Ionic Equilibrium Exercises

Ionic Equilibrium (Elementary) IONIC EQUILIBRIUM-I  Marked questions are recommended for Revision. PART - I : SUBJECTIVE QUESTIONS Section (A) : Acid-Base Concepts Commit to memory : Polyprotic Arrhenius acid : 2 or more replaceable H per acid molecule. Polyprotic Arrhenius base : 2 or more replaceable OH per base molecule. Acid – 1 H+ = its Conjugate Base Base + 1 H+ = its Conjugate Acid Amphiprotic species : H+ donor as well as acceptor. Lewis acid : Lone pair acceptor Lewis base : Lone pair donor A-1. (a) Select Polyprotic Arrhenius acids from the following : H3PO2, H3PO3, H3BO3, HCOOH, (COOH)2. (b) Write conjugate acids of SO42–, RNH2, NH2–, C2H5OC2 H5, F– (c) Write conjugate base of HNO2, OH–, H2CO3, HClO4. (d) Write conjugate acid and conjugate base of following amphoteric species : HS–, NH3, C2H5OH, H2O .. (e) Classify the following into Lewis acid & Lewis base : H+, FeCl3, (CH3)3N, F–, CH2 A-2. Classify the following into acid, base and amphiprotic species on the basis of protonic concept : (i) H2PO2– (ii) H2PO3– (iii) H2PO4– (iv) HPO32– 2– + + (v) HPO4 (vi) NH4 (vii) CH3COOH2 A-3. Comment upon H2O as an Arrhenius acid/base, Bronsted–Lowry acid/base and Lewis acid/base. Section (B) : Properties of water, pH scale, Autoprotolysis Commit to memory : Kw = [H+] [OH–] = 10–14 at 25°C [H+] = [OH–] (in water / a neutral solution) pH = –log [H+] ; pOH = –log [OH–] For H2O, pH & pOH  with  in temperature pH + pOH = pKw = 14 (for an aqueous solution at 25°C) Kself ionisation of HA = [A–] [H2A+] B-1. At –50°C, liquid NH3 has ionic product is 10–30. How many amide (NH2–) ions are present per mm3 in pure liquid NH3 ? (Take NA = 6 × 1023) Section (C) : Relation between Ka and Kb for conjugate acid - base pair Commit to memory : Ka (acid) × Kb (conjugate base) = Kw pKa (acid) + pKb (conjugate base) = pKw = 14 (at 25°C) C-1. What is ionisation constant of HOCl, if Kb of OCl– = 4 × 10–10 ? Also find its pKa. C-2. K a1 , K a2 and K a values for H3PO4 are 10–3, 10–8 and 10–12 respectively. If Kw (H2O) = 10–14, then : 3 (i) What is dissociation constant of HPO42– ? (ii) What is Kb of HPO42– ? (iii) What is Kb of H2PO4– ? (iv) What is order of Kb of PO43– ( Kb 3 ), HPO42–( Kb 2 ) and H2PO4–( K b 1 ) ? Ionic Equilibrium (Elementary) Section (D) : pH calculation : Strong acid solutions, Strong base solutions, Solutions containing mixture of two or more strong acids, Solutions containing mixture of two or more strong bases, Solutions containing mixture of strong acid and strong base Commit to memory : Strong acid solution: [H+] = Molarity of strong acid solution × number of H+ ions per acid molecule. Strong base solution: [OH–] = Molarity of strong base solution × number of OH– ions per base molecule. [H+ ]1 V1 + [H+ ]2 V2 Mixture of two strong acids : [H+]f = V1 + V2 Mixture of two strong bases : [OH–]f = [OH– ]1 V1 + [OH– ]2 V2 V1 + V2 Mixture of a strong acid and a strong base : D-1. Calculate pH of following solutions : (i) 0.001 M HNO3, (ii) 0.005 M H2SO4 , (iv) 10–8 M NaOH, (v) 0.0008 M Ba(OH)2 . (iii) 0.01 M KOH D-2. Calculate the pH of the following solutions : (i) 2.21 g of T OH dissolved in water to give 2 litre of solution. (Assume T OH to be a strong base) (ii) 0.49% w/v H2SO4 solution M (iii) Sr(OH)2 solution is diluted to quadruple volume. 