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    Ionic Equilibrium

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    6 lonic Equilibrium Chapter at a Glance tonic Equilibrium in Solutions (@) Electrolytes: Any chemical substance which can conduct electricity in its aqueous state or in its molten stae is called cleecolyte. Depending upon the degree of ionization we can classify che electrolytes as: (Strong electrolytes: These ae those electrolytes which get 100% ionized (i.e. a= 1). For example, HNO,, HCI, H,SO, NaOH, etc. i) Weak electrolytes: These are those electrolytes which get ionized upto 5% (i.e. = 0.05). For example, CH,COOH, HNO,, NH,OH all organic acids and bases ete (6) Tonic equilibrium Ic isthe point/state/stage at which the concentration of dissociated ions and undissociated clectroyre is in a state of equilibrium. It is shown by weak electrolytes. For example, CH,COOH+H,0=CH,COO-+,0° Ostwald's Dilution Law “The expression that correlates the varia Osewald’s dilution taw. hn BF the Weerce of ditsociation of ai electrolvte with dilltion is known as aw where Cis the initial concentration of the electrolyte in mol L~' and @is the degree of dissociation. (2). Forweak electrolytes: The degree of dissociation i small, hati, a”<« 1, therefore, 1 = @ Kony [Ke 7 a- (ev = [Fe (6) For strong electrolytes: @is large and cannot be neglected in comparison to 1. eae “Taw or at =KV—Keav or a +aK.V-K.V=0 Solution ofthis quadratic equation gives che value of a Concepts of Acids and Bases (@) Arrhenius concept ‘Acids are compounds that produce H’ ions in water. For example, HCI+H,0 H,0°(aq) + CI-@q) HO" is the acid species known as the hydronium ion. BETTI 08 cre crerasier ror weer (@) Bases are compounds tha produce OH" ions in water forming basic solutions (oralkaline/caustic solutions) NaOH(s) 42> Ni faq) + OF (aq) ii) Two substances that differ from each other only by one proton are referred to asa conjugate acid-base pair. Conjugate pai ncho, +0 —= Hors do aid base odd base Ww Conjugate pai (&) Lewis concept (@ Lewis acid is any ionic or molecular species that can accept a pair of electrons in the formation of a coordi- nate covalent bond. These substances have an incomplete valence shell, such as BF,, H, CO,, SO, i) Lewis base is any ionic oF molecular species that can donate a pair of electrons in the formation oF a coor- ate covalent bond. These substances have completed valence shells and unshared pairs of electrons, such asNHy,H,O, and O*. The pH Scale pH is the negative logarithm of hydrogen ion concentration. pH=-loglHt'Jor (H"]=10" POH =—logiOH pit + poH=14 (@) pH scale + Noacia can nave pit tess tnan 0: ‘+ No acid can have pH more than 7. ‘+ No base can have pH more than 14. ‘+ No base can have pH less than 7. (b) pH of water Acddunan, bunny ‘Water has pH 7 (neutral). Here, K_ is the ionization constant of water. K, at 258 K is 10° and at 373 Kis 10? 5. Acid-Base Equilibria and lonization Constants (@) Ionization constants of weak acids ® HA(aq) + H,0() = A“ +H,0° cu-a) ca Ca Gi) pK, of an acid can be represented as pK, =-logk, “The larger the K, the stronger and more fully ionized the acid and smaller is its value of pK, (b) Ionization constants of weak bases “The weak Bronsted bases and are proton acceptors. Let B be any weak base onceouueeu B+ HO = BH + OH ca-a) ca Cw ‘The base dissociation or ionization constant, K, is given by HOH} _(Ca?__ Ca® 1B) ~CQ-a)"1-@ Ki pK, of a base can be represented as pK, =-logk, (©) Relation between K, and K, (PK soe * (PK) sue = PK, = M4(at 25°C) (@) Ionization of polyprotic acids Each step has its own ionization constant, K,, which we identify as K, for che fist step and X., for the second, (©) pH of a mixture of two or more weak monobasic acids in water log Ku, + Kay where Ky Ky(HA) and Kz = K,(HB), C,= concentration of HA, C,= concentration of HB Buffer Solution ‘Any solution which resists the change of pH valuc even by addition of small amount acid or base. Bufercanbe Foe ey heii ace pl value <7 pHvalue>7 (CH,COOH + CH,COONS NHOH + NYCI pH=-log(tt (@) Buffer: Iris a weak acid + sal ofthat weak acid with strong base or weak base + sal of that weak base with strong acid. (b)_ Buffer capacity (g): Every buffer has the capacity to resist the change in concentration of solution by addition ‘of number of moles of acids or base in one liter solutions so to change the pH by one unit. Number of molesof acid orbase added 10 oneliter buffer solution ‘Changeof pH (©. pH of Buffer solutions: Henderson ~ Hasselblach equation (@ pH of an acidic buffer Buflercapacity(g)= = pK, +1og Salt PH=PK, +108 Sy (i) pH of basic buffer pOH= pK, +og StL » 8 Basel (Gli) Salt buffer: When a solution of a salt itself acts asa buffer. itis known as a sale buffer. These are salts of a weak acid and weak base. (iv) Buffer index: The buffer index is given by B.1.