Grand Masters aga e-Yo (= SSC etary rent iIONIC EQUILIBRIUM 6 Tonic Propuct oF WaTER ‘Water is amphiprotic and gives H° and OH on self ionization onic product of water, Ky = [H'] {OH} = 10" at 25°C. Xt depends only on temperature. It increases with increase in temperature PH value: PH = ~ log [10°] or [HsO"]= 10% rnilarly, POH =~ log [OH ] DH] = 19-78 And pH + pOH = pKy = 14 at 25°C For conjugate acid-base pair in ag. solution, ie. HA and A- HA+HLO ==20'+ AK, Thus, Ky = KxKy And, pKa + pKy = pKy = 14 at 25°C igher the pK. value, lower isthe acid strength and higher i the basi strength OSTWALD’s DILUTION Law Xt deals with the effect of dilution on weak electrolytes (weak acid or weak base). Degree of dissociation of weak electrolytes is proportional tothe square root of dilution Co* K where Ks = dissociation constant of weak electrolyte a= degree of dissociation (C= initial concentration of weak electrolyte {k, Wave 1, then a = foe [n,0"]=ca= fC In case of weak monobasic acid: pH = tog (H0"] = -log JK, i pH =>[pk, In case of weak monoacidic base: log] 0 pK, ~ logC] or pH = 14 ~ pOH=: ~Lpk, - log] 2) Eqs. (1) and (2) are applied only when a <1 and the value of C must be high Total [H30*] in mixture of two weak acid: [H07} =Total [OH] in a mixture of two weak bases: (OW KG oR - Total [130+] in a mixture of weak acid and a strong acid: dissociation constant Ki and C2 is the concentration of stayng issocia Common Ton Errecr The degne of dissociation of a weak electrolyte is suppressed by the addition of another strong electrolyte setenv corn in, Is called commen ion fet 1 case OF weak el {x I case aay other sir order to ke -ctrolyte containing X° or Y- ions is added, the equilibrium tends to shift to left in 1p K constant at given temperature. ())Athal newcalization point of weak acid Where HA} =[A ] DH = pk, My =, (13) At half neutralization point of weak base where [BOH} = [18] POH ~ pK, LOH] =K pH= 14 — pk, (iit) In case of weak dibasic avid (e.g, HyCOs), pH at half neutralization point is pK, +pK. pH» Seat? ‘Satt HYDROLYSIS Hydrolysis Degree of Sai Natu nt “constant ydrodysis 1,0") pH Sali of sirang a J sarong Kal Neural Nohydrohsis = pk, or weak acid Basie oa ONa ky ky Ks - “ pH= =o beeCM # £# = In case of salt of weak acid and (Newt, ifK, =k, and weak base, nature of medium will be ii) Basic, if Ky > k, ii) Acidic, if K, > Ky BUFFER SOLUTIONS: ‘A solution which resists change of pH on the addition of small amount of acid or alkali Acidic Buffer These are prepared by mixing weak acid and its salt with strong base or it contains a weak acid and its conjugate base, e.g. CHsCOOH and CH:COONa pit pK. log [orivgate base] [weak acid] Basic Buffer These are prepared by mixing weak base and its salt with strong acid or it contains a weak base and its ‘conjugate acid, e.g. NHOH and NHiCl {sal} (bse pOH = pK, + log, Salt Buffer Itis a salt of weak acid and weak base. “7 Buffer Range (2) Anacidic buffer is effective within pH range (pK. ~ 1) to (pk. + 1) (ii) A basic buffer is effective in pH range (pKy ~ pKy + 1) Buffer Capacity Butter capacity = NOt moles of acid bse added per live pee change in pH ft is maximum when For acidic buffer For basic buffer, 2— ‘SOLUBILITY PRODUCT (Ksp) Key of an electrolyte is the product of the molar concentration of its ions in a saturated solution with each concentration term raised to the power equal (o the number of ions produced on dissociation of one molecule of fat electrolyte, iven sal is constant at a given temperature, e.g, Kp for solute XxYb is axe + bY" Sa talue fora aS bS_ (Sis solubility) PRESKa ashy pyep TRS fasifhsp oF Sofaniny (8) «| a‘b’ ) ) Sot ion, €g. solubility of AgCI im presence of 4M (Solubility of a solute in the presence of common 10m, CE 7 AgNO g Ret gey (4) Solubility of salt of weak acid and strong base, ¢ 8: CHyCOONa in water CHyCOONA(S) = = CHsCOO + Na’ (Sx) 8 CTLCOO + H,O ===* CH;COOH + OH G9 x x hus, (S~ 98 = Ky, a and 2 (iit) Solubitity of salt of weak acid and strong base (CH;COONa) in an acid buffer of given pH strength (butfer does not have any common ion) is CHsCOONa CHsCOO + Na Sx § CH,COO + HY === CHCOOH x a 1 @ [HW [s-x] (iv) Solubility of salt of weak acid and strong base in a basic buffer of given strength y is CH:COONa ==" CH\COO + Na* S-) $8 CILCOO + HO === CHCOOH + on (Sox) x y (Mainly due to solution basicity) S(S =X) = Ky ay ney _K. 7 (-.) XK, Precipitation of Salts Gi) [Finnie product (1P) > Kep, precipitation takes place till IP equals K.». FIP Kay, no precipitate will be formed, Gi) Gili). 1F 1? ~ Sip, precipitate will not be formed, but the solution is at saturation stage THEORY OF INDICATOR Ostwald’s Theory Indicators are. Bev weak unpanic acids or tases. The unionized and ionized form of indicators have different colours. They chang? colours within cersaim pt range and are used for the determination of end point tn the titrationsHin +40 === 10+ ie Colour” Colour B HO Kaa (indicator constant) = & [Hin] depends only on temperature 7 [Hin] TO')= KA fn -} ‘Thus, pH= pKa + log ie] pH H" + HSOr strong HSOc == H’+ SO. Ki =1.310°M From first dissociation [H"] is 0.20 M Let x be amount of H” fram second dissociation Hence [H-}out = 0.20 M +x This in equilibrium gives HSO; == H + SO; 0.20M~x 0.20M + x x x0.20M +) 1 3,192M 020M—x x? + (0,2041.3x 107 )x — (1.3107 0.20) = 0 x= 0.0116M [Fo Jom = (0.2 + x)= 0.2116M [HSO,] = 0.2 —x = 0.1884M (SO? ]=x=0.0116M [HySO4} =0 Should Mg(OHy 0.10 M1 i) NB UR)OEE mu KE (Ostwald’s dilution Ia) 10° M Sol (OH) in0.10MNH.OH = \iex0* 0010 = 134 => [Mg""] = 0.01 M ' Jonte product = (Mg?") [OH = (0.01) (1 34 * 10°F Bx 108 > Kap As Ionic product is greater than Kup of Mg(OH)> » hence precipitation should oc 4 For the indicator thymol blue, the value of pH is 2.0 when half the indicator is present in tunionised form calculate the percentage of indicator In the unionised form in a solution of 4x10°M [H"] concentration. Sol. Since at pH ~ 2 half of inductor 1s present in untomsed form therefore {Hin} = (in-] {In} 4 + Jog 8 (Hin| PK. = pH = 2 pH of solution containing 4.0<10'M of H’ is pH = -log(4x10°)=24 ( {n° ) log] +2 |= pH—pk, =24-20-04 lel ray | “PH PKs =24 (it; {Hin} ‘Adding 1 on both sides (in 1+f (in| —liiel to 286 (in |+[Hin] 33 % of indicator in unionised from = 28.6 5 Given [Ag(NHa)o}° === Ag'+2NHG, K. = 6.2 x 10 and Kepagcn = 1.8 x10" at 298 K. Calculate the concentration of the compiex in 1.0 M equeous ammonia. Sol Ag(NH:)"iag) === Ag’(aq) > 2NHilaq) xty AgCl(s) === Ag’(aq) + Ct fag) (ery) oy In case of simultaneous solubality, Ag’ remains same in both the equilibrium Oty)2s [Ag(NH.) ( Fixe yey x maCia Sol. Sol, Given, [NH] = 2x = 1M eae ICT] = y because Ag’ obtained from AgCI passes