1000 (iv) 1 mL of 12 M HCl is diluted with water to obtain 1 litre of solution. D-3. Calculate the pH of solution obtained by mixing 10 mL of 0.2 M HCl and 40 mL of 0.1 M H2SO4. D-4. Calculate the pH of the resulting solution formed by mixing the following solutions : (a) 20 mL of 0.2 M Ba(OH)2 + 30 mL of 0.1 M HCl (b) 2 mL of 0.1 M HCl + 10 mL of 0.01 M Sr(OH)2 (c) 10 mL of 0.1 M H2SO4 + 10 mL of 0.1 M KOH. Section (E) : Ostwald dilution law, pH calculation : Solutions of weak monoprotic acid, Solutions of weak monoacidic base Commit to memory : AB (aq) = K eq C A+ (aq) + B– (aq) ; Keq = ; [A+] = [B–] = C  = CK eq Weak Acid (monoprotic) solution :  = Weak base (monoacidic) solution :  = [A + ][B – ] C . C C 2 = = [AB] C(1 −  ) (1 −  ) (both valid if  < 0.1 or 10%) Ka 1 ; pH = (pKa – log C) (both valid if  < 0.1 or 10%) 2 C Kb 1 ; pOH = (pKb – log C) (both valid if  < 0.1 or 10%) 2 C K a1 Basic strength of BOH1 1 Kb1 Acid strength of HA1 1 ; = = = = Acid strength of HA 2 2 Ka2 Basic strength of BOH2 2 Kb2 E-1. Acetic acid gets 1.3% ionised in its decimolar solution. What is be the ionisation constant of acetic acid? Ionic Equilibrium (Elementary) E-2. Prove that degree of dissociation of a weak monoprotic acid is given by : 1 = 1 + 10(pKa −pH) where Ka is its dissociation constant. E-3. Calculate the pH of a 500 mL solution of 1 M BOH. (Kb = 2.5 × 10–5) E-4. Whose pH increases by greater value on dilution from initial pH = 2 ? (a) CH3COOH solution (b) HCl solution. Section (F) : Salt hydrolysis, pH calculation : Solutions of salt of monoprotic acid and monoacidic base Commit to memory : Salt of strong acid and weak base : Kh × Kb = Kw ; h = 1 Kh ; pH = [pKw–pKb–log c] (valid if h < 0.1 or 10%) 2 c 1 Kh ; pH = [pKw+pKa+log c] (valid if h < 0.1 or 10%) 2 c 1  h  = Kh ; pH = [pKw+pKa–pKb] Salt of weak acid and weak base : Kh × Ka × Kb = Kw ;   1– h  2 Salt of strong base and weak acid : Kh × Ka = Kw ; h = F-1. Which of the following ions or compounds in a solution tend to produce an acidic, a basic or a neutral solution ? (a) C2H5O– (b) Cu+2 (c) SO32– (d) F– (e) NH4+ (f) CH3COONa (g) KNO3 (h) NaOCl (i) Na2CO3 (j) ZnCl2 F-2. Calculate pH of 0.2 M aqueous solution of sodium butyrate. Given : Ka of butyric acid = 2 × 10–5. F-3. A 0.25 M solution of pyridinium chloride C5H5NH+Cl− was found to have a pH of 2.75. What is Kb for pyridine, C5H5N ? F-4. Calculate the percentage hydrolysis & the pH of 0.02 M CH 3COONH4. Kb(NH3) = 1.6 × 10–5, Ka(CH3COOH) = 1.6 × 10–5. PART - II : ONLY ONE OPTION CORRECT TYPE Section (A) : Acid-Base Concepts Commit to memory : Polyprotic Arrhenius acid : 2 or more replaceable H per acid molecule. Polyprotic Arrhenius base : 2 or more replaceable OH per base molecule. Acid – 1 H+ = its Conjugate Base Base + 1 H+ = its Conjugate Acid Amphiprotic species : H+ donor as well as acceptor. Lewis acid : Lone pair acceptor Lewis base : Lone pair donor A-1. An acid with molelcular formula C7H6O3 forms three types of sodium salts. i.e. C 7H5O3Na, C7H4O3Na2 and C7H3O3Na3. The basicity of the acid is : (A) One (B) Two (C) Three (D) Six A-2. Select the incorrect option : (A) H3PO4 is a tribasic acid. (C) Sr(OH)2 is a strong diacidic base. (B) H3BO3 is not an Arhenius acid. (D) NH3.H2O is a strong monoacidic base. Ionic Equilibrium (Elementary) A-3. In