03 UME BASIC CONCEPTS & represents the tate ofa process in which the properties lke temperature, pressure ‘show any change with the passage of time. - Chemical equilibrium: When the rates ofthe forward and reverse reations become equal, the the reactants and the products remain constant. This isthe stage of chemical ‘equibrium, This equilibrium is dynamic in nature ast consists ofa forward reaction in which the reactants give product(s)and reverse reaction in which product(s) gives the original reactants. Equilibrium is possible only in a closed system at a given temperature. A mixture of reactants and products in the equilibrium slate is called an equilibrium mixture, In s homogencous system, all the reactants and products are inthe same phase, For example, in the gaseous reaction, Nog) + SH,lg) > 2NHy(g), reactants and products are in the homogeneous phase, Equilibrium in a system having more than one phase is called heterogencous equilibriom. “The equilibrium between water vapour and liquid water in a closed container is an example of heterogencous equilibrium 1,00) > 1,06) Equilibrium in Physical Processes ‘The stae of equilibrium attained between two physical phases ofthe same chemical compound is termed as physical equilibrium, (@) Solid-Liquid Equilibrium Av equilibrium [Rate of melting of ice = Rate of freezing of water ‘This happens at melting point of ie and freezing point of liquid water. This temperature is (°C oF 278 K. Tee and water are in equilibrium only at particular temperature and pressure For any pure substance at atmospheric pressure, the temperature at which the solid and liquid phases ae at equilibrium i called the normal melting point or normal frezing point of the substance. The system here i in dynamic equilibrium, (@) Liquid-vapour Equilibrium Avequilibrium, Rate of evaporation = Rate of condensation Water and water vapour are in equilibrium position at atmospheric pressure (1.013 bar) and at 100°C ina closed vessel. The boiling point of water i 1D(*C at LOLS bar pressure. For any pure quid at one atmosphere pressure (1.013 bar, the temperature at which the liquid and vapours are at equilibrium is called normal boiling point ofthe liquid. Boing point of the liquid depends on the atmospheric pressure. It depends on the alitude of the place; at high altude, the boiling point decreases.(6) Solid ~ Vapour Equilibrium: Let us now consider the systems where solids sublime to ‘vapour phase Ifwe place solid iodine in a closed vessel, after sometime the vessel gets filled Up with violet vapour and the intensity of colour increases with time. After certain time the intensity of colour becomes constant and at sis stage equilibrium is attained. Hence, slid iodine slimes to give fodine vapour and the iodine vapour condenses give solid iodine ‘The equilibrium can be represented a, (slid) — 1, (vapour) (@) Equilibrium Involving Dissolution of Solid or Gases in Liquids @) Solids in Liquids: When small quantity of sugar is added to water with stirring, it dissolves. Astage comes when no more quantity of sugar dissolves in this solution. Such ‘olution is termed ae saturated solution and has an equilibrium between the dissolved sugar and undissolved sugar Sugar (solid) ugar (in solution) Av equilibrium, Rate of dissolution = Rate of precipitation ‘The pressure exerted by the vapours in equilibrium with the liquid at a specific temperature is called vapour pressure ofthe hud (i) Gases in Liquids: When a soda water botle is opened, some of the carbon dioxide gas dlssolved int fizzes out rapidly. The phenomenon arises due to difference in solubility fof carbon dioxide at different pressures. There is equilibrium between the molecules in the gaseous sate and the molecules in solution, €(ga8) — CO, in solution) Arconstant temperature solubiliy of gases in water or other suitable solvent depends on ‘the applied pressure, This is known as Henry law According to Henry's ae "The mast of ‘a gorse pr ut mass ofthe oon le pes lomperature is proportnal fo the prose ofthe gas in equi th the sation ma porm=Kp where: m = mass ofthe gas dissolved in unit mass of solvent {P= pressure ofthe gas above solvent 4. General Characteristis of Equi (©) Equilibrium is possible only in a closed system ata given temperature (i) Both the opposing processes occur atthe same rate and there is a dynamic but stable condition, (i) All measurable properties ofthe sytem remain constant (Go) When equilibrium i auained for a physical process, iis characterised by constant value of one ofits parameters ata given temperature (©) The magnitude of such quantities at any stage indicates the extent tow process has proceeded belore reaching equilibrium. 5. Equilibrium in Chemical Processes-Dynamie Equilibrium Analogous to the physical syste the physical reactions alo atin a state” of equilibrium “These reactions can occur both in forward and backward directions, When the rates of the Forward and reverse reactions become equ, the the products This isthe slage of chemical equilibrium. ‘This equilibrium is dynamie in hues it consists ofa forward reaction in which the reactants give product(s) and reverse reaction in which product(s) gives the original reactants. 