ALLEN Jonic Equilibrium IONIC EQUILIBRIUM L INTRODUCTION Ionic equilibrium deals with the equilibrium of any substance with its ionsin solution. The substance producing ions are called electrolytes. According to conductivity, substances are of two types @ @) ) Non-Conductor : Those substances which do not show the flow of current or electricity. Ex. Non- metals, plastic rubber, wood, ete. Exception - Graphite is a non-metal but shows conductivity due to motion of free electrons. Conductors : ‘Those substances which show conductivity or flow of current are called conductors. These are of 2types: Metallic or electronic conductors : Those conductor which show conductivity due to motion of free electrons. Resistance increases with temperature. Ex. All metals, Graphite Tonic or electrolytic conductors : ‘Those conductors which show conductivity due to movement of free ions, Tons are in free state in the solutions of ionic compounds. On passing electric current through the solution, ions move towards oppositely charged electrodes, ic. the cation moves towards cathode (negative electrode) and the anion moves towards anode (positive electrode). ‘The current flows through the solution due to the movement of the ions. Resistance decrease with temperature. According to strength, ionic conductors are of two types ® @ o) © @w (@) @) Strong electrolyte : Those ionic conductors which are completely ionized in aqueous solution recalled as strong electrolyte For strong electrolyte the value of degree of dissociation is 100% i Strong acid + H,SO,, HCI, HNO, HCIO,, H,S0,, HBr, HI, HBrO,, HIO,, RSO,H Strong base + KOH, NaOH, Ba(OH), CsOH, RbOH Alll soluble salts + NaCl, KCI, CuSO, Weak electrolytes : Those electrolytes which are partially ionized in aqueous solution are called as weak electrolytes. For weak electrolytes the value of ais less than one. Weak acid: : HCN, CH,COOH, HCOOH, H,CO,, H,PO,, HPO, ete Weak base : NH,OH, Cu(OH),, Zn(OH,, Fe(OH),, AI(OH),,, ete —® 1JEE-Chemistry ALLEN 1.2. DEGREE OF DISSOCIATION /IONISATION, + When an electrolyte is dissolved in a solvent (H,O), it spontaneously dissociates into ions. + Itmay dissociate partially («-< 1) or sometimes completely (c. = 1) + Thedegreeof dissociation («) of an electrolytes the fraction of mole of the electrolyte that has dissociated under the given conditions. No.of moles dissociated “= No, of moles token initially 1.3. FACTORS AFFECTING THE VALUE OF DEGREE OF DISSOCIATION: ) Dilution :« « JW. So on dilution, vincreases Gi) Temperature : On increasing temperature, ionization increases so, cinereases (iii) Nature of electrolyte : (a) Strong electrolyte (b) Weak elecrolyte «= 100% << 100% (iy) Nature of solvent : Ifdielectric constant, 1, of solvent increases, then the value of c.increases, HO >u=81 DO >n=79 CH, > h= CO +n =0 Ex.1 Which one has greater a, or a, for the following equation @) NHOU+ (i) NHQH+D,0 >a, 5 a, Sol._ Dielectric constant of HO is more than that of D,O , soa,> a eee eee ee (») Mixing of Ions : Common ion Effect Odd ion Effect NH,OH == NH,’ + OH NH,OH == NH,’ + OH (On mixing NHC] On mixing HCL NH,Cl > NH, + Cr HCl +H +cr Due to mixing of common ion, concentration | Due to reaction of OH ions with H'ion, of ammonium ion will increase therefore | concentration of OH" will decrease equilibrium will shift in backward direetion| :. Equilibrium will shiftin forward direction mean: means a.decreases. ceincreases.ALLEN lonic_Equilibrium 1.4 OSTWALD'SDILUTION LAW (FOR WEAK ELECTROLYTE) + Fora weak electrolyte A’B dissolved in water, if ais the degree of dissociation then AB == AY + B initial cone cM o 0 cone-ateq. — C(1-@)M_— CaM CaM Then acconding to law of mass action, _ 1A‘ ‘a= [AB] c = (1 aj = Aissociation constant of the weak electrolyte /C (volume of solution in which 1 moleis present) is called dilution, so Ky = 7 yy | [Be = fKa.V + Asconcentration increases > adecreases © Atinfinite dilution «reaches its maximum value, unity. ty c= 2, ACIDS BASES AND SALTS. 2.1 Arrhenius concept : (@ Arrhenius Acid : Substance which gives H*ion on dissolving in water (H’ donor) Ex. HNO,, HCIO,, HCI, HI, HBr, H,SO,, H,PO, ete. ‘Types of acids . ete \ t Monoprotic or Diprotie or Triprotic or Monobasie acid Dibasie acid Tribasie acid * Gives single H * Gives two H * Gives three HT per molecule per molecule per molecule e.g HA(HNO., e.g HA {HSO,, eg HA HCIO,, HCH H,PO) (HPO) Gi) Arrhenius base : Any substance which releases OH (hydroxyl) ion in water (OH ion donor) Types of bases v i ae Monohydroxie or Dinydroxic or Trihydroxie or Monoacidie base Diacidic base Triacidic basic * Gives single OH * Givestwo OH Gives three OH™ per molecule. per molecule per molecule Ex.CsOH, RbOH Ex. Bo(OH), Ex. Fo(OH), NH,OH CalOH), —_—_. 3JEE-Chemistry ALLEN Gii) Strength of Acid or Base : 2.2 @ ai) aii) (a) _ Strength of acids or bases depends on the extent of its ionisation. Hence equilibrium constant K, or, respectively of the following equilibria givea quantitative measurement of the strength of the acid or base. @) HAS H+; dissocation orionisation constant of acid. (© Similarly BOH == BY+ OH; x_n _ (BOH] ~ issocation or ionisation constant of base (@) Larger the value of K, or K,,, strongeris the acid orbase respectively. Bronsted - Lowry concept : (Conjugate a - base concept) (Protonic concept) Acid : substances which donate Hare Bronsted Lowry acids (H* donor) Base : substances which accept H' are Bronsted Lowry bases (H’ acceptor) Conjugate acid - base pairs : In a typical acid base reaction, HX +B == X" + HB* HX + Bos HBT +) xX” acid * base ~ Conjugate * Confbgate | acid Base Conjugate pair + Forward reaction - Here HX being a proton donoris an acid B being a proton acceptoris a base. + Backward reaction - Here HB*being a proton donor is an acid X being a proton acceptoris a base. Acid Base Conjugate Conjugate Acid Base + HCl + HOT + + Hso; + NH, == NH; + soy + [FeH,O)*+ HO == H,O* + [Fe(H,0),(OH)* + Conjugate acid -base pair differ by only one proton. + Strong acid will have weak conjugate base and vice versaALLEN Jonic Equilibrium Acid Conjugate base Base Conjugate acid Hcl or NH, NH; HS, HSO, HO HO HSO, so; RNH, RNH! HO ow (iy) Amphoteric (amphiprotic) : Substances which can act as acid as will asbase are known as amphoteric HCl+ 1,0 —= H,0*+ cr base NH, + HO == NH; + OH acid (v) Classification of Bronsted - Lowery Acids and Bases : Bronsted - Lowery acids and bases can be (i) Molecular (ii) Cationic and (iii) Anionic Table -1 Type ‘Acid Base Molecular HCl, HNO,, HCIO, NH,, N,H,, Amines, H,SO,, H,PO,, H,O ete. HO, Alcohol, Ethers, ete. Cationic NH,*. N,H,*, PH,*, [Fe(H,0),OH|"* P*, [AICHO},]* ete. [AI(H,0),OH]* ete. Anionic HS", HSO,, H,PO, HSO, CI, Br, OH, HSO,, CN CO,*S0,".NH,”, CH,COO” ete] all amphiprotie anions 2.3 Lewis concept (electronic concept) : @ Acid: An acid is a moleculefion which can accept an electron pair with the formation of a coordinate bond. Ex. Electron deficient molecules : BF, AICI, ,ete. Cations: H', Fé Fe, Na’ etc Molecules with vacant orbitals : SE,, PP, Base : A base is any molecule/ion which has a pair of electrons which can be donated Molecules with lone pairs : NH,. PH,, H,O, CH,OH, Anions : OH’, H’, NH, . etc.JEE-Chemistry Al 3. PROPERTIES OF WATER @ ~~ Molar concentration / Molarity of water : 1000/ “eg/mole Molarity = No. of moles/itre = i) Tonic product of water : According to arshenius concept, HO ——= H’ + OH So, ionic product of water, K,=[H*)[(OH | = 10at 25° (experimental) Dissociation of water is endothermic, so on increasing temperature K increases. Gii) Degree of dissociation of water : decrease in concentration initially concentration = 2 2 18x 10" or 18x 107% [at 25°C] HO == H'+OH 3 a= Gv) Dissociation or ionisation constant of water : pactae (P}OH) _ 107107 6 HO == H'+ 0H K=K=" pop = gags = 18x 10 So, _pK,= pK, =~ log(1.8 x 10") = 16 ~log1.8 = 15.74 Ex.2. Atdissociation constant of heavy water is 4 x 10 at 33°C. If ts density is 1.04 g/mL. Calculate its ionic product & degree of dissociation. = (4.107 22) © 2.08 x 10 Sol K,=K{D.O, dh eee 7 Ex.3 Calculate ionie product of H,O at 50°C. Sol, AH = 13.7 x 10° cal Ex.4 The hydronium ion cone. in an ag. H,CO, solution is 4 x 10 M at 25°C OH ion cone. in the solution is : (Ayo (B)2.5 x10" (C)25x10— (D)2.5 10" M 208 TO = 12.6410" Answer :(D) Ex.5 Select the correct option from the following ? (A) pK yincreases with increase of temperature (B) pK, decreases with increase of temperature (C) pKy=14at all temperatures (D) pK, =pH at all temperatures Sol_@B) 6 ——ALLE lonic Equilibrium 4, Acidity and pHseale: @ Acidic strength means the tendency of an acid to give H,O" or Hons in water. greater then tendency to give H*, more will be the acidic strength of the substance. (ii) Basie strength means the tendency of a base to give OHions in water. So greater the tendency to give OFT ions, more will be basic strength of the substance. (iii) The concentration of H"ions is written in a simplified form introduced by Sorenson known as pli scale, pHis defined as negative logarithm of activity of H'ions. pH=-loga,,, (where a,,. is the activity of H*ions) (iv) Activity of Htions is the molar concentration of free H*ions or H,O* ions in a dilute solution, butunitless (v) Now pH=-log(H*]=7 and pOH=-log{OH]=7 for water at 25°C (experimental) pH=7=pOH => neutral pH<7 orpOH>7 = acidic at 25°C pH>7orpOH<7 = Basic Neutral Acidic strength <— | —> Basic strength increasing, increasing, +t 0 7 4 4.1 pH Calculation of different Types of sol (a) Strong acid solutior @_Ifconcentration of H’ ionsis greater than 10M, H ions coming from water can be neglected, So [H"] = nomnality of strong acid solution Gi) If concentration is less than 10M, H* ions coming from water cannot be neglected. So (H"] = normality of strong aci id Ex.6 Calculate pH of 1° M HCt solution. +Htions, from) wer in presence of this stro Sok HO == H + OH Wx x k= [HOH] 10*=xix+ 10°) = x 4+xx10*-10"=0 108s fae 1 TOY WAOT-110° _ 9955 197 2 2 : (H'] = 10.5 x 10*= 1.05 107 pH =-log (H"] = log 1.05 ~6.98 —® 7JEE-Chemistry ALLEN 4.2 Strong base solution : Caleulate the [OH"] which will be equal to normality of the strong base solution and then use K = [H'] x [OH] = 10, to calculate [H'] Ex.7 Calculate pH of 107 M of NaOH solution Sol. [OH] from NaOH = 107 [OH] from water =x < 107M (due to common ion effect) HO == of + - (x+107) x K,=[H') [OH] = 10™= x(x + 10°) x°+ 107x-10"*=0 = x=} x107=0618% 107 (6 =2.236) [OH] = 107 + 0.618 x 107= 1.618 x 107 pOH =7 - log(1.618) = 6.79 pH= 14 ~6.79=7.21 4.3 pH of mixture of two strong acids : If V, volume of a strong acid solution of normality N, is mixed with V,, volume of another strong acid solution of normality N,, then Number of H*ions from [-solution = N,V, Number of H* ions from II-solution = N,V, If final normality is Nand final volume is V, then NV=N,V,+N,V, [dissociation equilibrium of none of these acids will be disturbed as both are strong acid] where N ] 4.4 pH of mixture of two strong bases : Similarto above calculation N,V, +N.) (OH]=N="yoy where N= M xn n= Acidity of base | Ex.8 Calculate pH of mixture of (400 mL, x55, a 5 MH,SO,) + (400 mL, 5 a MHCI) +(200mL of water) 1 | 400 4 0 * 100%? = tooo» N2¥2 Sol. N.Y, a H’ ions from water will be neglected NV,+NV,=8x107 Ht] = 899° 29x 10° pH=3-log8 =2.1ALLEN Jonic Equilibrium Ex.9 500 mL of 10° M NaOH is mixed with 500 mL of 2.5 x 10° M of Ba(OH),, To the resulting solution 99 L water