CONTENTS
SECTION 1 Volumetric analysis 1.1 Important formulae 1.2 Acid-base titration Colour change of acid-base indicators at end point Chemical equations for acid-base titrations 1.3 Potassium manganate(VII), KMnO4, titration Balancing half-equations Balancing ionic equations for redox reactions Important half-equations for KMnO4 titrations Important ionic equations for KMnO4 titrations Precautions in KMnO4 titration 1.4 Iodine-sodium thiosulphate (Na2S2O3) titration Important equations for iodine-sodium thiosulphate titrations Precautions in iodine-sodium thiosulphate titrations
SECTION 3 Qualitative analysis Table 1 Table 2 Table 3 Table 4 Table 5 Table 6 Table 7 Table 8 Table 9 Table 10 Reactions with dilute hydrochloric acid Reactions with aqueous sodium hydroxide Reactions with aqueous ammonia Reactions with aqueous iron(III) chloride Reactions with silver nitrate solution Reactions with potassium chromate(VI) solution Reactions with potassium iodide solution Reactions of sodium ethanoate solution Reactions of sodium carbonate solution Identification of functional groups in organic compounds
Example 1 To determine the identity of X in X(OH)2 F1 is hydrochloric acid of concentration 0.1 mol dm3. F2 is a solution containing 6.85 g dm3 of X(OH)2. 25.0 cm3 of F2 required 19.85 cm3 of F1 for complete neutralisation. (a) Write the equation for the reaction between X(OH)2 and hydrochloric acid. (b) Calculate the concentration of X(OH)2 in solution F2. (c) Hence calculate (i) the relative molecular mass of X(OH)2 and (ii) the relative atomic mass of X. (d) Suggest an identity for X. Solution (a) X(OH)2 + 2HCl XCl2 + 2H2O (M1V )X(OH) 1 (b) 1 2 = 2 (M2V2)acid
1 Concentration of X(OH)2 = 2
(c)
(i) Concentration (in g dm3) = Concentration (in mol dm3) 6.85 Relative molecular mass = = 172.5 0.0397 (ii) 172.5 = X + (2 17) X = 138.5 (d) X is barium.
Example 2 To determine the identity of X in HXO4 F3 is 0.10 mol dm3 sodium hydroxide solution. F4 is an acid with molecular formula, HXO4. 25.0 cm3 of F4 required 21.00 cm3 of F3 for complete neutralisation. (a) Write the equation for the reaction between HXO4 and NaOH. (b) Calculate the concentration of HXO4 in solution F4. (c) Hence calculate (i) the relative molecular mass of X(OH)2 and (ii) the relative atomic mass of X. (The concentration of HXO4 is 8.44 g dm3) (d) Suggest an identity for X. Solution (a) HXO4 + NaOH NaXO4 + H2O (M1V1)HXO 1 (b) = 4 1 (M2V2)NaOH
0.1 21.00 Concentration of HXO4 = = 0.084 mol dm3 25 (i) Concentration (in g dm3) = Concentration (in mol dm3) 8.44 Relative molecular mass = = 100.5 0.084 (ii) 100.5 = 1 + X + (4 16) X = 35.5 Relative molecular mass
(c)
(d) X is chlorine. Example 3 NaOH solution is not used to standardise You are asked to determine the accurate concentration of a monoprotic acid because it is a acid, HX in F5 solution from the following experiment. The rough deliquescent solid. Thus, concentration of HX is about 1.0 mol dm3. it is difficult to find the By means of a pipette, 50.0 cm3 of F5 is transferred into a 250 cm3 accurate mass of NaOH as it absorbs the moisture volumetric flask. Distilled water is then added and make up to the mark from the air (deliquescent) on the volumetric flask. The solution is labelled as F6 solution. during weighing. F7 is prepared by dissolving 2.65 g of anhydrous sodium carbonate in 250 cm3 solution. 