5 3 Fig. 1: Attainment of equiltvium stato6. Law of Mass Action: It states that “The rate at which «substance macts is proportional its active ‘mass ad the rae of chemical reaction is proportional tothe product ofthe ative mases of he macing stances.” Jar concentration ix, number of Equilibrium and Equilibrium Constant Consider a simple reversible reaction in equilibrium state A+p—c+D A and B) and the products (C and D) exist, uate ata in which the reacta particular temperature Applying the lw of mass action, Rate of forward reaction « [A](B} (MIB) rly rate ofbackward reaction = {C)[D] ICID] clocity constants for forward and backward reactions, respectively. where andy represent the Av equilibrium sate, Rate of forward react = Rae of backward reaction. A{AH(B] = KICHLD] 3 TAB) Av constant temperature y and A, are constants. Therefore, Kwege 1 46 by another constant ing “3,7 HI) Kis known as equilbriam constant It has a constant value for given reaetion ata specific temperature Now consider a general reversible reaction md +nB= aC +0D ‘The equilibrium constant, K, may be written a8 “The concentration ratio of the products and reactant is also termed as concentration quotient and is represented by °Q”. Hence at equilibrium rerio a urer Relationship between Q, and K, () HQ, > K, then the reaction proceeds towards backward direction. (i) IQ, < K,, then the reaction proceeds towards forward direction. (ii) 1Q. = K,- then equilibrium state is aained. 8. Relationship between K, and K.:Consider the general reversible reaction mA + nhac + 8D Te equilibrium constant for this reaction in terms of concentration may be expressed as ray Ke urer|. Characteristies of Eq or Cre; @ where C4, Gp Ge and Cy represent the molar concentrations of 4, B, Cand D respectively. A,B, Cand D are gaseous species, the equilibrium constant in terms of partial pressures may the written as re) ‘her fc and represent paral presure of bane dB, Cand repeciney ‘suming se este ea ten acordng to el gas equation eat a po ber pacer where, seoneemaion in makes For the gases A,B, Cand D, the partial pressures may be writen as ART Po = CoRT Substituting these values f py. Pe and Py in equation (i), we get WGoRTIC RT! ica tc RTP c.chinny** cope = KART = KT Lb no 6, i sete, scoring uation) K,= COCR, = Gas constant T= Alu temperature and An = no. of moles of gaseous products — no, of moles of gaseous reactants ‘We can draw following conclusions from the relationship between Kyand K, (@) When number of moles of products and reactants are equal ie, An = 0, then Ki (W) When Bn > 0, Ky > K, (9 When an <0, Ky < K, @ Ata given temperature, the equilibrium constant for a particular reaction has a definite value (i) Ie is independent ofthe inal concentration ofthe reactants and the direction from which equilibrium has been reached. (i) IT the reaction is reversed, the value of equilbrivm constant is als inverse (G0) I the chemical equation is divided by 2, the value of equilibrium constant for the new equation is square root ofthe previous value of K. “Writing Expressions for Equilibrium constant (K) () The concentration of pure solidi, active mass of solid is taken as unity. (i) When the reaction components are in liquid phase, their concentrations are variable and thus included in equilibrium expression, However, iiquid component is present in excess (eg. solvent, its concentration remains almost constant and hence taken a any11. Le Ghatelier’s Principle: I is stated as, ifa sytem in equilibrium is subjected to a constraint, such as change in concentration, temperature oF pressure, then the equilibrium shifts in a ditection in order to undo or reduce the effect ofthe change. (@) Effect of Change of Concentration: This principle says that increase in concentration of eating species sil shift the equilibrium in that direction where iti consumed, (i) Increase in concentration of any of the reactant, shits the equilibrium in the forward direction Gi Increase in the concentration of any of the products, shills the equilibrium in the backward direction (6) Effect of Change of Temperature: According .o the principle increase in temperature of the system will shift the equilibrium in that direction in which heat is absorbed. Ia reversible reaction isexothermic in forward direction, then tisals endothermicin backward reaction, Soin such ease, (i) Endothermic reactions shift che equilibrium in the forward direction with inerease of temperature (a Exothermie reactions shift the equilibrium in the backward direction with inerease of temperature (o) Effect of Change of Pressure: According to Le-Chatelicr’s principe, inerease in pressure on, the equilibrium will shift tin that direction in which there is decrease in number of moles. {) Increase of pressure shifts the equilibrium in the direction where number of moles decreases or An = 0 i) Decrease