is added. Calculate pH. Sob, [OH] = 0020500 282.5:10" 3 x 105M x 105M V,= 1001 no. of moles of [OH initially = no. of moles of [OH] 3x 10°=M,x 100 M,=3x 107< 10° HO == H’ +0 x (x+3x107) K,=x(x+3 x 107) = 10 =(Z_| x 107 302 x 107 [OH], = 3.302 x 107 — ee eS See 4.5 pH of mixture of a strong acid and a strong base : * Acid Base neutralisation reaction will take place. ‘The solution will be acidic or basic depending on which component has been taken in excess. + IfV,volume of a strong acid solution of normality N, is mixed with V, volume of a strong base solution of normality N,. then Number of H*ions from [-solution = N,V, Number of OH ions from II-solution = N,V, If N,V,>NV, WONY,> NY, yg NS -NGV i NV. NV, (H]=N=—y oy [OH] =N= yy, Solution wil Solution will be acidic in nature bebasic in nature 4) 10°" torr)JEE-Chemistry ALLEN Ex.10Caleulate pH of mixture of (400 m1, 3 M Ba(OH),) + (400 ml, a MHCI)+(200 mL of water) x10", so pH Ex.11 What will be the resultant pH when 150 mL of an aqueous solution of HCI (pH = 2.0) is mixed with 350 mL of an aqueous solution of NaOH (pH = 12.0) ? Sol. pH of HCL [HCl] = 10M. pHof NaOH = 12, pOH=2 [NaOH] =1 HCl + NOH —> NaCl + HO Meg. initial 150x107 350x107 0 0 =15 =35 Meg. final 0 2 1s 1s 2 [OH] from Nal pOH = ~log[OH ] =-log (4 x 10°) pOH = 2.3979 pH = 14 ~ pOH = 14 ~ 2.3979 = 11.6021 4.6 pH of a weak acid or weak base (monoprotic) Solution : + Weakacid does not dissociated 100 % therefore we have to calculate the percentage dissociation using K dissociation constant of the acid. + Wehaveto use Ostwald’s Dilution law (ashave been derived earlier) HA —=HY+ & t=0 c a) Cu-a) Co Cu If acc1>(1-a)s1> KeCe >a (is valid if @ <0.1 or 10%) ari=ce=cf& WxE So pi = 3 (pK, loge) On increasing the dilution > CY =e and [H"W pt 10 —__,ALLE lonic Equilibrium Ex.12 Caleulate pH of : (a) 10" M CH,COOH (b) 10° M CH,COOH (c) 10° M CH,COOH Take K,=2x 10° Sol. (a) CH,COOH == CH,COO” + Ht cul-«) Co Ca Oy Jato? (@>0.1) [H'] = 10x 0.1314 = 1.314x 10* > pH =4 -log(1.314)<3.8 (© _ Ifapproximation is used the, « fx o Sowe haveto do the exact caleulation, 2x 10*= 1077 => ax 0.95 or 95% [H"] =0.95 x 10°=9.5 x 107 > pH=7—log(9.5) = 6.022 + Atvery low concentration (atinfinite dilution) weak electrolyte will be almost 100% dissociate, so behave as strong electrolyte. (pH) of 10M HCl = pH of 10°M CH,COOH Ex.13 K, for acid HA is 2.5 x 10° calculate for its decimolar solution at 25°C. @ % dissociation Gi) pH (iii) OH ion concentration So. HA —= H+ A c 0 0 Ca) Ca Ca HHA, {HA} fs { 25.10" c Ty 1/10 =5x 104 = 0.05% wo o (C=1/10M) Gi) [H*}=Co «5x107=5 x 10% mol/l. So pH=5-log 5 ii) (H*] (OH] = 1x 10 1JEE-Chemistry ALLEN Ex.14 Determine the degree of dissociation of 0.05 M NHOH at 25°C ina solution of pH = 10. Sol, NH,OH NH, + OH c 0 0 Given, pH = 10 [H']= 10" [H'] [OH] = 1x 10" 1x10 ay pe 210 [OH] = 10+ Cc 0.05 =2x 107 or 0.2% [5 The concentration of [H']and [OH] of the 10" M aqueous solution of 2% ionised weak acid is : (A)2 x10" Mand 5 x10" M (B)1 x10" Mand 3 x10" M (©)2 10% Mand 5 x10" M (D)3 x10? Mand 4x10" M Sok (A) (W]=Ca=2x 107M of (01) = py =5x 10M Ex.16 When a 0.1 N solution of an acid at 25°C has a degree of ionisation of 4%, the concentration of OH presentis : (A) 2.5 x 10% (B)25 x10" (C)2.5 x10" (D)2.5 x10" Sol (©) 10 : x10°M or [OH] = Sx 10"N [H*] =Ca=0.1x4 x 10" I Ex.17 The degree of dissociation of acetic acid ina 0.1 M solution is 1.32 x 10°. Calculate dissociation constant of acid and its pK, value : Sol. CH,COOH cHCOO + ot Initially ot 0 0 atequilibrium —0,1(1-0.0132) 0.1x 0.0132 0.1x 0.0132 [CH,COO“IH'] _0.1«0.01320.10.0132 a ‘3 = [CH,COOH] Oiq-0.013y = 1-76 10 12 —_—.at 4 Eee 48 pH of a mixture of weak acid (monoprotic) and a strong acid solution : + Weak acid and Strong acid both will contribute H*ion. + Forthe first approximation we can neglect the Hions coming from the weak acid solution and calculate the pH of the solution from the concentration of the strong acid only. To calculate exact pH, we have to take the effect of presence of strong acid on the dissociation ‘equilibrium of the weak acid. + If [SA]=C,and [WA] =C,, then [H'] from SA =C, the weak acid will dissociate as follows. HA == H+ A CG 0 0 +C,)C,0 Cil-0) Core, Ce Ker (axed) (The weak acids dissociation will be further suppressed because of presence of strong acid, common ion effect) K,=(Ca+C)a Total H*ion concentration = tC Ifthe total [H*] from the acid is more than 10°M, then contribution from the water can be neglected, if not then we have to take [H’] from the water also. pH of a mixture of two weak acid (both monoprotic) solution : + Both acids will dissociate partially + Lettheacid are HA, & HA, and their final concentrations are C, & C, respectively, then HA == H+ A HAS eee t=0 Gq oO oO Cc, 0 oO Ateq. Cl-a) Co,+Co, Ca, Cd-a) C+ Ca, Ca, Cyc (Coy +C,e4) (Cet +a] Cs, Ke = Clad K, C,(l-a,) {Since u,,.,both are small in comparision to unity) K,, =(C,o, + Cada, 3 K,, = (Cx, + C, TH] =Co,+ Ca, GK G VOR, +C CK + CR, + Ifthe dissociation constant of one of the acid is very much greater than that of the second acid then contibution from the second acid ean be neglected. He) otc,JEE-Chemistry ALLEN Ex.18 Calculate pH of solution obtained by mixing equal vol. of 0.02 M HOCI & 0.2 M CH,COOH solution given that K., (HOCI) =2 x 10 , K, (CH,COOH) =2 x 10% Also caleulate OH", OCT, CHCOO™ Sol. Final solution volumebecome double C=001, C,=01 (H") =(RGFR,G, = 2107001 2:10" 01 = f2r10%+ 2x10" =2 x 10° 0.3010 = 2.69 Cd -a,) Ca+Ce, Ca, (HOCT] = 10*(1-0,1)=9x 109M [CH,COOH] = 1071 - 0.01) «107 4.9 pHofa solution of a polyprotic weak a + Diprotic acid isthe one, which is capable of giving 2 protons per molecule in water. Letus take a weak diprotic acid (H,A) in water whose concentration is ¢ M. In an aqueous solution, following equilbria exist legree of ionization of HA in presence of HA” K,, = first ionisation constant of HA legree of ionisation of HACin presence of HA K,, = second ionisation constant of HA. Istep IIstep HA + HO== HA + HOt HA + HO== + HO" ateg. c(1-a,) ca,(1o,) (co #coyc,) at eq. cy (1c) cro (CaxFeao4) (H,O° HAC] _(HO*1A] K,),(H,01= Ray (Ky), (01 =" Tal 14 —_—.ALLEN Jonic Equilibrium {ects + 64 Heo (1 (cot +604 eet 4 {1-a) e(l-a,) {oa (1+ (ei e 1% Knowing the values of Ks, , Ky, and, the values of a, and o.,can be calculated using equations (i) and Gi) After getting the values of «, and «., [H,O"] can be calculated as [HO], = ca, + exe, Finally, forcalculation of pH cf If the total [H,O*] < 10 *©M, the contribution of H,O* from water should be added. * Ifthe total [H,0°] > 10°M, then [H,0*] contribution from water can be ignored. Using this [H1,0"], pHof the sotution can be calculated © Approximation : For diprotic acids, K,, << K,, and @, would be even sinallerthan c, 1-a, Land 1+0,01 Cot, x4 I-a, ‘Thus, equation (i) can be reduced to K,, This is expression similarto the expression fora weak monoprotie acid. + Hence, for a diprotic acid (or a polyprotic acid) the [H,O"] can be calculated from its first equilibrium constant expression alone provided K,, << K,,. Ex.19 Caleulate pH of (HS7, [S*], [CI] in a solution which is 0.1 M HCI & 0.1 M HS given that K,,(H,S) = 107, Ka, (H,S) = 10" als caleulate 0, & 0. So HCl + HS 0.1 (ost of [H"] comes from HCI] — + HS O1d-a) 107 Ca=O.1a, Cay 107 107 Kay= Gina Typ (1a = 1) = 10° 15JEE-Chemistry ALLEN 4.10 ISOHYDRIC SOLUTIONS 41 16 fi) Solutions of electrolytes are said to be isohydric if the concentration of the common ion present in them is the same and on mixing such solutions, there occurs no change in the degree of dissociation of either of the electrolyte. (ii) Let the isohydric solution is made by HA, and HA, acids, then [H’] of both acids should be equalice, RELATIVE STRENGTH OF WEAK ACIDS AND BASES Fortwoacids of equimolar concentrations. Strength of acid I) Strength of acid (I) Strength of base () [Ra Similanly forbases, grth af base ‘The modem method is to convert K, as a power of 10 and express acid strength by power of 10 with sign changed and call this new unit pK, Thus, if K, for acid is equal to 10“, pK, = 4. So higher pK, value means lower acid strength, that is, pK, Also, pK, = log K, SALTS @ Salts are the ionic compounds formed when its positive part (Cation) come from a base and its negative part (Anion) come from an acid. Gi) Salts may taste salty. bitter or sweet or tasteless. ii) Solution of salts may be acidic, basic or neutral. (iv) Fused salts and their aqueous solutions conduct electricity and undergo electrolysis. (v) The saltsare generally crystalline solids. ication of salts : he salts may be classified into four categories. @) Normal salt @) The salt formed by the loss of all possible protons (replaceable H” ions) Ex. NaCl, NaNO,, K,SO,, CaPO,),, Na,BO,, Na,HPO,, NaH1,PO, ete. () Acid salts a log K, Salts formed by incomplete neutralisation of polybasic acids. Such salts contain one or more replaceable Hatom, Ex. NaHCO,, NaHSO,, NaH,PO,, Na,HPO, etc. (ii) Above salts when neutralized by base form normal salts, ———~,ALLEN Jonic Equilibrium (Co) wo Ex. i) Basie salts : Salts formed by in complete neutralisation of poly acidic bases are called basie salts. These salt contain one or more hydroxyl groups. ‘Zn(OH)Cl, Mg(OH)CI, Fe(OH), Cl, Bi(OH),C! ete. Above salts when neutralised by acids form normal salts 5.2. HYDROLYSIS OF SALTS Salthydrolysis is defined as the process in which water reacts with cation or anion orboth of a salt to change the concentration of H* and OH ions of water. Salt hydrolysis is reverse process of neutralization. Water + Salt == Acid + Base ; AH = 4ve 5.2.1 Hydrolysis of strong acid - weak base [SA - WB] type salt — Ex. wo Gi) Gi) iv) CaSO,, NH,Cl, (NH,),SO,, Ca(NO,),, ZnCl, CuCl,, CaCl, NH,Cl + H,O == NH,OH+ HCL NH,"+Cl + HO === NHOH + Ht + Cr Net reactior NH," + HO NH,OH + Ht Inthis type of salthydrolysis, cation reacts with HO, therefore called as cationic hydrolysis. Solution is acidie in nature (SAWB) as [H']is inereased. plTof the solution is less than 7. Relation between K, , K,, & K, NH,’ + HO == NH,OH + Ht [NH,OH]H’ | INF] Hydrolysis constant K, For weak Base NHOH == NH,‘ + OI NH; [OH K, == I ] Gi) [NH,OH] For water HO == H'+ OH K,=lOH IIH) iii) Now multiplying Eq. (1) & (2) [NH,OH][H"] — [NH;][OH™ Peon x Oar = (H'] [OH] Eq.3) —_——-. 