25.0 cm3 of F7 required 20.95 cm3 of F6 for complete neutralisation using methyl orange as indicator. (a) Calculate the concentration of sodium carbonate in F7 solution. (b) Write the chemical equation for the reaction between sodium carbonate and HX. (c) Calculate the concentration of F6. (d) Hence, calculate the accurate concentration of HX in F5. Solution (a) Relative molecular mass of Na2CO3 = 106 2.65 4 Concentration of Na2CO3 = = 0.1 mol dm3 106 (b) 2HX + Na2CO3 2NaX + CO2 + H2O (M1V1) 2 (c) HX = 1 (M2V2)Na CO
2 3
Take Note
2 0.1 25.0 Concentration of HX in F6 = = 0.239 mol dm3 20.95 250 (d) Concentration of HX in F5 = 0.239 = 1.20 mol dm3 50
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2. The following steps are used to balance half-equations for redox reactions. Step 1 : Determine the oxidation number of the atom that undergoes oxidation or reduction. Step 2 : Balance the half-equation in terms of the total charge and the number of atoms on both sides of the equation. Step 3 : Calculate the number of oxygen atoms on both sides of the equation and add water (if necessary) on the side of equation that has insufficient number of oxygen atoms. Example 1 Balance the equation : MnO4 + H+ Mn2+ Step 1 The oxidation number of Mn decreases from +7 to +2. Hence, 5e must be added to the left-hand side of the equation. MnO4 + H+ + 5e Mn2+ not balanced Step 2 Balance the total charge and number of atoms on both sides of the equation MnO4 + 8H+ + 5e Mn2+ + 4H2O balanced Total charge on LHS of equation = 1 + 8 (+1) + 5 (1) = +2 Total charge on RHS of equation = +2 Total number of atoms on LHS of equation = 1Mn + 4O + 8H Total number of atoms on RHS of equation = 1Mn + 4O + 8H Hence, the half-equation is a balanced equation. Example 2 Balance the equation : XO2 XO3 Step 1 The oxidation number of X increases from +3 to +5. Hence, 2e must be added to the right-hand side of the equation. XO2 XO3 + 2e Steps 2 and 3 XO2 + H2O XO3 + 2e + 2H+ balanced Total charge on LHS of equation = 1 Total charge on RHS of equation = (1) + 2 (1) + 2 (+1) = 1 Total number of atoms on LHS of equation = 1X + 2H + 3O Total number of atoms on RHS of equation = 1X + 3O + 2H Hence, the half-equation is a balanced equation. not balanced
Step 2 Combine the half-equations into the ionic equation 5 equation (1) gives 5HCOO 5H+ + 5CO2 + 10e (3) 2 equation (2) gives 2MnO4 + 16H+ + 10e 2Mn2+ + 8H2O (4) Adding equations (3) and (4) gives 5HCOO + 2MnO4 + 11H+ 5CO2 + 2Mn2+ + 8H2O
Example 4 To find the mass of FeSO4.7H2O in 250 cm3 solution A sample of iron(II) sulphate crystals, FeSO4.7H2O, was dissolved in dilute sulphuric acid and made up to 250 cm3 with distilled water in a standard flask. 25.0 cm3 of this solution needed 25.80 cm3 of KMnO4 for complete reaction. (a) Write the ionic equation for the reaction between iron(II) sulphate and KMnO4. (b) If the concentration of KMnO4 solution is 3.16 g dm3, calculate the concentration (in g dm3) of (i) FeSO4, (ii) FeSO4.7H2O. (c) What was the mass of FeSO4.7H2O dissolved in 250 cm3 solution? Solution (a) 5Fe2+ + MnO4 + 8H+ 5Fe3+ + Mn2+ + 4H2O (b) (i) Step 1 Calculate the concentration of KMnO4 in mol dm3 Relative molecular mass of KMnO4 = 158 3.16 Concentration of KMnO4 = = 0.020 mol dm3 158 Step 2 Calculate the concentration of Fe2+ (M1V1)Fe2+ 5 = (M2V2)KMnO 1
