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138 B exercises * Indicators for acid-base titrations * Volumetric analysis and the correct use of apparatus such as volumetric flasks, pipettes and burettes * Primary standard and standard solution Important equations 1. In any aqueous solution [H,O°OH] = Ky sexe (10.1) where K,, is a constant called the ionic product of water. At 25°C Ky = 1.00 x 10-4 (mol/L? 2. For the generalised ionisation reaction of a weak acid, HA(aq) + H,O() = HgO*(aq) + A-(aq) save (10.2) _ [HOTA] Ky = Taal (10.3) Before starting exercises in this chapter, you should revise Exercises 15 to 24 in Chopter 4 and Exercises 55 to 71 in Chapter -5. Acids and bases, and conjugates THB) write equations showing the acidic nature of the following substances in aqueous solution. Use I1,0* for the hydrogen ion. (a) nitrous acid, HNO, (b) hydrobromie acid, HBr (0) sulfurous acid, H,SO5 (a) sodium dihydrogen phosphate, NaH,PO, (@) ammonium chloride, NH,Cl FEMI write equations showing the basic nature of the following substances in aqueous solution: (a) ammonia, NH; (b) pyridine, CsH3N (c) trimethylamine, (CH)3N (d) sodium acetate (ethanoate), CHyCOONa (e) sodium hydrogen phosphate, NagHPO, Give the conjugate bases for the acids in Exercise 1, and the conjugate acids for the bases in Exercise 2. Give the conjugate bases for the following acids (a) propanoic acid, CHy-CH,-COOH (b) perchloric acid, HCIO, AcIDS AND BASES HI 139 (© hypochlorous acid, HOCI (d) sulfuric acid, HS, (e) oxalic acid, H:C;0, Give the conjugate acids for the following bases: (a) aniline, C,Hs-NH, (a) sulfide ion, S*- (b) hydrazine, NjHy (e) hydrogen phosphate ion, HPO? (0 hypobromite, OBr The following substances are amphiprotic (amphoteric). Write two equations for reactions with water for each of them—one equation where the substance acts as a proton donor and the other where the substance acts as a proton acceptor: (a) HCO; (b) H,PO, (©) glycine, the simplest amino acid, HyN-CH,-COOH Write equations for the step-wise ionisation of the following acids: (a) carbonic acid, H,CO, —_(@) phosphorous acid, HPO; (diprotic) (b) oxalic acid, HC, () phosphoric acid, H,PO, (triprotic) For each of the above acids identify the acid and its conjugate base in each step. What is (i) the conjugate acid (ii) the conjugate base, of the following amphiprotic substances? (a) the hydrogen sulfite ion (b) the hydrogen oxalate ion, HC,O- (a) In each of the following reactions which reactant is acting asfan acid? What is its conjugate base? @) HCOOH + CO = HCOO- + HCO, Gi) CN- + HO, = HCN + HO,- ¥ (ii) HS- + NO, = HNO, + S (b) In each of the following reactions which reactant is acting as a base? What is its conjugate acid? (i) HSO,- + HS- = H,8 + SO; (i), CH,O + HCO, = CH,OH + CO- (ii) NHy + PO? & NH; + HPO?- Calculations involving [H,;O*], pH and [OH-] BERR) Calculate the pH of the following solutions: / *(a) 0.037 M hydrocholoric acid *(c) 0.014 M sulfuric acid (b) 0.245 M nitric acid (d) 0.207 M perchloric acid 140 @ exercises Calculate the hydrogen ion concentration in solutions having the follow- ing pHs: *(a) 3.87 (b) 1.42 (o) 5.92 (d) 8.43 (e) 11.21 as EER Calculate the pH of the following solutions: \ @(@).0.33 M sodium hydroxide (b) 0.0042 M potassium hydroxide (c) 0.024 M barium hydroxide (d) a saturated solution of magnesium hydroxide which is 1.36 x 10-* M HEB Calculate the hydroxide ion concentration in solutions having the follow- ing pHs _ *(a) 13.24 (b) 11.56 (c) 8.37 (d) 6.24 (e) 2.61 HEB) Calculate the pH of the solution that results from mixing “#50 mL 0.10 M nitric acid and 25 mL 0.10 M potassium hydroxide (b) 25 mL 0.050 M hydrochloric acid and 10 mL 0.20 M sodium hydroxide (©) 50 mL 0.015 M calcium hydroxide and 100 mL 0.012 M hydrochloric acid Weak and strong acids and bases ‘1 A chemist has 0.010 M solutions of four acids, L, M, N and P, and meas- ures the pH of each. The values are 4.2, 6.1, 2.0 and 2.7 respectively. Arrange these in order of increasing acid strength (weakest first, strongest last). Are any of these acids completely ionised? Justify your answers. GAZ 4 0.040 M solution of methanoic (formic) acid in water has a pH of 2.57. What fraction of the formic acid molecules has been jonised? Would you classify this acid as ‘strong’, ‘moderately weak’ or ‘extremely weak’? A 0.025 M solution of sodium hydrogen sulfate in water has a pH of 1.91 Is the hydrogen sulfate ion a strong acid (that is completely ionised)? Explain fully. HEB 0.20 M solutions of four bases, A, B, C and D, were prepared. They had pHs of 12.7, 13.3, 11.6 and 9.4 respectively. Arrange them in order of increasing strength as bases. Are any of these bases completely ionised? If so, which one(s)? Explain how you decided this. Ethanol, like all alkanols, is an extremely weak acid. Give the formula ’ for its conjugate base, the ethoxide ion. This ion reacts with water to re-form the alcohol; write the equation. This reaction goes to virtual completion. Describe the strength of the ethoxide ion, as a base, as ‘weaker than’, ‘similar to’, or ‘stronger than’ the hydroxide ion.