the reaction HC2O4– (aq) + PO43–(aq) bases ? (A) HC2O4– and PO43– (C) HC2O4– and HPO42– HPO42–(aq) + C2O42–(aq), which are the two Bronsted (B) HPO42– and C2O42– (D) PO43– and C2O42– A-4. The following equilibrium is established when HClO4 is dissolved in weak acid HF solvent : HF + HClO4 ClO4– + H2F+ Which of the following is correct set of conjugate acid base pair ? (A) HF and HClO4 (B) HF and ClO4– (C) HF and H2F+ (D) HClO4 & H2F+ A-5. Which of the following correctly explains the nature of boric acid in aqueous medium ? H2 O 2H2 O → H3O+ + H2BO3– → 2H3O+ + HBO32− (A) H3BO3 ⎯⎯⎯ (B) H3BO3 ⎯⎯⎯ 3H2 O → 3H3O+ + BO33 − (C) H3BO3 ⎯⎯⎯ H2 O → B(OH)4– + H+ (D) H3BO3 ⎯⎯⎯ Section (B) : Properties of water, pH scale, Autoprotolysis Commit to memory : Kw = [H+] [OH–] = 10–14 at 25°C [H+] = [OH–] (in water / a neutral solution) pH = –log [H+] ; pOH = –log [OH–] For H2O, pH & pOH  with  in temperature pH + pOH = pKw = 14 (for an aqueous solution at 25°C) Kself ionisation of HA = [A–] [H2A+] B-1. Which of the following expression is not true ? (A) [H+] = [OH−] = K W for a neutral solution at all temperatures. (B) [H+] > K W & [OH−] < K W for an acidic solution. (C) [H+] < K W & [OH−] > (D) [H+] − K W for an alkaline solution. −7 = [OH ] = 10 M for a neutral solution at all temperatures . B-2. pOH of H2O is 7 at 298 K. If water is heated to 350 K, which of the following statement should be true ? (A) pOH will decrease. (B) pH will increase. (C) pOH will remain 7. (D) Both (A) and (B). B-3. Kw of H2O at 373 K is 1 × 10–12. Identify, which of the following is incorrect : (A) pH + pOH = 12, for every aqueous solutions. (B) pH of H2O is 6. (C) H2O has increased from its value at 298 K. (D) H2O is acidic. B-4. In pure HCOOH liquid, concentration of HCOO– = 10–3 M at 27ºC. What is the self ionisation constant at 27ºC (K = [HCOOH2+] [HCOO–]) ? (A) 10–3 (B) 103 (C) 106 (D) 10–6 Section (C) : Relation between Ka and Kb for conjugate acid-base pair Commit to memory : Ka (acid) × Kb (conjugate base) = Kw pKa (acid) + pKb (conjugate base) = pKw = 14 (at 25°C) C-1. Given % HF + H2O Ka H3O+ + F– Kb F– + H2O HF + OH– Which relation is correct. 1 (A) Kb = (B) Ka . Kb = Kw Ka (C) Ka.Kb.Kw = 1 (D) Ka = Kw Kb Ionic Equilibrium (Elementary) C-2. Which of the following is incorrect ? (A) Ka (weak acid). Kb (conjugate weak base) = Kw (B) Ka (strong acid). Kb (conjugate weak base) = Kw (C) Ka (weak acid). Kb (weak base) = Kw (D) Ka (weak acid). Kb (conjugate strong base) = Kw Section (D) : pH calculation : Strong acid solutions, Strong base solutions, Solutions containing mixture of two or more strong acids, Solutions containing mixture of two or more strong bases, Solutions containing mixture of strong acid and strong base Commit to memory : Strong acid solution : [H+] = Molarity of strong acid solution × number of H+ ions per acid molecule. Strong base solution : [OH–] = Molarity of strong base solution × number of OH – ions per base molecule. [H+ ]1 V1 + [H+ ]2 V2 Mixture of two strong acids : [H+]f = V1 + V2 Mixture of two strong bases : [OH–]f = [OH– ]1 V1 + [OH– ]2 V2 V1 + V2 Mixture of a strong acid and a strong base : D-1. The [OH–] in 100 mL of 0.016 M HCl (aq) is : (A) 6.25 × 10–12 M (B) 3 × 10–10 M (C) 6.25 × 10–13 M (D) 1.6 × 10–3 M D-2. How many moles of NaOH must be removed from one litre of its aqueous solution to change its pH from 12 to 11 ? (A) 0.009 (B) 0.01 (C) 0.09 (D) 0.1 D-3. Which statement/relationship is correct ? (A) pH of aqueous solutions of 0.1 M HNO3, 0.1M HCl, 0.1M H at 25ºC is not equal. 