of pressure alters the equilibrium in the direction where number of moles increates or Av > 0 (i) Change of pressure has no effet, ifthe number of moles of gascous products is equal 0 no. of moles of gaseous reactants i. An (d) Effect of Addition of Catalyst: Addition of catalyst has no elfect on equilibrium because the ‘catalyst alters the rate of forward and backward reactions to the same extent. (©) Effect of Addition of Inert Gas: Addon ofinert gas (eg. He, Ne, Arete) tothe equilibrio system can be done at constant pressure or at constant volume. Atconstant volume No eect, whatever be the valve of At constant pressure Addition of inert gus favours forward reaction when An > 0 Adtion of inert gas fwours backward reaction when Ax < 0 ‘Addition of inert gas has no effect when An 12, Tonic Equilibrium in Solution: Chemical substances have been classified as electrolytes and non-clectrolytes based on their behaviour in aqueous solution or in molken sate. Substances ‘which are good conductor of electricity in their molten state or in their aqueous solutions are called electrolytes ¢4., NaC, CuSOy, acids, bases etc. On the other hand, a substance whose aqueous solution or molten sate do not conduct electricity iscalled a nomelectrolyte eg. urea, ‘lucose, starch, glycerine, et Depe clectrolytes. (@) Strong, electrolytes: The substances which ionize almost completely into the dissolved in water are termed as strong electrolytes eg, NaCl, HCI, H,SO,, KOH, NaOH, GuSO,, AgNOs et (6) Weak electrolytes: The substances which ionize ta smal extent when dissolved in water are «alled weak electrolytes ¢., HCOOH, CH,COOH, NH,, HCN, boric acid, ete. The degree “of ionization of weak elecrolytes in water depends on the nature of solute, temperature and ‘upon the extent of their ionization, these are lasted as strong electrolytes or weak fons whendilution. Further more, the degree of ionization of weak electrolytes increases on dilation at ‘constant temperature, 13, onisaton of Weak Electrolytes: Weak electrolytes are partially inised in aqueous solution and an equilibrium is sec up between the ions and unionised part of the electrolyte. Thiss known as ionic equilibrium. Let usconsider aceticacid (CH,COOH),a weak electrolyte. When dissolved in wateraequilbrium will exist between its ions and unionised acetic acid molecules CH,COOH + 1,0 CH,COO- (ap) + 1,0" (a) “The equilibrium constant, K, is writen as [CHC0071H,0") [CH,COOH|TH,O} Since in aqueous solution, molar concentration of water ie, [HO] is large and therefor considered to be constant. Therefore, K(H,O] i replaced by a new constant "K,” termed 28 ionization constant or dissociation constant of acid. Thus, [CH,COo7[H,0°) (CH, coon} Now suppose the inital concentration of acetic acid ise moles litre and ais the degree of ionization then the concentration of various species at equilibrium is as given below CH,COOH + Hy HCO“) +H," ag) < ° ° Initial cone ca) cn Eu ‘The degree of ionization is very small as compared to L, therefore (1a) i taken as 1, Thus, we get “This expression is known as Ostwald dilution law. lary, Fora weak base we have any where Kyi the dsocation constant of weak bie is he inal concentration and i the {eqrecof discon af weak base Since concentration is inversely proportional tothe volume of the sluon, V ontaining one mao electri therefore the degre of diexiton may be writen a VE.XD for weak acids /R,XT for weak bases ‘Thus, acording to Ostwald dilution law "The degree of ionization of «weak electra is inser proportional tthe square rot of moar concentration “The degre of ionization of wea elec is diets proportional tthe square rot of vale ofthe solution containing one mole of he elect" and a14, Acids, Bases and Sats (@) Arthenius Concept of Acids and Bases: According to Arthenius theory, acids are substances tha dlsocates in water to give hydrogen fons Hi (a and bases are substances that produce hydroxyl ions OH (ag). The ionization of an acid HiX(aq) can be represented by the following equations HX (ag) + Hap) + Xa) HX(ap) + 1,00) > HO" aq) + Xap) (©) The Bronsted-Lowry Acids and Bases: The Danish chemist, Johannes Brénsted and the English chemist, Thomas M. Lowry gave 2 more general definition of acids and bases According to Bronsted-Lovery theory, acid is substance that is capable of donating hydrogen ion Hand bases are substances capable of accepting a hydrogen ion, H short, acids are proton donors and bases are proton acceptors, The acid base pair that ditfers only by one proton is called a conjugate ack-base pa. Consider the example of dissolution of NH, in HO represented by the following equation: -“—— NHyiag) + HO Niji) + OF re re Levon —t (6) Lewis Acids and Bases: G.N. Lewis in 192% defined an acid as a species which accepts electron pair and base which donates an electron pat. A typical example is reaction of tlectron deficient species BF, with NH. BF, does no have a proton but sll acts as an acid and reacts with NH, by aecepiing its lone par of electrons, The reaction can be represented