4
0.020 = 0.103 mol dm3 25.8 25 Relative molecular mass of FeSO4 = 152 Concentration of FeSO4 = 0.103 152 = 15.7 g dm3 (ii) Relative molecular mass of FeSO4.7H2O = 278 Concentration of FeSO4.7H2O = 0.103 278 = 28.6 g dm3 (c) Mass of FeSO4.7H2O dissolved in 250 cm3 solution 28.6 = = 7.15 g 4 Concentration of Fe2+ = 5 Example 5 To find the concentration of Na2C2O4 F1 is a solution containing oxalic acid, H2C2O4 and sodium oxalate, Na2C2O4. F2 is 0.10 mol dm3 sodium hydroxide solution. F3 is 0.024 mol dm3 KMnO4 solution. 25.0 cm3 of F1 required 18.50 cm3 of F2 for complete neutralisation. 25.0 cm3 of F1 required 33.60 cm3 of F3 for complete redox reaction. (a) Calculate the concentration (in g dm3) of H2C2O4 in F1 solution (b) Calculate the concentration (in mol dm3) of C2O42 ions in F1 solution. (c) Hence, calculate the concentration (in g dm3) of Na2C2O4 in F1 solution. Solution (a) H2C2O4 + 2NaOH Na2C2O4 + 2H2O (M1V1)H C O 1 2 4 = 2 2 (M2V2)NaOH
1 Concentration of H2C2O4 = 2
Relative molecular mass of H2C2O4 = 90 Concentration of H2C2O4 = 0.037 90 = 3.33 g dm3 (b) 5C2O42 + 2MnO4 + 16H+ 2Mn2+ + 10CO2 + 8H2O (M1V1)C O 2 5 2 = 4 2 (M2V2)KMnO
4
5 Concentration of C2O42 = 2
(c) Total concentration of C2O42 = 0.0806 mol dm3 Concentration of H2C2O4 = 0.037 mol dm3 Concentration of Na2C2O4 = 0.0806 0.037 = 0.0436 mol dm3 Relative molecular mass of Na2C2O4 = 134 Concentration of Na2C2O4 = 0.0436 134 = 5.84 g dm3 Example 6 Acidified hydroxyammonium ion, NH3OH+, reduces iron(III) ion, Fe3+, to iron(II) ion, Fe2+. In the following experiment, you are asked to determine the chemical equation for the reaction between hydroxyammonium ion and iron(III) ion. F4 is a solution prepared by boiling 1.56 g of hydroxyammonium sulphate, NH3OH+HSO4 ,with excess iron(III) ammonium sulphate and dilute sulphuric acid. The reaction mixture is then made up to 250 cm3 with distilled water. F5 is potassium manganate(VII) solution containing 1.58 g of KMnO4 per 500 cm3. In a titration experiment, 25.0 cm3 of F4 required 24.4 cm3 of F5 for complete reaction. (a) Calculate the concentration of (i) NH3OH+HSO4, (ii) KMnO4 in mol dm3. (b) Calculate the concentration (in mol dm-3) of Fe2+ ions produced in F4. (c) Hence, calculate the number of moles of Fe3+ that react with 1 mol of NH3OH+. (d) The half-equation for the oxidation of hydroxylamine to nitrogen is: 2NH2OH N2O + H2O + 4H+ + 4e Hence, write a balanced redox equation between NH3OH+ ions and Fe3+ ions. Solution (a) (i) Relative molecular mass of NH3OH+HSO4 = 131 1.56 4 Concentration = = 0.0476 mol dm3 131 (ii) Relative molecular mass of KMnO4 = 158 1.58 2 Concentration = = 0.020 mol dm3 158 (b) 5Fe2+ + MnO4 + 8H+ 5Fe3+ + Mn2+ + 4H2O (M1V1)Fe2+ 5 = 1 (M2V2)MnO
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5 0.02 24.4 Concentration of Fe2+ = = 0.0976 mol dm3 25 (c) Fe3+ + e Fe2+ 1 mol of Fe2+ is produced from 1 mol of Fe3+. Number of moles of Fe3+ that have reacted with NH3OH+ = 0.0976 NH3OH+ : Fe3+ = 0.0476 : 0.0976 = 1 : 2 (d) 2NH2OH N2O + H2O + 4H+ + 4e Fe3+ + e Fe2+ 2NH2OH + 4Fe3+ 4Fe2+ + N2O + H2O + 4H+
In most direct titrations with iodine, a solution of iodine in potassium iodide is used. For simplicity, equation (3) is commonly used for calculation.