1 (B) For a dilute solution, pH = – log + [H ] (C) At 25°C, the pH of pure water is 7. (D) The value of pKw at 25°C is 7. D-4. Upon mixing equal volume of two solutions of strong acids having pH values 2 & 4, resulting solution will have pH : (A) equal to 3 (B) closer to 2 than 4 (C) closer to 4 than 2 (D) closer to 3 than 2 D-5. On adding 0.04 g solid NaOH to a 100 mL, (A) 0 D-6. (B) +0.3 M Ba(OH)2 solution, determine change in pH : 200 (C) –0.3 (D) +0.7 Upon mixing equal volume of a strong acid solution (HA) and a strong base (BOH) solution, pH of resulting solution : (A) may be less than 7 (B) may be greater than 7 (C) will be equal to 7 (D) Both (A) & (B) D-7. Which of the following solutions will have pH close to 1 ? (A) 100 mL of M/10 HCl + 100 mL of M/10 NaOH (B) 55 mL of M/10 HCl + 45 mL of M/10 NaOH Ionic Equilibrium (Elementary) (C) 10 mL of M/10 HCl + 90 mL of M/10 NaOH (D) 75 mL of M/5 HCl + 25 mL of M/5 NaOH. Section (E) : Ostwald dilution law, pH calculation : Solutions of weak monoprotic acid, Solutions of weak monoacidic base Commit to memory : AB (aq) = K eq C A+ (aq) + B– (aq) ; Keq = [A + ][B – ] C . C C 2 = = [AB] C(1 −  ) (1 −  ) ; [A+] = [B–] = C  = CK eq (both valid if  < 0.1 or 10%) Weak Acid (monoprotic) solution :  = Ka 1 ; pH = (pKa – log C) (both valid if  < 0.1 or 10%) 2 C Weak base (monoacidic) solution :  = Kb 1 ; pOH = (pKb – log C) (both valid if  < 0.1 or 10%) 2 C K a1 Basic strength of BOH1 1 Kb1 Acid strength of HA1 1 ; = = = = Acid strength of HA 2 2 Ka2 Basic strength of BOH2 2 Kb2 E-1. Which of the following has the maximum degree of ionisation ? (A) 1 M NH3 (B) 0.001 M NH3 (C) 0.1 M NH3 (D) 0.0001 M NH3. E-2. Ka for formic acid and acetic acid are 1.8 × 10–4 and 1.8 × 10–5 respectively. The relative strength of acids is : (A) 10 : 1 (B) 1 : 10 (C) 1 : 10 (D) 10 : 1 E-3. Ka for a monobasic acid, whose 0.1 M solution has pH of 4.5, is : (A) 10–10 (B) 10–8 (C) 10 × 10–4 (D) 10 × 10–6 Section (F) : Salt hydrolysis, pH calculation : Solutions of salt of monoprotic acid and monoacidic base. Commit to memory : Salt of strong acid and weak base : Kh × Kb = Kw ; h = 1 Kh ; pH = [pKw–pKb–log c] (valid if h < 0.1 or 10%) 2 c 1 Kh ; pH = [pKw+pKa+log c] (valid if h < 0.1 or 10%) 2 c 1  h  Salt of weak acid and weak base : Kh × Ka × Kb = Kw ;  = Kh ; pH = [pKw+pKa–pKb]  1– h  2 Salt of strong base and weak acid : Kh × Ka = Kw ; h = F-1. Aqueous solution of NH4Cl is ____ in nature due to behaviour of ____ ion in solution : (A) acidic ; NH4+ (B) alkalline ; NH4+ (C) acidic ; Cl– (D) alkalline ; Cl– F-2. The chloride salt of a certain weak monoacidic organic base is hydrolysed to an extent of 3% in its 0.1M solution at 25ºC. Given that the ionic product of water is 10−14 at this temperature, what is the dissociation constant of the base? (A)  1 x 10−10 (B)  1 x 10−9 (C) 3.33 x 10−9 (D) 3.33 x 10−10 F-3. The pH of 0.1 M solution of the following salts increases in the order : (A) NaCl < NH4Cl < NaCN < HCl (B) HCl < NH4Cl < NaCl < NaCN (C) NaCN < NH4Cl < NaCl < HCl (D) HCl < NaCl < NaCN < NH4Cl F-4. The degree of