BE, +oNH, > HN > BF, 15, Tonization of Acids and Bases ‘The strength of an acid depends upon the number of H ions produced in their aqueous solutions, Greater the number of H ions produced by an acid in aqueous solution, stronger isthe acd. Acds like HCl, H,SO,, HNO,, etc. ionise completely releasing large number of H ions. So, these acids are called strong acids. For such acids the molar concentration of H* ions in solution fs same as that of acid tel (On the other hand, the acids which are-not completely ionised in aqueous solutions are known, as weak acids eg, HCO, ete: The relative strength of weak acids can be compared in terms of their ionisation constants (@) Tonisation Constant of Weak acid in Water: Consider the weak acid HA, and its ii ration is¢ moles litre", I's the degree of ionisation the on ‘the equilibrium state ‘may be given as follows WA + HO == HOt + ox mol Lt o ° Initial cone (l=a) “a a Equilibrium cone Applying the law of mass action we get, 0°18) THATT,O}Since (H,0} is large enough to be considered practically constant, it follows, H0°181 xq,o)= Het Substituting AIH,0] by another constant K, (O71) 5 &, is called as ionisation constant ofthe ai Larger the value of K,, greater is the concentration of HO" and thus stronger isthe aca (6) Tonisation Constant of Weak Bases in Water: The ionization constant of weak base BOH in water may be written as BOH + H,0 — B* aq) + OFF a9) aia) a Equilibrium cone _ (BION “* ROH] (6 onic Product of Waters Water is weak lectrolye and ionises to 2 smal extent follows 1,0 + 0,0" +01 rium constant may be writen a8 Equi _1,0°110871 - TOF Since molar concentration of pure water i constant {HO} = 1,07 ]01" K,=h07}017] where isthe ionisation constant or ionic produc of wate. Hence, Tonic product of water may be defined 3s "The prt of te molar concentration of [H0" end [OH] on (@ pl Value: pit is defined as the negative logarithm of the [Hj0") con Inoles per lire. Mathematical itis expressed as 7 L PHL = logy lHyO"1 oF pH = los Sr Like pH, pOH may be expressed as pOH = —log (OH) Inthe above expressions. stands for power (pten:,a Danish word) of hydrogen or hydroxyl jon concentration, Mathematically p means ~log. Relationship between pH and pOH. k= 1H0"}08 “Takinglogon both sides, log Ky = log H0°I + ogi OFT log K, = “log H0" Hogi O#Sbstcating different vlics of [0°] in pl form (i pH <7 for acid solution (i) pH > 7 for basic solution (cy ptt =7 for neuval soltion (0) Relationship between K, and K, for an Acid and its conjugate base Let's consider weak acd HA, which undergoes fonsation in aqueous medium as HA+H,O—=H,0" ag) + Aon) moe) © Now, 1,0 is taken in excess. “The conjugate base A” alko acts asa weak base in water as A+ HLO—=HA+ On (HaoH Ko «i _ {HO"107 , (HAIOHT Now axxo i = (H,0°}107] = cK, = Ky or DK, + BK = PR pK, + pK = 1 16, Solubility Product: There are many compounds which appear to be practically insoluble in water. Infact, such compounds are ver limited solubility in water. These are known as sparingly soluble sals. For example, BaSO,, AgCl, PbCl, ZnS, ete. When these sparingly soluble sali are dissolved in water at particular temperature, an equilibrium is established between the ions and the sold salt Such solution is known as saturated solution of the silt. For example, a sturated solution of AgCl has the following equilibrium between the solid AgCl and the ions of AgCI in solution, xl) As ap # Crap Applying the conceps of equilibrium Fg" aghICH lag TACIONT Since the concentration of solid AgClis fixed, irespective of the amount of solid in contact with the solution, Therefore we can k a constant temperature Kx AgCI() = (Ag'IICE] K x AgCl6) is substiuted by another constant known as solubility product (Ky) [Ky = tag Cr] Relationship between Solubility and Solubility Product: Let the solubility ofa sparingly soluble binary electrolyte (AB) bes mole per live Abate Ky = (01X84a and ‘Thus, the solubility of a sparingly soluble inary electrolyte sequal the square 106t of is solubity product ‘Conon Yon Effect 1 tates that, fn te saltutin of a weak electra slut of strong electra 1 added whch furnishes im common to that furished bythe weak ee, the nation of wa lect appresed For example, NHOH isa weak electrolyte and fnises vo a small extent NH} 1087] ~SHOnT Whena strong cletrolytelke NH, lor NAOH isadded to NH,OH solution then the uibsim will shit to the let because ofthe high concentration of ether NH tons or of OF fons. In Corder to maintain K constant, she lontation of NHOH wil be suppreted. Buffer Solution: There are some solutions which rest the change in pH on addon of small amount of trong acid or alla Such solution are called ble solutions (@) Types of blfer solutions: These buler solutions are of wo ies (Acide buter is obtained by mixing equimolar quantities OF weak acid and is sl wilh a song base eg. 1. CH{COOH + CH,COONa 2. HCOOH + HOOK “The pH value of acc ulfer i usually less than 7. (i Basie buffer: I conan equimelar quanthic of weak base and is sah witha trong acid For example, 