in [Ag(NH) po] state Ky yxy i Be10" > y= bBxt0™ 0? Greg? 02910 y= 0539 « 10 = 90839 be. [Ag(NH)3] = 0.539 A solution has 0.05 M Mg” and 0,08 NH). Calculate the concentration of NH«Cl required to prevent the formation of Mg(OH); in solution. K sion = 9.0 x 10"? and jontzation constant of NHy Is 1.8 x 10%, The minimum {OH at which there will be no precipitation of Mg{OH), ean be obtained by Koy = [Ma] (0H P 290% 10 = (005) x {OH P [OH ]=1.34x105M Thus, solution having [OH ] ~ 1.34 +10°* M will not show precipitation of Mg(OH) in 0.05 M Mg These hydroxyl ions are to be derived by basic buffer of NH.CI and NH,OH po ox ef [NH [Ni,on] NHLOH === NH¢ + OH pOH = py + log. In presen of [NHACI], all the NH4’ are provided by H.C! as due to common ion effect, dissociation [NH ] [o03} NH = 0.067 M or [NH«Cl} = 0.067 M of NHLOH will decrease. Jop|OH J = -logh 8 10° + tog A solution contains a mixture of Ag’ (0.10 M) and Hg” (0.10 M) which are to be separated by selective precipitation. Calculate the maximum concentration of iodide ion at which one of them get precipitated completely. What percentage of metal ion is precipitated ? Kip Agh= 88x 10°", KepHgh = 2.5 x 10 K, (Agi) = 8.5910" =[Ag IE] [1] required to start precipitated of Agl 85x10! : = SZ 2 85x10"M 0. alg) = 2.510-=S810"M Whew jt j eaches t9 310°", At gots previpitated almost completely When tok: staits precipitating Ag’ +2CN;, the equilibrium constant, Ke at 28°C fs 4.0.x 19°? inally 0.10 M in KCN and 0,03 For the reaction, {Agi Caleulste the silver ion concentration in a solution which is Min AgNO. Soi. S10 aU) Very high value of K, show that complex forming equilibrium is spontaneous and almost all the Ag’ lon would have reacted leaving x M in Solution: LAs(CN), | initial 003M 01M 0 Ateqm xM — (0.1-0.03x2)M_ 0.03M x1o% -—_203 x(0.1-0.03%2) 10"M Ag+ 2CN 9. UA, is an acidic indicstor (Kix = 107) which dissociates into aqueous acidic solution of 30 mi of GES POLK = 1 1. Kr = 1» 10, Ky= 1x 10°) then find out the concentration ratio A ing that Ils and Ly posses colour P and Q respectively and colour P over colong Q. hen concentration of Hs is 120 times than that of le and colour and when concentration Of Is i 127 times of HI.. What is the pH range ‘Vs solution Ts thteated with 30 ml of KOH sotution, then what molarity of KO 2 vot e reach te equivalence poiut with indicator? Sot. HsPOs F TPO: Neglecting “a” w.rt. 1 a Ten see015 IT — F = Ys7l0° = Vo.6ox10% = 0816 x 10-082 « 10 aC = 0.82 x 107 x 0.15 = 0.123 x10! (H] = 1.23 x 104 pH = -log {H"] = 3.91 For an acidic indicator, Ke Hl, = Hy Now. when P colour predominates over Q colour, then pH = pKa + logi20 pH = 7+ logi20 = 9.0279 When Q colour predominates over P colour, then ! H = pKin~ log— = 4,896 tas For colour P, 1 BHS7+ log = 4896 For colour Q pH 2 7+ log!20 = 9.0279 pH range of the indieator is 4,896 ~ 9.0279 At) neutralization point, the acid HPO, will be conver into KH;PO,, here pHi of the solution 2 PK + PK, _3+7 2 2 At the 2™ sep of neutralization, the acid HsPO will be converted into KPO. pk, +pK, 7413 _ 14 2 The equivalence point will be obtained when acid HsPO, will change into K:HPO. + n-factor of the acid = 2 300,15 normality of KOH = 2*0842 9g hore the pH of the solution = Molarity of KOH = 0.3 M nn AASdi Prob. 1. Calculate the pH of a bufier solution that is 0.250 M in formic acid and 0.100 M in sodium formate, PKs of formic acid is 3.74. Sol p= pk, + log {S24 [Acid] PH =3.74+1og! 23.34 025 Prob. 2. Calculate the PH of 0.1 M solution of NaHCO; given CO, + H,O == HCO; + H* HCO; == H* + Coe Sol. Since in solution of salt containing an ampholeric onion, pH of solution is K, =4.2*107M =4.2x107M i PH=31pK, + pK] So pH of NaHCO; solution PH = 2f-log(424107) -Iog(4.8<10"")) =8.35 Objective Questions Prob. 1. The Ky of Mg(OH): is 1 x 107? 0.01 M Mg(OH): will precipitate at the limiting pH (a) 3 (B)9 5 (D8 Sol (Mg?) [OH P= 10 0.01 « [OH = 10 (oP = 10 [OH}= 105M (H'] = 10° M, and pH = -log (10°) =9 Hence, (B) is the correct answer. Prob. 2, certain ion BY has Arrhenius constant for basic character, (¢.¢, constant 2.8 10°, The equilibrium constant for Lowry ~ Bronsted basic character is (A) 28107 (B) 3.57 « 108 (C) 3.57% 10° (D) 2.8 « 107 So B +H a Bronsted base B +H,O—=HB+OH, Arrhenius base FSA AEBy equation () and ny x, (epllon | [a ya | K iB juny [ETOH Jk eee Menee, (D) ts the correct answer Prob. 3. The pOH of 10° MCI is We (Bo (©) @and7 (D) Tand 8 Sol (CY 1 weak monoueidic base {K, = 110" at 25°C) as nitrated with {> M HCI ra water at Prob. 4.2 Sink of 25°C The concentration of H’ at equivalence pont is (K_ = 110 “at 28°C) (A) 3.7810°M (B) 3210 M (©) 32x10°M {D) 2710 M Sol BOH + HCL-—BCL+ 0 « B+ HOS=SROH + I ch Ch =n K, ving h = 0.27 (hence h cannot be ignored with respect io 1) Ch =0.180.27=2.7«10' M S {nu Hence, (D) is the correct answer Prob. 5, What in general may be the general criteria of choosing a suitable indicator for a given titra (A) The indicator should have a broad pH range {B) pH at the end point of titration shiould be elose to neutral point of indicator {C) Indicator should have neutral at pH = 7 (D) The indicator must show a sharp change in colour near the equivalence point of titration point Sol. (B.D) Prob, 6, An aqueous solution of 1.0 M ammonium formate assuming conyplete dissociation and pk, CHCOOH §. pKe (Nib) = 4.8, With the help of above data find ut correct sistement aut of the following (A) pH of solution ~ 6.5 (By solution is basic in nature (©) pH of the solution = 7.5 (D) solution is aewie in Sol. (A, D) —_—————————— SSeSBy equation (i) anit) {uB][on | _ ]=k, Hence, (D) isthe correct answer Prob. 3. The pOH of 10* MHCIis (ys (B) 6 (C) 6 and7 (D) Tand & Sol. (C) Prob. 4.2.5 mL. of =M weak monoacidie base (K, = 110" at 25°C) is titrated with au HCH in water at 25°C. The concentration of H’ at equivalence point is (K, = 1x10 at 25°C) (A) 3.710" (B) 3. (C) 3.2«10°M (D) 2.710 x10™M M Sol. BOH + HCi—+ BCI + H,0 c B + HO==BOH +H c(h) ch ch Solving h = 0.27 (hence h cannot be ignored with respect to 1) [ur ]=Ch=0.1x0.27=2.7x107 M Henee, (D) is the correct answer. Prob. 5. What in general may be the general criteria of choosing a suitable indicator fora given titration? (A) The indicator should have a broad pH range (B) pH at the end point of titration should be close 10 neutral point of indicat (C) Indicator should have neutral at pH ~ 7 (D) The indicator must show a sharp change in colour near the equivalence point of titration point Sok (B,D) Prob. 6, An aqueous solution of 1.0 M ammonium formate assuming comp! © 3.8, pe (NHs) = 4.8, With the help of above data find out correct statement out ofthe following {B) solution is basie in nature (D) solution is seidie in nature ete dissociation and pK. C (A) pH of solution = 6.5 (C) pH of the solution = 7.5 Sol. (A, D) g 00HProb. 