17JEE-Chemistry Al () Degree of hydrolysis — (Represented by h) NH,’ + HO == NH,OH + Ht ie oO 0 C-Ch ch ch Ginitial concentration at equilibrium) NH.OH[H"] ch [NH] (1-8) Since h 10.26 = 14 -log C-4.74 > log C=9.26- 10.26 =-1.0 c=10'M (NH,Cl] = 107M Wrragio, = 107 x 53.5 gL 35 gl 5.2.2 Hydrolysis of [WA — SB] type salt: Ex. KCN, NaCN, K,CO,, BaCO,, K,PO, NaCN +H,O == NaOH + HCN Nat + CN + H,O == Nat + OH + HCN CN +H,0 == HCN + OF @__Inthistype of salt hydrolysis anion reacts with water therefore called as anionic hydrolysis. Gi) Solutions basic in nature as [OH] increases. ii) pHof the solution is greaterthan 7. (iv) Relation between K,, K,, K, CN’ + HO == HCN + OH [HCN] OH | [HCNJOHH] (CN-IH"] ICN 1HCNI = [HOH] () Degree of hydrolysis : CN +10 == HCN + On c 0 0 Initial concentration at equlibrium -ch cho Gh [Hen Torr] TN] ae K, (-h) ince h <<<< I, therefore (Ih) +1 K,=ch* K,JEE-Chemistry ALLEN (vi) pHof the solution [OH] = Ch [or] (H"] RK On taking ~log on both sides [log K, + logK, log ] wile 1 1 pH=7+ 5pK,+ 5 lose Ex.22 Calculate the pH and degree of hydrolysis of 0.01 M solution of NaC. for HON is 6.2% 10° Sol. NaCN isa salt of strong base NaOH and weak acid HCN. Na* does not react with water whereas CN reacts with water as here under CN + HO == HCN + OF [HCNIOH]_ K, 10% wo TENT K 62x10 6x 10% Let, x moles of salt undergo hydrolysis then concentrations of various species would be [CN] = (0.01 ~x) *0.01, [HCN] = x [OH] =x K= Gora 16x10" x= 16x 10° x=4x 10% [or] 4x 10°M Ky __10" [H,0*] = eu 40°) = 10H] = 4.199 = 025 * 10 20 —__,ALLEN Jonic Equilibrium Degree of hydrolysis Ex.23. Caleulate for 0.01 N solution of sodium acetate - (® Hydrolysis constant (ii) Degree of hydrolysis (iti) pH Given K, of CH,COOH =1.9 x 10°. Sol For CH,COONa + HO == CH,COOH + NaOH Initial = C 0 0 After CU-h) ch ch 10 O10 pe fk = [26:10 “¥o “¥ 001 [OH] from NaOH, a strong base = Ch = 0.01 x 2.29 x 10¢=2.29 x 10M. 5.26 x 10° wo 9 x 10M 5.2.3 Hydrolysis of (WA = WB) type salt : Ex. NH,CN, CaCO,, (NH), CO,, ZnHPO, NH,CN + HO == NH,OH + HCN NH,’ + CN’ + HO == NH,OH + HCN Solution is almost neutral but it may be acidic or basic depending upon the nature of acid & base & [pFT oF the solutionpis near to |For WA= WB Types of salt K,>K, 1. Hydrolysis | Cationie-anionie ic-eationic | Neutral hydrolysis 2, Nawre Acidic Neutral E —_—————~ 21JEE-Chemistr) 3. @ ai) Gi) 22 pH pH<7 pH>7 pH=7 Relation between K,,K,,K, & K,, NH,’ + CN” + HO == NH,OH + HCN [NH,OH HCN] "TNH: J[CN’] @ (NH,OH][HCN] | [NH;][OH"] | [H'J[CN] [INHy]{cn-] “ Oa Tacny “PTIOW K,xK,xK,=K, NH + CN'+H,O == NHOH + HCN c iG 0 0 Initial concentration atequilibrium C-Ch C-Ch ch on NH,OH HCN] [NH ][CN"] Since h ccc 1 Then (1-h)=1 KL or hes -() pH of the solution From eq. (iii) «lor [HEN] _K,«[HeI [en] K Kxh C-Ch~1-h Since h<<<<1,(I—h)#1 [H']=K,xh [Now put the value of h from eq, ( (H"]=ALLEN Jonic Equilibrium fe] On taking ~log on both sides 1 1 pH=7+ 5 pK, ~ 9 PK, Note : Deg ¢ of hydrolysis of [WA — WB] type salt does not depend on the concentration of salt, Ex.24 Salt of weak acid and weak base (i) Calculate pH of the mixture (25 mL of 0.1 M NH OH + 25 mL of 0.1 M CH,COOH). Given that K,: 18 x 10%, and K,= 1.8 x10" Sol. NHOH + CH,COOH > CH,COONH, + 1,0 Initial millimoles 25x 0.1 25x 0.1 0 0 =25 =25 = Final milli moles 0 0 25 25 As salt is formed (salt of weak acid and weak base) and pH will be decided by salt hydrolysis pky+pKy—pk, 1 pH = 8 Et 55 (log 10 — log 1.8 x 10% + log 1.8 x 10%) =7 Ex.25 In the following which one has highest / maximum degree of hydrolysis. (2) 0.01 M- NHC (2)0.1M-NHCI (3) 0.001 M-NH C1 (4)Same Sol. [3] he fhe if C decreases, h increases ¢ Ex.26 In the following which one has lowest value of degree of hydrolysis. (1) 0.01 M -CH,COONH, (2) 0.1 M—CH,COONH, (3) 0.001 M- CH,COONH, (4)Same Sol. [4] Ex.27 Find out the concentration of [H"] in 0.IM CH,COONa solution (K, = 10°) Sol. Salt is [WA - SB] type —_—__. 23JEE-Chemistry ALLEN K, OF I0* TT = Pe = apt = OPO = fF = 10° Ex.28 Calculate the degree of hydrolysis of a mixture containing 0.1N NH OH and 0.1N HCN K,=10" & K,=10% Sol, Salt is [WA WB] IAT™ =i = 10" 5.2.4 Hydrolysis of [SA — SB] type salt : Ex. NaCl, BaCl,, Na,SO,, KCIO, ete. NaCl + HO == NaOH + HCI Na* + Cl + HO == Na* + OW + HY + Cr H,O = H'+ OH (Itis not salt hydrolysis) ()) Hydrolys of salt of [SA SB] is not possible (2) Solution is neutral in nature (pH'= pOH=7) (3) pHof the solution is 7 5.2.5 Hydrolysis of Amphiprotic Anion : NaHCO,, NaHS, ete., can undergo ionisation to from H* ion and can undergo hydrolysis to from OH (Na" ion is not hydrolysed) (a) @ HCO, + HO =="= co} + H,0* (acid) Gi) HCO; + HO <2 H,CO,+ OH (base) (b) Similarly for H,PO; and HPO} amphiprotie anions. (pK, +PK., ) (pK, + PK, ) 7 and PH eaoe) “| z | NaHCO, —+Na"+ HCO; HCO; + HO—8223H1,00, +0H- HCO; +H,O—==CO¥ +H,0° H’ and OH also react z. We can safely assume that both reactionshave nearly same degree of dissociation 24 —_—. EALLEN Jonic Equilibrium [H,Co,] [coz] a Kw [HCOOH] 4 [H.c0,] Divide Q)by 3) pKo, + pKap 2 [H']= JKa;Ka, = pk Ex.29 Calculate the pH of 0.5 MN PO; + H,O == HPO? + OH ; K,(PO;*) = 24 x10" Sol. HPO? and PO? are conjugate acid and base so K, x K, _ 10 = Bad 2.38 10, in aqueous solution KsHPO; =4.17 x 10% pK, =—log K, H=7+ 5 pK,+ 4 loge or pH=7+ 5 pK, + 5 log pH= 3.04 DO YOUR SELF-1 QT Hydrogen ion concentration in mol/L in a solution of pH = 5.4 will be - [AIEEE-2005] (A) 3.88 x 10° (B) 3.98 x 108 (C) 3.98 x 10° —(D) 3.68 x 10°* Q2 Solid Ba(NO,), is gradully dissolved in a 1.0x 104M Na,CO, solution. At what concentration of Ba? will a precipitate begin to forin? (Kgp for Ba CO, = 5.1 x 10) [AIEEE-2009] (A)81x10%M — (B) 8.1.x 107M (©)41x 103M (D)5.1x 105M Q3_ In aqueous solution the ionization constants for carbonic acid are K, =4.2 x 107 and K, =4.8 x 10! [AIEEE-2010} Select the correct statement fora saturated 0.034 M solution of the carbonic acid :- (A) The concentration of H* is double that of CO,” (B) The concentration of CO,"" is 0.034 M (©) The concentration of CO,” is greater than that of HCO, (D) The concentrations of H* and HCO; are approximately equal 6 BUFFERSOLUTIONS A solution that resists change in pH value upon addition of small amount of strong acid orbase or when solution is diluted is called buffer solution, ‘The capacity of a solution to resist alteration in its pH value is known as buffer capacity and the mechanism of buffer solution is called buffer action. 6.1 Typesof buffer solutions (A) Simple buffer solution (B) Mixed buffer solutionJEE-Chemistry ALLEN 62 63 6.3.1 26 SIMPLE BUFFER SOLUTION : A salt of weak acid and weak base in water e.g, CH,COONH,, HCOONH,, AgCN, NH,CN, Buffer action of simple buffer solution Considera simple buffer solution of CH,COONH, since it is a salt will dissociated completely. CH,COONH, —> CH,COO" + NH,* Ifa strong acid such as HCI is added then HCl—> H"+ Cr ‘The H’ ions from the added acid (HC!) combine with CH,COO ions to form CH,COOH, which is a weak acid so will not further ionized, 10 rise in H* ion cor ‘Thus there constant, centration and the pH remai CH,COO” + Ht == CH,COOH (Weak acid) Ifa strong base is added as NaOH NaOH —> Na* + OP NH, + OH’ == NH,(OH) (Weak base) Thus change in OH ion concentration is resisted by NH? ions by forming NH,OH which is a weak base. So it will not further ionized and pH remains constant. pHof a simple buffer solution :- Spee H=7+2 pk, -4 pk, p= 7+ pk, - 3H MIXED BUFFER SOLUTIONS : Acidic buffer solution : An acidic buffer solution consists of solution of a weak acid and its salt with strong base. The best known example is a mixture of solution of acetic acid and its salt with strong base (CH,COONa), Otherexample HCN + KCN, (H,CO, + NaHCO,) —> blood CH,COOH == CH,COO + HY (Weakly ionised) (CH,COONa —+ CH,COO” + Na* (Highly ionised) When a few drops of an acid (HCI) are added to it, the H* ions from the added acid (HC}) combine with the CH,COO”ionsto form CH,COOH. Thus thereis no rise in H* ion concentration and the pH of solution remains constant. On the other hand, when a few drops of base(NaOH) are added, the OI of the added base reacts with acetic acid to form unionise water and acetate ions. CH,COOH + OH == H,O + CH,COO- ‘Thus there is no increase in OH ion concentration and hence the pH of the solution remains constant,ALLEN lonic_Equilibrium pH ofa acidic buffer solution (Henderson equation) : Considera buffer mixture (acidic buffer) HA +NaA — (CH,COOH + CH,COONa) where A=CH,COO, A = CH,COO HA ==Ht+ A" NaA—+Na*+A Applying law of mass action to dissociation equilibrium of HA (HA) = qriay + 80 (H) king k Ht] slog K, + og HA! taking log, ] =log K, + log (>) HAI -log [H*] = - log K,- log iw tal pH =pK, + log ja) [A] = Initial concentration of salt as itis mainly comes from salt (HA] = Initial concentration of the acid (Sal) pH= pK, + log j,3 gj (itis known as Henderson-Hasselbalch equation.) Note : A solution can act as buffer only if ratio of concentration of salt to acid is between 0.1 10 10. CH,COOH =: ~~ CH,COONa 1 10 pH=pK,+1 10 1 pH=pK,-1 ‘Thus pH range of an acidie buffer solution is ( pk, +1) to (pK,— 1) pH range = pK, #1 Maximum bufferaction will be only when ratioof concentration of acid and saltis 1. Soformaximum buffer action, pH= pK, Ex.30 How much volume of 0.2 M solution of acetic acid should be added to 100 mL of 0.2 M solution of sodium acetate to prepare a buffer solution of pH = 6.00 ? (pK, for acetic acid is 4.74) [Salt] Sol. pH=pK, + log jacqj [Salt] Jog {aul = pH pK,= 6.00~ 4.74 = 1.26 Moles of CH,COONa in solution °0"9? 0.02 Let, volume of 0.2 acetic acid added = V ml. V0.2 1000 Moles of acetic aci —_——-. 27JEE-Chemistry ALLEN 0.02 _ o7 7182 1000 V=5.49 mL Ex.31 Calculate the pH after the addition of 80 mLand 100 mL respectively of 0.1 N NaOH to 100 mL, 0.1 N CH,COOH. (Given pK, for CH,COOH = 4.74) Sol. 180 ml. of 0.1 N NaOH is added 10 100 ml. of 0.1 N CH,COOH, acidie buffer will form as COOH + NaOH —+ H,CCOONa + HO Initial 0.01 eq. 0.008 eq. 0 0 Final 0.002 eg. 0 0.008 4. [CH,COO"| 0.008 pH = pK, + log (ey, coon) = 474 + lon pons = 5.542 If 100 mL of 0.1 N NaOH is added is added to 100 mL of 0.1 N CH,COOH, complete 0.1 neutralization takes place and the concentration of H,CCOONa = M =0.05M Now, pH =7 + } pK,+ 3 log C=8.72 32 Calculate the pH of a solution when 0.20 moles of HCI is added to one litre solution containing - (a) 1 M cach of acetic acid and acetate ion ? (b) 0.1 M each of acetie acid and acetate ion ? Given K, for acetic acid is 1.8 x 10%. Sol. (a) Initially [Acetic acid] =1 M [Acetate] = 1 M Now 0.2 moles of HCl are added to it. HCL + CH,COO” > CH,COOH + Ct Mole before reaction 0.2 1 H o Mole afier reaction 0 08 12 02 + New [CH,COOH] = 1.2 ; [CH,COO™] = 0.8 [conjugate] 2 plt=pk,+ log 8 1 pH =—log 18x 10° + log 28 = 4.5686 (b) In I case initially [Acetic acid] = [Acetate] = 0.1 M Now 0.2 mole of HCl are added to it HCl + CH,COO” +» CH,COOH + cr iM Mole before reaction 0.2 Ol 0.1 0 Mole after reaction 0.1 0 0.2 Ol [HE] from free HCl =0.1M . pHs Note:CH,COOH no doubt gives H” but being weak acid as well as in presence of HCl does not dissociate appreciably and thus, H* from CH,COOH may be neglected. 