1 NHOW + NHCL 2. GHANH, + GH,NHCr (© Batter seton: The ailiy ofthe buller solution to rest the change in is pH value on addon of small amount of tong aid or song base elle buffer ation Lt us consider an acidic buller containing squimolar amounts of CH,COOH and GH,COONa to understand the bufer acon. Buller solution has lage eoncenuation of species namely CH,COO™, Na and unionibed CH,COOH. cH,cooH —-c#,coo-+ #* NH,OH = Nuj +01" CH,COONa —- CH,COO"+ Nat When fe drops of Hl are added to this buffer solution, the H” ions of HCl immediately ‘combine wth CH,COO™ ions o form undinocated acetic aid molecules, CH,CO0"Ua) + 1" (a9) — CH,COOHL “Thus, there willbe no appreciable change in ts pH value Likewise, if few drops of NaOH are added to baller solution, the OH" ions (provided by NaOH ill combine wih I” ions present in bufer solution to form unionised water rolecules, Thus additonal ions ate neutralised by acetic ac and the pH of te solution ‘emai almost constant. CH,COOH — 1 +CH1,COO™ Ht! +01" —H,0 Similarly, abasic bufer solution consisting of equimolar amounts of NH,OH and NH,CI has large concentration of ions, CI ions and unionised NH,O!NHJcL— NH +r NH,OH — NH} +H" When few drops of HCl are added to it, the H” ions of HCL are neutralised by OH" ions of ‘weakly ionised NH,OH 1, the pH ofthe solution is almost restored, NH,OH (ag) — NH} a) + OF-ap) OF (a) +H" aq) — HO On the other hand, if few drops of NAOH are added othe bulfer solution, the OH ions provided by NaOMl combine with NH to form weakly ionised NHOH. Thus the pl of the solution remains slmont constant. Duma 1. A liquid is in equilibrium with its vapour in a sealed container ata fixed temperature. The ‘volume of the container is suddenly increased. (i) What isthe inital effect ofthe change on vapour pressure? (id) How do rates of evaporation and condensation change initially? (Gi) What happens when equilibrium is restored finally and what wil be the final vapour pressure? ‘Ans. @) The vapour pressure will decrease due to increase in volume. {i Since, the temperature i fixed, the rate of evaporation will remain constant. However the rate of condensation will be low initially due to lesser number of molecules per unit volume inthe vapour phase, (ii) When equilibrium s restored, the final vapour pressure willbe the same as original vapour pressure because at equilibrium the rates of evaporation and condensation are equa 2. WhatisK, forthe following equilibrium when the equilibrium concentration of each substance * {S0,]= 0.60M, [0,] = 0.82M and [S0,] = 1.90M? 250,(@) + 0,(@) —=280,(@) [0st 4.99" [S0,G)104%—)) (0.607 (0.82) 2.229 L mor 3. Ata certain temperature anda total pressure of 10° Py oft atoms. 1:@—21@) Caleuate Ky forthe equilibriom. Ans. Paral presture of atom (>) = 9240.10" Pa = x10! =s0x10'P, Partial pressure of Tf) ine vapour contains 40% by volume a _aanios? 67x10" Pu gaxigt —-67*10" Fa4 Ans. Ans. Ans. For the following em Write the expression forthe equilibrium constant, K, foreach of the following reactions: (0) 2NOCI()— 2NO(g) + Cl(z) 6) 2041803120 (i), CH,COOCH, (oq) + HO() — CH, COOH (a9) + C:H,OH (09) (i) Fe (ag) + 30H" (aq) — Fe(OH) 519) ©) 1) + — 2) (NOWI*IChE (oc WK, =INOY@HO4eN { Gu0G)] = [CyNON,0 {CHsCOOH (ap ICsH0H (a9) {CuO (6) + 4NO2(@) + O28) OK, (it) K, = £ COG ea ae 1 oR = (Fe(OH), 8 FF amOW wal ; ox tuo = 0) w= OE cuyen= (fr 5. Find out the value of K, foreach ofthe following equilibria from the value of Ky (9 2NOCI(g)— 2NO() + Clg) Ky = 18 X 107 2500 K {6 CaC05(s) — C40(s) + 602(6): K, (0) For the reaction, 2NOCK(g) Ky = Kaen Ky 1.8107 TeN™ Doss 500) (eR = 0.0881 Lbar mor Ky (a For the reaction, €4C04() —= C406) + CHE), Ae eee i Gen™ * Daa 167 1073 K 2NO(g)+ Clg): An = (2+ 1)-2 x 438x104 873 librium, K, = 6.8 10" at 1000 K. NO(e) + Os()—=NOa(g) + O2(e) oth the forward and reverse reactions nthe equim are elementary bimolecular reactions. What is K, for the reverse react Keer) = wax 7 Kenan) 63x10"7. Expl why pure liquids and solids can be ignored while writing the equilibrium constant cea’ rac ns (reir Pre i) = Naam. Mee me Conseant (The density ofa pure solid or a pure liquid is constant at constant temperature) 8. Reaction between N, and O, takes place as follows 2Ni(g) + Ox(g) —2N,0) Ifa mixture of 0.482 mol N; and 0.933 mol of ©, allowed to form N,O at a temperature for which K, ‘of equilibrium mixture. fs placed in a 10 L reaction vessel and 2.0 % 10°, determine the composition Ane. Suppose mole of Ny ea il equiiriom i ataned re) 28,06) Intl noms 048? : Molsat equilibrium 0482-2 0933-3 Hence equim, ons 0482-2 (Nr = S102" Sy Since, the value of K, forthe reaction (K, = 20% 10°) ix very smal the vale of must be very small Therefore, inten = 2882=2 = 2482 go4s2mot 0933-2 (oxon=eE = 2888 and mowl=a INO@ [N2@)(02@)] Wetave, 20x10 = (wos) .0085 which gives, x 6.6 10 (Ns) = 0.0882 mot L* [04] = 0.0958 mot 1" 9, Niutic oxide rencts with Br, and gives nitrosyl bromide as per reaction given below: 2NO() + Brig) — 2NOBrig)When 0.087 mol of NO and 0.0437 mol of Br, are mixed in a closed container at constant temperature, 0.0518 mol of NOB is obtained at equilibrium. Calculate equilibrium amount of NO and Bry Ans. 2NOw) + Bag) = —= 2NOBIE) Initial nwo moles 0.087 0.0837 : Motesacequltrinm 0087» 0497-2 * Given that = 0.0518 No. of moles of NOG) at equilibrium = 0.087 - 0.0518 = 0.0852 moles and number of moles of Brg) at equilibrium = 0.0197-£ = 00187 20588, 087 = x 0x1 2504(4) + O1(g) — 280,10) ‘What is K, at this temperature? ‘Ans. For the given reaction, an =2-@41) 10, ALA50K, Ky bar for the given reaction at equilibrium. 