=2.303 etn where is number of moles of acid and y is number of moles of sale. (») Buffer range: Ic is generally accepted that a solution has useful buffer index provided hat the value of {Sale}/[Acid] lies within the range 10-0.1. Hence, from Henderson equation we have PK, + log(0.1) < pH < pK, + logl0 BETIS 0. solubility product, chen the solution is containing more salt than ie can dissolve, therefore, precipitation starts and continues til ionic product becomes equal to solubility product. Se = HBO, is acid sili 1,80, +1,0->1B01D,r +H" (1) monobasic @) dibasic G) tribasic @) none 2, Which ofthe followingis the strongest acid? Solution ( HCO, 2) HBO, (1) 1,80, is monobasic acid (3) HO, (@) HINO, Solution (1) ‘The acidic character of oxyacids decreases down the group and increases along the period. Also, acidity inereases with inerease in oxidation number of central atom, 3. The degree of dissociation of 0.05 M NH, at 25°C in a solution of pH = 11 will be a) 0.02 @) 0.04 @) 001 @) 08 Solution o NH.OH = NH; + OH Initialeone. C o 0 tea. a) Ca Co [NH;]10H] Therefore, Ton Given that pH = 11 and using pH + pOH. pOH =3, 4, we get (OH = 10° Substituting C= 0.05 M, we get a= 0.02, 4. The conjugate of POF is (1) HPO, @) 1,00; @) HOY @) HOY Solution (4) Conjugate acid and base dfers by one proton hence the conjugate acid of POY is HPO 5. The conjugate base of hydrazoic acid is, a NH, @ NH @) N; @) Ny Solution @) NHN; 6. At 50°C, the self-onization constant (ion product) of NH, is Ky =10°°ME, How many amide ions are present per mm*of pure liquid ammonia? (1) 600 ions mm? @) 6x 10Fions mm (8) 6x 10tions mm @) 60 ions mm? Solution a 2NH,D=NH; +NHy Thus, INH] = 10" mol L* INH] = 102! 6 x 10? ions mmr =600 ions mm? onc counenu SE 7. The pH of an aqueous solution of 0.1 M solution of a ‘weak monoprotic acid which is 1% ionized is mi a2 @3 au Solution @ Hoek Initial cone. 0 o Lxot Leo een 100 "100 Therefore, 095 pHl=3 8 Consider the reaction, A- + H,0" => HA + H,0. The k, vvalue for acid HA is 1.0 x 10, What isthe value of K for this reaction? (1) Lox 108 @) Lox 210x104 (@) 10% 104 the reverse of the ionization reaction of HA, hence the equilibrium constant isthe reciprocal of K, 0x10" 9. Which of the following solution will have pH value close 101.0? (1) 100 mL of 4/10 HCI + 100 mL of M/10 NaOH. (2) 55 mLof M/10 HCI+ 45 mL.of M/10 NaOH (3) 10 mL of M/10 HCL +90 mL of M/10 NaOH (4) 25 mL of M/5 HCI +25 mL. of M/5 NaOH Solution (4) The answer has to be either (2) oF (4) since only in these two choices, HCL is greater than NaOH (only when HCL isin greater amount, pH can be acidic) In option (2), 10 mL of 4/10 HCL will be left out after neutralization, }0x(M/10) p= LOMO) _ 99 iW too 001M ‘Therefore, pH=2 10, Calculate the pH of a solution prepared by mixing 2.0 ml of strong acid (HCH solution of pE1 3.0 and 3.0 mL. ofa strong base (NaOH) of pH 10.0. 25 @ 35 45 65 Solution 2) Number of milliequivalents of HCL=2 x 10 We know that pH + pos 14 10+ pOH= 14 po =4 Number of milliequivalents of NaOH =3 x 10 The resulting solution is acidic. BETSEY 08 cre crensrnr ron neer jun 2 21023210") mea. _ @+3mb, Ax 1M or pH =-logit log(3.a x 10+) 11, Which salt among the following undergoes hydrolysis? (a) CH,Coor @) KNo, (@) Nacl @) Ks0, Solution (1) Salts of strong acid and strong base does not undergo, hydrolysis. 12. Calculate the pH at the equivalence point in the ttra- tion of 25 ml of 0.1 M formic acid with a 0.1 M NaOH solution (given that pX, of formic acid = 3.74). a az @) 922 @) 837 @) 6.06 Solution @) At the equivalence point, 0.05 M of HCOONa (sodium, formate) is formed. This problem is solved by the con- ining concep aby on pity, pk, bige aan -(oas)e( 43274) biog (e}-(po%)-zh000 2 13, Asolution of benzoic acid is titrated with NaOH. The pH of the solution is 4.2, when half of the acid is neutral- ized. Dissociation constant of the acd is 1) 631 x10 @) 32x10° 8) 87x10" @) 6.42 «10+ Solution (1) ‘The reaction involved is C,H,COOH + NaOH =C,H,COONa+H,0 Athalfneutralization 0.5 05 ‘a buffer solution of weak acid and its salt. Therefore, [salt] = pK, + log SAL jaime 1 plt=pK, 4.2=pK, 9K, =6.31%10% 14, ‘The precipitate of AgCIO, (K,, = 1.9 « 10%) is obtained when equal volumes of which ofthe following are mixed? (1) 104M Ag + 104M CxO @) 107M Ag + 109M CO (8) 102M Ag’ + 102M Cro (8) 104M Ag + 109M CO Solution @) Precipitation occurs when the ionic product (IP) exceeds K, value. When equal volumes of two solutions, are mixed, the concentration of each is reduced to half, ‘Therefore, In frstease, we (Faro) (ero) txt =1.25 10" 2 2 8 As, IP- K,, therefore, precipitation occurs. 