28 —__,ALLEN Jonic Equilibrium 6.3.2 Basie buffer solution : A basic buffer solution consists of a mixture of a weak base and its salt with strong acid. The best known example is a mixture of NH,OH and NH,Cl. NH,OH == NH," + OH- (Weakly ionised) NH,Cl > NH,’ +1 (Highly ionised) When afew drops of a base (NaOH) are added, the OH" ions from NaOH combine with NH," ions to fom feebly ionised NH OH thus there is no rise in the concentration of OH ions and hence the pH value remains constant. NH,’ + OH == NHOH If a few drops of a acid (HCI) are added the H* from acid combine with NH,OH to form H,O and NH,’ ions. NHOH +H* == NH/+H,O ‘Thus the addition of acid does not increase the H" ion concentration and hence pH remains unchanged. pH of basie buffer solution : NH,OH == NH,’ + OH NH,Cl > NH,’ + Ct (INH; [OH K,[NH.OH] _K,[Bese] © [NAg] [Salt] (INH; mainly comes from salt) K, [Base] [Base Jog [sok] > POH =low K, log Fs.) [sett] POH = pK, +logepace) > pH= 14 —pOH pOH range : A solution can act as buffer solution only if ratio of concentration of salt to base is from 0.1 to 10. NH,OH NH,Cl 1 10 10 1 So pOHrange is pK, 1JEE-Chemistry ALLEN * Condition for maximum buffer action : [NH,OH] INH,Cl] 1 1 pOH = pk, + boat pOH=pK, and pH'=14—pK, Maximum buffer action because pH remains constant Ex.33An organic base B has K, value equal to 1 x 10°. In what amounts should 0.01 M HCland 0.01 M solution of B be mixed to prepare 1 L of a buffer solution having pH =7.0 ? Sol B+H,O == BH'+ OH [BH OH] al age [BH’] pOH= pK, + log “Br 2 10%) + Jog OH 7g 4 tog BH > —log (10%) + log gr > 7=8+ log pr I (BH'] 8 BI BH) gt BI =10°=01 Let, volume of HCI taken = xL. ‘Volume of base taken = (1 =x) L After the reaction, millimole of BH* formed = 0.01 x (x) Millimoles of base left = 0.01 (1-2x) [BH] __ x i-2q = BI x = 0,083 L = Volume of HCL ‘Volume of base = 917 L 34 Which of the following buffers containing NH,OH and NH C1 show the lowest pH value? cone. of cone. of NH,OH (mol L") NH_Cl (mot L*) (A) 050 050 (B) 0.10 050 30 —_—_—_.ALLEN Jonic Equilibrium (C) 050 150 (D) 050 0.10 salt Sol. (B) pOH= pk, + log I for NH,C1 = 0.5 and NH,OH = 0.1 pOILwill be maximum and so pH will be minimum, Ex.35 A solution of weak base BOH was titrated with 0.1 N HCL. The pH of the solution was found to be 10.04 and 9.14 after the addition of 5 mL and 20 mL. of the acid respectively. Find the dissociation constant of the base. Sol Case I BOH + HCl —>» BC + HO Millimole before reac. a 0 0 Millimole afterreac. (a-0.5) 0 05 Os Boy : pOH == log K, + log jpop oti) PH=10.04 so pOH=3.96 0.5 4 3.96=-logK, +log nll) Case I: BOH + BER PaE eerie rete Millimole before reac. a O.1x 20 = 0 oO Millimole afterreac. (a2) 0 2 2 [BCl] oe POH =—log K, + log iggpyj (iil) + pH=9.14 . pOH=4.86 ie sea) 4,86 =—log K, + log a Solving Eqs. (ii) and (iv). K,= L81 x 10 7. INDICATORS ‘The stage of titration when complete reaction occur between the solution called equivalent point. ‘The stage of titration when sudden change in colour of solution is observed is called end point. A perfect indicator response sudden colour change exactly on completion of reaction, An indicator is a substance which response sudden change in colour of solution at the end point orneutral point of the acid-base titration, At end point N,V, = N,V, (i) The indicators in acid-base titration changes colour on changing the pH of solution Gil) Allthe acid-base indicators are either weak organic acid orbase and having different colour for unionized and ionised form. ii) A mixture of two colouris recognized ina single colour if the cone. of oneis 10 times or more than that of others. (This 10 time is flexible) —___. 31JEE-Chemistry ALLEN HA =—— > A + Ht colour X colour Y Diss. const. or Conisation const)=K,=K,, = ELAl : : eens aA c [Aq H= pK, +log. PR HL iA] {a) The solution will appear only of colour Y, if imal 210 = pH>(pK+b [A] 1 (b) The solution will appear only of colour X.if FF7A}S7q = PIS (pK- 1) pl of solution below and above which solution appears in a single colour is called pH range of indicator. Indicator pH range Colour change DK, Methyl orange 32-45 Pink to yellow 37 Methyl red 44-65 Red to yellow Sl Litms 55-75 Red to blue 7.0 Phenol red 68-84 Yellow to red 18 Phenolpthalein 83-105 Colourless to pink 96 Ex.36 The disso. const. of a basic indicator is 2 x 10. Calculate its pH range. Sol. 5.7-7.7=pOH pH=63-83 Ex.37 The pH range of an acidic indicator HIn is 4.0 - 3.2 . Caleulate dissociation constant, Also h calculate — for the appearence of solution in single colour. 2 5x 10°,4 Sol. Diss. constant 9.1 TITRATION OF STRONG ACID AGAINST STRONG ALKALI: ‘The graph (A) shows how pH changes during the titration of 50 cm! of 0.1 M HCI with 0.1 M NaOH. NaOH (aq) + HCI (aq) —> NaCl (aq) + H,0 ‘The pH of 0.1 M solution of HCI in the beginning would be 1. As alkali is added, the pH changes slowly in the beginning. However, at the equivalence point pH changes rapidly from about 3.5 to 10. Itcan be shown by simple calculations that pH of the solution is 3.7 when 49.8 cm’ of 0.1 M NaOH solution have been added. The pH suddenly changes to 10 after addition of 50.1 cm of the NsOH solution, Thus, any indicator having pH range between 3.5 to 10 will identify the equivalence point. This means that any one of phenolphihalein, methyl orange orbromothymol blue could be used asan indicator. 32 —__,ALLEN Jonic Equilibrium 72 73 r| t Prestph alata (EPH oeres foes net ana N 8) 0 0 80 100 Volume of base/em: Volume of base/em? © @) Lo oO 50 100 0 50 100 ‘Volume of base/em® Volume of base/em? Titration curves : (A) strong base with strong acid ; (B) weak base with strong acid ; (C) strong base with weak acid ; (D) weak base with weak acid, TITRATION OF STRONG ACID AGAINST WEAK ALKALI: ‘The graph (B) shows how pH changes during titration of 50 em! of 0.1 M HCI with 0.1 M NH, HCI faq) + NH,OH (aq) —> NH {Cl (aq) + HO In this case, the pH changes rapidly from 3.5 to 7.0 at the equivalence point. Methyl orange, methyl red and bromocresol green are suitable indicators forthis type of titration. Phenolphthalein isunsuitable because its pH range lies outside the vertical portion of the curve. TITRATION OF WEAK ACID AGAINST STRONG BASE : The graph (C) shows how pH changes during titration of 50 em’ of 0.1 M CH,COOH with 0.1 M NaOH. CH,COOH (aq) + NaOH (aq) —> CH,COONa (aq) + HO (® ‘The vertical portion of thistitration curve lies between pH range 70 10.6. Phenolphthalein is suitable indicator for this titration. Methyl orange is not suitable for this titration because its pH range lies on the flat portion of the curve.JEE-Chemistry ALLEN 7.4 TITRATION OF WEAK ACID AGAINST WEAK BAS! ‘The graph (D) represents the titration curve obtained for titration of 50 em' of 0.1 M CH,COOH with 0.1 MNH, CH,COOH (aq) + NH,OH faq) —> CH,COONH, (aq) + H,0 (4) For this type of titration there is no sharp increase in pH at the equivalence point, No indicator is suitable for thistype of titration Ex.38 Bromophenol blue is an indicator with a value of K,= 6.84 10°. At what pH it will work as.an indicator? Also report the %e of this indicator in its basie form at a pH of 5.84. Sol HBPh == H*+ BPhr [H*}1BPh] HapH, When BPh” = HBPh, indicator will work. Thus [H"] = 6.84 x 10% pH=5.165 Also if pH = 5.84 or [H*)] = 1.44 x 10°, then (H‘}IBPh] +>" THBPh] _ M4x104Ca K, or 684x10%= “Gor = 0.83 of 83 % 7.5 Titration of Poly protic acid v/s S.B. : 50 mL of 0.1 M H,PO, agent 0.1 M NaOH. Calculate pH when vol. of NaOH added is (a) 0 mL. (b) 25 mL. (©) 50 mL. (@)75 mL. (e) 100 mL. (8) 125 mL (g) 150 mL. (h)200mL =) 90m. ok, 7.pKy,=11 (@) pH=12 (pK, -log C) = 12.8 +1) =2 (b) H,PO, + NaOH == NaH,PO,+H,0 =0 5Mmol 2.5 Mmol 0 7 25Mmol 0 2.5 M mol pH=pK,, +log 1/1 = pK, =3 (©) Solution of HPO, amphoteric species Voume of NaOH pK PK _ 347 pH= PPh = re 34 —__,ALLEN Jonic Equilibrium (@) NaHPO, + NaOH —> Na,HPO, + HO 0 SMmol 5 M mol 0 - 2.5M mol 25Mmol = pH= log 1/1 + pK,,=7 (€) HPO,” solution (amphoteric species) PK tok pH z () Na,HPO, + _ 25 pH=pK,, + log 1/1 =0 (@) 3*eq, pt Na,PO, solution [Na,PO,] = 5/200 = 1/40 pl = 1/2(pK, + pK,, +log C} = 1/2 (144 11-2 +04) = 11.7 (h) 200ml. hydrolysis of Na,PO, can be neglected in presence of NaOH [NaOH] = 5/250 = 1/50 pOH=17 pH=123 @ 90m. NaH,PO, + NaOH — Na,HPO, + H,O 5 4 0 1 0 4 pK, + log 4 10. SOLUBILITY (s) & SOLUBILITY PRODUCT «,) 10.1 SOLUBILITY = Atconstant temperature, the maximum number of moles of solute which can be dissolved in a solvent to obtain 1 litre of saturated solution is called solubility. Solubility depends on the following — @® Temperature Presence of common ion ii) Nature of solventJEE-Chemistry ALLEN 10.2 SOLUBILITY PRODUCT(K,): Whena sparingly soluble salt such as AgClis put into water, a very small amount of AgCl dissolves in water and most of the salt remains undissolved in its saturated solution. A solution which remains in contact with undissolved solute is said to be saturated. The salt AgCl is an elecrolyte, its dissociation occurs in solution. Hence. the quantity of AgCI that dissolves in water dissociates into Ag* and Cl-ions. Thus, in the saturated solution of AgC] an equilibrium exists between undissolved solid AgCl and its ions, Ag’ and Cl-ions. AeCy Be Aa, + according to law of mass action Ag’ |. Cr nel fa Since, the concentration of undissolved solid AgC] is constant. Thus, the product K.[AgCl] gives another constant which is designated as K,, So, K.[AgCl] = [Ag*](CH] K, = [Ag"] (CH K, for CaCl, Cals) = Ca{ag)+ 2CHaq) Solubility product in terms of concentration of ions K, = [Ca®?] [CHP K, for AICI, AICL(s) = Al”(aq)+3CHaq) Solubility product in terms of concentration of ions K,, = [Al] [CH]? General form ABs) = xA*(aq) + yB*(aq) K, =[A°} [BSP ‘Thus, solubility produet is defined as power equal to the number of ions given by when the solution is saturated. 1¢ product of con of the ions raised to a he dissociation of electrolyte ata given temperature 10.3. APPLICATION OF SOLUBILITY PRODUCT (K,) + 10.3.1 To find out the solubility (S) : 36 @ K, of AB (Mono-mono, di-di, tri-tri valency) type salt — Ex. NaCl, BaSO,, CH,COONa, CaCO,, NaCN, KCN, NH,CN, NH,C1 ete. ABS) = Atag) + Biag) 0 0 (as) s sALLEN Jonic Equilibrium Gi) K,,of AB, or A,B (Mono-di or di-mono valency) type salt— Ex. CaCl, CaBr,, K,S, (NH,),$0,, K,$0,, K,CO, ete. ABS) == AMaq) + 2B aq) 0 2s Gii) General form: AB@q) <== xA*%ag) + yBAaq) a 0 0 as xs ys K,=(A". [BAP K, = xs (ys 10.4 COMMON ION EFFECT ON SOLUBILITY : Solubility of substances always decreases in the presence of common ion, According to Le-Chatelier’s principle, on increasing common ion concentration equilibrium shifts in backward direction until the equilibrium is reestablished so, the solubility of substances decreases. Ex. Find out the solubility of AgC] in water and in the presence of CM —NaCl solution? AgCl == Agt +) Cr CM.NaCl SM SM (Let solubility of AgCl is S mol L*) Ag’) [Cr] In NaCl solution NaCl —> Nat + Cc Cc 2 Let solubility of AgCl in the presence of NaCl solution is S’ mol L* AgCl == Agh +) Ch s suc K,,=[Ag'T [CH K,=8' S'+O =s'*SC (Neglecting the higher power terms of S’) peeJEE-Chemistry ALLEM 105 SIMULTANEOUSSOLUBILITY : ‘When two sparingly soluble salts are added in water simultaneously, there will betwo simultaneous equilibria in the solution. 10.6 SOLUBILITY IN APPROPRIATE BUFFER SOLUTIONS : Appropriate buffer means that the components of buffer should not interfere with the salt or only H* or OH ions should be interacting with the ions of the salt. 10.7 EFFECT ON SOLUBILITY BECAUSE OF COMPLEX FORMATION : Solubility of AgCl in aqueous NH, is roughly 10,000 times as its solubility in water, due to complex formation. AgCl(s) = Ag*(aq) + CF (aq) Ag*(aq) + 2NH,(aq) = Ag(NH,), (aq) s Kremtin = Kessain =K, Kati and asta 108 CONDITION OF PRECIPITATION IONIC PRODUCT (IP OR Q,): + onic product (IP) of an electrolyte is defined in the same way as K,,. The only difference isthat ionic product expression contains the initial concentration of ions orthe concentration at any time whereas the expression of K,, contains only equilibrium concentration, Thus, for AgCl IP=(Ag*], (Cr, and K, = [Ag*],,{CI], + Ionic product changes with concentration but K,, does not + Todecide whether an ionic compound will precipitate, its K, is compared with the value of ionic product. The following three cases arise @ PK, : Thesolutionis supersaturated and hence precipitation of the compound will occur. ‘Thus, a saltis precipitated when its ionic product exceeds the solubility product of the salt 10.9 SELECTIVEPRECIPITATION : When the k,, values differthen one of the salt can be selectively precipitated. DO YOUR SELF- QU The solubility in water of a sparingly soluble salt AB, is 1.0.x 10° mol L~". Its solubility product will be [AIEEE-2003] (A) Lx 105 (B) 1x 10? (4x 105 D)4x 10” Q2. The solubility of Mg(OH), is x moleflt. then its solubility product is-_ [ATEEE-2002] (Ax? (B) 5x3 (© 4x3 (D) 2x? Q3_ The molar solubility in mol L-' of a sparingly soluble salt MX, iss. The corresponding solubility product is Kg. 