7, w Which of the following compounds‘ions can act as Bronsted acid as well asa Bronsted base? A) CO, (B) Kc (©) thso, (D) He Sot py Prob. & irs Sis solubility of a sparingly soluble salt M:Xs, its solubility product is equal to (ay ase 5 eB) 218 (6s 7 ues (D) 108 S* Sol (py ——— SS eA SANECM ls Reasoning Type This section contains Reasoning Type Questions. Each question contains STATEMENT-1 (Assertion) and STATEMENT-2 (Reason), Each question has 4 choices (A), (B), (C) and (D) out of which ONLY ONE 's correct. STATEMENT-1: A solution of 2: 1 molar ratio of CHyCOONa and HC! results in acidic buffer. and STATEMENT-2: An acidic buffer is a mixture of weak acid and its salt with strong base. (A) Statement-| is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1 (B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement (C) Statement-l is True, Statement -2 is False. (D) Statement-1 is False, Statement-2 is True, Sok (A) ‘Which of the following statement (3) is (are) correct? (A) The pH of 1.0 x 108M HCI solution is 8 (B) The conjugate base of HPO; is HPO,” (C) Auto protolysis constant of water increases with temperature (D) When a solution of a weak monoprotic acid is titrated against a strong base at half neutralization point, pH= 4 pK. Sok Only (B) and (C) are the correct answers. Hence (B) and (C) is the correct answer. 3. Choose the correct statement (s) out of the following (A) In CH;COOH/CH;COONa buffer, the reserve acidity of the solution is due to CHyCOO ions (B) it is not necessary that an acidic substance must contain hydrogen ions (C) HCO; is both Bronsted base and Bronsted acid (D) Sodium carbonate does not contain OH ~ ions and thus is not a base Sol, (A),(B), (C) are the correct answers but (D) is wrong Hence (A), (B) and (C) are the correct answer.a COMPREHENSION eS wer the questions: the ions of an cl 1 any concent ecyte raised 10 power of thei coefficients in the trac isnt constant and varies with change aed solubility product Ko ipitation takes lace will not take place. jon vakes place Read the following passage and ans “The product of the concentrations 0 balanced chemical equation in the solutton a aaa akon Ton product of thesauri 0/000 {0) When Ky = Kay the solution st strated and no pect {ii) When Ky < Kip the solution 1s unsaturated ancl precipita fia) When Ke > Koy the solution i supersaturated and precipita “Answer the following questions: ee + 10-%, The solubility of the ae the sli pod of sparingly sible salt MX 25° is2.5 » 10”. The solubility of the Ss is se w : (C) 1.25% 10° (p) 5* Sol. (Dy Prob, 2. Which ofthe following is most soluble? . Casket 10 *) (B) MnS (Kop = 7% 10") (©) CuS (Ky = 810%) {D) AgaS (Kp = 6% 10) Sol. (B) Prob. 3. The concentration of Ag’ ions in-a given saturated solution of AgCl at 25°C is 1.06 * 10° *g ion per titre. The solubility product of AgCl is: (A) 0.353 » 10." (C) 11210" Sol. (D) (B) 0.53010 " (D) 2.12 * 10 (MATRIX-MATCH TYPE QUESTION 1 Match the following: CHCOOH (pK. © CHsCOONa (0.1 M) COOH (0.1 M)- le | Buffer sotution COOHIpK, = 4.74, 0.1 M) + NHAOH | (7) | pH <7.at 25°C Le iM i ©(D) | CH:COONa (300 ml oF 0.1 M) + HCI (100 | ml of 0.1 M) ae (A) | 50 ml of 1M 7 CHSCOOH | (p) 4.74 F0.05 M NaOH * 50 ml of 0.1 M CHsCOO ) 8.72 Te ) 8.72 ; cheoor oe | 50 ml of 0.1 M NaOH + 50 ml of 0.10 M CHxCOOH o7_ (D) | 50 ml of 0.05 MNH.OH + 50 ml of 0.05 MCHsCOOH | (s). 12.30 a L@ 10.2 4.74, pK for NH.OH = 474) {Given log 0.333 Sol (A) (9) (B) > (PO) (QD) > (0)peal 3,4 and § by appropriately matching the information given in the three columns of the following table. | Salt of weak acid and | weak base | (| pH=H2[pKutpKetlogC] Salt of weak acid and I oes | . | | 2H | m ees | | pH=IAIpKerPKrpKe] | | 7co9 ) fe Na, + 2H, jf} a 1 —C—Oll + Fe(OH), ——> | Salt of strong acid CD | ond strong base | Gi | pI [=1/2[pKa-pKy-logC] | (®) 9 \ | | i | | (cx,-!-0) et 3 L — | | - + | Salt of strong acid i | gy | HCI+ NaOH—> | | ww) | and weak base \» | PH=1/2{pKs] | | act (eee ae — 3. Which of the following combination is correct ? ALO G@® [B} (mp @ P) [c] aD Gi) [D] Gv) GS) 4. ‘Which of the following combination is correct for salt of strong. acid and ot base ? {A} ain @) @) {B) (Al) (iii) (S) [Cc] Gil) Q) D] (aI (iv) (S) For the given salt in Column-I which the incorrect combination for salt of strong acid. and weak base ? {A} (IN) fivy(Q)— (B) G1) Gi) S) [C] (IY) (iii) (S) [D] )@@®) ‘Sol. A a SG SUSAN SESSSINGLE INTEGER ANSWER TYPE QUESTIONS \ Caleuate the percentage dissociation of 0.5 M NID at 25e¢ in a sotution of PHT 12 Sol. Q NUOU 2 NI, OW ‘ i. 0 cea) oC pi 1 tO PS or OH J 10 2 jou Cato 10° 10 as 0.5 <1 or %e - pee eee nd point, Dissociation constant for the eid HA in 3 10 and degrce of hydrolysis, ht Sok 0) HA 4 NaOH 2 Nad #110 (weak acid) sate stant solution, [NAA = 0.08 M As NaA isa salt of weak acid and strong base 1 hydrolysis as As HOe==HA+OU pil 7 6 [pKa + togC] T+ ts [ log(S x 10°) 4+ log 0.05] +15 fo 0.6990 + 0.69902 ]=9 stant of a substituted benzoic acid at 25°C is 1.0 x 10. The pH of a 0.01 M The dissociation ¢ solution of its sodium satis Sol (8) K, (CsHeCOOH) = 1 x 104 pH of 0.01 MCxlisCOONa C\11,COOH OH! €.H,COO' + H.C x, Kegon Ko I-h 10" 1078 S teh erere Vee) JOH} = 6.01 b= 001 x 104~ 108 (H]- 10" pH=S 4 0.15 mote of pyridimium chloride fs been added into 500 em’ of 0.2 M pyridine solution, Calculat 2 M pyridine solution. Cateulate pli of the resulting solution assuming no ehange in volume —_& r we in volume, (Kh pyran) = LS x 10" My O15 {Pyridium ehloride] ~ 500 1000 = 0.3 M Pyridine ~ 0.2M \ mixiure of pyridine and salt pyridinium chloride fonms a basic bufferSol Sol. Sol. [an] { ase] POH = pk, + log POH = - og 15 10° + fog (039) 020] log 1.5 + Blog? togt.5 = 9 [On| = 10° IWT= 10 so. pH 5. (0. millimole of CdSO, are presence in 10 ml. acid solution of 0.08 N HCL Now H2S is passed (© precipitate all the Cd? ions, What would be the pH of solution afler filtering of precipitate boiling of HS and making the solution 100 mL by adding HO? 2 CASO, + HCL + HS —9CUS + H,80, Millimole added 0.1 100.08 8 After reaction 008, or OL Millimoleof H'lel= 08 + O1x2=10 From HCI From H»SOx Total voume = 100 mL. 1 H'] = —— = 107M, pH =2 a ico pl K, for butyric acid is 2 x 10°. Calculate pH in 0.2 M aqueous solution of sodium butyrate. 