1 2 In the following reactions, iodine produced by the reaction is titrated against sodium thiosulphate solution. H2O2 + 2H+ + 2I 2H2O + I2 (H2O2 I2 2S2O32) IO3 + 6H+ + 5I 3H2O + 3I2 (IO3 3I2 6S2O32) 2Cu2+ + 4I Cu2I2 + I2 (2Cu2+ I2 2S2O32) 1 2 1 6 1 1
Example 1 To determine the concentration of iodine solution F1 contains 20.0 g of Na2S2O3.5H2O per dm3. F2 is an iodine solution. 25.0 cm3 of F2 required 22.5 cm3 of F1 for complete reaction. Calculate (a) the concentration (in mol dm3) of iodine in solution F2, (b) the mass of iodine required to prepare 200 cm3 of F2. Solution (a) Relative molecular mass of Na2S2O3.5H2O = 248 20.0 Concentration of Na2S2O3.5H2O = = 0.0806 mol dm3 248 2S2O32 + I2 S4O62 + 2I (M1V1)I 1 = 2 2 (M2V2)S O 2
2 3
1 Concentration of I2 = 2
(b) Relative molecular mass of I2 = 254 Mass of iodine = (0.0363 254) 200 = 1.84 g 1000
Example 2 To determine the percentage purity of hydrated sodium sulphite, Na2SO3.7H2O F3 is a solution containing 11.1 g of hydrated sodium sulphite, Na2SO3.7H2O per dm3. F4 is 0.050 mol dm3 iodine. F5 is 0.025 mol dm3 sodium thiosulphate solution. 25.0 cm3 of F4 is mixed with 25.0 cm3 of F3. The resulting solution required 18.90 cm3 of F5 for complete reaction. Sulphite ion reacts with iodine as represented by the equation Solution Step 1 Calculate excess iodine SO32 + I2 + H2O SO42 + 2HI
0.025 18.90 Number of moles of S2O32 that reacted with excess I2 = = 4.725 1000 2S2O32 + I2 S4O62 + 2I 1 Number of moles of excess I2 = 4.725 104 = 2.36 104 2 Step 2 Calculate amount of iodine reacted with SO32 0.050 25 Number of moles of I2 added = = 1.25 1000 Number of moles of I2 reacted = 1.25 103 2.36 103 104 = 1.014 103
104
Step 3 Calculate mass of pure Na2SO3.7H2O SO32 + I2 + H2O SO42 + 2HI Number of moles of pure Na2SO3.7H2O = 1.014 103 Relative molecular mass of Na2SO3.7H2O = 252 Mass of Na2SO3.7H2O in 25.0 cm3 solution = (1.014 103) Mass of Na2SO3.7H2O in 1000 cm3 solution = 0.256
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252 = 0.256 g
1000 = 10.24 g 25
Step 4 Calculate percentage purity of Na2SO3.7H2O 10.24 % purity = 11.1 100 = 92.3
Alternative method Step 1 Calculate the volume of iodine that did not react with the sulphite ion 2S2O32 + I2 S4O62 + 2I (M1V1)I 1 2 = 2 (M2V2)S O 2
2 3
1 Volume of I2 = 2
= 4.73 cm3 Step 2 Calculate the volume of iodine that reacted with the sulphite ion 25.0 4.73 = 20.3 cm3 Step 3 Calculate the concentration of Na2SO3.7H2O SO32 + I2 + H2O (M1V1)SO 2 1 3 = (M2V2)I 1
2
SO42 + 2HI
0.050 20.3 Concentration of SO32 = = 0.0406 25 Relative molecular mass of Na2SO3.7H2O = 252 Concentration of Na2SO3.7H2O = 0.0406 252 = 10.23 g dm3 Step 4 Calculate the percentage purity of hydrated sodium sulphite 10.23 % purity = 11.1 100 = 92.2 %
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Take Note 1. The density of solution is usually assumed to be 1.0 g cm3. Hence, the mass of solution = volume of solution used. 2. The mass of solution does not include the mass of solid added to water. For example, when 1.0 g of NaOH is added to 100 cm3 of water, the mass of solution is 100 g and not 101 g.
