromate) Q (©) Calculate the % yield ofthe experiment — assume that you made 191 g ofthe complex. w | © Whyis the yieé ess than 100% @ (©) Write the ionic half-equations for the reduction of Cr0,?> ions in acid solution 10. C* ions, and Cr3* ions to Cr ions, @ (©) Why was the screw cap left open unti the solution went blue? oO | (0) Why do the chromium) ethanoate complex and the hydrated cchromiumti) ion have different colours? oO © Make sure that your yield is >50%, © Make sure that you know how to measure melting | @ Remember to record all masses to 00l g temperatures and how to recrystalse a sold. all volumes to | cm? and meting temperatures @ Record the shape and colour of an inorganic | to IPC. product. | — i Edexcel ASIA2 ChemistryManganate Redox Titrations ‘The purple colour of manganate can makeit The redox titration between Fe with MnO,- (purple) is avery common difficult to see the bottom af meniscus in ‘exercise. This titration is self indicating because ofthe significant colour _the burette. change from reactant to product, Hf the manganateis in the burette then the ‘Min, aq) + BH (oo) + SFe* oa) Min? fag] + 4H,0 i+ SFe™ lag) ‘end point ofthe titration will e the fest Purple colourless Permanent pink colour. Colouriess > purple Detailed Procedure : how much iron in iron tablets + Weigh accurately two "ferrous sulphate’ tablets * Grind up the tablets with a little 1M sulphuric acid, using a pestle and mortar. + Through 2 funnel, transfer the resulting paste into a 100em® volumetric flask. Use further small volumes of 1 M sulphuric acid to rinse the ground-up tablets into the flask, * Then add sufficient 1M suiphuricacid to make up the solution to exactly 100em?. Stopper the flask and shake it to ‘make sure that all the contents are thoroughly mixes. They will not all bein solution although the Fe?* ions which were present in the tablets willbe dissolved + Titrate 10.0 em? portions ofthe solution with 0.0050 M potassium manganate(Vi). The end-point is marked by the first permanent purple colour. Choosing correct acid for manganate titrations, “The acid is needed to supply the 8H" fons. Some acids are not suitable as they set up alternative redox reactions and hence make the titration readings inaccurate. Only use dilute sulphuric acid for manganate titrations. lnsufficent volumes of sulphuric acid will mean the solution isnot acidic enough and MnO, will be produced instead of Min [MnO {aq) + 44'(aq) + 3e- > MnO, (s) + 2H,0 The brown MnO, will mask the colour change and lead to a greater (inaccurate) volume of Manganate being used in the titration, Using a weak acd like ethanoie acid would have the same effect as it eannet supply the large amount of hydrogen, jons needed (8H") {eannot be cone HCl as the CI ions would be oxidised to Cl, by MnO, as the E® MaO,/Mn > E> C1,/¢h MnO tag) + BH*(aq) + Se~ > Mn?*(aq) + 41,00) E44.51V Gi,lag) +2¢° 3 2Cr(aq) E#1.36V “This would lead to a greater volume of manganate being used and polsonous Ct, being produced. Itcannotbe nitric acid as it is an oxidising agent, It oxidises Fe? to Fe™ as E® NO,/HNO,> E* Fe™/Fe®* NOS (aq) +34"(aq)+2e° > HNO, (aq) + H,0(H) E° #0.94V Fe’ (aq}+e" > Fe** (aq) E4O77V This would lead to 3 smaller volume of manganate being used. Example 3. Manganate titration Step :find moles of KMa0, A2.41g nail made from an alloy containing ron is dissolved in 100cm* acid. The solution formed contains 002% 3.8/1000 Felt) ions este :10cm* pertions ofthis solution are titrated with potassium manganate (Vil) solution af 0.020. $.80em? of KiinO, were needed to resct with the solution containing the iron. What isthe percentage of ron by mass In the nail? ‘Step 2: using belanced equation find motes Fe in 10cm? oes of KMNO, X'S =9.8x104 mol Step 3:find moles Fe™ in 200m 8x10 molx 19 10% mal Step 4 find mass of Fe in 8.8110 mol rmass= moles x RAM = 9.820955: MnO ging) * 8H yg) + SFG “> Ming + 4H,0 + Se sae Step Sfiné % mass 547/2.41x100 l 226% masOther useful manganate titrations With hydrogen peroxide Ox #,0; > 0, + 2H" +2e ed Mn0,(aq) + 8H"(aq) + Se” > Mn? (aq) + 4H,0 Overall 2M1n0, (aq) + 6H"(aq) + SH,O, > 50, + 2Min?*(aq) +8H,0 With ethanedioate 0x €,02° > 2€0, +26 Red MnO, aq) + BH"(aq) + Se” > Min?