9) NaBu + H,0= 1 io (i-h) ou (y= 10° pH-9 A certain buffer solution contains equal concentration of X~ and HX (Ka for X~ is 10-!9) what is pH of buffer? “) For a conjugate acid -base pair we have KA(HX) « Kil X= 104 Ka aio 0 [Wx] =[X] {salt] So pH =pk, +log S44 Fe ae] =4Tie 12 40 mL. of HCI, pil of the solution addin 8 50 mL of 0.05 M NaCOs is titrated against 0.1 M bey oa 0,477, log? = 0.30). (Express answer in Will be {Given : For HsCOs, pK, = 6.35 pK, = 10.33: 108 __earest integer). Soh (6) . es eG: Initial milli moles $00.05 40x0.1 Final - 18 . Heo, + H H,€0, Initial mith moles 2.5 eae Final \ Is i oe pH =pK, +log 29 = 6.173 = PS. *1°87H,c0,] 9 lina haffer solution, cone. of (NH.):SOs and NH.OH are 0.2 M and 0.4 M calculate pH of solution If Ky, 10" Sok (9) {salt} DOH = pK, + logs ree hase] (PK, = “log, =-10RK sy) Ky $10" 2 NHL XK on = K. aust so = Tg 04 OH = ~1og lO” + log = fi 2. 84 pH =10- pOH=14-5=9 NUMERICAL VALUE ANSWER TYPE Prob. 1. The total number of different kind of buffers obtained during the titration of HsPO. with NaOH are Sol, 3.00 Prob. 2. What is the pH of an aqueous solution of ammonium acetate (K, = Ky = 1.8 « 10)? So 7.0 Prob, 3. What is the solubility of Cd(OH)> in a buffer solution having pH = 8 ? [K(Cd(OH):) = Sol. 0.025 Prob. 4. Jf the equilibrium constant for the reaction of weak acid HA with a strong base is 10° Sol. 3x10] "then determine pH of 0.| MNaA solution, 9.00 Prob. §.A small quantity of phenolphthalein (an acid indicator) is added to a decimolar solution of Sodium Sol. butyrate. Calculate the ratio of the coloured to the colourless form of 1 the indivator. K, for butyric acid 5 x 10°, K for the indicator 3.075 x 10” and K, = 10°, Take fog 1.23 = 0.09 0.25 ——— LESS SEDELECTROCHEMISTRY TYPES OF CELLS Electrolytic Celi Ivica device in which conversion of electrical energy into chemical energy is done. Electrochemical Cell [tis also known as Galvanic or Voltaic cell. It is a device in which chemical energy is converted into electrical energy. FARADAY’S LAWS OF ELECTROLYSIS First Law ‘Weight of substance deposited (W) « quantity of electricity passed weQ ort 7Q or W=Zit where Z = electrochemical equivalent, = current in amperes One Faraday (F) is the quantity of charge carried by one mole of electrons, 1 F = 96.487 coulombs = 96500 coulomts. By combining first and second law, we get, Wo ixt” 96500 ELECTROLYTIC CONDUCTANCE : i Conductance (C) = = Resistance(R) ‘The unit of conductance is ohm! or mho. The electrolytic conductance of a solution depends upon the follow —— LeeeeetrrrrrlcC SBE AEE (i) Number of ions Gi) Mobitity of ions (iii) Magnitude of charge on each ion SPECIFIC RESISTANCE AND SPECIFIC CONDUCTANCE If *¢7 is the distance between two electrodes, ‘a * is the area of cross-section of the electrode, R is resistance Raf a £ R=pxs ( = is called cell constant) a Where p Specific resistance or ‘Tesistivity. 114 mR Specific conductance (x) = Cx! a ip (oPeeifie conductance or conductivity) The unit of x is 2 cm’ or $m, is also defined as conductance per ce of electrolytes. Equivalent Conductance(,,) KxXV Where V = Volume of solution in ce containing 1 gram-equivalent of the electrolytes x 5 O00 C(gmeg/litre) where N= normality ora, Molar Conductance (a,,) pecifie conductance « Volume in cc containing one mole ofthe electrolyte wx tO ogy ‘(mole / lit) M where M = molarity The unit of specific conductance is" em? mot and in SI system, the unt is So? mol” Thus, a, =n, where n = n-factor of electrolyte = iM ECl Effect of Dilution on Conductance The value of 1, tle of and »,.inereases and aitains a limiting value at infinite dilution, ie. 7 and A. Tn case of weak elect i eal hae 18 mainly due to increase in number of ions (due to increase in degree of dissociation), hah : sie But in case of strong electrolytes, its due to increase in mobility of fons ie of AS and 4;, of strong electrolytes can be extrapolated experimentally while for weak electrolytes Kohlrausch’s law is applicable Strong electrolyte, eg NaCl . S ‘ + = oo KoHLRAUscH’s Law AA infinite dilution, molar conductivity is given by the sum of equivalent conductivities of contributing ions. For example, for AxBy AS ENASHYA Applications (3) Determination of degree of dissociation (a) ono (ii) Determination of solubility of sparingly soluble salts 100% ¢ Here, Cis molarity of solution or solubility of solute (iii) Calculation of dissociation constant of weak electrolyte a=22and K, = SS = Ca? whena << a a Similarly, Ky can be calculated for weak base. ELECTROCHEMICAL CELLS (i) le consists of usually two halfcells, which are linked by an electrical connection and salt bridge. Salt bridge is made up of inert electrolyte end its function is to maintain electrical neutrality in solutions of half-cell. (ii) The electrode at which oxidation takes place is called anode (negatively charged) and the electrode at which reduction takes place is called cathode (positively elarged) (i) Electrode potential is defined as the tendency of an electrode to lose (oxidation potential) or gain (reduction potential) electrons. The relative value of electrode potential is measured by the reference electrode (standard hydrogen electrode or SHE).(iv) TUPAC cell representation. Zn) Zn8O, CuSO, !Cu c c Anode Cathode C\ and Cz ‘Two parallel vertical lines ((\) r¢1 Incase of a gas the gas is indicated after the le of cathode. PtH, (H” or H 1 H,.Pt Anode Cathode: concentrations in mole’ ttre of electolyi solutions. presents salt bridge 00 ein case of anode and before the electrode incase (0) EMF ot Exar = Engst) Eee = Eepannie) + Enpcatode) where rp = reduction potential cop = oxidation potential passe) or Bog = Ej jaman ~ Ena For spontaneous cell reaction, Esa should be postive (vi) Nernst equation Ege Fy et i - oF 2.0891 gpk (when T 298K, R= 8314 Fol! KF = 96500 C) 2 At equilibrium Eee = 0 0.059 log Keg logk ot Es = Era Applications of EMF Measurement (i) Determination of equilibrium constant (i) Determination of pH of the solution. Pela) (pH?) | CI” (IM) | HasCl, Hg (Calorel electrode or reference clectrode) Cell reaction: Hy(g)——3 2H +e", = 0.0 volt Hg,C1,(6 2HgQ) + 2Ch, Bite) +He, Cl, (s) 2H (aq) + 2Hat 0.0591 ra? £4, PL hogl J asa activities ofall other reagents and proviuets can be taken 0.0591 (iii) Determination of Kw of sparingly soluble salts Cell reaction, Ag(s)-—3 Ag’ +e AgX(s)+e° > Ag(s)+X AgX(s)—? Ag” eee TESS a ee nee0.059) ve = Bay log K,, 1 ‘tequiibrium, Esa * 0, Thus, E:, = 0.0591 log K,y (Ws) Determination of ionization constant of weak acd or weak base. For cell, BUHAY, HA(C) | Cu"(C3) | Cu o.oso1 [HT wT or Egy = E0051 (RG) € Ths () Determination of thermodynamic data . d(AG*) | AG’ = aH fo) (Gibbs-Helmholtz equation) dp (dee : | =) “pr (Temperature coefficient ofthe emf of the cell) On comparing Gibbs-Helmholtz equation with AG’ = AH® - TAS®, we get as--| #4G)] L aT J Applying AG = -nPE.. ( \ as np{ Ee) \ aT ), ‘TYPES OF HALF~CELL S.No Type Example Half-cel reaction 1. Metalsmeta ions hal-cel AgiAg'(ag) Ag(s)—9 