Notes Qualitative Analysis (Raffles Institution Year 4 Chemistry)

Types of Reactions 1. Precipitation Reaction (forming a solid) 2NaOH (aq) + ZnCl2 (aq) Zn(OH)2 (s) + 2NaCl (aq) 2. Acid-Base Reaction H2SO4 (aq) + 2NaOH (aq) Na2SO4 (aq) + 2H2O (l) 3. Redox Reaction Metal + Non-Metal: 2Na + Cl2 2NaCl Combustion: C + O2 CO2 Displacement: Cl2 + 2KI 2KCl + I2 Others: 2FeCl2 + Cl2 2FeCl3 4. Decomposition CuCO3 CuO + CO3 5. Complex Formation Zn(OH)2 (s) + 2NaOH (aq) Na2Zn(OH)4 (aq) Zn(OH)2 dissolves in NaOH to form an aqueous complex salt (sodium zincate). How to know if two aqueous compounds will react? If you switch the ions around and a gas/pure liquid/solid would form, there is a driving force for reaction. Hence, it will react.

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Physical Tests to Identify Substances pH pH test is used to determine the acidity and alkalinity of a substance. However, the pH test cannot be used to identify an unknown substance without other tests. Colour Most substances can be identified by their distinctive colour. Colour White Blue Green Dirty Green Pale Green Orange Yellow Pale Yellow Greenish Yellow Purple Colourless Black Reddish Brown Colour Blue Brown/Reddish Brown Orange Yellow/Brown Purple Pale Red Violet Smell Most gases are odourless. For example, oxygen, hydrogen and carbon dioxide are odourless. Other gases have very distinguishing smell. For example, ammonia gas has a pungent smell, sulfur dioxide smells of burnt matches and chlorine gas has a choking odour. Done by Goh Zuo Min 4M Compound BaSO4, PbSO4, CaSO4, PbCl2, AgCl Most Na+, K+, Ca2+, Zn2+, Al3+, Pb2+, NH4+ Compounds All Cu2+ Compounds except CuO, CuCl2, CuCO3 All Ni2+ Compounds, All Cr3+ Compounds, CuCO3, CuCl2 Fe(OH)2 All Fe2+ Compounds, FeSO4 K2Cr2O7, Pb3O4 PbI2, ZnO (yellow when hot, white when cooled) AgI Cl2 gas KMnO4 Most gases (e.g. O2, CO2) CuO, C, MnO2, I2, Metal powder like Fe filings Fe(OH)3, Cu (reddish brown/pink/brown) Liquid Cu2+ (aq) Compounds I2 (aq), Br2 (aq) K2Cr2O7 (aq) FeCl3 (aq) KMnO4 (aq) Co(NO3)2 (aq) I2 dissolved in organic solvent

Solubility in Water The solubility test is very useful If an unknown substance is soluble in water, it may be sodium chloride but it cannot be silver chloride or barium sulfate as they are insoluble. Flame Test Oxygen relights a glowing splint. Carbon dioxide extinguishes a burning split. Hydrogen extinguishes a burning splint with a pop sound. Solubility Rules All carbonates, hydroxides, oxides are insoluble except Group I and SPA. All nitrates, Group I, SPA are soluble. All chloride, iodides, bromides are soluble except LS. All sulfates soluble except LBC. LS = Lead(II), Silver LBC = Lead(II), Barium, Calcium SPA = Sodium, Potassium, Ammonium Compounds

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Identification of Cations 1. Cations are positively charged ions, which are usually derived from metals. 2. Cations react and form precipitates with alkalis. 3. From the colour of the precipitate (insoluble metal hydroxides) and whether the precipitate is soluble in excess alkali, the cations can be identified. 4. Cations are identified using two types of test reagents a. Aqueous sodium hydroxide b. Aqueous ammonia Testing Using Aqueous Sodium Hydroxide (NaOH) Sodium hydroxide dissociates into sodium ions and hydroxide ions in water. NaOH (aq) Na+ (aq) + OH- (aq) 1. Add a few drops of NaOH (aq) to the sample salt solution. 2. Observe for any changes (formation of precipitates, effervescence) 3. Add NaOH (aq) in excess until no further change is observed (dissolution of precipitate) Cation Ca2+ Pb2+ Al3+ Zn2+ Cu2+ Fe2+ Fe3+ NH4+ Precipitate formed White, Ca(OH)2 White, Pb(OH)2 White, Al(OH)3 White, Zn(OH)2 Blue, Cu(OH)2 Dirty Green, Fe(OH)2 Reddish Brown, Fe(OH)3 No Precipitate Solubility in Excess Insoluble Dissolves, Colourless Solution Dissolves, Colourless Solution Dissolves, Colourless Solution Insoluble Insoluble Insoluble -