*{aa} + 44,0 Overall 2MiaOg aq) + 16H*(eq) +5C,0,2 (29) > LOCO. te) + 20An*(aq) + BHO") With iron (i) ethanedioate both the Fe'* and the C,0,* react with the MnO, MnO, reacts with SFe* and 2 MnO, reacts with SC,0,2 Ma0;{aq) + BH’(aq) + SFe* > Mn (aq) + 41,04 SFe 2MnO, (aq) + 16H*(aq) + 5C,0,2 > 10C0, + 2Mn* (aq) + 8H,0 50 overall 3NIn0 (aq) + 24H"(aq) + 5FeC,O, -> 10CO, + 3Mn* (ag) + SFe™* +12H,0 So overall the ratios 3 Mn0,’to 5 FeC,O, ‘The reaction between MnOy and 0,2 Is slow to begin with (as the reaction is between two negative ions), To do asa titration the conical flask can be heated to 60° C10 speed up the initial reaction. Example 4 A LAI2 ¢ sample of impure FeC,0,.2H,0 was dissolved in an excess of cilute sulphuric acid ‘and made up to 250 cm* of solution. 25.0 cm? Of this solution decolourised 23.45 cm? of a (0.0189 mol dm? solution of potassium manganate(Vii Whats the percentage by mass of FeC,0,.2H,0 in the original sample? EDTA titrations Stept : find moles of Kino, moles = conex vol | 0.0189 x 23.45/1000 2 4.83x104 mol Step 2: using balanced equation find moles FeC,0,.2H,0 in 25cm? = moles of KMnO, = 7.39x10% mol 5/3 [see above for ratio} ‘Step 3: find moles FeC,0,.2H,0 In 250 em? = 738x104 mol x1 = 739x103 mol ‘Step 4 find mass of FeC,0,.2H,0 in 0 7.39103 enol mass= moles x Mr= 729x108 x 179.8 = 1.335 Step 5; find % mass sass = 1.33/1.412 x10 294.1% ‘The formation of the stable EDTA complex with metal ions can with the choice of suitable indicator be done in 2 quantitative titration [cuth,0)* + EDTAY > [CU[EDTA + 64,0 Example 5 ‘A river was polluted with copper() ions. 25.0 cm* sample ofthe river water was titrated with 20.0150 ‘mol dm solution of EDTA, 6.45 crn? were required for complete reaction. Calculate the concentration, in mol dirv3, of copper) ions in the river water. Step! :find moles of EOTAY moles = conex vel = 0.0150 x 6.45/1000 = 9.68410 mol ‘Step 2: using balanced equation find moles Cu At ratio = 9,68x10 mol Step 3 : find cone Cu* in 25em* = 9.68x10% /0.025 0.00387 mold" Always the same 1:1 ratio with any metal ionUncertainty Readings and Measurements ‘Measurements the values taken as the difference between the Readings ] the values found from asingle | judgement when using a place of equipment judgements of two values — — (e.g using 2 burette ina titration) ‘The uncertainty of a reading (one judgement) is at least 20.5 of the smallest scale reading. The uncertainty of a measurement (two judgements) Js atleast 1 of the smallest scale reading. Calculating Apparatus Uncertainties Each type of apparatus has a sensitivity uncertainty sbalance 0.001 g volumetric flask 0.1 em? "25.em* pipette 0.1 en? sburette (start & end readings and end point) 0.15 ems Suncertainty=3__ uncertainty x10 Measurement made on apparatus eg. forburette Souncertainty = 0.15/average titre res 00 result add all the incividual equigment uncertainties together. Calculate the percentage errar for each piece of equipment used by To caleulate the maximum percentage apparatus uncertainty in the final To decrease the apparatus uncertainties you can either decrease the sensitivity Uncertainty by using apparatus with 2 _reater resolution (finer scale dhvisions ] or ‘you can Increase the size of the measurement made, —- Uncertainty of a measurement using 2 bburette If the burette used in the titration had an uncertainty for each reading of +/— 0.05 cm? then during a titration two readings would be taken so the uncertainty on the titre volume would be #/-0.10 em? . Then often another 0.05 is added on because of uncertainty Identifying the end point colour change Reducing uncertainties in a titration lower apparatus uncertainty wl lo the error the concentration of the substance in the burette, Replacing measuring cylinders with pipettes or burettes which have “To reduce the uncertainty ina burette reading itis necessary to make ‘the titre a larger volume. This could le done by: increasing the volume and concentration of the substance in the conical flask or by decreasing Iflooking at a series of measurements in an investigation, the experiments with the smallest readings will have the highest experimental uncertainties. Reducing uncertainties in measuring mass Using a mare accurate balance or a larger mass willreduce the ‘uncertainty in weighing 2 solid Weighing sample before and after addition and then calculating difference will ensure a more accurate measurement of the