Calculate the amount of heat absorbed in the experiment. Calculate the number of moles of HCl used. Calculate the number of moles of MHCO3 used. Calculate the number of moles of MHCO3 reacted. (The relative molecular mass of the metal hydrogen carbonate = 100) (e) Calculate the enthalpy change for the reaction. Solution (a) H = mcT = 50.0 4.2
1.0 50.0 (b) Number of moles of HCl used = 1000 = 0.05 4.7 (c) Number of moles of MHCO3 used = 100 = 0.047 (d) MHCO3(aq) + HCl(aq) MCl(aq) + H2O(l) + CO2(g); H (+)ve HCl is in excess. Number of moles of MHCO3 reacted = 0.047 1.05 (e) H = = 22.3 kJ mol1 0.047 Example 2 To determine the partition of an organic acid, HOOC(CH2)nCOOH between water and ether. F3 is a solution of an organic acid, HOOC(CH2)nCOOH. F4 is 0.1 mol dm3 NaOH solution. F5 is 0.01 mol dm3 NaOH solution. 40.0 cm3 of F3 is added to a bottle, followed by 60.0 cm3 of ether. The bottle is tightly closed and shaken vigorously. After 30 minutes, 10.0 cm3 of the ether layer is pipetted out and titrated with F5. Then, 10.0 cm3 of aqueous layer is pipetted out and titrated with F4.
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The experiment is repeated using (a) 50.0 cm3 of ether and 50.0 cm3 of F3. (b) 40.0 cm3 of ether and 60.0 cm3 of F3. Results
Titration results Experiment Volume of solution used 40 cm3 F3 + 60 cm3 ether 50 cm3 F3 + 50 cm3 ether 60 cm3 F3 + 40 cm3 ether Volume of F4 (V1) 12.5 cm3 Volume of F5 (V2) 18.25 cm3
15.5 cm3
23.4 cm3
18.8 cm3
28.1 cm3
(a) Plot a graph of V1 (on the y-axis) against V2 (on the x-axis). (b) Based on the graph, determine the partition coefficient for the organic acid between water and ether. Solution
Solution
20
V1 (cm3)
10
10
15
10 V2 (cm3)
20
30
Concentration of acid in aqueous layer (b) K = Concentration of acid in ether layer Concentration of acid is proportional to the number of moles of alkali used. V (20 10) 1 = = 0.67 (30 15) V2 V1 0.1 K = V2 0.01 0.67 0.1 = 0.01 = 6.67
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NO2
Brown
Pungent
Explanation PbCl2 formed. Solubility in concentrated HCl due to formation of H2PbCl4 AgCl formed. On exposure to sunlight, Ag deposited Sulphur formed PbCl2 formed. PbCl2 is insoluble in water but dissolves readily in hot water
Explanation The basic hydroxides, M(OH)2 are formed The amphoteric hydroxides are formed Mn(OH)2 is formed; oxidised by air to Mn(OH)3 The basic hydroxide, Fe(OH)3 is formed The basic hydroxide, Fe(OH)2 is formed, Some Fe(OH)2 is oxidised to brown Fe(OH)3 The basic hydroxide, Ni(OH)2 is formed The basic hydroxide, Cu(OH)2 is formed The amphoteric hydroxide, Cr(OH)3 is formed