Ag+ - Gas ion half-cel! Pt(Ho)/H"(3q) Hy——— + 2 3. ‘Metal insoluble salt anion half- Hg,Hg:Ch|Ct(aq) calomel 2Hg(l) + 2Ci(aq)-—+> HCl: + 2e" cell electrode 4, Oxidation’ reduction half-cell Pj Fes © au ° 5 Quinohydrone Pr [Quinohydrone| H"(aq) SS i. wa on ° 6 Metal, metal oxide hydroxide Hg/HgO|OH"(aq), Hg(1}+20H (aq)->He0(s)+14:0()}+ 2e half-cellCONCENTRATION CeLLs Electrolyte Concentration Cell of different concentrations, EMF ; electrolyte : Electrodes are identical and immersed in solution of the se enttion 0 Fowst COBEN: AS he hit generated due to tendency of electrolyte to diffuse from concentrations becomes equal, the EMF tends to become 2°70 Zn\Zn""(Ci) | ZC) Eeti = Ecatnose— Eaaode en Mag Gq Electrode Concentration Cell electrolytic solution. . , dipped in sam Potential difference between identical electrodes at different activities, OP Pt(Ha) | HCI (1M) | Pt(Ha) Pi Py FH) 9H (aa) +e WaM)+e LH) Ty +3) 0591 5B 2 PR 0.0591 4.7 ea en SUAS eee nr en<< ILLUSTRATIVE PROBLEMS Sol. The Galvanic cell under consideration is POHL, (g)thar /H (a= 1)\| MaO,.Mn’ .H Pt Anode halfeell: HY (a = 1} 94H (thar) +6 Cathode halfcell: MnO, + 8H + Se —+ Mn’ + 4H,0 Initial Cone, Ol o8 Gy After reaction with Fe? (0.01) (0.08) (0.09) So, electrode potential of indicator electrode E =F Oot |, — eel ie, 0) 0; ac; a? iMno 0 3151-208 pg 009) _ = "(001 (0.08) cou 5 eT«10 #151 Abhay (5.36% 10% = 151-0149 = 1.395 ‘Thus, potential of an indicator electrode versus the SHE is 1.395 V Mass Au deposited _ Eq Mass of Cu deposited Eq 197 Eq mass of Au = 6s Eq mass of Cu = 08 Mass of Cu deposited5, 3 =4,7625 8: ‘o Mass of Cu deposited = 9.85% "797 Zit Applying w= [H"] = 6.63 x 10% moldmr* CiHsNH; + H20 5 CoHsNH2 + 130" (H07] = 6.632107 V32 {cat nt [2.0] (cn electrodes Ew 2.118% 10" 43 x 10° moidm™Niomic weight Sol (i) Eq. wt. of Cr= — ange in oxidation number per mole Chi “+ 96500 coulomb deposit 2 am (Cry 24000 coulomb wil deposit ~ $2 2400 gm = 2.1854 um of Cr 6 * 96500 Gi) Wey = 1.Sgon, i= 12.5 ampere Eo = 1 $ Ww Eit os 52x12.S«t 56500 696500 °. t= 1336.15 sec. Sol, Atanode : Zn -»2n** + 20 At cathode: Cu?" +2e> Cu Cell reaction; Zn + Cu? > Zn™"+ Cu [As electricity is withdrawn from the cell, the concentration of Cu’ decreases while that of Zn” increases at -Bea hog fed 1=1.103 oe os fa] ne * [eu If x molellit is the amount of Cu2 that is eanverted to Cu when the cell potential drops to 1 V then,Sol. The cell reaction is M+ 3 Ag’ —-—>3 Ag + M™ Applying Nerst equation, pe 0.0501, [M"] ‘cet = Eten ~ log ois] 0.0018) 042 = Bey 2.0584 (0.0018) 2. ~ 0.064 3 (0.01) Ezy = (042+ 0.064) = 0.484 volt Eben = Etatase ~ Ease Boe =(0.80 -0.484) = Sol, a ‘Weight of solution before discharge ~ 3800 1.294= 4520 ¢ ‘Weight of H:80: before discharge = nas = 1766.31 ¢ ‘Weight of solution afterdischarge = 3500 x 1.139 = 3986.5 g ‘Weight of 12:0. after discharging ~ aax3986.5 =1973¢ Loss in mass of H:SO, during discharge = 1766.31 - 797.3 = 969.01 g Now from first law of electrolysis, w = 2% 96500, Qx98 96500 Q = 954178.21 coulomb: ‘Ampere —hour Coulomb _ 954178.21 969.01 = 3600 3600 = 265.04 ampere-hour. Ee ISTRY]S15 H,0(1)+C10, (ag) 2H" (aq) +C1O, (ag) + aq) + 2H (aq) +26 —2CI0, (ag) + H,0(7) 6x= 0. 15.16 = 0.0193 =19x 10%Prob. 1. Calculate the mf of the cell. My(s)/Ma’” (02 la (uae MAE 2,37 volt ion is devteased 10? 1M? = 408 volt E, ns rote emf if coneeneration ‘What will be the effect on © Sol. 0.80 - (237) Cell reaction. Mg > Axio} 0.1566 = 3.0134 volt aM = (3.17 0.1477) volt = 3.0223 Volt. Objective Questions Prob, 1. The standard electromotive Fore of he cell Fe|Fe* ap [| Cd ial C4 0.125 V Ky the value of AS® at 25°C would be Ifthe temperature co-efficient of emt (A) -20, 125 KK" (B) -24.125 KI K" (C) -26.125 KJ K" 2.125 KK" @ 0.125x2%96500 24.125x KI K" Hence, (B) is the correct answer Prob, 2. The solution of CuSO, in which copper rod is imn copper rod is immersed is dilutec i potential will is diluted to 10 times, the reduction sie (A) Increase by 0.030 V ? : (B) Decrease by 0.030 6 (C) Increase by 0.059 rease by 0,030 {C) Increase by 0.059 V comets Tea eSas Ef, = Gand *Ha(g) and *H,0° in SHE are 1. (ar) (cs) as Bj, = Oand *Ha(g) and “H;0° in SHE are 1 =E,~0.030V Hence, (B) is the correct answer. Prob. 3.1fE)., =-044V and BY, =0.77V. What is”... ? (A) - 0.036 V (B) -033V (©) +033 (D) +0.0367 V Sol. Fe}, +H, (g)+2H,O(aq)——» Fe(s)+2H,0" (aq); AG; 1, (g) + H,0 (aq) > Fe" (aq) +11,0°; AG! . 3 Fe (aq) +3 Hy (g)+38,0 ag} —Fe(3)+ 34,0" (aa); 3G; = AG +46; n,FES +n, FES +n, >nFi 0.036 >E non, Hence, (A) is the correct answer. Prob.4, Electrolysis of dil. HsS0s generates H2S:0s (per disulphurie acid). What current is needed to produce HS,Oeat the rate of I mole per hour assuming 75% charge efficiency, (A) 71.48 amp. (B) 17.48 amp. (©) 35.74 amp. (D) 53.74 amp, Sol. 280, —2c" +H,S,0, 2 mole/hr electrons need to be released = 2F = Sr (assuming 75% charge efficiency) 5.96500 C =ix60*60 i= 71.48 amp. Hence, (A) is the correct answer. Prob. $.Calculate the standard Gibbs free-energy chao Cw (ag) +1 (ag) —> Calor) Given:Culfor) ce =< Cufar) et (ag) CU (aq) +e Cu(or) B= O83 (B) 135.1 (p) -178V (A)-67.85 (C) LI8V "2 OITV Sol Culler) re Culor)+1 (aa) : AG! = -1ePx(-0.17V) Cu (aq) re 9Cufor) BT = 0.53V AG® = 1x Fx (0.53) = -0.53F he AG® forthe reaction: Cu’ (ag)+ 1 (84) —>Cul(or) AG" AG! -0.53F (0.178) = -0.10F 0.70% 96500) = -075501 67.55k) Henee, (A) is the correct answer AG! Prob, 6. Standard five energy of Cu’ | Cu half cell, if SRP of Cu? |Cuand SRP of Cu” | Cu" are 0.34 and (0.16 V respectively, will be: (where “Fis Faraday constant) (A) 0.424 (B) +052 F (©) 042 F (D) -0.52F Sol, (D) (Cu 420 —aCu, AG, =-2F 0.34. Cu +e Cu, AG, = AG, +AG, aN): Cu Cu" +e AG, = FX0.16, Prob.7. Which of the following is/are correct fora lead acid battery supplying electrical energy? (A) PbSOs is formed at one electrode only (B) Pb+H,SO, —»PbSO, + H, (C) Weight of electrolyte decreases (D) PbO> accepts electrons as well as protons Sol. (CD) Reactions Prob. 8. Pb(s)| PbSO, || Pol, |Pb(s) Which of the following expressions represent the emf of the above cell at 25°C? (0) 2089), (x) Sol (A) EE Cea ESa7 << Prob. 9. Litt ofthe following statements is/are correct?” ®) see of one cm? of a solution is called specific conductance (C) The Hagneuduetanee increases while molar conductance decreases on progressive dilution uting equivalent conductivity of weak electrolyte cannot be determined exactly by. Sspolating the plot of A,, against YC (C = concentration of the electrolyte) ) The conductance of metals is due to the movement of free electrons oO Sok (A, C, Dy Prob. 10. If the half cell re: the half cell reaction A+ @ -—» A ;has a large negative reduction potentials, then which is/ere not correct’? ‘“) “A ss readily reduced (B) A’ is readily oxidised is readily reduced (D) A is readily oxidised Sol (A,B,O) Greater the reduction potential, the more easily that species ean be reduced. COMPREHENSION The cell potential for the unbalanced chemical reaction Hg} + NO, + H,0° —+Hg” + HNO, +H,0 +e Voltmeter Is measured under standard conditions in the electrochemical cell shown in the diagram were 0.02 V. Answer the following questions. 