hydrolysis of a salt of weak monobasic acid and weak monoacidic base in its 0.1 M solution is found to be 50%. If the molarity of the solution is 0.2 M, the percentage hydrolysis of the salt should be : (A) 100 % (B) 50 % (C) 25 % (D) None of these Ionic Equilibrium (Elementary) PART - III : MATCH THE COLUMN 1. Match the Column. Column-I (A) HCl (B) KOH (C) NH3 (D) BF3 (p) (q) (r) (s) Column-II Lewis acid Arrhenius acid Lewis base Arrhenius base  Marked questions are recommended for Revision. PART - I : ONLY ONE OPTION CORRECT TYPE 1. The self ionisation constant for pure formic acid, K = [HCOO H2+ ][HCOO–] has been estimated as 10–6 at room temperature. The density of formic acid is 1.15 g/cm 3. What percentage of formic acid molecules in pure fomic acid are converted to formate ion ? (A) 0.002% (B) 0.004% (C) 0.006% (D) 0.008% 2. pKa for an acid HA is 6. The value of K for the reaction A– + H3O+ (A) 1 × 10–6 (B) 1 × 108 (C) 1 × 10–8 HA + H2O is : (D) 1 × 106 3. 10–6 M HCI is diluted to 100 times. Its pH is : (A) 6 (B) 8 (D) 7.02 (C) 6.98 4. Which of the following solutions has a pH exactly equal to 8 ? (A) 10–8 M HCl solution (B) Solution containing 10–8 M H+ –6 (C) 2 × 10 M Ba(OH)2 solution (D) 10–8 M NaOH solution 5. 10 mL of a strong acid solution of pH = 2 are mixed with 990 mL of another strong acid solution of pH = 4. The pH of the resulting solution will be : (A) 3 (B) 3.3 (C) 3.7 (D) Molecular formula of both strong acids should be known to answer above question. 6. % dissociation of a 0.024 M solution of a weak acid HA (Ka = 2 × 10–3) is : (A) 0.25% (B)  29% (C) 25% (D)  0.29% 7. For a weak base BOH, Kb = 10–4. Calculate pH of 10–4 M BOH solution. (Take log 6.2 = 0.79) (A) 10 (B) 9.79 (C) 8 (D) None of these 8. Four separate solutions of sodium salts NaW, NaX, NaY and NaZ have pH 7, 9, 10 and 11 respectively, when each solution has concentration 0.1 M. Then the strongest acid is : (A) HW (B) HX (C) HY (D) HZ PART - II : SINGLE AND DOUBLE VALUE INTEGER TYPE 1. 2. If an acid-base reaction HA(aq) + B– (aq) HB(aq) + A– (aq) has Keq = 10–4, how many of the following statements are true ? (i) HB is stronger acid than HA (ii) HA is stronger acid than HB (iii) HA and HB have the same acidic strength (iv) B– is stronger base than A– (v) A– is stronger base than B– (vi) B– and HB are conjugate acid-base pair – (vii) A is the conjugate base of acid HA. (viii) HA can be HSO4– and HB can be HCOOH. – – – – (ix) A can be F and B can be CN . What is pOH of an aqueous solution with [H+] = 10–2 M and Kw = 2 × 10–12 ? Report your answer after dividing by 2 and round it off to the nearest whole number. 3. Percentage ionisation of water as follows at certain temperature is 3.6 × 10 –7 %. Calculate Kw and pH of water at this temperature. 2H2O H3O+ + OH– 4. 0.1 mole HCl is dissolved in distilled water of volume V. Then, at lim , (pH)solution is equal to ..... V→ Ionic Equilibrium (Elementary) 5. Determine pKa (H2O) + pKa (H3O+). 6. What volume (in L) of water must be added to 1 L of 0.1 M solution of B (weak organic monoacidic base; ionisation constant = 10–5) to triple the % ionisation of base ? 7. If pHx% is the pH of a 1 M weak monoprotic acid which is x % ionised, then find the value of  pH50%    × 100.  