mass added. Calculating the percentage difference batween the actual value and the calculated value If we calculated an Mr of 203 and the real value is 214, then the calculation isa follows: If the stuncertainty due to the apparatus < percentage clfference between the actual value and the calculated value then there isa ciscrepancy in the result due to other errors. ithe stuncertainty due to the apparatus > percentage difference between the actval value and the calculated vvalue then there is no discrepancy and ll errors in the results can be explained by the sensitivity of the equipment.Required Activity 3. Investigation of how the rate of a reaction changes with temperature Experiment: sodium thiosulfate and hydrochloric acid In tine experiment aetween sodium thiosulfate and hydrochloric acid we usvally measure reaction rate as 1/time where the time isthe time taken for a crass placed underneath the reaction mixture to disappear due to the cloudiness of the Sulfur Nas5O,+ 2HC) > 2NaCl +50, +5+4:0 isis an approximation for initial rate of reaction as it does not include the change in Ereentston tat Wecan ure tetoesune me avasaene te amount of Sulfur x produced to block out the cross in each experiment is the same and constant so each time ‘we do the experiment the same amount of sulphur is produced. The change in concentration of sulfur therefore the same for each experiment so only the time taken to. 4 reach this concentration is relevant. ‘Typical Method ‘»Measure 10 em? of 0.2M hydrochloric acid and 10 cm? of sodium thiosulfate in separate clean measuring oflinders. Put the solutions in separate boiling tubes ‘Choose a temperature to investigate use water bath to get the twa solutions to that temperature by placing the boiling tubes in the water bath ‘Place the flask on the centre of the large cross; frst add the sodium thigsulfate to the flask. Then add the hydrochloric acid and start the stopwatch and swirl to mix the solutions. ‘Stop the clock when the crass disappears and note the time, “Repeat the experiment for four more different temperatures (maximum temperature should be 70 °C) Analysis of results to calculate Activation Energy ‘The Archenius equation can be rearranged Ink= constant = Ea/(R7) = a Gradient = - Kis proportional tothe rate of reaction so Ink canbe 2 far replaced by Irate) & fa = - gradient xR From plotting a graph of In{rate) or In k against 1/F the Barso activation energy can be calevated from measuring the sradient ofthe line Example 8 w 0.0023 0.003 0031 0.0082 00330034 Feperatore Tee T 16 TK) vt @ | ar | ow amon 2973 | ocoss6a | 53 | oorsass | 39703} 21 . sins | coos | 26 | oonesr | siz} 5 3u72_| ooossss | 1s | ons | -azae| 325 ” ss_[ oooser [12 [ous [aus | § , 3356 | oomss [6 | oncs667 | ars ° a6 c fnk=y [The gradient ehowe SoMa Yoet | always be ve 4a " In above example gradient =-5680 use a line of best fit Ea =-gradient xR (8.31) use all graph paper $680 x8.31 ‘choose points far apart on the graph to 227200) mol calculate the gradient ‘The unit of Ea using this equation will be Jmol, Convert Into Kd mol" by dividing 2000 fa=M72W moltRequired activity 4: Testing for cati ns: Group 2, NH,* ‘Method: adding dilute sodium hydroxide 3a} Place about 10 drops of 0.1 mol dm metal ion salationin # test tube. b) Add about 10 drops of 0.6 mol dm sodium hydroxide solution, mixing wel ©) Continue to aéd sodium hydroxide solution, dropwise with gentle shaking, untilin excess This test can be used on group 2 metal ions and transition metal ions. Results for Group 2 - ‘The results inthis test are an application of the trend that group Il hydroxides become more soluble down the group Magnesium hydroxide is classed as insoluble in water and ul gppear ass white precbitane, ‘A suspension of magnesium hydroxide in water will appear slighty alkaline (pH 9) so same ‘Simplest lone Equation for formation of Mg(OH), (s} hydroxide ions must therefore have been | Me? (aq) + 204{ag) > MelOH(s produced by a very slight dissolving, Calcium hydroxide is classed as partially soluble in water and will appear asa white precipitate (it may need more sodiurn hydroxide to be added before it appears compared toa ‘magnesium solution.) ‘A suspension of calcium hydroxide in water will ‘appear more alkaline (aH 14) than magnesium hydroxide as itis more soluble so there