Lead hydroxide, zinc hydroxide and aluminum hydroxide are amphoteric hydroxides. They react with excess sodium hydroxide to form complex salts that are soluble in water. Lead(II) ions can be distinguished from aluminum(III) ions by the addition of chlorine ions. Lead(II) chloride is insoluble while aluminum(III) chloride is soluble. Lead(II) ions can be distinguished from aluminum(III) ions by the addition of aqueous potassium iodide. Pb2+ ions form bright yellow lead(II) iodide, while Al3+ has no visible reaction.

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The green precipitate of iron(II) hydroxide turns brown in contact with air due to the slow oxidation of Fe2+ to Fe3+ by oxygen. This is a possible source of error during qualitative analysis. To test for ammonium, NH4+, warm the mixture. Pungent ammonia gas should evolve and it will turn damp red litmus paper blue. Ammonium does not need the aqueous ammonia test. Testing Using Aqueous Ammonia (NH3) Ammonia dissociates partially to form ammonium and hydroxide ions in water. NH3 (g) + H2O (l) NH4+ (aq) + OH- (aq) 1. Add a few drops of NH4OH (aq) to the sample salt solution. 2. Observe for any changes (formation of precipitates, effervescence) 3. Add NH4OH (aq) in excess until no further change is observed (dissolution of the precipitate) Cation Ca2+ Pb2+ Al3+ Zn2+ Cu2+ Fe2+ Fe3+ NH4+ Precipitate formed No Precipitate White, Pb(OH)2 White, Al(OH)3 White, Zn(OH)2 Light Blue, Cu(OH)2 Green, Fe(OH)2 Reddish Brown, Fe(OH)3 No reaction Solubility in Excess Insoluble Insoluble Dissolves, Colourless Solution Dissolves, Deep Blue Solution Insoluble Insoluble No Reaction

Only zinc hydroxide and copper(II) hydroxide dissolve in excess aqueous ammonia because they form soluble complex ions in excess aqueous ammonia. Aqueous ammonia is a weak base and does not have enough OH- ions to form the Ca(OH)2 precipitate.

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Identification of Anions 1. Anions are negatively charged ions, which are usually derived from non-metals. 2. The tests used to identify anions are specific and yield distinct results for different anions. 3. Anions are usually identified using four types of test reagents. a. Aqueous silver nitrate/nitric acid b. Aqueous barium nitrate/nitric acid c. Aqueous lead(II) nitrate/nitric acid d. Aqueous sodium hydroxide/aluminum foil Observations of Anion Tests Anion CO32Test Add dilute hydrochloric acid. Observation Effervescence. Carbon dioxide gas is produced. The gas forms a white precipitate with limewater. White precipitate AgCl is formed. Yellow precipitate PbI2 is formed White precipitate BaSO4 is formed. Pungent ammonia gas is produced. The gas turns damp red litmus paper blue.

ClISO42NO3-

Add dilute nitric acid, followed by aqueous silver nitrate. Add dilute nitric acid, followed by aqueous lead(II) nitrate. Add dilute nitric acid, followed by aqueous barium nitrate. Add aqueous sodium hydroxide, followed by a small amount of aluminum powder or Devardas alloy. Warm the mixture.

NO3- cannot be used in above tests, since the reagents are nitrates.

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Identification of Gases Identification Test for Gases using Colour and Odour Gas H2 O2 CO2 NH3 SO2 Cl2 I2 HCl NO2 Colour Colourless Colourless Colourless Colourless Colourless Greenish Yellow Violet Colourless Brown Odour Odourless Odourless Odourless Pungent Smell of Burnt Matches Choking Odourless Choking Pungent

Identification Test for Gas using Specific Chemical Tests Gas NH3 CO2 Cl2 H2 O2 SO2 HCl Observation Gas turns damp red litmus paper blue Gas forms a white precipitate when bubbled in limewater Gas turns damp blue litmus paper red, then bleaches Gas extinguishes lighted splint with a pop sound Gas relights a glowing splint Reacts with acidified potassium dichromate (VI) to turn orange K2Cr2O7 to green Gas turns damp blue litmus paper red; Reacts with NH3 to produce dense white fumes

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