2.0 « 10!" x 0.0881 > 450 L mot = 748 x 10" Lot un. 2HI@) — Ha) +1) 2H —= Whe) + b®) ‘Ans. Initial pressure o2am Presureateqitivam atain 223004 92004 =008atm = 0.08atm (020.08 is the decrease in the pressure of HI) PHM Ps 08% 0.08 fi 00" 12, Amisture of 157 moles of Nz .92 moles of and 8.18 moles of NH, i introduced ino 20 L reaction vessel a 500 K. At this temperature, the equilibrium constant, K, fr the reaction Nx + 3H, (@) — 2NH, (is 1.7 10% I the reaction mixture at equilibrium? Ifnot, what Ke 0 isthe direction ofthe net reaction?Ans. Ans. 4 Ans. 15. No(g) + 3H, (g)—= 2NH3(g) (NH: @)!" (8.19207 (No@)1THe@))” 57) (1.92)° OP ar) sen that Keurx we Obviously, QeK ‘Therefore, the reaction is notin equilibrium because Q, # K,- It will proceed in the reverse direction 2.38 2108 (= 201) @ “The equilibrium constant expression for a gas reaction i, _ INHSI*104)" iNor'tH,0F Wirite the balanced chemical equation corresponding to this expression. ANO(@)+ 6H,0@) — ANH) + 5024) ‘One mole of 1,0 and one mole of CO are taken in 10 I. vessel and heated to 725 K. At ‘equilibrium 405 of water (by mass) reacts with CO according tothe equation, H,0(@) + CO) —H, (6) + CO) Caleutate the equilibrium constant for the reaction. “The given reaction i 1,0) + CO™) — Hale) + COsig) Initial number of moles of H,0@) = | Lao 100 Number of moles of Hj0() left unteacted = 1 = 04 = 0.6 From the given equation itis clear that 04 moles of HjO(@) react with 04 moles of COW) to form 0.4 moles of Hig) and 04 moles of CO, The total volume is 10 litres. Therefore, at ‘equilibrium, Number of moles of 1,0() reacted « 100.4 tr 0(g1 = 1524 =28.-0.06 molt! =04 06 : cowi=424=98 = 0 06malt 4 M4 0.04 mol" Te@= 160,401 = $4 = 0.04 mol! {Hs COLe _0.043.0.04 TH.0@IICOW)I ~ 006x008 ‘AC 700K, equilibrium constant forthe reaton: HG) + 1a) —2H1@) 4s 54.8. 1F 0.5 mol 1 of His present at equilibrium at 700K, what are the concentration of Hq) and Ig) assuming that we initally started with HIg) and allowed ito reach equilibrium 3 700K? Hence, K 044Ans. Ans. 1. ‘The given reaction can be written 3s 2HI1(g) — Ha()+ tale) L ye the reverse reaction, BERTH S2x10% (because forthe = 548) As the number of moles of Hy and N, are equal, their concentrations at equilibrium will also be ‘qual For this reaction, Suppose (14.49) = HG = x mol Lt Given than (HI) = 05 mol = Hideto (HI@) ie Lapxtot= 2x2, ‘05 or se = (182 10 0.1%» 0.068 mot L* Hence, atequiibrium, [H.69] = (6) = 6.068 mol ‘What is the equilibrium concentration ofeach of the substances in the equilibrium when the concentration of ICI was 0.78 M > 2C@®—L@)+Ch@; K= 014 Suppose at equilbrium, {fe = (Cig = «mol Lt aiclgy —= bg) + Chi Init cone o7sM ° ° Conc-oF equilibrium (0.78-29M aM ot Given that, Keon Dro en x, = fetch rere ia os = XE (o78-25) or at = 0.14(0.78 ~ 2x)" or 2 = (OTH0.78-2) = 0374(0.78-2) or y= 0202-0748 on 748s = 0292 029 on v= S22 oor Hence, equilbrium concentrations wil be: 0.167 M 78~(2 * 0.167) = 0446 M K, = 0.04 atm at 899 K forthe equilibrium shown below. Whats the equilibrium concentration of GH, when itis placed in a flask at 40 atm pressure and allowed to come to equilibrium? C_He(g) — CoHy(@) +H)Ans. 18, Ans. ‘Suppose the partial pressure of CyH decreases by p atm tll equilibrium i attained, Cik@) —= GI® + He) Inia pressure 0am 0 ° Pressireat Equilibrium 40~p ’ ’ on vor 0-7 or p= 016-008 or P+ 00% -0.16 =0 0.04 VOOH=DAKEOAT _—o.0420.801 2x 2 Taking postive value paoss [CH\G)] = 40-7 = 4.0- 0.98 = 8.62 atm formed by the esction between ethanol and acetic acid and the equilibrium is CH,COOH() + C,H,0H™) — CH,COOC, Hs) + 1,00) (@ Write the concentration ratio (reaction quotient), Q, for this reaction (note: water is notin ‘excess and is not a solvent in this reaction) (id) At 298 K, ifone starts with 1.00 mol of acetic acid and 0.18 mol of ethanol, there is 0.171 ‘mol of ethyl acetate inthe final equilibrium mixture. Calculate the equilibrium constant. ii) Starting with 0.5 mol of ethanol and 1.0 mol of acetic acid and maintaining it at 23 K, (0.214 mol of ethyl acetate is found aftr sometime. Has equilibrium been reached? _ [OHLCOOCAHY (IHL) © @ = (CH, COON OIGH-OHO) CH,COOH () + C,H,0H0) IsCOOC H+ HOU) (tii moles 1.00 as o ° Molesatequiibrivm 100-0171 018-0171 om om 0.829 09 dhe volume ofthe reaction mixture is VL, we have at equibium, e11,coon a= 52" mot et (catt0110y= 222 matt! 0.7 [cH,COOC, Hs) mol L! (0 ()= 222 at! [CHCOOC,Hs(0)1H200) * = (GH, COOH DIG HON]19. Ans. 20, Ans. 0.710.171 