1 Choose the correct statement for the given cell diagram (A) Compartment (X) has less pH than compartment (Y) (B) (Y) compartment has acidic solution (C) Current will flow from Y —» X through internal supply (D) AG? for the above cell reaction is less than 1 KI at the equilibrium Sol (B) Equilibrium constant for cell reaction is: a (A) 10° (a) e? Oc (D) 10° MP-CHENISTRY-ELECTROCHEMISTR:ae mot of HNOs in the sbove given ceth) Then the volume of gases liberated ay + formauion of OT aution of CuSOs quired fo If same amount of charge (hie 18 sed for eloetrolysis of 01M, LT aqueous 8 STP will be ct (A) 2.24 fitre (py So tie (py 1 2 ttre (C) 22.4 htre Sol (Dy - ‘Amount of electricity required to form 0.1 mole of HNO? = 0.2 At anode : H,O-—>20, (g) #24" (29) 2 tl So, moles of O: produced at anode = 55 1.12 titres gl- Volume of Os(g) produced at STP MATRIX-MATCH 1 Match the Column — 1 with Column (A), Specific conductance, (B) Molar conductance. (9) | Inereases with increase in the distance between parallel platespersia 2, Sand 4 by appropriately matching the information given in the (hree columns of the following a Dry vell oO | Zntthe V HyOls) > ZnO(s) © Hy) MO dh | Lead battery (ii) | 20, + On» 2120 L@ t ae —| (11) | Mercury cell cy | 2b + 2POO, + A112SOy 9 APOSO.# HHO [RY | S| JOY) | Puch cet | giyy | 22.1 2MnO2 2NIWCI > i) | 4 | } | ZnCl, + MmOy + INH) + 1hO } ia - 2 Which of the follows ng combination ix incorrect ? 1A} (4) (Oy (BJ Ny Gay (Sy [C] AN ()Q) [UD] cy) (i) (5) ‘ Which of the following combination is correct ? TALC) Gin) FR) (A) 0) (Oy Ie} avy avy (Py {D} Gy) 4 Which of the following combination is correct ? TA} dy Gi) (Oy IBLAD Gay (e} UI GQ) (D} dv) (8) Sot. 208 1. Dp ae Answer 5,6 and 7 by appropriately matching the information given in the three columns of the following table, J | Cugsyi (aq) | Zn’ (aq) | Zn(s) ha ov | (P)_| Spontaneous | || | - - | i) | Awts)| Av (aq) |) Ca’ (aq) | Cuts) Gi) | 076V | (Q) | Non-spontaneous | ay | Zin(sy| Za’ (aq PH" (aq) | Hg) | Pes) Ta | LIV | (R) | At equilibrium | hay) | Pads) 41, (2) |W" (aq) [LH (aqy | (a) Pus) | (ivy | 0.46V | (8) | Can't be predicted | | - enn L _—__| 5 Which of the following combination is correet ? 1A} (1) Gi) (Q) {B] (1) 4G) (P) IC} aD (iv) (Q) {DP} (VY) (ii) (S) 6 Which of the following combination is incorrect ? TAT () Git) (Q) 1B} @V) G(R) {C] GM) Gi (Py [D] (ID) Git) (S) a Which of the following combination is correct ? [A] (1) (iii) (Q) (B] (HH) (i) (PY [C] (1) Gi) (R {D} AV) (ivy (5) So 5. 6D 7A CRIESi OS SINGLE INTEGER : 1 ANSWER TYPE sorte Vind the current ig amperes required to deposit 2.977 Of gate Pett howe (At We of Pal = 106-4) jv af AUC Sole v the eteetralynl of bY Sok (3) PU te a pg Wit F 96500 2.977 _ixtndis0 (106.474) 96500 1 Fampere i cee "feats ie 10% then find the value of"? Cal (ag) + ANE, (aq) ==2[Ca(NI,), P (04s oeg PAV 8 gy oot y| Sol (7) hog K, ES aseSol. ¢ following table of standard reduction potentials: Reduction half reaction: = Egy (in V) X°* 426° 9x! io Yr e2e——>¥ 9.69 2 420° —5z 0.21 tow “1.38 For @ balanced equation of the overall cell reaction that delivers the hightest voltage, calculate Ejay for the reaction 2.85 Used the two half reactions that have the most positive and the most negative standard reduction potentials, respectively. Anode: 2W-—»2W* +2e” (Oxidation) Cathode :X°* +e” +X" (Reduction) Net cell reaction : 2W + X?* —» 2W* +Xx* Bean = Bs 0 ~ Ede = L47~(-1.38)= 2.85 V Prob. 2. If for the half cell reactions Sol. Cu +267 Cu; E°=0.34V Cu +e"—+Cu*; B= 0.15V Calculate AG® of 2Cut——>Cu +Cu, -36.67 Anode: 2Cu* ——>2Cu +2¢7 Cathode :Cu?* +2e° —>Cu Net cell reaction: 2Cu* +Cu Cu, n=2 Been = (En p eathode ~ (ERP anode = (0.34 -0.15) V=0.19V AG? = ~nFE%y, = -2x96500%0.19 = 2220500%0.19 55 36.67 kd 1000 Prob. 3. A solution containing 4.5 mM Cr,03- of and mM of Cr shows a pH of 2. Calculate the potential of Sal. half cell. Standard potential of the reaction: Cr,0}7 ——>Cr°* is 1.33 V. 1.07 ‘The balanced half cell reaction is Ch OFfaq) + 14Hfaqy + 60° —> 2CKQhy +720; (n=6) (5x107) (4.5x107 107)"60s 8 670 1133-026) volt= 1.07 volt Zn?" (0.1M)| Zn at 298K Prob. + Caleulate the EMF ofthe following cell: ZnjZn*” {0 016)[ Zn" ( Sok o.n205 Mhe reactions atthe to hal-cell are At anode Zy ~—+n™ (001M) + 2¢ Atcathode Zn™*(0,1M) + 2¢ ——Zn Net cell reaction -Zn2* (0,1M) > Zn="(0.01M), (n =2) Product of Agi Sok 13,36 The given cell is; Common ion ee oe Ag) Agl, 0.05(M) K1||0.0SM AgNt Anode: Ag) ——>Ag*(C=%) +e Cathode :Ag”(0.05M) +e” —>g,,, 8 Teatiose Substituting the value of (Ag"Inot in Nemst equation, we have fayid state is one of the ph ci Packed and are held toga 2 a! Sales Of matter in which particles (molecules, ions or atoms) are closely “16 together by strong intermolecular forces. TYPES OF SoLins Solids are broadly divided INL two types, Crystalline solids: The con ’ Amorphous solids: the con The differences between crystal ent particles are arranged in a regular fashion utuent particles are not arranged in ine and amorphous solids, 4 proper fashion = Crystalline Amorphous They have sharp melting poi ey bave sharp melting points ‘They melt over a range of temperature They are anisotropic They are isotropic. They undergo clean cleavage. ‘They undergo irregular cleavoge. Types of Crystalline Solids Depending upon the constituent partic! there are four types of crystalline solids, Crystal type Constituent partictes Binding force Examples Ionic Positive and negative ions Electrostatic forces of | NaCl, KNO,, LiF BaSO, etc. attraction Covalent Atoms Covalent bonds Diamond, silicon, quartz Molecular Molecules van der Wat's Solid CO. 13, Sp, ice forves/Hydrogen bonds Metailie Positive ions and mobile Metallic bonds All metals and slioys electrons LATTICE AND UNIT CeLL Crystal Lattice: A regular arrangement of the constituent particles of a crystal in three-dimensional space. It is also termed as space lattice. Unit Cell: The smallest thre mensional portion of the space lattice which when repeated over and agr ections produces the complete space lattice. a PETESTypes of Unit Cells Simple: Partictes are present at all comers cles Face-centred cubic (FCC): In aldition 19 the PAHS Centre of every face. ct End-face centred: in aittion o the paises 60 ‘Opposite faces, en : Body centred cubic (BCC): in addition 1 the particles the body of the unit cell mers, there is one particle PFESEA on th fon the comers, e centre of One Pir OF two, e particle in the © rs, one pa re is one particle present within Crystal Systems lls are given below . ses and types of unit ls af RIVET ‘Types of crystal systems, their axral ratios, angles and {¥Pes O° ‘Unit cell Bravais lattices Aviad angles —- - Crystal syster sees is oe - ‘Simple, BCC, FCC ‘Cubic a=bee a=p=7=90" simple, BCC Tetraponal simple, FCC, end-face centred, BCC Orthorhorbie oe ‘simple, end-face centred Monoclinic anpemrey aon . imple Triclinic sper si . 