25x10" Inthird case, v-(JoW')(boe) s,IP-5,>5,>5, @) S,>5,>5,<5, Solution @) The reactions involved are as follows 1 ag’ +c 1, =Ca® +2 O01 2x0.01 = Nat + cr 001 001 oat AgNO, = Ag’ + NO; 005 0.05 0.05 18, One liter of a saturated solution of CaCO, is evapo- rated to dryness due to which 7.0 mg of residue is lef. The solubility product for CaCO, is () 49x 10* @) 49x 105 (8) 49 10° @) 49x10" onc counenu ST Solution (8) Number of moles of CaCO, x10" 10 Moles of CaCO, in I liter solution =7 x 10° the residue is -7x10" CaCOs) = Ca® + COP 7x10% 7x10 a] x(COF] 71077 10% 9x10" 19, [M(OHD,| has K, = 4 x 10" and solubility 104 M. Find the value of x. ami a2 @3 aa Solution (2) [M(ON), will ionize as [MCOH),|=M4x0H" wot xt Ky =(M") [OH] 4 10S (10-9 (10-4 By inspection, we can find that the relation will hold {good when Therefor arta ie meee y Level | Strength of Acids/Bases and Conjugate Acid-Base Ps 1. Which among the following is the strongest base? @) Be(con), @) Mgom, @) BaloH), (4) sor), 2. The conjugate acid of NH; is a NH; @) NH, (3) NHOH @) NH, 3. The conjugate base of H,0" is. a HO @) on @ Ww (@) None ofthese 4. Which ofthe following species is an acid and also a con- Jjugate base of another acta? a) Hs0; @) S90, @) OW @) HO 5. Inthe reaction 1, + 15. The Lewis base is we et @r (@) None ofthese 6 The compound that is not a Lewis acid is (1) BE, @ atl, (@) NF, (@) soci 7. Which ofthe following isa Lewis base (1) BE, (2) Nev (@ NHy (@ CHOH 8. The dissociation constants of acids HA, HB, HC and HD are 2.6 x 10°, 5.3% 10°, 1.1 x 10%, 7.5 x 10% respectively. ‘The weakest acid among these acids is (HA @ HB @) HC @ HD H for Weal/Strong (Monobasic/Monoacidic) ‘Acids/Bases, K,, Common lon Effect and Mixtures of Acids and Bases 9. Which of the following substances when added into a solution of acetic acid will not suppress its degree of dissociation? (1) ai Het (2) CHOONa (3) water (@) dil 1180, BRETT 08 cre crensier ron neer 10, 1fan aqueous solution at 25°C has twice as many OH as, pure water, its pOH will be a) 6.699 @) 7307 @7 @) 698 11, The pH of a soft drink is 3.82. ts hydrogen fon concen- tration in mol L* will be () 1.96% 102 @) 1.96 «10° (8) 15 «10+ (@) 1.96 « 10" 12, pH ofa 10M NaOH is nearest to a 10 @7 a) 4 @ 10 13, Let K,at 100°C be 5.5 « 10" NE. Ifan aqueous solution at this temperature has pH 6, its nature will be (a) acid @) alkaline, (3) neutral. (4) canitsay. 14, The pH of a solution concentration will be (1) reduced to half. 2) doubled (3) reduced by 1000 times. (4) increased by 1000 times. 15. One liter of water contains 107 mol of ions, Degree of ionization of water is ) 18 «107% @) 0.8% 109% (3) 36«10°% @) 36% 107%, 16, Which of the following will occur if@ 0.1 M solution of a weak acid is diluted to 0.01 M at constant temperature? (2) (HE will decrease 10 0.01 M. 2) pit will decrease, (8) Percentage ionization will increase. (A) K will increase 17, The pH of a solution is 7.00. To this solution sufficient base is added to increase the pH to 12.0. The increase OFF ion concentration is (a) Stimes, 2) 1000 times. (8) 10%times. (@) Atimes. 18, If the degree of ionization of water is 1.8«10* at given, temperature, its ionic product will be a) 18x10 @) 1x10 @) 1x10" @) 16710 19, The pH of an aqueous solution of 0.1 M solution of a weak monoprotic acid which is 1% ionized is mi @2 @ 3 @®u 20. A monoprotic acid in 40.1 M solution ionizes to 0.001%, Its ionization constant is ) 10x10 @) 1.0x10° 8) 10x10" @) 10x10" eased from 3 106; its H 21, 100 mL of 0.2 M HCI are mixed with 100 mL. of 0.2 M CH,COOH, the pH of the resulting solution would be nearly at @) 02 @) 13 @ 16 Salt Hydrolysis 22, Which of the following, when mixed, will give a solution with pH greater than 7? (1) 0.1 MHCI +02 MNacl (2) 100 mL.0.2MH.8O, + 100 mL0.3 M NaOH (3) 25 mL of 0.1 MHNO, +25 mL0.1 MNH, (4) 100 mL.0.1 MCH,COOH + 100 ml.0.1 M NaOH 23, Ifasalt of strongacid and weak base ishydrolyzed, which ‘of the following formulae's to be used to calculate degree of hydrolysis X? o Beigeg Ka cone of these xe () None of th 24, Ionization constants of weak acid HA and weak base BOH are 3 x 107 each at 298 K. Percentage hydrolysis of their salt at 0.1 M concentration is (1) 40% 2) 50% (3) 75% (a) 33.33% 25, Equilibrium constant forthe following reaction is 10 CH,COOH + 0H" = CH,COO” +H, Hence the equilibrium constant for CH,COOH+H,0= CH,COO+H,0" is (1) 1.8108 2) 18x10 (3) 18105 (8) 5.5510" 26. Which of the following salts undergoes anionic hydrolysis? (1) Cuwo,), @) NHL @) ala, @) K,CO, 27, Assuming 100% ionization, which will have maximum, pie (1) 001 MNCL 2) 001 MINII),S0, (3) 0.01 M(NH),PO, (4) equal 28. ‘The pH of a solution obtained by mixing 100 mL. of (0.2 M CH,COOH is with 100 ml. of 0.2 M NaOH would, be (pK, for CH,COOH = 4.74 and log? = 0.301) (1) 47a 2) 887 (3) 9:10 (@ 857 29, Which of the following salts when dissolved in water will, hydrolyze? (1) Nac @ Ki (@) NHC (@) Nas 30, Which one ofthe foo aa @) NO; \ganions does not hydrolyze? @) cw os 31, The following reaction occurs in the body CO, +H,0=H,C0, =H" +HCO; 1f€O, escapes from the system (2) pH will decrease, (2) hydrogen ion concentration will decrease, (8) H,CO, concentration remain unaltered. (8) forward reaction will be promoted, 32, The compound whose 0.1 M solution is basic is. (2) ammonium acetate, 2) ammonium chloride, (8) ammonium sulphate. (@) sodium acetate. 