's' is given in terms of Kg, by relation : [AIEEE-2004] (A) 8 = Kg, / 128)! (B) s = (128K) "4 (C) 8 = 256K)" @) $= Ky/256)" 38 —_—_—_.ALLEN lonic_Equilibrium Q4 The solubility product of a salt having general formula MX,, in water is : 4 x 10° 2, The concentration of M2* ions in the aqueous solution of the salt is - [AIEEE--2005] (A) LOx10°-4*M = (B) 2.0 x 10°°M (C)4.0x 10M (D) 16x 104M Q5_ Ina saturated solution of the sparingly soluble strong electrolyte AglO, (molecular mass = 283) the equilibrium which sets in is ~ [AIEEE-2007] AglO, === Agha + Iie; If the solubility product constant K,, of AgIO, at a given temperature is 1.0 x 10-8, what is the mass of AgIO, contained in 100 ml of its saturated solution 7 (A) 28.3 x 10 (B)283x10%g (10x17, D)LOx 104g Q6 The pK, of a weak acid, HA, is 4.80. The pK, of a weak base, BOH, is 4.78. The pH of an aqueous solution of the corresponding salt. BA, will be - [AIEEE-2008] (A) 9.58 {B) 4.79 (©) 7.01 (D) 9.22 Q.7_ Solubility product of silverbromide is 5.0 x 10°’, The quantity of potassium bromide (molar mass taken as 120 g mol ') tobe added to 1 litre of 0.05 M solution of silver nitrate to start the precipitation of AgBr is :- [AIEEE-2010] (A) 5.0x 10% g¢ (B) 1.2.x 107% g (C) 12x 10% ¢ (D) 6.2 x 10% ¢ Q8 At25°C, the solubility product of Mg(OH), is 1.0 x 10-11, At which pH, will Mg ions start precipitating in the form of Mg(OH), from a solution of 0.001 M Mg?* ions ?[ AIEEE~2010] (A8 (B)9 (C) 10 (D) 11 Ex. 39. (i) Al, (SO,),(s) = 2Al*(aq) + 3803(aq) K,=2? x 3x (8) sd x 27x SS = 108 5° (ii) Na, KPO {s) = 2Na°(aq) + K*(aq) + POZ(aq) K,=2 x 1 x 1 (SP = ds! (iii) NaKRbPO {s) = Na'(aq) + K'(aq) + Rb*(aq) + PO;(aq) K, Ex Px ExT x (Syn st Ex. 40. If solubility product of the base M(OH), is 2.7 x 10, the concentration of OH- will be (3x 1 (3x 104 Qo ir Answer :(3) Ex. 41. The solubility of BaSO, in water is 1.07 x 10° mol dnc. Estimate its solubility product. Sol. Solubitit y equilibrium for BaSO BaSO,., Bal, SO%,., Now, $= 1.07 x 10°M Hence, K, = (1.07 x 10 145 x 10°JEE-Chemistry ALLEN Ex, 42.The solubility product of AgBr is 5.2 x 10-%, Caleulate its solubility in mol dm and g din, (Molar mass of AgBr. = 187.8 g mot") Sol. The solubility equilibrium of AgBr is AgBry == Agi + Bray The molar solubility S of AgBr is given by 2x 10° mol dm The solubility in g dmv® = molar solubility (mol dnr*) x molar mass (g mol”) = 7.2 x 10? x 187.8 = 1.35 x 107 g div? Ex. 43.What is the maximum volume of water required to dissolve 1 g of calcium sulphate at 25°C. For calcium sulphate, K,= 9.0 x 10°. Sol. CaSO,(aq) Ca’* (aq) + S07 (aq) IfS is the solubility of CaSO, in moles Ca*] x [S03 1S= (RK, = Jo0x107 =3x 10" mol Lt 3 x 10" x 136 gL = 0.408 gl! For dissolving 0.408 g of CaSO, water required = IL : i Seas Ber “1 Fordissolving 1g CaSO, water required = 5 gggl =2.45L Ex. 44.Equal volumes of 0.04 M CaCl, and 0.0008 M Na,SO ,are mixed. Willa precipitate form? K,, for CaSO, = 2.4 x 10% Sol. CaCl, + NaSO, > CaSO, + 2NaCl Millimole added 0.04V 0.008% 0 0 Suppose V ml. of both are mixed av. 0.04V [Ca*] = ooh) _ 0.0008 [SOL] = Sy + (ca*] [80%] = SEY SOOBN gx 19° Thus, [Ca’*] [SO] in solution < K,, 8x 10% 24x 10% + CaSO, will not precipitate. 40 —__,ALLEN Jonic Equilibrium Ex. 43.Caleulate simultaneous solubility of silverthiocyanate and sliver bromide in water given that 5 x 10 respectively. K,, of silver thiocyanate = 10" and k,, of silver bromide Sol. Let the solubility of AgSCN be x and that of AgBr is y, then AgSCN == Ag’ + SCN AgBr == Ag’ + Br xty ox rty oy JOP =x(x+y) (i) 5x10" = yx +y) sum (ii) 2 08x 107 and x= 8.16 x 107 On solving we get, So Ex. 46.What [H"] must be maintained in saturated H,S(0.1 M) to precipitate CdS but not ZnS, if [Cd**] = [Zn**] = 0.1 initially ? K,,= (CdS) = 8 x 10” K,,= (ZnS) = 1 x 107 K.-S Ld x 107 Sol. In order to prevent precipitation of ZnS (Zn"*] [S"] < K, ZnS) = 1 x 10% (ionic product) or (0.1) [S*} <1 x 10" or [8] <1x 10" This is the maximum value of [S*-] before ZnS will precipitate. Let [H*] 10 maintain this [S°-] be x Thus for HS = 2H" + S* PISS) a.t0™ K-"HS] o1 11x 107 or =x=[H*]=0.1M No ZnS will precipitate at a concentration of H’ greater than 0.1 M Ex. 47, What must be the concentration of ag. NH {eq.) which must be added to a solution containing 4x 10°M Ag’ and 0.001 M NaCl, to prevent the precipitation of AgCl. Given that K,(AgCl) = 1.8 x 10° and the formation constant of [Ag(NH,)3J* is 10° 6 Sol. Calculate silver ion concentration which can be allowed to remain in the solution, 18 x 10" = [Ag*}[CE] kK, maton _ 18x10" [Ag*] = yo, = 18 x 107M, This quantity is so small that almost all the Ag* ion will be consumed. ———-9 AlJEE-Chemistry ALLEN : 10° Ag’ + 2NH, == [Ag(NH, k= 4x10" b 0 18x07 (b-8x 10") 4x10" K aa = Tab => b=0.0445 Ex. 48. 0.10 mol sample of AgNO, is dissolved in one litre of 2.00 M NH, Is it possible to form AgCl(s) in the solution by adding 0.010 mol of NaCl ? (Kapaa = 18 x 10, Kesgieigth = 16 x 107) Sol Ag* + 2NH, == [Ag(NH,),] 010M 2.00 0 0.10-0.10 (2-0.20 M) 0.10 =0 80M Iris assumed that all Ag* ions have been complexed and only xamount is left _TAGINES ISI “= Tag TINS > 0.10 xU.80P 16x10" = x= 1.93 x 10°M = [Ag*] undisolved {CT} = 1.0 x 10° M FAg*TICt] Hence, AgC1 (s) will not precipitate. Ex. 49.What is the concentration of Ag’ ions in 0.01 M AgNO, that is also 1.0 M NH, ? Will AgCl precipitate from a solution that is 0.01 M AgNO, 0.01 M NaCl and 1 M NH,? KjAg(NH,]2) 10° ; KfAgCl) = 1.8 x 10". Sol. Let us first assume that 0.01 M AgNO, shall combine with 0.02 NH, to form 0.01 M Ag(NH,); and the consider its dissociation. 1.93 x 10° 1.0.x 107 = 1.93 x 10" < 18 x 10 IK, SARC fp AgNO, —> Ag(NH) sulnitial cone. 0.01M 0 0 001M sult €g. CONE. Ag(NH,),’ == Ag® + (0.01 ~x) x (0.98 + 2x) =0.01M 20.98 M Equi, cone Sincex <<< I 42 —_—.ALLEN Jonic Equilibrium [Ag"IINHP TAgINH 88 x 10° 5.88x10* «0.01 (Ag*] =~ hogy = 12 x 10 M Further, ionic product of AgCl = [Ag] [CY] = (6.12 x 107°) (0.01) = 6.12 x 10°" Because the ionic product is smaller than K,, = 1.8 x 10", no precipitate should form. ANSWERS: DO YOUR SELF-1 QI AnsiC) Q2 Ans(D) Q3 Ans.(D) DO YOUR SELF-2 QI Ansic) Q2 Ans(C) Q3 Ans(D) Q4 Ans(A) QS Ans(B) Q6 Ans(C) QT Ansic) Q8 Ans(C)JEE-Chemistry ALLEN PREVIOUS YEARS MISCELLANEOUS QUESTION QI What willbe the resultant pH when 200 mil of an aqueous solution of HCI(pH = 2.0)is mixed with 300 ml of an aqueous solution of NaOH (pH = 12.0)? Ans, pH= 11.3010 {HF} [OFF] = 10% 300 ml 200 ml w + Of ==HO t=0 mm 2 3 - + mm - 1 - 1 2x10" pOH = 3 - log 2 pH = 11 +log 2 = 11.3010 Q2 The pHof 0.1 M solution of the following salts inereases in the order [JEE 1999] (A) NaCl < NH,Cl < NaCN < HCI (B) HCl < NH,Cl < NaCl < NaCN (C) NaCN < NH,Cl < NaCl < HCl (D) HCl < NaCl < NaCN < NH,CI Ans. (B) Sol, NaCl pi=7 NHCI pH<7 NaCN pH>7 HCI pli<7 HCI NaCl +H, 6 «1000 Oe 100H =0 100 150 Hc + NaOH > AcNa +10 t=0 100 50 ne Cesena so [pH = pKa =5 ~ log 1.75] [pH = 4.75]JEE-Chemistry ALLEN Q8_— Asolution which is 10 M each in Mn®*, Fe**,Zn* and Hg** is treated with 10M sulphide ion. If K,,, MaS, FeS, ZnS and HgS are 10715, 108, 10° and 10 respectively, which one will precipitate first? [JEE 2003] (A) Fes (B) MnS (C) Hes (D) ZnS Ans, (C) Sol. LP = [M"] [S*] = (10%) 10") = jo” IP>K, Hg$ will ppt first Q9 Will the pH of water be same at 4°C and 25°C ? Explain, [JEE 2003] Ans, No, it will be > 7 at 0°C. Sol, H,O—=H" +OH AH=+Ve On increasing temp reaction will move in forward direction hence [H*) will increase and pH will decrease Q.10 0.1 Mof HA is titrated with 0.1 M NaOH, calculate the pHatend point, Given Ka(HA)=5x 10-and ace l [JEE 2004] Ans, pH=9 Sol. pH= sl" +p +logC, ] = Fli4+6-tog5 +1090 i] $[20-1-07] 1 [18.3] 7ls3] pH=9.15 QUI HX isa weak acid (K, = 10). It forms a salt NaX (0.1 M) on reacting with caustic soda, The degree of hydrolysis of NaX is (A) 001% (B) 0.0001% (C)0.1% (D)05% [JRE 2004] Ans, (A) Sol. =10" %h =107 = 0.01% QU2_ CH,NH, (0.1 mole, K,, =5% 10“) is added to 0,08 moles of HCl and the solution is diluted to one litre, resulting hydrogen ion concentration is (A) 16x10! (B)8 x 101 (©)5x 10 (D)2x 10 [JBE 2005] Ans. (B) 46 —_—.lonic Equilibrium ee ime ati lLy Sol. CHNHOH + HCL > CHYNHCL + #0 t=Omole 0.1 0.08 a. a t mole 02 é 08, - pOH = pkb+log4 pOH = 4—log5+log4 ~toe[O1] =-Hoe{ $10 Sa0=8e10" Ans. [B] QI3. If Ag* + NH, = [Ag(NH,)]* K, = 1.6 x 10° and [JEE 2006] [Ag(NH,)I* + NH, = [Ag(NH,),]* : K, = 6.8 x 10° ‘The formation constant of [Ag(NH,),]* is (A) 6.08 x 10° —(B) 6.8 x 10% (©) 16 x 10° (D) 1.088 x 107 Ans(D) Q.14 The species present in solution when CO, is dissolved in water (A) CO), H,CO,, HCO; , CC {B) H,CO,, CO, (©) CO, HCO, (D) CO, , H,CO, Ans. (A) 2 X10" at 25°C) is titrated with 7 MHClin water 2 QS. 2.5 mL of | Mweak monoacidic base (Ky = at 25°C. The concentration of H* at equivalence point is, [JEE 2008] (Ky =1x 10" at 25°C) (A)3.7x108M — (B)3.2x107M — (C)3.2x10*M —(D)2.7x 107M Ans, (D) Sol. No. of geq of BOH = no. of geq of HCEJEE-Chemistry ALLEN Q16 Qu7 Ans, Qs Ans, 48 10h? +h-1 = 0 pe zityie4o 20 he! v4l-1 20 Solubility product constants (Ky) of salts of types MX, MX, and M,X at temperature ‘T’ are 4.0.x10°8,3.2x10" and 2.710 "5 respectively. Solubilities (mol dn) ofthe salts at temperature "T’ are in the order: (A) MX > MX, > M,X (B) M,X > MX, > MX [JEE 2008] (C) MX, > M,X > MX (D) MX > M,X > MX, o) MX M,X 27S} = 27 x 10"* 8,>8,>8 MX >M,X > MX. Ans, (D) ‘The dissociation constant of a substituted benzoic acid at 25°C is 1.0 x 10-4. The pH of a 0.01 M solution of its sodium salt is [JEE 2009] p= $116)=8 Ans, 08 Aqueous solutions of HNO,. KOH, CH,COOH and CH,COONa of identical concentrations are provided. The pair(s) of solutions which form a buffer upon mixing is(are)- (JEE_ 2009] (A) HNO, and CH,COOH (B) KOH and CH,COONa (C) HNO, and CH,COONa (D) CH,COOH and CH,COONa ©.)ALLEN Jonic Equilibrium EXERCISE-S-1 Q3 Q4 Q6 Q7 Qs Q9 Q10 Qu IONIZATION CONSTANTS AND pH Calculate the number of H* present in one ml of solution whose pH is 13 G) K,, for HO is 9 x 10 at 60°C, What is pH of water at 60°C, (log 3 = 0.47) (Gi) Whatis the nature of solution at 60°C whose ) pH=6.7 (b) pH = 6.35 ‘The value of K,, at the physiological temperature (37°C) is 2.56 x 10-4. What is the pH at the neutral point of waterat this temperature? (log 2 =0.3) Caleulate pH of following solutions: @ 0.1MHCI (b) 0.1 MCH,COOH (K,= 1.8 x 10) (log V1.8 =0.13) (©) 0.1 MNH,OH (K,= 1.8 x 10°) 108 MHCI [V40i = (20.02)] [log 1.051 = 0.03] (© 10° M NOH () 10M CH,COOH (K,= 1.8 x 10) (g) 10° MCH,COOH (K,= 1.8 x 10) [401 = (20.02)} [og 1.051 = 0.03] (bh) Decimolar solution of Baryta (Ba(OED,), diluted 100 times. (log? = 0.3) @ 10 mole of KOH dissolved in 100 L of water. (@ Equal volume of HCI solution (PH =4) + 0.0019 N HCI solution Calculate (a) K,fora monobasic acid whose 0.10 M solution has pH of 4.50. (b) K, fora monoacidie base whose 0.10 M solution has a pH of 10.50. Calculate the ratio of degree of dissociation (o./t,) when an acetic acid solution is diluted 100 times. Assume ct << 1, even on dilution. [Given K,=10-SM] Calculate the ratio of degree of dissociation of acetie acid and hydrocyanic acid (HCN) in | Mtheir ven K, 8x10": K, x10") How many moles of HCl must be removed from 1 litre of aqueous HCI solution to change its pH from 2 to 32 respective solution of acids.