20% 0.000 CH,COOH (+ CsH,0H0) IsCOOC HS (+ HO() (i) tna motes 10 05, 0 ° Molesat equilibrium — 1.00-0214 0.500.214 02M o2u4 0786 0.286 0214 0214 v7, > Trae ase 24 veer Since, Q. # K,, equilibrium has not been reached ‘A sample of pure PCI, was introduced into an evacuated vesel attained, concentration of PCL, was found tobe 0.5 X 10° mol L ‘what are the concentrations of PCI, and Cl at equilibrium? PCI3(g) — POIs ig) + Cl) PCs) — PCL) + Clte) Since, the number of moles of PCIg) and Cl,() are equa, their concentrations at equi ‘ill also be equal. Suppose, at equilibrium. [PCA] = (Ch,@)] =x mol Lt ven tha at equilibrium, (PCL) = 0.5 x 10° mol [Pel @iIC@) Pa@ 178K. After equilibrium was Ifvalue of Kis 83 10°, 3x10" 89x10 or ee Sx 10x05 x ON Hence, [PC,@)] = [Cl,g)] = 0.08 mol E> ‘One of the reaction that takes place in producing steel from iron ore is the reduction of iron(II) oxide by carbon monoxide to give iron metal and CO. 0.02 FeOU) + COG) — Fe(s) + CO4(); K, = 0.265 atm at 1050K ‘What are che equilibrium partial pressures of CO and CO, at 1050 K if the inital partial pprestures are: Poy = 14 atm and Pop, = 0.0 atm? FeO) + CO) —= Feb) + COs) Initial pressure = — Lat = 0s0atm Pos 280 osm Since, Q, > Ky the reacion will proceed in the reverse direction. On account of this partial pressure of OG, will decrease while that of CO will increase. Suppose, the decrease in the partial pressure of CO, ip atm,a Ans. 2, Ans. Atequilibrium, Pony = (80) atm and Peg = (LA + p) atm, Peo we have Tae o 0.285 x (LA + p) = 080-9 o sn 0208 1388p o 0.359 atm Pay sii = 14+ 0.389 = 1.289 And Py acer = O80 =O.» O46 atm Equilibrium constant, K, forthe reaction Ne(g) + 3H, (g) —= 2H, (g) at 500 K is 0.061 At a particular time, hs 30 mol L" Ny 2.0 mol L” Mand 05 mol Nol) + 3H lg) — 2NHy(@: &, = 0.061 For the given se of conditions, INH@I?____ sit [Ns@)IHa|@I — 6:00)% (2.00) a= =0.0104 einen 2BrClig) — Brig) + C1) for which K.= $2 at 500 K. If inital 3.3 x 10° mol, what is its molar concentra Inia cone ol "> 30x10" = Cone at equilibrium (mol) (3.30%10°—3) _ Bawls [Brcl@ z Bax ‘Taking square root on both sides, we get 5.66 20.30% analysis shows that composition of the Ely Is the reaction at equilibrium? If notin ‘which direction does the reaction tend to proceed to reach equilibrium? 1eQ, < K, the reaction is not at equilibrium, twill proceed in the forward direction, ne monochloride, BrCl decomposes into bromine and chlorine and reaches the pure BrCl is present at concentration of inthe mixture at equilibrium? BrCl) Brig) + Clee)23. Ans. m4, or 0.037 11.32% or (1+ 1132. © 0087 0.037 or 0x10" 50% 10x = 3.0 10 mol Lt ‘At 1127 K and 1 atm pressure, a gaseous mixture of CO and CO, in equilibrium with solid carbon has 90.55% CO by mass €() + COs() — 200) CCaleulate K, for this reaction atthe above temperature, [the sotal mass ofthe gaseous mixture at equilbyium i 100 g then Equilibrium concentration of BrCl 30 103.0% 10° ‘mans of CO) = 90.55 g and mass of COg) = 100 90.55 = 9.45 g Number of moles of COW) 3.234 moles ( molar mass of CO = 28 g/mol molar mass of CO, = 44 gol) and number of moles of CO,e) “Total number of gascous moles "34 40.215 = 3.449 moles 234 Poo = Fg X1= 0.998 atm _ ‘ota no. of moles Partial pressure = total pressure) 021s Sag and 10.062 atm Hence, forthe reaction ©) + COs(@) —= 2006) fy fe OE ay Fortheabreeation, an 2-11 Ky = KART) Ky 1419 Ke 0.153 (erp ~ (0821x1127) Calculate () AG? and (i the equilibrium constant forthe formation of NO, from NO and O, at 208K, NOW) + 40x09) where A,G(NO,) = 52.0 kffmol 2, G1NO) = 87.0 fmol 3,610.) = 0 hjimol 1Ox(g) Ans. @ AG" = 240% products) -2A0"(reactanis) or 4,0" (NOs) (Bp GINO] + $4 C(O)25, Ans. 26. Ans. 2, 61M (R= © 25058 S14 x10 208 (or K = antilogy, 6.1841 = 1.862 x 10° ‘Does the number of moles of reaction products increase, decrease or re ‘ofthe following equilibria ix subjected to a decrease in pressure by increas © PCI) — PCL) + Chie) Gi) C0) + CO2(~) — C2056) (i) 3Fe(s) + 48,0) — Fe, 045) + 41200) According to Le Chatelier’s principle, if the pressure on the system is decreased, then the ‘cquilbrium shits in the direction in which the number of moles of gases more. @ No, of moles of products wll increase on decreasing pressure as the forward reaction willbe Favoured i) No. of moles of products will decrease as the backward reaction willbe favoured. remain the same asthe numberof moles of gatcous subtances is ‘Which ofthe following reactions wil get affected by increasing the pressure? Also, mention ‘whether change will cause the reaction to go into forward or backward direction. @ COC) — COW + Chie) (i) CHA) + 25216) — C511) + 2,810) Gi) Cx) + 8@ — 260) (i) 2H, + COW —CH,OH® (©) €aCOs(9) —= C20) + 60148) (i) ANHs(@) + 502(@) — 4NOG) + 6HLO(@) (@ reaction will go in the backward direction asp > {a reaction wll remain snallected 38 np = nt (i) reaction will goin the backward direction a p> (Go) reaction will goin the forward direction asp < gi (0) reaction wil goin the backward dirction a np > nt (0) reaction will goin the backward direction a np > np. “The equilibrium constant forthe following reaction i 1.6 X10* at 1024K H,() + Bra(g) —2HBr(@) Find the equilibrium pressure of all gases if 10.0 bar of HE: iner at 1024K. introduced into a sealedAns. 