89. An aqueous solution of CuSO, is acidic. @) basic. (3) neutral. (4) amphoteric. 4. The dissociation constant of an acid HA is x 105, the pH of 0.1 M solution of acid will be approximately a3 @s @1 @6 35. 100 mL of 0.2 M HCl Is mixed with 100 mL. of 0.2 M CH,COONs, the pH of the resulting solution would be neatly (pK, for CH,COOH = 4.74) mt @ 07 (3) 2875 @) 16 36. A0.1 Msolution of HCN is 0.01% constant for HCN is a 107 @) 108 ized, the foniz @) 10° @) 10° 37. The aqueous solution of potash alum is acidic due to hhydrolysis of we @) Ar 8) SOF (4) presence of acid in its crystal as impurity. Buffer Solutions 38, To prepare a buffer of pH = 8.26, amount of (NH,S0, to be added into 500 mL. of 0.01 M NH,OH solution px, (NH) = 926) 1s ) 0.05 mot @) 0.025 mot 8) 0.10 mol (4) 0.005 mot 39. What is the pHi of solution which has 1 mL NHOH (conc. 0.1 M) 1 mLand (NH)),S0, concentration 0.05 M. Given that K,(NH,OH) = 10°. a a7. onc counenu SS as (@) 474 Qo (a) 826 ‘The pl! ofa buffer containing equal molar concentra: tions of a weak base and its chloride (K, for weak base = 2x 10%,log2=0.3) is, a5 Qo @7 @) 93 pH of a mixture containing 0.10 MX: and 0.20 M HX is [pK 00) =) (1) 4 +1og2 (3) 10+ 1og2 (2) 4-log2 (A) 10-40g2 When sodium acetate is added to an aqueous solution of acetic acid its pH (1) increases. (3) remains constant. (2) decreases. (4) none of these, Which ofthe following will not function as buffer solution? (1) NaOH + NH,OH (2) Nal,PO, + Na, HPO, pH of following butfer solution is: 2 102M CH,COOH + 3x 102M (CH,COO),Ca. (pk, of OOH = 4.75) (y 427 @ a7 (@) 523 @ 70 ‘There is no effect of dilution on pH of which of the following? (1) 0.01 MCH,COOH + 0.01 M CH,COONa (@) 0.01 MH,COoNH, (3) 001 MNHOH +001 MNH,CI (4) Inall the eases The pH of a buffer is 6.745. When 0.01 mol of NaOH is added to 1 L of it, the pH changes to 6.832. Its bulfer capacity is (1) 0.187, @) os (3) 0076 (@) 0.896 pH of 0.01 (NH),SO, and 0.02 M NH,OH buffer 26) is (1) 9.26 (474 (2) 9.26 + loge (A) 4.74 + loge Which ofthe following mixture will bea buffer solution when dissolved in 500 mL. of water? (1) 0.20 mol ofaniline and 0.20 mol of HC (2) 0.20 mo! of aniline and 0.20 mol of NaOH (8) 0.20 mol of NaCl and 0.20 mol of HCL (4) 0.20 mol ofaniline and 0.1 mot of HCL ETI 08 cre crenwsier ron neer Solubility and Solubility Product 49. The precipitate of CaF, (K, = 1.7 x10") isobtained when, equal volume of following are mixed (1) 10*M Ca" + 104M FQ) 102M Ca + 10° ME (8) 105MCa*+109MF (4) 10°MCa* + 105 ME When HCl gas is passed through a saturated solution of common salt, pure NaCl is precipitated because () HCtis highly ionized in solution. (2) HClishighly soluble in water. (3) the solubility product of NaCl is lowered by HCl (@ the ionic product of [Na'} exceeds the value of solubility product of NaCl 51. What is correct representation for the solubility product, of Sns,t (a) [Sm 185) @) [sn SF (3) [Sn [51 @) [soe SF 52, Which of the following is most soluble? () BIS (K,= 1107) MnS (Ky =7 x10") (8) CuS(K,=8% 10") (4) ARS (Ky =6« 10%) 53. ‘The solubility product of BaSO, is 1.5 « 10+. The precipi- {ation in a 0.01 M Ba® ions solution will start on adding 1,80, of concentration a 107M @) 108M (3) 107M @) 10*M 54. The molar solubility of calcium phosphate is S. What is, its solubility product? as @) 1085" st 108 @ & (ay 108 © te oy 85. Thesolubility ofA,X, is.xmol da. Its solubility products, a) 36 @) 64x 10%" @) 16x" 4) 1.25 « 104" Level I Strength of Acids/Bases and Conjugate Acid-Base Pairs 1. Which of the following are amphiproticin nature? a on @) 1,00; (3) HSO; @) HE 2. The conjugate base of [Cxtt4,01,C1}" ts [cxt,0.)" @ [cto 01 @) [cxt,0,c1f" @ [cxt,0,,0rcI) 3, Which one of following is the strongest acid? a) H,P0, @) HPO, (8) HPO, (4) Equally 4. \ compound ha behave ng the formula NH,CH,COOH may (1) only asan acid. (3) both as an acid and base. @) onlyasa base, (4) neither acid nor base. pH for Weak/Strong (Monobasic/Monoacidic) Acids/ Bases, K,, Common lon Effect and Mixtures of Acids and Bases, 5. Equal volumes of two solutions of a strong acid having, pH 3 and pit 4 are mised together. The pH of the result: ing solution will then be equal to a) 35 @) 326 @7 @) 10 6. The pH of 10*MHClis, m7 Qs (@) 7.02 (@) 698 7. An acid solution of pH 6 is diluted thousand times. The pl of solution becomes approx. w? a6 @4 as 8. Which of the following will oceur ifa 0.1 M solution of a ‘weak acid is diluted to 0.01 M at constant temperature? (1) [H} will decrease t0 0.01 M. 2) pit will decrease @) K, will decrease. (4) Percentage ionization will increase. 