[ -icH.c008) = Hex) = ‘The pH of aqueous solution of ammonia is 10. Find molarity of solution. K,, (NH,OH) = 10%. ‘The solution of weak monoprotic acid which is 0.01 M, has pH = 3. Calculate K, of weak acid. Boric acid is a weak monobasic acid. It ionizes in water as. BOH), + H,0 = BOH); + H*:K,=8 x 10 Calculate pH of 0.5 M boric acid. ———-9 49JEE-Chemistry ALLEN Qu Q13 MIXTURE OF TWO OR MORE ACIDS/BASES ‘The pH of the solution produced when an aqueous solution of strong acid pH 5 is mixed with equal volume of an aqueous solution of strong acid of pH 3 is = Calculate pH of following solutions : [log 0.3 = - 0.522] (a) 0.1 MHLSO, (50 mil) + 0.4 M HCI 50 (aml) (b) 0.1 MHA + 0.1 MEB [K, (HA) =5 x 10%; K, (HB) =4 x 105] Q.14 Calculate pH of a solution containing 0.1M HA (Ka = 10°) & 0.1 MHICL Qs Q16 Qu7 Q18 Qus Q20 Q2: Q2: Q24 Qs Q26 Q27 Q28 Q29 50 POLYPROTIC ACIDS & BASES What are the concentration of H*, H,C,O,, HCO, and C07 ina 0.1 M solution of oxalic acid ? [K, =10? Mand K, = 105M] [v41=6.4] Calculate pH of 0.2 M- B(OH), solution. (Ky, = 2.x 105;K,,=4 x 10, log? = 0.3) HYDROLYSIS What is the OH concentration of a 0.18 M solution of CH,COONa. [K (CH,COOH)=18 x 105] Calculate the pH of a 2.0 M solution of NH,CI [K,, (NH) =2 x 10°] 0.25 M solution of pyridinium chloride C.H,N*Cl- was found to have a pH of 2.699. What is K, for pyridine, CJH,N ? dog? = 0.3010) Calculate the extent of hydrolysis & the pH of 0.02 M CH,COONH,. IK, (NH,}= 1.8 x 10°, K (CH,COOH)=1.8 x 10-5] Calculate the percent hydrolysis in a 0.06 M solution of KCN, [K,(HCN) = What is the pH of 0.1M NaHICO,? K, x10} K,=5x 10"! for carbonic acids, ‘The acid ionization (hydrolysis) constant of Zn?*is 1.0% 10° (a) Calculate the pH of a 0.001 M solution of ZnCl, (b) What is the basic dissociation constant of Zn(OH)"? BUFFER SOLUTION Calculate the pH of solution containing 0.1M - HCN and 0.1M- NaCN. Ka of HCN = 10° Calculate the pH of solution containing 0.2 M - NH,OH and 0.1 M— NH,CL. K, of NH,OH = 18x 10 dog? = 03, log 1.8 = 0.26) 0.4 mole CH,COONa is added in 500 ml 0.4 M—-CH,COOH solutions. What is the pH of final solution ? K, of CH,COOH = L8 x 10-5, (log? = 0.3, log 1.8 = 0.26). Abufferof pH9.26 is madeby dissolving x moles of ammonium sulphate and 0.1 mole of ammonia into 100 mL. solution. If pK, of ammonia is 4.74, calculate value of x. Determine [OH"] of a 0.050 M solution of ammonia to which sufficient NH,CI has been added to make the total [ NH ] equal to 0.100.[Kyxut,) 8x 10%, pK, = 74] Calculate the pH of a solution containing 0.2 MHCO, and 0.1 M CO,? (K,(H,CO, ) = 4 x 107; K, (HCO, ) =4 x 101] ———-,ALLEN lonic_Equilibrium Q30 Calculate the pH of a solution prepared by mixing 50.0 mL of 0.200 MHC,H,O, and 50.0 mL. of 0.100 M NaOH. Kyci,coom =1.8 x 10°, pK, = 4.74] 31 50 mL of 0.1 M NaOH is added to 75 mL of 0.1 MNH,Clto make a basic buffer. If pK, of NH} is 9.26, calculate pH. Q32 Calculate the pH of a solution which results from the mixing of 50,0:ml of 0.3 M HCI with 50.0 ml of 0.4 MNH,. IK, (NH,) = 8x 10°, pK, = 4.74] Q.33_ In 100ml buffer solution of 0.1M CH,COOH & 0.1M CH,COONa, how many millimoles of NOH should be added to increase it’s pH by 0.3. Given (log 2 = 0.3) ACID BASE REACTIONS & TITRATIONS Q.34 Calculate OH” concentration at the equivalent point when a solution of 0.2 M acetic acid is titrated with a solution of 0.2 M NaOH. K, for the acid = 10°, Q.35 Calculate the hydronium ion concentration and pH at the equivalence point in the reaction of 22.0 ml of 0.10M acetic acid, CH,COOH, with 22.0 mL. of 0.10 M NaOH. [K, = 2 x 10] Q.36 Calculate the hydronium ion concentration and the pHat the equivalence pointin a titration of 50.0 ml of 0.40 M NH, with 0.40M HCLIK, = 2x 10] Q37 CH,COOH (50 ml, 0.1 M)is titrated against 0.1 M NaOH solution. Calculate the pH atthe addition of O mil, 10 ml 20 ml, 25 ml, 40 ml, 50 ml of NaOH. K, of CH,COOH is 2 x 10°. {log 2 =0.3010, log3 = 0.4771] INDICATORS Q38_ Fortheacid indicatorthymol blue, pH is 3 when half the indicators in unionised form. Find the % of indicator in unionised form in the solution with [H*] =4 x 10-* M. Q39 Bromophenol blucis an acid indicator with a K, value of 6 x 10-5, What % of this indicatoris in its basic form ata pH of 5? X10“, Por Q.40__ At what pH does an indicatorchange colonrif the indicatoris a weak acid with K,., which one(s) of the following neutralizations would the indicator be useful ? Expl: (a) NaOH + CH,COOH (b) HCL + NH, (©) HCl + NaOH Q41 Anacid indicatorhas a K, of 3 x 10°S. The acid form of the indicators red & the basic form isblue. By how much must the pH change in order to change the indicator form 75% red to 75 % blue? [log 3 = 0.4771) SOLUBILITY & SOLUBILITY PRODUCT'S Q42 Thevaluesof K,, forthe slightly soluble salts MX and QX, are each equal 104.0% 10-8, Which salt ismore soluble? Explain youranswer fully. Q43 The solubility of PbSO, in wateris 0.0608 g/L. Calculate the solubility product constant of PbSO,. Molar mass PbSO, = 304 g/mole Q44_ How many mole Cul (K,, = 5x 10°!) will dissolve in 1.0 L of 0.10 M Nal solution ? Q.45 A solution of saturated CaF, is found to contain 4 x 10“ M fluoride ion. Calculate the K,, of CaF, Negleet hydrolysis. —_——-. 51JEE-Chemistry ALLEN Q46 Qa7 Q48 Qa49 Q50 Qsl Qs3 52 ‘The solubility of ML, (formula weight = 60 g/mol) in water is 2.4 x 10° 9/100 mL. solution. Calculate the solubility product constant for ML, Calculate the solubility of A,X, in pure water, assuming that neither kind of ion reacts with water. For A,X, Ky, = 1.08 x 10° Determine the solubility of AgCl in 0.1 MBaCl,, [K,, for AgC Calculate solubility of Ca,(PO,), (K,, = 10") in presence of 0.1 M CaCl, solution. SIMULTANEOUS SOLUBILITY Caleulate the Simultaneous solubility of AgSCN and AgBr. K,, (AgSCN) = 3.2 x 107 K, (AgBr) = 8 x 10-8, x 10-10] COMPLEX FORMATION Calculate the solubility of AgCl in 0.2 M- NH, solution, Given :K,, of # x 10", Ky of Ag(NH,),*= 8 x 10°. SOLUBILITY, CONSIDERING HYDROLYSIS Caleulate the solubility of AgCN in a buffer solution at pH = 3.0... Given : K,, of AgCN = 8x 10", K, of HCN =5 x 10, PRECIPITATION A solution has a Mg?* concentration of 0.0010 mol/L. Will Mg(OH), precipitate if the OBE concentration of the solution is [K,= 1.2.x 10-"!] (a) 10° mol. (b) 10 mol? 200 mil of 2 x 104M ~ AgNO, solution is mixed with 400 ml of 1.2 x 10° M— NaCl solution. Predict whether precipitation of AgCl will occur or not. Ksp of AgCl = 2 x 10" Calculate the minimum mass of Na,SO, needed to just start precipitation of BaSO, from 500 ml of 2x 105M - BaCl, solution. Ksp of BaSO, = 8 x 10°.ALLEN Jonic Equilibrium EXERCISE S-I1 Qu Q4 Qs Q6 QT Q8 Q9 Q10 What are the concentrations of H*, HSO; S07 and H,SO, in 0.20 M solution of sulphuric acid? Given: H1,S0,—> H* +1180; ; strong HSO; 2 Ht + SO} 07M Nicotine, C,H, ,N,, has two basic nitrogen atoms and both can react with water to give a basic solution Nic (aq) + H,O () 2 NicH* (aq) + OFF (aq) NiclI* (aq) + H,0 (1) 2. NicI1,* (ag) + OH (aq) K,, is8 x 107 and K,, is 10-1. Calculate the approximate pH of a 0.20 M solution. An aqueous solution contains 0.01 MRNH, (K,,=2x10-*) & 10M NaOH. The concentration of OWT is nearly Caleulate the pH of 1,0 x10" M sodium phenoxide, NaOC,H,, K, for HOC,H, is 0.6 x 10". Calculate the pH of 0.1 M solution of (i) NaHCO,, (ii) Na, HPO, and (iii) NaH,PO,, Given that: CO, + H,O —= Ht + HCO; ; K,=4.2x 107M HCO; — H*+ cod; K,=4.8x 10M H,PO, —= H*+ H,P0;; K,=7.5x 10°M HPO; == H*+ HPO}: K,=6.2x 10M HPO} == I+ pod; K,=10x10"M (log 4.2 = 0.62, log 4.8 = 6.8, log 6.2 = 0.80, log 7.5 = 0.88) An ammonia-ammonium chloride buffer has a pH value of 9 with [NH] =0.25. What will be the new pIif 500 ml 0.1 M KOH is added to 200 ml buffer sotution (K,,=2x 10) [log 2 = 0.3] 10 ml of 0.1M weak acid HA(k, = 10°) is mixed with 10 ml 0.2M HCl and 10 ml 0.1M NaOH. Find the value of [A] in the resulting solution, 150 ml of 0.5 MHCN (Ka =3.75 x 10) was reacted with 1.5 MKOH for complete neutralisation, What will be molarity of HCN at equilibrium. How much AgBr could dissolve in 1.0 L of 0.40 M NH, ? Assume that Ag(NH,},* is the only complex formed. [K,(Ag(NH,);) = 1 x10; K,, (AgBr) = 5 x10] [50 =7] Calculate solubility of Pb, (K,, = 1.4 x 10-8) in water at 25°, which is 90% dissociated. ce (amas) 1.78.JEE-Chemistry ALLEN EXERCISE O-1 Single correct QU The conjugate acid of NH; is (A) NH, (B) NH,OH (©) NH} (D) N.H, Q2 Which of the following is not a Bronsted acid:- (A) CH.NH (B) CH,COO- (©) HO (D) HSO; Q3 Inthe reaction HNO, + H,O === H,0* + NO, the conjugate base of HNO, is = ) HO (B) HO* (©) NOs, (D) H,0* and NO Q.4 — Outof the following, amphiprotic species in aqueous medium are I HPO! mn OH M HPO, IV HCO, (A)LULIV (B) land U1 (C)Mland IV (D) All Q5 When ammonia is added to water, it decreases the concentration of which of the following ion (A) OFF (B) H,O* (©) NHY (D) NH & OH Q6 Which of the following pair is Lewis acid & Lewis base & Product of these is also Lewis base (A) BF, , NH, (B) SIC, 2CP—(C) CH? , POC,H, (D) All of these Q7 onic product of water will increase, if = (A) Pressure is decreased (B) His added (C) OH is increased (D) Temperature is increased Q8 At 60°C, pure water has [H,0*]=10-°7molMit. what is the value of Ky, at 60°C = (A) 10% (B) 10°? (C) 10-7 (D) 10-4 Q9 Liquid NH, ionises to a slight extent. At a certain temperature its self ionization constant Kay 10°. The number of NH,* ions present per 100 em? of pure liquid are (A) 107 (B) 6.022 x 10 (C) 6.022 x 107 (D) None Q.10 The pH of solution is increased from 3 to 6. Its H* ion cone. will be (A) Reduced to half (B) Doubled (C) Reduced by 1000 times (D) Increased by 1000 times QA. pOH of [1/200] mol/m* H,SO, aq.) solution at 25°C is- 2 B5 9 DL QU2 Degree of dissociation of 0.1 N CH,COOH is - (Dissociation constant = 1 x 10-5) (A) 10% (B) 10+ (C) 10% (D) 107 i QU3. The pH of a 0.02 M ammonia solution which is 5% ionised will be :- : (A)2 ® ©s5 (D)7 i Q.14 The pHofan aqueous solution of 1.0 M solution of a weak monoprotic acid which is 1% ionised is # Al (B)2 3 Du { QIS The concentration of [H*] and concentration of [OH] of a 0.1 M aqueous solution of 2% ionised 2 weak acid is [ionic product of water =1 x 10] i (A) 0.02 x 103 M and 5 x 107! M (B) Lx 103 Mand 3 x 10" M i (©) 2 x 10 Mand 5 x 10” M (D) 3 x 10? Mand 4x 10° M | 54 eS EALLEN Jonic Equilibrium QI6 Qi7 Qs. Q19 Q20 Qi Q2 What is the quantity of NaOH present in 250 ce of the solution, so that it gives a pH = 13 = (A) 10 (B) 10" g (C) LOg (D)4.0¢ An aqueous solution of HCI is 10° M HCL The pH of the solution should be: (a9 (B) Between 6 and 7(C) 7 (D) Unpredictable The moles of H* from H,O in a 1, J§ x 107 M HCI solution at 25°C, is (V5 =2.23) (A) 107 (B)685x 10° — (C)3.85x 10° (D) 10* Which one of the following has highest pH:- (A) Distilled water (B) 1 MH, (©) 1 M NaOH (D) Water saturated with chlorine 8 gm NaOH and 4.9 gm H,8O, are present in one litre of the solution. What is its pH AL (By 13 © 12 (D)2 M Lo mbof 14,80, is mixed with 40 ml of © 11,80, The pHTof the resulting solution is 200024 200 Al (B)2 ©2 (D) none of these Which of the following solution will have pH close to 1.0? (A) 100 ml of M/100 HCl + 100 ml of M/10 NaOH (B) $5 ml of M/10 HCI + 45 ml of M/10 NaOH (C) 10 ml of M/10 HCI + 90 ml of M/10 NaOH (D) 75 ml of M/S HCL + 25 ml of M/S NaOH A solution with pH2.0 is more acidie than the one with pH 6.0 by a factor of: (M3 (B)4 «€) 3000 (D) 10000 ‘The firstand second dissociation constants of an acid H,A are 1.0x 10 and 5.0 x 10-Mrespectively. ‘The overall dissociation constant of the acid will be (A) 5.0 x10 (B) 5.0x10!5 ©) 50x10" (D) 0.2 x105 If pK, for fluoride ion at 25°C is 10.4, the ionisation constant of hydrofluoric acid in water at this, temperature is (A) 4x10" (B) 3x 108 (C) 25x 104 (D) 2x10 pHof an aqueous solution of NaCl at 85°C should be (a7 (By>T <7 (p)0 1 cc of 0.1 N HClis added to 99 cc solution of NaCl. The pH of the resulting solution will be (a7 (B)3 «4 D1 ‘The degree of hydrolysis of a salt of weak acid and weak base in it’s 0.1 Msolution 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 What is the percentage hydrolysis of NaCN in N/80 solution when the dissociation constant for HCNis 2x 10° and K, = 10x 10-4 (A)2 (B) 5.26 (C)8.2 (D) 9.6 —_——-. 