White precipitate insoluble in excess Mg , Ca or Ba NaOH present 2+ White precipitate soluble in excess NaOH Pb , Zn2+ or Al3+ present White precipitate turns rapidly to brown; insoluble in excess NaOH Mn2+ present Brown precipitate, insoluble in excess NaOH Fe3+ present Dirty green precipitate, insoluble in Fe2+ present excess NaOH Green precipitate, insoluble in excess Ni2+ present NaOH Blue precipitate, insoluble in excess NaOH Cu2+ present Bluish-green precipitate, soluble in excess NaOH to form a green solution Cr3+ present
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*Mn2+ present
*Fe2+ present
Fe3+ present
Cr3+ present
Cr(OH)3 formed
Green precipitate, soluble *Ni2+ present in excess NH3(aq) to form light blue solution Blue precipitate, soluble *Cu2+ present in excess NH3(aq) to form dark blue solution
Ni(OH)2 formed which dissolves in NH3(aq) to form the complex ion [Ni(NH3)6]2+ Cu(OH)2 formed which dissolves in NH3(aq) to form the complex ion, [Cu(NH3)4]2+
Explanation Formation of iron(III) benzoate, (C6H5COO)3Fe Formation of iron(III) carbonate; CO2 liberated because FeCl3(aq) undergoes hydrolysis to produce H+ ions
Explanation (CH3COO)3Fe or (HCOO)3Fe formed. On heating, (CH3COO)3Fe or (HCOO)3Fe undergoes hydrolysis to form the basic salt, e.g. (CH3COO)Fe(OH)2
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Observation Solution turns brownish-red; black deposit may also formed Solution turns deep purple/ violet I present
Inference
Inference
Explanation AgCl formed. Dissolves in NH3(aq) because of complex ion formation, [Ag(NH3)2]+(aq) AgBr formed
Br present
I present
AgI formed
Ag+ ions react with these anions to form insoluble salts. Insoluble salts of weak acids are soluble in HNO3 C6H5COOAg is insoluble in cold water but soluble in hot water
C6H5COO present
Inference Ba or Pb present Ba2+ present Reducing agent, such as SO32 or NO2 present
2+
Explanation BaCrO4 or PbCrO4 precipitated BaCrO4 precipitated Reducing agent reduces CrO42 to Cr3+ (green)
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Explanation 3CH3COO (aq) + Fe (aq) (CH3COO)3Fe red solution On heating, (CH3COO)3Fe + 2H2O (CH3COO)Fe(OH)2 + 2CH3COOH brown precipitate 3CH3COO(aq) + Al3+(aq) (CH3COO)3Al colourless (CH3COO)3Al + 2H2O (CH3COO)Al(OH)2 + 2CH3COOH white precipitate
Al3+ present
Explanation 2H + CO
+ 2 3
H2O + CO2
Na2CO3 is a base. A base will react with NH4+ to give NH3(g) These cations react with CO32(aq) to form insoluble metal carbonates MnCO3 precipitate is oxidised to Mn(III) salt Brown precipitate is Fe(OH)3. Fe2(CO3)3 is unstable and undergoes rapid hydrolysis to form Fe(OH)3. Fe3+(aq) is acidic and reacts with CO32 to give CO2 These cations react with CO32(aq) to form insoluble metal carbonates
White precipitate, turns brown Mn2+ present Brown precipitate, gas liberated turns limewater milky Green precipitate
Sweet-smelling odour
RCOOH present
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