8. Ifthe ionic product of water varies with temperature as, follows and the density of water is nearly constant for this range of temperature, then the process is H+0H=H0 fiempro 0S CC« O1Mx 0292% 1008x 291% Sarax x Parca @) endothermic. @) ionization. (1) exothermic. @) cantsay. 10, The dissociation constant of acetic acid at a given tem- perature is 1.69 x 10°. The degree of dissoci 0,01 M acetic acd in the presence of 0.01 M HCLis equal to @) 041 @) 013 (3) 1.69. 109 @) 0.013, n of LL. IfpK, of F-ion at 25°Cis 10.83, the ionization constant of HEF in water at this temperature is (1) 175x105 @) 35210 (3) 6.75% 10" (@) 5.3810 12, IK, = 10° for aweak acid, then pk, for its conjugate base would be tonic cquiusrum [REY @ 10" ae +pK, @) 10" as (4) pit=7-P Pe 1, At 25°C, the pH of pure water is 7. It dissociates 21, The aqueous solution of NH,CN is slightly alkat 1,01) + H,0() = H,0" + O1F because H0°(aq) + OFF (aq) = 21,01) at 25°C; ANP =-13.7 keal_——_()_CNion hydrolyzes toa greater extent than NH; on. mol! pH of water of at 37°C is expected to be (1) greater than 7. @) less than 7. @) equal to7 G@) none ofthese is tue 14, A dilute HCI solution saturated with H,S (0.1 M) has pH value 3. The [S*] is (Given the dissociation constants of H,Sare K, = 1107, K,=13x10") ay 2x1 @) 24x10 (@) 3x10 @ 13%10M 15, Dissociation constant of wo acids HA and HB are respectively 4 x 10" and 1,8 x 104. The pH value of which acid will be higher for a given molarity of their aqueous solution? a HA @) Both are same @ HB @) Cannot be determined 16, The following equilibrium exists in aqueous solution CH,COOH =CH,COO™ +H. Ifdil. HClis added without change in temperature, the (2) concentration of CH,COO- will Increase. 2) concentration of CH,COO- will decrease. @ o 17. Inan aqueous solution of wiprotic acid HA, which ofthe following is true? ap y= 3101 @) > 3181 (3) (H)<314") (4) tH = (041 18, The dissociation constants of HCOOH and CH,COOH are 1.8 x 10 and 1.8 x 10° respectively. [H,0*] ina solu- tion which is 0.1 M CH,COOH and 0.01 M HCOOH is approximately () 19% 102 @) 36%10° @) 19x 10¢ (@) 3.6% 10° Salt Hydrolysis 19, The dissociation constant of a weak acid is 1.0 x 10°, the equilibrium constant for its reaction with strong base is @) 10x10 @) 1x10 @) 10x10" @ 10x10" Calculate the pH of 0.1 M NaHCO, solution. (Dissocia- tion constants of H,CO, are K, and K,) 2) NH; fon hydrolyzes to a greater extent than CN’ ion (3) both hydrolyze to an equal extent. ) itisa salt 22, The pH of 10% M aqueous solution of barium acetate (CH,COO),Ba is 8.52. Calculate the value of n. (PK, of acetic acid’ = 4.75.) a2 @1 @4 4) none of these 23, H,0 + H,PO,=H,0"+H,PO; : pk, =2.15 H,0 + H,PO; =H,0' + HPO; ; pk, =7.20 pH of 0.01 M NaH,PO, is (1) 9.350 @) 4675, () 2675 @ 7.350 24, Calculate the pH of C' M Na,S solution. (K;,K, of H,S are 5.0 108, 2.5 « 10" 25. pH of 0.5 M Ba(CN), solution ( pk, of CN-is (1) 8.35 @) 335 @) 9.35, @ 9.50 Buffer Solutions 26. When 100 ml. of 0.4 M CH,COOH is mixed with 100 mL of 0.2 M NaOH, the [H,0°] in the solution is approximately [&,(CH,COOH) = 1.8 « 10"), (1) 18x 10* @) 18«10° @) 9x10" @) 9x 10% 27. pK, for acetic acid is 4.75. What should be the ratio of concentrations of acetic acid and acetate ions to have a solution with pH! 5.05? (1) 1:10 @ Ww: @ 12 @ 221 ‘What will be the final pH iF 0.2 mol of NaOH is added to 1 Lof buffer solution consisting of 0.4 M CH,COOH and, (0.3 MCH,COONat (pX, of CH,COOH = 4.75)? BME 08 Ky genn > Kein! () gat (3) Aat 2) Agor (4) Allwill precipitate simultaneously 7. There is solution which is one molar w.rt. each Mand X* ons present in it. The K, of M(OH), and X(OH), are 4.0 10" and 2.7 x 10" respectively . 'NH,OH solution isadded gradually to the above solution which of the fol- lowing will happen? (1) Both M(OH), and X(OF), will precipitate together, 2) M(OH), will precipitate first. (8) X(OM, will precipitate first (4) None of these will precipitate with NHOH solution. 38, The solubility of CaF, (K,, =.4 x 10") in 0.1 M solution of NaF would be (1) 34%10"M (@) 34% 109M @) 34x10"M @) 34x 10M 39. The solubility product of a sparingly soluble salt AB at room temperature is 1.21 x 10. ts molar solubil (1) 121x106 @) 1.21102 @) Lax iot @) 11x10? 