55JEE-Chemistry ALLEN Q30 Q3l Q38 Q39 Q40 Ql 56 ‘The compound whose 0.1 M solution is basic is (A) Ammonium acetate (B) Ammonium chloride (C) Ammonium sulphate (D) Sodium acetate Ifequilibrium constant of CH,COOH + H,O == CH,COO- + H,0* is L8 x 10, equilibrium constant for CH,COOH + OH- == CH,COO- + H,0 is (A) 1.8 x10 (B) 1.8 x 10% (C) 5.55 x 10% (D) 5.55 x 10!° ‘The pK, of a weak acid, HA, is 4.80. The pK, of a weak base, BOH, is 4.78. The pH of an aqueous solution of the corresponding salt, BA, will be (A) 8.58 (B)4.79 ©701 (D) 9.22 ‘The highest pH value is of = (A) 0.1 M NaCl (B) 0.1 M NH,CI (©) 0.1 M CH,COONa (D) 0.1 M CH,COONH, pH of K,S solution is:- (M7 (B) Less than 7 (C) More than? (D) 0 Degree of Hydrolysis of 75, solution of KCN is (Given Ka = 1.6 « 10°) (A)25% 108 (B)2.5 x 107 (©) 25» 104 (D) 25 « 105 A solution of FeCl, in water acts as acidic due to = (A) Acidic impurities (B) Ionisation (C) Hydrolysis of Fe*(D) Dissociation If 40 ml of 0.2 M KOH is added to 160 ml of 0.1 M HCOOH [K, = 2x10-, the pOH of the resulting solution is (A34 (B)3.7 7 103 1 MNaCl and 1M HCI are present in an aqueous solution. The solutio (A) nota buffer solution and with pH <7 (B) not a buffer solution with pH > 7 (C)a buffer solution with pH<7 The pK, of a weak acid (HA) is 4.5. The pOH of an aqueous buffered solution of HA in which 50% of the acid is ionized is : (A) 45 (B) 25 (9s (D) 1.0 To a 50 ml. of 0.05M formic acid, how much volume of 0.10M sodium formate must be added to get a buffer solution of pH = 4.0 ? (pK, of the acid is 3.7) dog? = 0.3) (A) 40 ml. (B) 4 ml. (C) 50 ml. (D) 100 ml. Which can act as buffer > (A) NH,OH + NaOH (B) HCOOH + HCl (C) 40 ml. of 0.1 M NaCN + 20 ml. of 0.1 M HCl (D) All of themALLEN Jonic Equilibrium Q42 Q43 Qa Q45 Q46 Qa7 Q48 Qa4o Q50 Qs2 If equal volume of 0.05 M ammonium hydroxide solution is dissolved in 0.001 M ammonium, chloride solution, What will be the OH ion concentration of this solution : K,(NH,OH) = 1.8 x 10% (A) 3.0 x 104 {B) 4.6 x 10% (C) 9.0 x 104 (D) 9.0 x 10% Calculate the pH of a buffer prepared by mixing 600 ce of 0.6 M NH, and 400 ce of 0.5 MNH,CI. K, for NH; = 1.8 x 10° , (log 1.8 = 0.26) (A) 11.3 (B) 9.0 (C) 9.52 D5 pK, for NH,OH at certain temperature is 4.74. The pH of basic buffer containing equimolar concentration of NH,OH and NH,CI will be: (A) 7.74 (B) 4.74 (aa) On addition of NaOH to CH,COOH solution, 60% of the acid is neutralised. If pK, of CH,COOH 37 (D) 9.26 is 4.7 then the pH of the resulting solution is = (A) More than 4.7 but less than 5.0 (B) Less than 4.7 but more than 4.0 (©) More than 5.0 (D) Remains unchanged Henderson equation pH — pK, = 5 will be applicable to an acidic buffer when (A) [Acid] = [Conjugate base] (B) [Acid] x 10° = [Conjugate base] (C) [Acid] = [Conjugate base] x 10° (D) [acid] = 2 [conjugate base] What amount of sodium propanoate should be added to one litre of an aqueous solution containing 0.02 mole of propanoic acid (K, = 3 x 10% at 25°C) to obtain a buffer solution of pH 4.7 (A) 4.52 x 107 mol (B) 3.52 x 10 mol (C) 2.52 x 10? mol (D) 3 x 107 mol ion of NH,C] and NH,OH is 1 : 1, When it changes in 2: 1, what will be the value of pH of buffer ? In a buffer solution the ratio of concen (A) Increase (B) Decrease (C) No effect (D) None ‘The buffer solution play an important role in = (A) Increasing the pH value (B) Decreasing the pH value (©) Keeping the pH constant {D) Solution will be neutral ‘The total number of different kind of acidic buffers obtained during the titration of HPO, with NaOH are : (a3 (B) 1 2 (D0 Which of the following solutions does not act as buffer (A) HPO, + NaH PO, (B) NaHCO, + H,CO, (©) NH,Cl + HCl (D) CH,COOH + CH,COONa Half of the formic acid solution is neutralised on addition of a KOH solution to it. If K, (HCOOH) = 2 x 10+ then pH of the solution is : - dog 2 = 0.3010) (A) 3.6990, (B) 10.3010 (C) 3.85 (D) 4.3010 When 0.02 moles of NaOH are added to a litre of buffer solution, its pH changes from 5.75 to 5.80, What is its buffer capacity = (A) 04 (B) 0.05 (C) - 005 D) 25 —_——-. 57JEE-Chemistry ALLE Q.54 Calculate pH when 100 ml of 0.2M NaOH is reacted with 100 ml of 0.2 M CH,COOH (K,= 105) (Ao (B)7 ©5 (D)2 Q55 AL90°C,, pure waterhas [H*] = 10M, if 100 ml of 0.2 M HNO, is added to 20 ml of 1 MNaOH at 90°C then pH of the resulting solution will be Cv (B)6 ©7 (D) None of these Q56 When 20 ml of M NaOH are added to 10 mi of M HCI, the resulting solution will- (A) Turn blue litmus red (B) Tum phenolphthalein solution pink colour (C) Tum methyl orange red (D) Will have no effect on either red or blue litmus Q.57 Therapid change of pH near the stoichiometric point of an acid-base titration isthe basis of indicator detection. pH of the solution is related to ratio of the concentrations of the cé gate acid (HIn) and base (In-) forms of the indicator by the expression := [Hin] [Hin] (A) log. jg] = PK, - PH (B) log | = PH- PK, ©) log tin] (©) log jpypy= PH + PK, (@) log jay PK ~ PH Q.58 Calculate the pH range in which an acid indicator with K,,, (indicator) = 1.0 x 10-5 changes colour when the concentration of the indicator is 1 x 10°'M. (A)Se1 By Wed (34 @) 8st Q.59_In.what pH range will a 1 x 10M solution of an indicator will K, (indicator) = 1 x 10-" change colour’? (A) 7.01 (B) 3.021 (5541 @) 021 Q.60 Indicator which is used in the titration of CH,COOH & NaOH = (A) Methyl orange (B) Methyl red (©)Phenolphthalein (D) Litmus Q61 Phenolphthalein is a - (A) Strong acid (B) Strong base (C) Weak base (D) Weak acid Q.62 pH-range of Methyl red indicator is — (A) 42-62 (B) 68-108 (8-96 (D) 68-82 63 In the volumetric estimation of HCI, if we make use of phenolphthalein as an indicator, which base is unsuitable for the titration = (A) NaOH (B) RbOH (©) KOH (D) NHOH 064 Phenolphthalein does not act as an indicator for the titration between = (A) KOH and H,S0, (B) NaOH and CH,COOH (C) Oxalic acid and KMnO, (D) Ba(OH): and HCL Q.65 For weak acid and strong base titration, the indicator used is (A) Potassium di-chromate (B) Methyl orange (©) Litmus (D) Phenolphthalein 58 —____,ALLEN Jonic Equilibrium Q66 Qe7 Qs Q09 Q70 Qn Qn. QT qm Qi5s ‘The solubility of isy mol dar. Its solubility product is (Ay? (B) 64 y* ©)36y> (D) 108 y* If Ky for HgSO, is 6.4 10°, then solubility of this substance in mole perm? is (A) 8 x04 (B) 6.4 x10% (C)8 x 10° (Ds If the solubility of AgCI (formula mas 43) in water at 25°C is 143-10+ gm/100 ml of solution then the value of K,, will be == (A) Lx 10% {B) 2x 105 (Ctx 10" (D)2« 10 One litre of saturated solution of CaCO, is evaporated to dryness, 7.0 g of residue is left. The solubility product for CaCO, is:- (A) 4.9 x 103 (B) 4.9 x 10% (©) 4.9 x 10° (D) 4.9 x 107 A,B, is a sparingly soluble salt of molar mass M (g mol ) and solubility x g lit. The ratio of the molar concentration of B*-to the solubility product of the salt is x 1M 1M! me oe D) w (BY « (D) None (A) 108 Tmt ae Solubility of Ag,CrO, (K,, = 4 x 10) in 0.1 M K,CrO, solution will be == (A) 10° M (B) 10°M (C)4x10°M (D) 5x 107M How many times solubility of CaF, is decreased in 4 x 10M KF (aq,) solution as compare to pure water at 25°C. Given K,, (CaF) = 3.2 x 10"! (A) 50 (B) 100 ©) 500 (D) 1000 At 30°C, In which of the one litre solution, the solubility of AgsCO, (solubility product = 8 x 10“) will be maximum :- (A) 0.05 M NaCO, (B) Pure water (C) 0.05 M AgNO, (D) 0.05 M NH What will happen if the pH of the solution of 0.001 M Mg(NO,), solution is adjusted to pH = 9 (K,, of Mg(OH), = 8.9 x 10%) (A) ppt will take place (B) ppt will not take place (C) Solution will be saturated (D) None of these Na,PO, which should be added in 101 of 1.0 x 105 M- BaCl, solution without any precipitation of BaPO,), is [Ksp of Ba,(PO,),] = 4 x 10 (A)2x 104 gm (B) 0.328 gm (©) 0.164 gm (D) 0.82 gJEE-Chemistry ALLEN RCISE Single correct : QU. The pH of the solution produced when an aqueous solution of strong acid pH 5 is mixed with equal volume of an aqueous solution of strong acid of pH 3 is = (A) 33 (B) 35 (45 (D) 4.0 Q2 How many moles of HCI must be removed from 1 litre of aqueous HC! solution to change its pH from 2 to 3 :- (AL (B) 0.02 (C) 0.009 (D) 0.01 Q3_— Which of the following is most soluble in water? (A) Mis (K, = 8x1077) (B) ZnS (K,,= 7x10") (C) Bi,S, (K,,= x10) (D) Agy(PO,) (K,,= 18x10") Qe4 Solubility of AgBr will be minimum in (A) Pare water (B) 0.1 M CaBry (C) 0.1 M NaBr (D) 0.1 M AgNO; QS pHof solution at first 1/4% equivalence point of Na,CO, when titrated with HCI will be (for H,CO, K,, = 107; K, = 10) (A) 7+ log 3 (B) 7 = log3 (C) 11 + log3 D) 11 = log3 Q6 — Anacid-base indicator has a K, = 1.0 x 10-5. The acid form of the indicator is red and the basic form is blue, Calculate the pH change required to change the colour of the indicator from 80% red to 80% blue. (A) 1.20 (B) 0.80 (aa) Assertion /Reason = QT Statement-1 pH of 107 M NaOH solution is exist between 7 to 7.3 at 25°C. Statement-2 Due to common ion effect ionization of water is reduced. (A) Statement-1 is true, statement-2 is true and statement-2 is correct explanation for statement-1 ) Statement-1 iste, statement-2 is tre and statement-2 is NOT the comect explanation forstatement-1. (D) 140 (D) Statement-1 is false, statement-2 is tue, Q8__ Statement-1 : On dilution of a concentrated solution of CH,COOH . the concentration of [H*] decreases, Statement-2 : Increase in volume is more than the increase in degree of ionisation, (A) Statement| is true, statement-2 is true and statement-2 is correct explanation for statement- 1. (B) Statement-1 istme, statement-2is true and statement-2 is NOT the comect explanation for statement (C) Statement-1 is true, statement-2 is false. (D) Statement-1 is false, statement-2 is tue. Multiple correct Q.9 — Which of the following is correct for 0.1 M BOH solution (K, = 10 i] (A) pH of solution is 11 (B) OH concentration is 10 mol/. (C) it’s salt with HCI (ie. BC) form the acidic solution in water (D) Phenolphthalein indicator can be used during the titration of BOH with HCL 60 —___,.ALLEN Jonic Equilibrium Quo Qu Qld Qs Q16 For weak monobasic acid, HA, the dissociation constant is 2 x 10° ,at 25°C, Which of the following is/are correct regarding this acid? [log2= 0.3] (A) A + HO SHA + OH; K,, = 5 x 10” (B) The equilibrium constant for the reaction of HA with ag. NaOH is 2 x 10° (C) The pH of 0.1 M, HA solution is 3.35 (D) solution of A” is basie If K, & K, be first and second ionisation constant of H,PO, and K, >> K, which is/are incorrect. (A) [H"] = [H,PO;1 (B) (H*] = yK [H,PO,] (CK, = [HPO; J (D) [H*] = 3[PO3] 10 mil. of a solution contains 0.1 M NH,Cl + 0.01M NH,OHL. Which addition would not change the pH of solution = (A) Adding 1 ml, water (B) Adding 5 mil. of 0.1 M NHC (©) Adding 5 ml. of 0.1 M NHOH (D) Adding 10 ml. of 0.1 M NHC] When equal volumes of the following solutions are mixed, precipitation of AgCL(K,, = 1.8 x 10-9) will occur only with: (A) 10M (Ag*) and 104 M(CI") (B) 10-5 M (Ag*) and 10° M (CI) (©) 10 M(Ag*) and 10° M(CI) (D) 10" M (Ag*) and 10" MCI) Paragraph for Q.14 to Q.16 8 gm weak acid HX (molecular mass = 80) is dissolved is 100 ml water. (K, = 10“) Find pH of solution- (A) 33 (B)2 © If itis titrated with 0.25 M NaOH find pH at equivalence point (logs = 0.7) (A) 9.15 (B) 8.65 (©) 4.65 (D) 4.85 (D)3 Find (H*] if 10° mol HCI is added to 100 ml original solution (V41=6.4 ; V5 =2.24) (A) 0.62 x 107 (B) 1.62 x 102 (C) 2.7 x 10? (D) 0.27 x 10% MATCH THE COLUMN: Quy ‘Match the effect of addition of 1 M NaOH to 100m 1 MCH,COOH Gn Column D with pH Gin Column ID: Column-I Column-IT (A) 25 mL of NaOH P) pK, (B) 50 mL of NaOH Q pK,+log3 (©) 75 mL of NaOH (R) pK,-log3 (D) 100 mL of NaOH ‘s) ZlPk, + pK, - log 2] —_——-. 