pH10%  8. If the equilibrium constant for the reaction of weak acid HA with a strong base is 109, then determine pH of 0.1 M NaA solution. 9. What is the concentration of CH3COOH(aq) in a solution prepared by dissolving 0.01 mole of NH+4 CH3COO– in 1 L H2O ? Report your answer after multiplying by 9 × 105. [Ka(CH3COOH) = 1.8 × 10–5; Kb(NH3.H2O) = 1.8 × 10–5] PART - III : ONE OR MORE THAN ONE OPTIONS CORRECT TYPE 1. Which statement(s) is/are correct ? (A) All Bronsted bases are also Lewis bases. (B) All Bronsted acids are not Lewis acids. (C) Most cations are acids and most anions are bases. (D) All Bronsted bases are also Arrhenius bases. 2. Select the incorrect statement(s) : (A) NH4+ (aq) is a strong acid. (C) H– is a weak base. 3. (B) CH3COO– (aq) is a weak base. (D) HS– is a weak acid as well as a weak base. For pure water : (A) pKw increases with decrease in temperature. (B) Absolute dissociation constant decreases with decrease in temperature. (C) H2O increases with decrease in temperature. (D) Both pH and pOH decrease with rise in temperature. 4. One litre of a strong acid solution contains 10–5 moles of H+ ions. Then : (A) pOH = 9. (B) Percentage ionisation of water in solution is 1.8 × 10–9 %. (C) Number of OH– ions per mL of solution = 6.022 × 1015. (D) [H+ ]from H2O = 10–9 M 5. Equal volumes of 0.2 M HCl and 0.2 M Sr(OH)2 are mixed. Which of the following statement is/are correct ? (A) [Sr2+] = 0.1 M (B) [Cl–] = 0.1 M (C) pH of resulting solution = 13 (D) Solution is neutral. 6. If 0.1 M CH3COOH (Ka = 1.8 × 10–5) is diluted at 25°C, then which of the following will be correct ? (A) [H+] will increase. (B) pH will increase. (C) number of H+ ions will increase. (D) Ka will increase. 7. Degree of hydrolysis for a salt of strong acid and weak base : (A) is independent of dilution (B) increases with dilution (C) increases with decrease in Kb of the bases (D) decreases with decrease in temperature. 8. Equal volumes of following solutions are mixed, in which case the pH of resulting solution will be average value of pH of two solutions. (A) Aqueous HCl of pH = 2, aqueous NaOH of pH = 12 (B) Aqueous HCl of pH = 2, aqueous HCl of pH = 4 (C) Aqueous NaOH of pH = 12, aqueous NaOH of pH = 10 (D) Aqueous CH3COOH of pH = 5, aqueous NH3 of pH = 9. [Ka (CH3COOH) = Kb (NH3)] Ionic Equilibrium (Elementary) PART - IV : COMPREHENSION Read the following passages carefully and answer the questions. Comprehension # 1 pH calculation upon dilution of a strong acid solution is generally done by equating nH+ in original solution & diluted solution. However, if strong acid solution is very dilute, then H + from water are also to be considered. Take log 3.7 = 0.568 and answer the following questions. 1. A 1 litre solution of pH = 4 (solution of a strong acid) is added to the 7/3 litre of water. What is the pH of resulting solution ? (A) 4.52 (B) 4.365 (C) 4.4 (D) 4.432 2. A 1 litre solution of pH = 6 (solution of a strong acid) is added to the 7/3 litre of water. What is the pH of resulting solution ? Neglect the common ion effect on H2O. (A) 6.4 (B) 6.52 (C) 6.365 (D) 6.432 Comprehension # 2 Consider a solution of CH3COONH4 which is a salt of weak acid & weak base. The equilibrium involved in the solutions are : CH3COO– + H2O CH3COOH + OH– ..........(1) – NH4 + H2O NH3.H2O + H+ ..........(2) H+ + OH– H2O ..........