1. The solubility product of BaCrO, is 2.4 x 10°” MP. The maximum concentration of Ba(NO,), possible without precipitation in a 6x 10M K,CrO, solution is (1) 107M @) 12x10"M (3) 6x 10M (@) 3x10", 41, The solubility ofsparingly soluble substance AgCl can be increased by the addition of (1) ag. NH, @) Both @) ag. Nac @) None ofthese 42, The solubility product of Hf, can be best epresented as () tng FIFE 2) igs @) (MgP Ir @) (HgP UE Previous Years’ NEET Questions 1, Calculate the pOH of a solution at 25°C that contains 110+ M of hydronium ions, that is, H,0- aa @7 @4 ao (AIPMT 2007) 2. Aweak acid HA has aK, of 1.00 x 104. 10.100 mol ofthis, acid is dissolved in 1 L of water, the percentage of acid dissociated at equilibrium is closest to (1) 0.100% @) 99.0% @) 1.00% @) 99.9% {AIPMT 2007) 3, Equal volumes of three acid solutions of pH13,4.and 5 are mixed in a vessel. What will be the H' ion concentration inthe mixture? 4 10. () Lirx109M 8) 37x10'M @) 11x 104M @) 37%10M (alpMr 2008) Equimolar solutions of the following were prepared in water separately. Which one of the solutions will record the highest pH? @ cal, 8) Bact, @) scl, (4) MgCl, (alps 2008) The ionization constant of ammonium hydroxide is £77 x 10° at 298 K. Hydrolysis constant of ammonium chloride () 5.6510" @) 5.6510" (8) 650% 10" (4) 5.65 «10 (AIM 2009) What is the [OH"} in the final solution prepared by mixing 20.0 ml. of 0.050 M HCL with 30.0 mL of 0.10 M Ba(on) a 012M (@) 040M @) 010M (4) 0.0050 M (AIPMT 2009) The dissociation constants for acetic acid and HCN at 25°C are 15x10 and 4.5%10-, respectively. The equilibrium constant for the equilibrium would be CN" +CH,COOH = HCN +CH,COO™ @) 30x10" @) 30x10 (8) 30x 10% (@) 30x10" (AIPMT 2009) If pH ofa saturated solution of Ba(OH), is 12, the value ofits Ky is (1) 4.00% 10° (3) 5.00% 10° @) 500% 10+? (4) 4.00% 10+? (AIPMT PRE 2010,2012) In a buffer solution containing equal concentration of B-and HB, the K, for B-is 10. The pH of buffer solu: tionis m7 @)4 a6 @ 10 (AIPMT PRE 2010,2012) What is{H*] in mol L* of a solution, that is, 0.20 M in CH,COONa and 0.10 M in CH,COOH? K, for CH,COOH = 1.8 «10% ra 13, im onc counenum SE () Laxi0s @) 18x 10° (3) 9.0% 10¢ (@) 35x 104 (AIPMT PRE 2010) ‘An increase in equivalent conductance ofa strong elec- trolyte with dilution is mainly due to (1) 100% ionization of electrolyte at normal dilution @) increase in both, that is, number of ions and ioni mobility of ions. (3) increase in number ofions. (4) increase in ionic mobility of ions. (AIPMT PRE 2010) AA buffer solution is prepared in which the concentra: tion of NH, is 0.30 M and the concentration of NH,Clis 0.20 M. If the equilibrium constant, k, for NH, equals 1.810%, what is the pH of this solution? (1) 873 @) 9.08 (8) 943, (@ 1172 (AIPMT PRE 2011) In qualitative analysis, the metals of Group I can be separated from other ions by precipitating them as chloride salts. A solution initially contains Ag’ and Pb ‘ata concentration of 0.10 M. Aqueous HCI is added to this solution until the Cl- concentration is 0.10 M. What will the concentrations of Ag* and Pb be at equilibri uum? (K;, for AgCL = 1.8 x 10°, K, for PbCL, = 1.7 « 105) (1) [Age] = 1.8 « 10-7 M; [Pb] = 1.7 104M, (2) [Ag] = 1.8 «10° 710M, (8) [Agi] = 1.8 « 10" M; [Pb] =8.5 « 10° M, (4) [Ag] = 1.8 « 10° M; [Pb] = 1.7 109M. (AIPMT MAINS 2011) Buffer solutions have constant acidity and alkalinity because (1) these give unionized acid or base on reaction with ‘added acid or alkali. (2) acids and alkalies in these solutions are shielded from attack by other ions, (G) they have large excess of H* or OH ions. (4) they have fixed value of pH. (AIPMT PRE 2012) Equimolar solutions of the following substances were prepared separately: Which one of these will record the highest pH value? (1) Bac, @ uc @ aici, 4) BeCl, (AIPMT PRE 2012) BEI 0. CH,COONa + H,0 =c Atr=0 100%02 — 100%0.2 0 0 pH=—logica} At ° o 100 «0.2 log(0.1 » 10°) 20. (4) The ionization reaction is HA = Ht 4 & a oo ede eee 29. (8) Only NUCL will hydrolyzed as itis salt of WBSA. “c Rest are salts of strong base and strong acid and will not hydrolyze ca 1 009=10" 30, (3) NO; isananion of strongacid (HNO,), therefore, will 21. (1) Due to common ion effect, CH,COOH willbe dissoci- not hydrolyze ated even less 32, (4) CH,COONa is a salt of weak acid and strong base. 10x02 Therefore, (HCI o1M ‘Therefore its pH is greater than 7 Wehave pl 33. (1) In CuSO, CuP* hydrolyzed as SO; Is anlon of song acid and will not hydrolyzed. Cu" +H,0-4(Cu(0H) +H ‘Therefore, the solution will be acidie due to cationic hydrolys logJK =O) logifi0* 107) =3 35. (8) The reaction involved is he CHCOO-'Nat + HCL CHCOOH + Nact = @ 1000.2 100 «0.2 o o 0 0 100 «0.2 CH,COOH+OH" = CH,COO™+H,0; K,= 1.810" (0) scaycoome!2*22.9 H,0 2H" +011; K-10 @ a 200 Equilibrium constant for the reaction CH,COOH + H,0 pl palhils Salve =C) = CH,COO- + H,0* can be calculated from Eq. (2) + Eq. (0) Therefore, Ky=K, < K,=1.8% 10" «10° = 1.8% 107 26. (4) CO} will undergo anionic hydrolysis. 