61JEE-Chemistry ALLEN TABLE TYPE QUESTION : Column-1 Column-I Column-IIl (solution) (pH of solution) _ (Introduction about solution) (A) CH,COOHO.2M,1L)+ — ®) 18 (1) pHis determined by strong acid NaOH (0.1M, 1L) (B) CH,COOH@AM,1L)+ — Q) 7 (2) Buffer solution at its HCI @.1M, 1L) maximum buffer capacity (C) CH,COOHO.IM,1L)+ —(R) 9 (8) pHis determined by salt NH,OH (0.1M, 1L) hydrolysis. (D) NH,Cl 200 ml, 0.1M) ©) 5 (4) pHis determined by buffer + NaOH (100 ml, 0.1M) solution (Given : K)oy,coon = 10° + (Kyu on = 10°) Q.18 Which of the following is incorrectly matched (AAS -4 (®)B-P-1 (D-R-2 @c-q-1 Q.19 If0.15 mole NaOH is added in solution (B) of column-I then which of the following is correct (8-3 ®s-4 OR-1 @P-3 Q20 If0.1mole HCl is added in solution (A) of column-I then pH of the resulting solution will be (7 (B) 13 (C) 3.0 M1 62 —_—_.ALLEN Jonic Equilibrium Q3 Qa Qs Q6 Qr Qs Qo J-MAIN The Ky, for CrOH); is 1.6 x 10, The molar solubility of this compound in water is :- [AIEEE~2011] (D dex10"” (2 sfoxio™ (3) Yi.6x10-" 127 (4) 1.6 x 1099/27 An acid HA ionises as HA == Hts AW The pH of 1.0 M solution is 5. Its dissociation constant would be = [AIEEE-2011] (a) 1x 1040 5 (3) 5x 108 (4) 1x 105 IfK,, of CaF, at 25°Cis 1.7 x 10-19, the combination amongst the following which gives precipitate of CaP) is = [JEE-MAINCnline)-2012] (2) 1x 102MCa and 1x 10SMF (2) 1 x 104 M Ca and 1 x 104 MF (3) 1x 103MCa%and 1x 10SMF (4) 1 x 10? MCa®* and 1 x 103 MF ‘The pH of a 0.1 molar solution of the acid HQ is 3. The value of the ionization constant, Ka of this acid is = [AIEEE~2012] (1) 1x 107 (2)3 x 107 (3) 1x 10% (4) 1x 10% How many litres of water must be added to 1 litre of an aqueous solution of HCl with a pH of 1 to create an aqueous solution with pH of 2? [AIEEE~2013] aor @09L @)20L (4) 9.0L Solid Ba(NO,), is gradually dissolved in a 1.0 x 10“ M Na,CO, solution. At which concentration of Ba, precipitate of BaCO, begins to form ? (K,, for BaCO, = 5.1 x 10”) (1) 5.1 x 105M (2) 8.1 x 107M (JEE-MAIN(Online)-2013] (3) 4.1 x 105M (4) 7.1 x 108M NaOH is a strong base. What will be pH of 5.0 x 107M NaOH solution ? (log? = 0.3) (JEE-MAIN(Online)-2013] (1) 13.70 (2) 13.00 (3) 14.00 (4) 12.70 Which one of the following arrangements represents the correct onder of solubilities of sparingly soluble salts Hg,Cl,, Cr,(SO,),. BaSO, and CrCl, respectively ? (JEE-MAIN(Online)-2013] (K,} ee 4 =|", © (ios, ar) What would be the pHof a solution obta and making the volume equal to 500 mL (Ka = 1.75 x 10%, pKa = 4.76) (1) 4.76 < pH <5.0 (2) pH< 4.70 (3) pH of solution will be equal to pH of acetic acid (4) pH =4.70 ned by mixing 5 g of acetic acid and 7.5 g (JEE-MAINOntine)-2013] of sodium acetateJEE-Chemistry ALLEN Q.10 In some solutions, the concentration of H,O* remains constant even when small amounts of strong acid or strong base are added to them. These solutions are known as -[JEE-MAIN(Online)2014] (1) Colloidal solutions (2) Tme solutions (3) Ideal solutions 4) Buffer solutions irconium phosphate [Z14(PO,),] dissociates into three zirconium cations of charge +4 and four phosphate anions of charge -3. If molar solubility of zirconium phosphate is denoted by S and its solubility product by K,, then which of the following relationship between S and K,, is coneet ? Qu (WS = (Kaa (2)8={K,/(6912)"? | JEE-MAIN(Online)-2014] (3)S = (K,/6912)17 (4) S = (K,,/6912}7 Q.12 pK, of a weak acid (HA) and pK, of a weak base (BOH) are 3.2 and 3.4, respectively. The pH of their salt (AB) solution is (JEE-MAINOMfine)-2017] w72 (269 @)70 (4) Lo QUB Addition of sodium hydroxide solution to.a weak acid (HA) results in a buffer of pH6. ionis: constant of HA is 10-5, the ratio of salt to acid concentration in the buffer solution will be (JEE-MAINOntine)-2017] w (21:10 (3) 10:1 (4) QU4 50 mL of 0.2 M ammonia solution is treated with 25 mL of 0.2 M HCL. If pK, of ammonia solution is 4.75, the pH of the mixture will be:- [JEE-MAIN(Online)-2017] (1) 8.25 (24.75 3)9.25 (4) 3.75 Q.15 Which of the following salts is the most basic in aqueous solution ? [JEE-MAIN (Offine)-2018] (1) CH,COOK (2) FeCl, (3) Po(CH,COO), (4) AKIN), Q.16 Analkaliistitrated against an acid with methyl orange as indicator, which of the following isa correct combination ? Base Acid Endpoint (JEE-MAINCOffine)-2018] (1) Stwong Strong Pinkish red to yellow (2) Weak Strong Yellow to pinkish red (3)Strong Strong Pink to colourless (4) Weak Strong Colourless to pink Q.17 An aqueous solution contains 0.10 M H,S and 0.20 M HCI. If the equilibrium constants for the formation of HS~ from H,S is 1.0 x 107 and that of S® from HS~ions is 1.2x10-" then the concentration of S* aqueous solution is [JEE-MAINOffine)-2018] 3x10 (2) 6x107" GB) 5x107 Sx10% Q.18 A aqueous solution contains an unknown concentration of Ba®*. When 50 mL of a 1 M solution of Na,SO, isadded, BaSO, just begins to precipitate. The final volume is 500 mL. The solubility product of BaSO, is 1x10-!°. What is the original concentration of Ba?* ? [JEE-MAIN(Offine)-2018] ns (1) 2x 109M Q)11x 109M — GB) 10x 101°M_— (4) 5x 109M 64 —_—_.ALLEN Jonic Equilibrium Q.19 Following four solutions are prepared by mixing different volumes of NaOH and HCI of different concentrations, pH of which one of them will be equal to 1? [JEE-MAIN(nline)-2018] (1) 75m Muci+ 25m Naou 2) 100m Myc1+-100mL M sou. 5 5 10 10 (3) S5mL HCL + 45m M NSO 4) 60mL MCL 4omt NaOH 10 10 10 10 Q.20 The minimum volume of water required to dissolve 0.1 g lead (IT) chloride to get a saturated solution (K.y of PbCl, = 3.2 x 10°; atomic mass of Pb = 207 u) is : (JEE-MAIN(Online)-2018] (1036 L 2)0.18L (3) 17.98 L (41.798 L E —_—————~ 65JEE-Chemistry ALLEN J-ADVANCE Ql Q2 66 In 1 L saturated solution of AgCl [K(AgCI) = 1.6 x 10), 0.1 mol of CuCl (K,,(CuCl) = 1.0 x 10%] is added, The resulta 1 concentration of Ag* in the solution is 1.6 x 10°. The value of ‘x’ is. (JEE-2011] The initial rate of hydrolysis of methyl acetate (1M) by a weak acid (HA, 1M) is 1/100" of that of a strong acid (HX, 1M), at 25°C. The K, of HA is, (JEE 2013] (A) Lx 10" (By 1 x 10% (C) Lx 10° D) 1x 10% The K,, of Ag,CrO, is 1.1 x 10 at 298 K. The solubility (in mol/L) of Ag, CrO, in a 0.1 M AgNO, solution is (JEE 2013) (A Lix 107 By LI x10" (Lx 10? (D) Lx 10” Paragraph For Questions 4 and 5 When 100 mL, of 1.0 M HCl was mixed with 100 mL of 1.0 M NaOH in an insulated beaker at constant pressure, a temperature increase of 5.7 °C: was measured forthe beaker and its contents, (Expt-1). Because the enthalpy of neutralisation of a stron: id with a strong base is a constant (57.0 kImoF), this experiment could be used to measure the calorimeter constant. In a second experiment (Expt-2), 100 ml. of 2.0 M acetic acid (K, = 2.0 x 10 *)was mixed with 100 mL of 1LOM NaOH (under identical conditions to (Expt-I)) where a temperature rise of 5.6 °C was measured. (Consider heat capacity of all sofutions as 4.2 Jg“K and density of all solutions as 1.0 g ml.) Enthalpy of dissociation (in kI mol”) of acetic acid obtained from the Expt-2 is [JEE 2015] (A) 10 (B) 10.0 (© 245 () 514 ‘The pH of the solution after Expt-2 (A) 28 (B47 (©) 5.0 () 7.0 ‘The solubility of a salt of weak acid(AB) at pH 3 is Y x 10° mol L”. The value of Y is__. (Given that the value of solubility product of AB (K,,) = 2 x 10 and the value of ionization constant of HB(K,) = 1 x 10°) [JEE 2018]ALLEN Jonic Equilibrium ANSWER KEY EXERCISE-S-I QI Ans6.022x107 Q2 — Ans.(i) 6.53 ; (ii) (a) Basic , (b) Acidic Q3 Ans6.8 Q4 Ansa) 1, (b) 2.87, (c) 11.13 (4) 6.97, (e) 7, 6. (2) 6.97, th) 11.304) 9. G3 QS Ans(a) K,= 10%, (b) K,= 104 Q6 Ans.10 QT Ans173.2:1 QS Ans.0.009 Q9 Ans.L.1 x 10M QUO Ans.L.11 x 10+ QU Ans.4.7 QU2 Ans3.3 Q13- Ans(a) 0,522, (b) 2.522 Qld Ans. (1) QS Ans. 0.027 M, 0.073 M, 0.027 M, 10-5 M QuU6 Ans. 11.3 Q.17 Ans.10°M Q.18 Ans pH QU9 Ans K,=6.25 x 10-1 Q20 Ans.0.56%, pH=7 Q21 Ans.1.667% Q.22 Ans&.3 Q.23 Ans.(a) 6, (b) 1x 10 Q24 Ans. 9.0 Q25 Ans. 9.56 Q26 5.04 Q27 Ans. 0.05 mol Q28 Ans. [OH] = 9.0 x10*M Q.29 Ans.(10.1) Q30 Ans4.74 Q31 Ans.9.56 Q.32 Ans. 8.7782 Q33 Ans(3.33) Q.34 Ans. 10°M Q35. Ans. 8.7 ,[H,O*] Q36 Ans.5,10SM 2x 10°MJEE-Chemistry ALLEN Q37 Ans. (i) 2.85, (i) 4.0969, (iii) 4.5229, (iv) 4.699, (v) 5.301, (vi) 8.699 Q38 Ans. [HI,] = 80 % Q39 Ans 85.71% Q40 Ans. (b), (©) Q41 Ans.ApH=0.954 Q42 Ans. QX, is more soluble Q43° Ans. 4x 10° Q44 Ans. 5x 10"! Q45. Ans. 3.2x 101 Q46 Ans, 2.56 x10 Q47 Ans. 1.0 10 molfit Q48 Ans. 5x 10M Q49 Ans.5 x 107 Q.50 Ans. 4x 107 mol/L AgBr, 1.6 x 10 mol/L. AgSCN QS51 Ans. 8x 108M Q52 Ans. 4x 102M Q53Ans(a) no precipitation will occur, (b) a precipitate will form Q54 Ans.No. Q55 Ans.0.284 gm EXERCISE QI Ans, 0.209M, 0.191 M.9.13x10°M,O Q2 Ans. 10.6 Q3 Ans. (2x 104M) Q4 Ans. pH = 10.52 Q5 Ans. 8.35,9.60, 4.66 Q6 Ans.(9.6) QT Ans.(10“M) Q8. 103M) Q9 Ans. 2.8 x 10 mole Q10 Ans. 1.6 x 107 EXERCISE O-1 QT Anstay Q2_ Ans Qs Ansic) Q4 Ans(C) Q5 Ans.(B) Q6 Ans.C) Q7 AnsiD) Qg Ans.(D) Q9 Ansic) Q.10 AnsiC) QUI. Ans (C) QI2 AnsiD) Q.13 Ans(B) Q14 Ans(B) QIS Ans(C) Q.16 AnsiC) QUT Ans.B) Q18. Ans.iC) Q.19 AnsiC) Q.20 Ans.(B) Q21 Ans) Q.22 AnsiD) Q23 Ans.(D) Q24 Ans(C) Q25 AnsiC) Q26 Ans(C) Q27 Ans.B) Q.28 Ans(B) Q29 Ans.A) Q30 Ans.D) Q31 AnsiB) Q32 Ans(C) Q33. AnsiC) Q34 AnsiC) Q35 Ans(B) Q36 Ans.C) Q.37 Ans(D) Q.38 Ans(A) Q39 Ansi(C) 68 ————-»ALLEN Jonic Equilibrium Q.40 Ans(C) Q41 Ans.(C) Q42 Ans.(B) Q43 AnsiC) Q44 Ans.(D) Q45. Ans(A) Q46 AnsiB) Q47 Ans.(D) Q48 Ans.(B) Q.49 AnsiC) Q50 Ans.(A) QS1 AnsiC) Q52 Ans(A) Q53 Ans(A) Q54. Ansa) Q55. Ans.(B) Q56 Ans.(D) Q57 Ans.(A) Q.58 Ans(A) Q59 Ans(B) Q60 AnsC) Q61 AnsiD) Q62 Ans.A) Q63 Ans.D) Q.64 Ans) Q65 Ans.(D) Q66 Ans.) Q.67 Ans(D) Q68 Ans(C) Q69 Ans(A) Q.70.80L(C) QTL. Ans.(B) Q72. Ans.B) Q73 Ans(D) Q74 Ans(B) Q75 Ans.) EXERCISE O-I QT Ansiay Q2 AnsiC) Q3_ AnsiD) Q4 AnsiB) Q5 Ans (C) Q6 Ans(A) QT Ans.{A) Q8 Ans.A) Q9 Ans. (A,B,C) Q.10 Ans.(A,B,C.D) QUL Ans.(D) Q12 Ansa) Q.13 Ans(A) QU4 AnsiB) QIS Ans(B) Q.16 Ans (B) QU7 Ans. A - (R), B- (P),C - (Q), D- (S) Q.18 Ans.(D) Q.19 Ans.(B) Q.20 Ans.(C) J-MAIN: QI Ans.3) Q2. Ans.(1) Q3 Ans.) Q4 Ansid) QS. Ansi4) Q6 Ans.) Q7 Ansi4) QB Ans.(1) Q9 Ans1) Q.10 Ansa) QUL Ans.) Q12 Ans2) Qu13 Ans(3) Q14 Ans3) QUIS Ans(1) Q16 Ans(2) Q17 Ans.) Qs Ans(2) Q.19 Ans(1) Q.20 Ans.(2) J-ADVANCE Qu Ansi7) Q2 Ans(A) Q3 AnsiB) Q4 Ans(A) QS Ans(B) Q6 Ansi4.47)