7 imple Rhombohedral, a=paye a pe Hexagonal in all, there are seven crystal systems and fourteen Bravais lattices Law of constancy of interfacial angles: The ansles between the ria or rah of & rye The a ape ofthe ci (called interfacial angles) are always same icrespective of the size indexer oe ‘The interfacial angles are measured with the help of an instrument called g¢ Cusic Systems Number of Particles per Unit Cell (Cubic) 1 Contribution of each atom present on the comer Contribution of each atom present on the face = 1 Contribution of an atom present on the edge = 3 Contribution of each atom within the body = 1 I No.of atoms presen in simple unit cell= x8 =1 1 No. of atoms present in FOC = a (comer atoms) +56 (face) No. of atoms present in BCC x8 (comers) +1 (body centre) =2 In case of hexagonal close packing (hep), no. of atoms per unit cell = 6 FCC arrangement and cubic close packing (ccp) arrangement are same and it has closest packing in cubic crystal system (packing fraction = 0.74, ie. 74% of unit cell is occupied by atom) aeCoordination Number vated Han MuAH EH He the muimhes af its cle Hat an atom Has in iv et ect Por olemental solids. (4) Conteltnation nny ce Neyghbonrs (oppositely charged ions in case of ionic erystad) Fu simple cubic structure — 6 Coontination oumber of FOC structure 12 GH) Coordination manher ot HOt a STRUCTURE OF Tonic Crystats Comm types oF structure 1 Rock sal (NaCI type * possessed by siniple jonie compounds (AB type) are Cavstunn chore (CaCh type (ZnS) type Mato features af NaCl ype steueture: (thas FOC arrangement of ions Gi) Na andl CL ions have 6 : 6 coordination (11) Pach anit cell has four NaCh nits 14) Examples: Halides of alkali metals (except those of Cs) and those of NH}, oxides and sulphides of 1 Zine Men alkaline carth metals (exept Be nin Features of CCL type struct (4) thas BCC arrangement of ions la ). halides of Ag (except Ag!) Gi) Cs! and CL rons have 8 8 coordination (ii) Bach wait eet has one CsC1 unit (8) Examples: Csbir, Osh, CCN, THBr, THC ete, Main features of ZnS type struc G)TEhas FOC arrangement of $ ions (ii) Zn!" and S* tons have 4 4 coordination (tetrahedrally arranged) Examples: CuCl, CuBr, Axl ionic compounds of AB, type Jonie solids Main features Buorte (ak) type (1) thas cep arrangement of Ca?" ions and F> fons in al {etrahedral voids, (in) Ca?! and F jons have 8 : 4 coordination. Antifluonite structure (i) Anions in cop arrangement and cations in all tetrahedral eats NaO voids. i)_Coordination umber ratio of cation anion is 4: 8, Types oF CLOSE PACKING The arrangement of atoms to form close packed structure can be done by two different ways, ing (hep) The pattern of arrangement is ABABAB ... type and the space (i) Hexagonal close px occupied is 74%, (ii) Cubic close packing (cep): The pattern of arrangement is ABCABC ... type and the space occupied is 74%, SAEa oe sed tetrahedrally around 1, ach sphere is surrounded by four spheres 7878 ix spheres. ch sphere is surrounded by sik SEEN The radii of the voi : eres ( ids in terms of radii of packing spheres re) st (of tevahedral said 0588 {When no distortions = he mat) 0 taeda void = ataWhon mo distortion it umber of voids in j we terms of number of atoms see ne e tatihedral voids = No. of atoms in the close packed arrangs voids 2 x No, of atoms or octabedral vo! ment oF octahedral voids No. often vids inc All noble pase op=4 ral voids cep = & ent cp arrangement. ' have cep arrangement except He which has hep a ricnal STONgEMeSs 1 uy ‘The relationship between radius ratio( £.], coordination number and s! lated F below: Coordination numb Structural arrangement ‘oordination number tr Triangular ‘Tetrahedral Ovtahedsal Body’ centred cubic, ‘The relationship between atomic radius (r) and the edge (a ofthe uait cel is given below for elemeniy crystals and non distorted ionic cerystals: _ ae ean Body centred Face centred Packing Fraction (Undistorted Crystals) olume oe yf Packing Fraction = Volume occupied by spheres of u Volume of unit cell Ee Type of unit cell Packing Fraction Simple unit cell Body centred unit cell Face centred unit cel! 4 jay RASTheoretically. the density of ZxM axN, a cubic unit cell can be caleulated by following equation where p- density of unit celt Z - n0. of formula t a dge length of the unit cell : No ogadro’s number DEFECTS IN CRYSTALS Metal Excess Defects Formation of non-stoichometric compound due to excess of any of the ions forming the compound. For example, NaCI heated in Na vapour tums yellow Metal Deficiency Defects Its a defect in which if any one of the positive ions is missing from its lattice site, then ity extra negative charge 1s balanced by some near by metal ion acquiring two charges instead of one. This type of defect 1s found in compounds of transition metals. Schottky Defect The defect in which equal number of cations and anions are missi density of the crystal decreases Frenkel Defect from their lattice sites. As a result, the The defect in which cations are missing from their lattice sites and occupy interstitial sites. As & result, the density of the crystal remains unchanged. -__—— ees TEESSol, P0414 xr = 7.52107 nm Boney st samp of te Fen Os What percentage of rons preva ig 7 isa mixture of Fe® and Fe" ions Fea; 0 is a non-stoichiometric compound. It isa mint 7 Let, x atoms of Fe ions are present in the compound or are 9 So, (0.93 ~ x) atoms of Fe? ions are. present in the compouns Tn the compound, Total postive charge + Total negative charge = 0 Xx (+3) +(0.93 —a) x (42)-2=0 eer ees or xt2x093=2 x2 014 % of Fe™ ions present = 94 190 = 18.053 093 " secolar welght 75 ghmol Is $A hich then ind the radius of metal atom. (Ns = 6% 108, cy. 26x10 x(5x : 75 fi i = 2= Unit eell is BCC. => a are ~ 500% JF pm = 216 pm 8 fi red cubie lattice with density 5.20 p/em' and edge lengtt of as ofthe element which contains 3.01 x 10% atoms, RSE 2glem’, M=? 