36, (1) The ionization reaction is Dee oe loth HCN = H+ CN 27. (1) We know PH=5(PK. ~ pK, log) j too In option (A): €=0.01 M Cla) Ca Ca K,=Ca* Therefore, K,=0.1 x (0.01 « 10} =10% 37. (2) K,S0,-Al,(S0,),-24H,0= Potash Alum Only AP* hydrolyzes, therefore, cationic hydrolysis takes place or the solution is acidic. 38. (2) Let the amount of (NH,SO, be a moles. Therefore, [NH;]= 2a INH) = pK, +10 POH = PKs + 08 OF 2a 14-826)=(14-9.26)+log—— 28 : ve ” "8500 0.01% 10) 2195 25x10 0F 0025 mol am int 48. Wek portepky+ (awesnow pot pk, og, M On +g] 2= 02 pores eG WBS: ) 0. (Wehave pole 40, (4) We POH = pk; tog “2S4) pOH= pk =5-log2 pli=14-poH =olog2=93 41. (4) pH= pk, + log! ii 1 cost] 44. (3) pH= pk, +1ogLCOO1 tog 22021 8 (x 107) es crater cacy « MIS OFNAOH aed Change ni aaa oF i INH;] 47. () p PK, °8NHON onc counenun SE poste pt pH = 14 pOH 48, (8) Option (1): Amiline (WB) + 1ICI (SA)—+ WASB (Salt hydrolysis) 02mol— 0.2mel 02 mol Option @) Aniline (WB) + NaOH (SB)-+ Common ion effect 02mol”02:mol Option @): NaOH ($B) + HCI (SA)-> SASB (Salt hydrolysis) ‘O2mol 0.2mol 02 mol Option () Aniline QB) + HCL(SA)—> WASEs | WI ©2mol“ oimol 0. mol_ 0.1 moh Basic bulfer 49. (2) Precipitation occurs when ionic product > Ky, oF (Ca |[F-P> Ky that is, (Fe }aee (1) The reaction is Sn, = Sn® +83 Kyo{sn"1ISt1 Bi. 53. (4) IFionic product > solubility product, then the solu tion is containing more salt than it ean dissolve, there fore, precipitation starts and continues till ionic product becomes equal to solubility product. Ua" [SOF }> 1.5 «10% [0.01){80}>1.5 107 [SOF ]>1.5 «107 54, (2) The reaction is Ca(PO,)), = 3Ca* + 2POF ss Ky-ICa" PROF # = (357257 =1088" 55. (4) The reaction is AX, 2A" 45K" 2x ax Kyo xP xP 1.25 «1087 Level Il 2. (4) Conjugate base of (CrtH,0),C1F or (Cr(H,0)OH)CIY. (CrtH,0,C1F -H* 5. (2)Weknow pil logit BERN O8JECTIVE CHEMISTRY FOR NEET ov +10" = =log| =3.26 6. (4) Since, the concentration of HCts 10, contribution, (of H,0 isto be taken into account. Hol = H+ 10" 0 0 lot+x 10 H+ On tts ox 13, Atr=0 At tat, 0 HO “ K,=[H°HOH] 0" +x1(x)=10 x H10%r-10"=0 15. 7. (1) The solution remains acidic buts near pH=7as new concentration is 10° HO= HY + OW xe" x 16, (x+10%)(x)=10" 1074 ft" IH j=107 1° Z 9. (1) As temperature increases, onization constant iereases (K), therefore, reaction goes in the forward irection, that is, reaction is exothermic. 10. (@) The dissociation reaction is CHCOOH = CH,COO” + w © 0 0 Cl-a)= Ca+0.01 0.01 (Due to common ion effect) ca 18, {CH,COO" IH" COOH] 1.69 10° = a x 0.01 a= 1.69 x 10° Therefore, K, sca oon 11. @)We have (pky),. +(PK yw Ky 19. = (2) (PK n+ (PR (PK yp = 4-10.83 (Kg = 10" 2675 x 10" 5+ pk, (2) Iv is given that aH is negative, therefore as the tem: perature increases, K, increases or pK, decreases. Hence, new neutral point or PA» <7 Ee 2 “ HS 22H'4 8%; K, HFS") S18" ]=13% 10 M (1) Weknow | pH =—logitt” logiVK* 0) (pH yy ==logt yt x10 x C) (PH =-log( JLB» 107 * C) ‘Therefore, (pHa >(PEys ac Idi. HClis added to the above equilibrium reaction, the ‘concentration of CH,COO- will decrease due to the com- ‘mon ion effect, that is, suppression in the degree of dis sociation of a weak electrolyte by adding a strong elec- trolyte containing a common ion, Here, HCLis a strong electrolyte, when it is added it splits into H’ and Cr ions. Asa result, H" is the common ion in the equilibrium and hence the concentration of CH,COO" decreases. COOH = SH,COO™ +H HAS OH FHATK, cle reyes xty HATS HY + HANK, sly" xtyez y~ HAP HE + AK, ye xtye RP yRs [ASK > Ka Kyl ‘Therefore, [H"]= x >> 3A" ]=32 (1) For the mixture of two weak acids (HCOOH + CH,COOHD, we have VEGTRSG [i810 x 001+ 8x10" x0. = V6 «107 = 1.9% 107 in @) HAO 2A +110; Therefore, K= 42> =10° 20, (1) NaHCO, isan amphiproti salt. he H,cok) HCO; Li com, Therefore, p= (px, +pK,) 2 22, (1) We have [CH,COO"]=107 xn 1 stone vite. +0 lac 50-475» gto n=2 23. (2) Nalt,PO, an amphiprotic salt, 1 = Lepk, +k, pH= (0K, + PK.) -leise720 =4.675 +pK,+10g0) =4ad+a4—93ielogh) 935 26. (2) The reaction is, CH,COOH + NaOH 10x04 100% 0.2 100 «02 o = CH,COONa + 1,0 100% 02 The pH value for acidic buffer can be calculated as, iSal pit= pk, +log ea 5) 4 jog tx 0.2) = -Hogt.8 105) + og tPO= 02) ~logitt'I= ~logt.8 « 10] =9 1H" or H,0°1=1.8 x 10 27. (8) pHi can be calculated as ICH,Coo") iCH,COOH| (CH,COO™ IcH,CoOn| pH= pK, + log, 5.05~ 4.75+log. [cH,coom_ 1 [cH,CoO7| "2 onc cone SES 28. (2) The reaction is CH,COOH 4 NaOH > CH,COONa + H,0 oa 02 02 0 plt= pK, log, 3 32. (1) Wehave a Sela 18+S=1.8 ‘Therefore, from Eq, (1), we get 1.810% 18 oe 83 (I) The reaction is KOH), = AP*+ 30H K,=1AP HOH? 10" =1AP"]00"? [a]=10°M 35. (3) AGSCN == Ag + SCNT SHS AgBr = Ag’ + Br S48, Ky SIAB"IISCN™]=(5, +815) o Kya IAB BE I= (5, +5,18,) a ‘On adding Eq, (1) and Eq, 2), we get [Rpt Ra = (5, +5,)~188) f2 10 25x10 =[Ag"] [Agt}= 1.310% 36, (3) The one with lower K,, will requite lesser [Ag] 10 precipitate and thus will precipitate first. 