will be | Simplest ionic Equation fr formation of Ca(OH) (3 ocerietrantde lens presentan selution; C3 (aq) + 20H¢%@q) > CalOH), (3). Strontium and barium salts will nt form a hydroxide precipitate on addition of sodium hydroxide due to their high solubility. The solutions wil be highly alkaline Results for Group 3 Aluminium salts will form a white precipitate of [AIH O,)40) + 30H fea AUH,O) (OMI yy 3HO 9) aluminium hydroxide which will dissalve In excess sodium hydroxide to farm a colourless solution ANHLON(OH)s ig + OF aq) FANOHMT a 340 Results for transition metals Copper solutions form a blue ppt, [CulH:O}T* jag #ZOH og CulHaO}e(OHIe 4 * 24,0 py iron {l) solutions form a green ppt (FelH, Oh} (gq) # 20H ug > FetHzO),(OH), a 2H,0 ») iran (il) solutions form a brown ppt [FetH.O}.I* (ug) * 30H ug) > CUlHO}s(OHDs y+ 3H2O Testing for Ammonium ions (NH,) 8) Place about 10 drops of 0.1 nol drs’ ammonium chloride in atest tube Results: alkaline b) Add about 10 drops of 04 mol dir sodium hydroxide solution. Shake the mixture | ammonia gas is released «}__Warm the mixture in the test tube gently using a water bath Wwhieh turns the red 6). Test the fumes released from the mixture by holding apiece of damped litmus litmus paper blue aperin the mouth of the test tube. ‘The results in this test are an application of the trend that Group I! sulfates become less soluble down the group ‘Method: adding sulfate ions 2} Place about 10 drogs of 0.1 mol dm-3 metal ion solution in atest tube. bb] Add about 10 drops of 1.0 mal dm sulfuric acd (or other soluble sulfate solution. ¢) Continue to add sulfuric acid solution, dropwise with gentle shaking, until in excess ‘magnesium and calcium salts will not form a sulfate precipitate on addition of sulfate ions due to their high soluality Strontium and berium solutions will form white precipitates with addition of suifate fons Full equation : Srl,{a] + Na,S0, (aq) > 2NaCl (ag) + 550, (5) lonic equation: S* (aq) + $0,*(aq) > $150, (3. lanic equation: Ba** (eq + $0,*(aq) > BaSO, (3).Required activity 4: Testing for anion: Group 7 (halide ions), OH, CO," SO, Testing for presence of a sulfate ion BaCl, solution acidified with hydrochloric acid is used as a reagent to test for sulphate ions. If acidified Barium Chloride is added to a solution that contains sulfate ions @ white precipitate of Barium Sulfate forms (Other anions should give a negative result which is no precipitate forming Simplest ionic equation Ba (aq) + S0,"aq) > 8aS0, (3). ‘The hydrochloric acid is needed to react with carbonate Impurities that are often found in salts which would form a white Barium carbonate precipitate and so give a false result. You could not used sulphuric acid because it contains sulphate lons and so would glve a false positive result 2HCI + Na,CO, > 2NaCl + H,0+C0, Fiating due to CO, would be observed if a carbonate was present. ‘Testing for presence of halide ions with silver nitrate. ‘The role of nitric aids to react with any carbonates present to prevent formation of the This reaction is used as 3 test to identify which halide im is precipitate Ag,COs, This would mack the desired present. The test solution is made acidic with nitrie acld, and observations ‘then Silver nitrate solution is added dropwise | aiwo, +10,c0,> aniavo,+h0+c0, Fluorides produce no precipitate Chlorides produce a white precipitate ‘Ag'(aq) + CF (a9) > AgCI) Bromides produce a cream precipitate ‘Ag'{aq) + Br (aq) > AgBris) lodides produce a pale yellow precipitate As'leg)+ (eq) > Aals) The silver halide precipitates can be treated with ammonia solution to help differentiate between them If the colours laok similar: Silver chloride dissolves in dilute ammonia to form a complex ion AgOls) + 2NH fog) FARINA (a) + Ct (2 Colourless solution Silver bromide dissolves in concentrated ammonia to form 2 complexion ‘AgBr(s) + 2NHa(aq) > [Ae{NH),I° (aq) + Br°(aa) Colourless salution Sliver iodide does not react with ammonia ~ itis to0 insoluble. ‘Testing for presence of carbonate ions ‘Add any dilute acid and observe effervescence. ‘Bubble gas through limewater to test for CO,—will turn limewater cloudy Fizzing due to CO, would be observed if carbonate was 2HCL+ Ma,CO,-> 2NaCl+H,0+C0, present Testing for presence of a hydroxide ions Alkaline hydroxide ions wil turn blue litmus paper eed