300 pm=3x10" m=3x10"em 17 x10 em’ N, = 6.023%10"ave BNA 5.256.0230108 42710 4 2113 emo! 6023810" atoms have 21.19 g 3.01410" atoms hhaye - 21 13%3.0 5 002 4 ' (B) For NaCl unit cell (edge-length =), = 5 (€) The void space in a bee unit cell 1s 0.68 (1D) The void space Yo in a face centred unit cell is 26% Bb Sol. In bee structure, +6 = Henee, for CsCl, refs 2 2 (A) is correct. Since, NaCl erystallizes in foe structure 2r. + 2r.~ edge length of the unit cell a a SSSASe |) Hence,r+ =f 2 (B)is comect Since packing ftion of a bee unit cell is 0.68 Void space = | 0.68 = 0.32 (C) is not correct In fee unit cell, PF = 74% VE = 100-74 = 26% (D) is vorrect. Hence. (A), (B) and (D) are the comect answers, Prob 6.4 mineral having the formula ABy ccrystallises in the cubic close packed lattice, with A-aioms Sccupying the lattice points. Now, select the correct statement(s) of the following: (4) Co-ordination number of A-atoms is 8 (B) Co-ordination number of B-atoms is 4 (©) Fraction of octahedral sites occupied by B-atoms is 50% (D) Fraction of the tetrahedral sites occupied by B-atoms is 100% Sol (A, B, D) {mn antiuorite stricture anion B* are present in all octahedral voids and cation A?* forms cep lattice. Hence, A, B, and D are the correct answers Prob. 7. Which ofthe following is tue for an ionic compound A.B crysillizes in ant-uorte type (A) Cation is occupying tetrahedral void (B) Cation is occupying octahedral void (©) Iftons present at one body diagonal are removed the new formula will be A,B, (D) The ratio of radius of A’/B” is in between 0.414 to 0.732 Sol. (A,C) In antifuorite type structure cation occupies all tetrahedral void. When ions of one body diagonal will be removed then two comer B- will be removed and 24° from tetrahedral voids will be removed, New effective formula = A, By. 50 A,B, For coordination number 4: 4 in tetrahedral geometry radian ration lies between 0.224 to 0.414 REASONING TYPE QUESTIONS |. Assertion: In rock salt structure, all the octahedral voids inthe close packing of anions are occupied by cations, Reason: In rock salt structure, the distance of closest approach between two anions equal to half the face diagonal of the unit cel Sol, Assertion» True Reason > True but not correct explanation, COMPREHENSION SESSGES co, The ReIMMININE SPACE (2OY)) ig ee Read the paragraph carefully and answer th follow culate - Im NCP or CCP, consituem patices occupy 74% OF NE availible 8 : ds or holes a spheres remains unoccupied and is called asso queer ener onsidering the close inthe secon i close Jng arrangement, each sphere ore there, 1 and octahedral voids are ed arrangement thet Tist layer, touching each other. Tetrahedra IER is the radius oF the spheres in the close pac! R (radius of tetrahedral void) = 0.225 R Prob. 1. tn the figure given below, the site marked as S83 © cere ace o— (B) cubic void (A) tetrahedra vahedtal void (Pca the above (€) octahedral void Prob. 2. If the anions (A) form hexagonal close packing and cations (B) occupy only 23rd octahedral vords jn it, then the general formula ofthe compound is (A) AB (B) AB (©) AB {D) AB ed whereas 1/8th of tetrahedral voids are Prob, 3. in the spinel structure, oxide ions ate cubie close pack 5 spinel structure, oxide fons ate eu in «by B cations, The general form ‘occupied by A?’ cations and 1/2 ‘of octahedral voids are occupies of the compound having spinel structure is (A) ABO. (B) AB:O: (C) ABs» Prob. 4. Mark the false statement: (A) CsCl erystal always shows Schottky defect (B) Crystals having F-centres are coloured and paramagnetic (C) Photosenstivty of AgBr is due tothe presence of Frenkel defect in ths crystal (D) None of the above In Schottky defect (A) cations are missing from the lattice sites and occupy the interstitial sites (B) equal number of cations and anions are missing (C) anions are missing and electrons are present in their place (D) equal number of exira cations and electrons ate present in the interstitial sites AnswersH Brose See} MATRIX ~ MATCH TYPE 1 Mutch the Coluina with the Column 1 sg her of cations and anions awe 1 AR) Metal excess iyi stoichiometry in NaCl BO) Oecupaney ot tet (DY Amon vacaney wid ssi {p) spinel stractur i j ot @) deo Hhedhal aut octahedal vouds | (7). Sehotthy detect Peed th tapped electron |G) Fecentre iaszestans () Frenkel deteee deh CY 9 OY ED) > 8) Mateh the type af defi charactensstics in Co osresponitiv A) = _( 1D) | Storchometne defect no : Fe | Non-stoichiomeine detec a te Density of the crystals de : a oad s (s)_[ KCI erystal doped with SrCis on on HW Density of the crystal J Sok A= PLB DMCS EOD Gans) a Answer 3,4 aad 5 by appropriately matching the information given in the three columns of the following table, fH | Cubic 7 io @) 41 Which of the following combination is correct 9 LAL Gy [PB] Ub GDR) [CH Gan ID} AV ants) 4 Which of the following combination is incorrect” AAP acy {BE dnb Gn) (Py [eh dyy an (gy (D} AV) wy (R s Which of the Sollowing combination is correct” {AV Gin eR) (BPA GY IC} Hu @) Dj city ain iP) Sot. 3. A ADE SB SINGLE INTEGER ANSWER TYPE s NaCl type stricture, such that latice points ary occupied by Band A’ are An rnc erystal Av B p soids. [Pall the face centred tons are removed, the number of \ rons jeft an ete unit ell oF AB is So 4) Ail comers as well as face centres are occupied by B rons unit cell of AB has 4.4. sons lc up of two elements A tat Wr > So) und Blut, Wt > 32) Asatoms are present at each nS APE present at alternate face-centres as Well ay at is A Ng (where Ny ts Avogadro's aunther! unit fof cubic umt cell, while Bate 16.24 he of this solid co So (2) Formula of the sold is AB Formuta W1. of the sob Now. 120 g solid contains © Ny umt cell ars 40 g solid contamns ~ 2Ng unit cell CRS{otal no. of atoms attached to 3. Metal A crystallizes ina lattice with coordination n°. é. ia will be doa Son, el unit if atoms lying on two body diagonals are Fe ol. (a) 2 body diagonals. CN =8 so metal erystallizes in BCC, so total 5 atoms will be lying on ae yoved? NUMERICAL VALUE ANSWER TYPE Prob. 1. Radius ratio (ideal) for octahedral geometry 1S Sol 0.414 Prob, 2. Ratio of atoms at face placed by comer in fee is” Sok 0.98 fic 8” comer hedral void is x ru. x is? Prob. 3. In cep of atoms Atra), the radius of B that can fit in feta Sol 0.225 Prob. 4. Packing fraction of simple cubic is Sol, 0.524 Prob. 5. Ratio of Z of bee to fec is Sol. 0.50 2 0.50 Prob. 6. Ratio of octahedral to tetrahedral voids in cep is Sol 05 oO4 Td 8 Prob. 7, Ratio of Z in simple cubic (sep) packing by HCP is Sol. 0.16 Prob. 8, Ratio of nearest neighbours to next nearest neighbours in sep is : Sot 0.50 S450 12 Prob. 9. The length of body diagonal of a cube in x a where a = edge length, then value of x in decimal is Sol. 1.73 Ba Prob.10,Void space fraction of fec is Sol 0.26 1-0.74 = 0.26