38, (3) The reactions are as follows: =r + OF S 2840.1 Na + o 0 ol on [Ca® IF P= 510.17 (As 28 << 0.1) BETIS 08 cre crenwsinr ron neer 39, (4) Fora saturated solution ofa sparingly soluble salt AB, the following solubility equilibrium would exist. AB(Saturated salt solution) = A“(aq) + B'(aq) {fdhemolar solubility ofthe salts; then [A*)=.$ mol dim [8"]= mol dm. Therefore, solubility products given by K,=[AIIB"1=(5 moldm*)(S mol dim)= $* mol? dm* iven that K, = 1.21 x 10-, so the molar solubility is S= Ky = Stab" = 1.110? 40. (1) Let the concentration of Ba(NO,), be C Ionic product of BaCr0, = [C] x [6% 104] Solubility product of BaSO, = 2.4% 10 For no precipitation to occur, ionic product < K, or Cx6x104S 24x10 €04% 10% F410" 5, 42, (8) The reaction can be represented as Hg,l, = Hg!" +2 Therefore, K, Merc Previous Years’ NEET Questions 1, @) We know that, at 25°C 1HO710K 1 10"*[0111 To find pOH, we can tse the value of [OH+] pOH =-loglOH] Jog 10+ 2 2. (8) For a weak electrolyte, degree of dissociation is given by @ ‘Therefore, % a= 0.01 x 100= 1% 3. (@) Wehave pH =-logitt The concentration of solution with pH3, 4,5 will be 10%, 104,10 respectively Therefore, 10°V+ 104+ 105V. 10°V(1 + 10% + 10%) 3. (2) Mole equivalents of acid = 20 «0.08% (3) We know pHi + pOH Lu Ha x10" 3 =37%10°M (9) The basie strength increases as we move down the ‘group. Bac Ba + 2c In water, Ba** form Ba(OH), whi ‘water, thus, gives maximum pH. highly soluble in (2) The reaction involved is NH;+H,0 = NHOH +H Hydrolysis constant is given by k, Rue Lo" 177 «10 5.465 «10 Mequiv Mole equivalents of base =30 0.1 x2=6 M equiv Mole equivalents of (OH left Mequiv or} = 522" , 1000 IM (1) The dissociation constants for acetic acid and HCN are given by x, HIE THCNT IH*IICH, COO) ICH,COOHT 510 5x10" ‘Therefore, the equilibrium constant us aK 15x10? 1 45x10 K, x10" =3.3 x10" 4 Since, pH= 12. Therefore pOH =2.=9 [OH] For the reaction Ba(OH), = Ba + 20H" 6) es) 102 M= $= 10/2. tonic equiusrum [REY 10. n om 13, Ma 18. 16. Substituting the values, we get | lox, H=4 be w (8) Acidic buffer is a mixture of acetic acid and sodium acetate. The salt sodium acetate is completely dissoci ated in aqueous medium while acetic acid being a weak acid is partly dissociated. At equilibrium, CH,COOH = Haq) + CH,COOa) ‘The dissociation constant can be expressed as {cH,coon *{CH,COO"] x10 «0.10 020, =9 x10 mol" IW I=K, (4) Strong electrolytes have a= 1, therefore, at high dilu- tion the ionic mobility increases, resulting in inerease in equivalent conductance. : eel @Wehave POH = Pky + lon} Therefore, pOH 74 + loge? Tee BOS On solving, we get pOH = 4.57 We know that pH = 14 pOH. Substituti yg the value, we get pH = 9.43, (4) We have AgCl = Ag’ + Cl PCL, = Pb + 2Cr = [Pb* ICP 1.7% 105 [Pb [0.17 [Pb = 1.7 109M (1A buffer contains solutes that enable it to resist large changes in pH when small amount of either strong acid or strong base are added to it. Ordinarily, the buffer consists of ovo solutes, one providing # weak Bronsted acid and other a weak Brénsted base. (4) BaCA, because it isa salt ofstrongacid and strong base. (8) Na,CO, isa salt of strong base (NaOH) and weak acid (H,CO,). The reaction is characterized by salt hydrolysis reaction. 18, 19. a1. 1Na,CO, (aq) = 2NaOH(aq) +H, Sodium hydroxide undergoes complete ionization and the concentration hydroxide ions make solution alka- ne, so the pH of the solution becomes more than 7. (2) We know, AG = 2.308 RT log K,, 63.3% 10" =-2.303 8.314 x 298 xlog Ky, =11.09 = log kK, K,=8x10" () The solubility of Ag.C1O, is maximum, thus, it will Maximum (8) Mixtures of weak acids and their salts or weak bases ‘and their salis are known as acidie buffer and basic buffers, respectively. The solution of HCI, and NaClO, isa mixture of strong acid and its salt thus, cannot act a8 an acidie butter. (4) HCL is a strong acid. It dissociates completely into fons. Thus, the aqueous solution of FIClisa best conduc tor of electricity. arene, Maver = MrsonViwon — MuoVner MyVox = 0.1 1-0.01 x1 Max 20.09 jorr)= 22-0015 OH = log [OH] = og (0.045) = We know pH + pOH = 14 ‘Therefore, pH = 14 ~1.35 = 12.65 (2) For My V(S) = M“(aq) + (aq) Therefore, [62% 10) = 7.8 10" mol L" NY,(9) = M¥(aq) + 3¥ (aq) =278' BETTIS 08

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