(3) If we add these three reactions, then the net reaction is : CH3COO– + NH4+ + H2O CH3COOH + NH3.H2O ..........(4) Both CH3COO– and NH4+ get hydrolysed independently and their hydrolysis depends on : (i) their initial concentration K K (ii) the value of Kh which is w for CH3COO– and w for NH4+. Ka Kb Since both of the ions were produced from the same salt, their initial concentrations are same. K K Therefore unless & until the value of w and w or Ka and Kb is same, the degree of hydrolysis of ion Ka Kb can't be same. To explain why we assume that degree of hydrolysis of cation and anion is same, we need to now look at the third reaction i.e., combination of H+ and OH– ions. It is obvious that this reaction happens only because one reaction produced H+ ion and the other produced OH– ions. We can also note that this reaction causes both the hydrolysis reaction to occur more since their product ions are being consumed. Keep this thing in mind that the equilibrium which has smaller value of equilibrium constant is affected more by the common ion effect. For the same reason, if for any reason a reaction is made to occur to a greater extent by the comsumption of any one of the product ion, the reaction with the smaller value of equilibrium constant tends to get affected more. Therefore we conclude that firstly the hydrolysis of both the ions ocurs more in the presence of each other (due to consumption of the product ions) than in each other's absence. Secondly, the hydrolysis of the ion which occurs to a lesser extent (due to smaller value of K h) is affected more than the one whose Kh is greater. Hence, we can see that the degree of hydrolysis of both the ions would be close to each other when they are getting hydrolysed in the presence of each other. Now answer the following questions : 3. In the hydrolysis of salt of weak acid & weak base : (A) degree of hydrolysis of cation and anion is different (B) degree of hydrolysis of cation and anion is same (C) degree of hydrolysis of cation and anion is different and they can never be assumed same. (D) degree of hydrolysis of cation and anion is different but they are very close to each other when they are getting hydrolysed in the presence of each other. Ionic Equilibrium (Elementary) 4. For 0.1 M CH3COONH4 salt solution given, Ka (CH3COOH) = Kb (NH3.H2O) = 2 × 10–5. In this case, degree of hydrolysis of cation and anion are : (A) exactly same (B) slightly different (C) can't say (D) different but can be take approximatly same (MAIN) / PROBLEMS (PREVIOUS YEARS) (MAIN) O FFLINE PROBLEMS 1. 2. 3. The conjugate base of H2PO4– is : (1) PO43– (2) P2O5 (3) H3PO4 (4) HPO42– What is the conjugate base of OH– ? (1) O2 (2) H2O (3) O– (4) O2– Hydrogen ion concentration in mol/L in a solution of pH = 5.4 will be : (1) 3.98 × 108 (2) 3.88 × 106 (3) 3.68 × 10–6 (4) 3.98 × 10–6 4. The first and second dissociation constants of an acid H 2A are 1.0 × 10–5 and 5.0 × 10–10 respectively. The overall dissociation constant of the acid will be : (1) 5.0 × 10–15 (2) 0.2 × 105 (3) 5.0 × 10–5 (4) 5.0 × 1015 5. The pKa of a weak acid, HA, is 4.80. The pKb of a weak base, BOH, is 4.78. The pH of an aqueous solution of the corresponding salt, BA, will be : (1) 4.79 (2) 7.01 (3) 9.22 (4) 9.58 6. Three reactions involving H2PO4– are given below : (i) H3PO4 + H2O → H3O+ + H2PO4– (ii) H2PO4– + H2O → HPO42– + H3O+ (iii) H2PO4– + OH– → H3PO4 + O2– In which of the above, does H2PO4– act as an acid ? (1) (ii) only (2) (i) and (ii) (3) (iii) only (4) (i) only 7. The pH of a 0.1 molar solution of the acid HQ is 3. The value of the ionization constant, K a of the acid is: (1) 3 × 10–1 (2) 1 ×10–3 (3) 1 × 10–5 (4) 1 × 10–7 8. How many litres of water must be added to 1 litre an aqueous solution of HCl with a pH of 1 to create an aqueous solution with pH of 2 ? (1) 0.1 L (2) 0.9 L (3) 2.0 L (4) 9.0 L 9. pKa of a weak acid (HA) and pKb of a weak base (BOH) are 3.2 and 3.4, respectively. The pH of their salt (AB) solution is : (1) 6.9 (2) 7.0 (3) 1.0 (4) 7.2 10. Which of the following salts is the most basic in aqueous solution? (1) FeCl3 (2) Pb(CH3COO)2 (3) Al(CN)3 (4) CH3COOK (MAIN) ONLINE PROBLEMS 1. Assuming that the degree of hydrolysis is small, the pH of 0.1 M solution of sodium acetate (Ka = 1.0 × 10–5) will be : (1) 5.0 (2) 6.0 (3) 8.0 (4) 9.0 2. The conjugate base of hydrazoic acid is : (1) N–3 (2) N3– (3) N2– (4) HN3– Ionic Equilibrium (Elementary) 3. What quantity (in mL) of a 45% acid solution of a mono-protic strong acid must be mixed with a 20% solution of the same acid to produce 800 mL of a 29.875% acid solution ? (1) 330 4. (2) 316 (3) 320 (4) 325 Following four solutions are prepared by mixing different volumes of NaOH and HCl of different concentrations, pH of which one of the them will be equal to 1? M M HCl + 100 mL NaOH 10 10 M M (3) 60 mL HCl + 40 mL NaOH 10 10 M M HCl + 25 mL NaOH 5 5 M M (4) 55 mL HCl + 45 mL NaOH 10 10 (1) 100 mL (2) 75 mL EXERCISE - 1 PART - I A-1. (a) H3PO3, (COOH)2 (b) HSO4–, RNH3+ NH3, (C2H5)2OH+, HF (c) NO2–, O2–, HCO3–, ClO4– (d) Conjugate acids: H2S, NH4+, C2H5OH2+, H3O+ Conjugate base: S2–, NH2–, C2H5O–, OH– .. (e) Lewis acid: H+, FeCl3, CH2 Lewis base: (CH3)3N, F– A-2. Acidic – (vi), (vii) ; Basic – (i), (iv) ; Amphiprotic – (ii), (iii), (v) A-3. H2O – Arrhenius acid, Arrhenius base, Bronsted–Lowry acid, Bronsted–Lowry base, Lewis base but not Lewis acid. B-1. 600 ions / mm3 C-2. (i) 10–12 (ii) 10–6 (iii) 10–11 (iv) K b 1 < Kb 2 < Kb 3 D-1. (i) 3, (ii) 2, (iii) 12, (iv) 7.02, D-2. (i) 11.7, (ii) 1, (iii) 10.7, (iv) 1.92 D-3. 0.7 E-1. 1.69  10–5 E-2. Refer class notes / sheet theory. E-3. 11.7 E-4. HCl F-1. (a) Basic (g) neutral F-2. 9 C-1. (b) acidic (h) basic (c) basic (i) basic F-3. 2.5 × 10–5 ; 4.6 D-4. (v) 11.2 (a) 13 ; (b) 7 ; (c) 1.3. (d) basic (j) acidic (e) acidic (f) basic Kb = 8 × 10–10 F-4. 0.625%, pH = 7 PART - II A-1. (C) A-2. (D) A-3. (D) A-4. (C) A-5. (D) B-1. (D) B-2. (A) B-3. (D) B-4. (D) C-1. (B) C-2. (C) D-1. (C) D-2. (A) D-3. (C) D-4. (B) D-5. (B) D-6. (D) D-7. (D) E-1. (D) E-2. (D) E-3. (B) F-1. (A) F-2. (A) F-3. (B) F-4. (B) PART - III 1. (A) → r; (B) → s; (C) → r; (D) → p Ionic Equilibrium (Elementary) EXERCISE – 2 PART - I 1. (B) 2. (D) 3. (C) 6. (C) 7. (B) 8. (A) 4. (B) 5. (C) 3. Kw = 4 × 10–14, pH = 6.7 7. 30 4. (ABD) 4. (A) PART - II 1. 4 (i, v, vi, vii) 2. 5 (Actual answer = 9.7) 4. 7 5. 14 8. 9 9. 50 6. 8 PART - III 1. (ABC) 2. (AC) 3. (ABD) 6. (BC) 7. (BCD) 8. (AD) 5. (ABC) PART - IV 1. (A) 2. (D) 3. (D) EXERCISE – 3 JEE(MAIN) OFFLINE PROBLEMS 1. (4) 2. (4) 3. (4) 4. (1) 5. (2) 6. (1) 7. (3) 8. (4) 9. (1) 10. (4) JEE(MAIN) ONLINE PROBLEMS 1. (4) 2. (2) 3. (2) 4. (2)