28. Ans. For the reaction ahr H®) + Bre Initial presure 10.0 bar 7 I Pressureat equilibrium 10.0~ pat Fear bar For the above reaction 25x10 Further, = 635% 10% Pi Pan 4, Poe fe Hence, 65x10 = 2 2 0-H “Taking square root of both sides, we have £ ta? P 25x say or 005-50 10 p =p or I+ 50x 10°) = 005, 005 or = 4.98310" bar Te soxaos 8x10" Hence, a equilibrium, : 98210" <9 soe10 Pie Pars = SION = 24910" bar and pig, = (10.0~p) = 10.04.98 x 10 = 9.95 bar Dihydrogen gas is obtained from natural gas by pa ‘endothermic reaction: CH (g) + 1,0) — COW) + 311,(@) (@ Write an expression for K, forthe above reaction. (dd) low will the values of K, and composition of equilibrium mixture be affected by idation with steam as per following (@) increasing the pressure (6) increasing the temperature (0 using a catalyst? bea Pt Fess. Paco (2) (a) Equiloriom wil shift inthe Backward direction 38 mp >t (6) Equilibrium will shift in the forward direction because the reaetion is endothermic Ox, (6) Composition of equilibrium mixture wll yemain unchanged. However, the equilibrium willbe ain eater “The value of Ky will rem n unchanged in (a) and (eK, will increase in ()29, Describe the effet of : (addition of (9 addition of CHLOH (removal of CO (i) removal of CH,OH. ‘on the equilibrium ofthe reaction: 21h (@)# COl@) — CHLOH) Ans. @) Equilibrium wil shi oa (i) aura wl hi (Go) Equibrue wl shi 30, AL473 K, equilibrium constant K, for decomposition of phosphorus pentacloride, PCI, is £83 X 10°. If decomposition is depicted a, PC) —=PCL ig) +C@ — A,H= 12404j mot (0 Write an expression for K, forthe reaction, (i) Whats the value ofK forthe reverse reaction at the same temperature? (Gi) What would be the effect on K, if (a) more PCL, is added (b) pressure is increased (0)the temperature (PCAC) TPCL@T inthe forward direction rium wll shift in the backward direction, the backward direction, in the forward direction Ans. @) Ke re, the value of K, isnot affected by addition of veaciants. ‘Therefore, k, will main unchanged. (0), will remain unchanged K (0 Since K, favour the forward reaction as the an increase in temperature wi reaction is endothermic. Thus, K, will increase. Hence, the value of K, will increase or increasing temperature. 31. Dihydrogen gas uscd in Haber's process is produced by reacting methane from natural gas ‘with high temperature steam. The first stage of two stage reaction involves the formation of CO and Hy. In second stage, CO formed in first stage is reacted with more steam in water gos shift reaction, COW) + H,0G) — COL) + #219) vessel at 400°C is charged with an equimolar mixture of CO and steam such that ‘eo = Puzo = 40 bar, what will be the partial pressure of Hy at equilibrium? K = 10.1 at 40°C. fa react ‘Ans. Suppose the partial pressure of Hat equilibrium isp bat: COG) + HOG — COs) + Hei Initial pressure 40 40 oo Pressureat equilibrium 40-p — 40-p oP ‘0. Pie Fea PatoepeeeeeEae j Wo- px ao \Fo=p, or ggup TOI =s.a78 or p= 3.178 40-9) or pe i272-s.178p or SATSp + p= 12712 bar p= 127124178 bar p= 3.04 bar 32, Predict which ofthe following reaction will have appreciable concentration of reactants and products: © Ch@—2C1@ kK, = 5x10" Gi) Chi) +2NO@ —2NOCIQ) Ke= (i) C1y(g) + 2NOx(@) — 2NO,C1Q)K,= 18 ‘Ans. (@) For reaction (a, K; is very low. Therefore, the concentrations of products willbe very low. (i) For reaction (b),K, is quite high. Therefore, the reaction will proceed almost to completion and there willbe no appreciable concentration of reactants, (ii) The reaction (has a moderate value of K, and will have appreciable concentrations of both reactants and product 88. The value of K, forthe reaction 30.(@) concentration of O; in air at 25°C is L6 X10" (Oyen (ow Lose dex 044g) i 2.0 X10 a 25°C. IF the equilibrium what is the concentration of O,? Ans. or 20x10 oF (Og) = 2.0% 10 x (1.6 x 10 = 8.192% 10% 2.86 « 10" M 84, ‘The reaction, CO() + SH,(¢) — CH,(g) + H,0( is at equilibrium at 1800 K ina I L flask. It also contain 0.30 mol of CO, 0.10 mol of H and 0.02 mol of H,O and an unknown amount of CH, in the flask, Determine the concentration of CH, in the mixture. The equilibrium ‘constant, K, forthe reaction atthe given temperature is 3.90, HIELO) CO@ NHL {CHeyx0.02 0.30% (0.107 Ans. 3.90%0:302(0.10)" oR 85. 10% mol38. Ans. 36, Ans. 3h. Ans. 38, Ans. 30, Ans. Ans. a, Ans. a2. Ans. 43, Ans. Classy the following species ‘What is meant by the conjugate acid-base pair? species: HNO,, CN", HCIO,, 087,00}, ands -Aconjugate acid-base pie that fers only by one proton. Conjugate pairs ofthe given species ate NO, HCN, C105, HE, HO, HCO3 and HS" respectively ‘Which of the followings are Lewis acids? 140, BF,, H', and NH} BRM" and NH} ‘What wil be the conjugate bases forthe Bronsted acd HE, H,S0, and HCO? F-.HSO; and C (Conjugate base = Conjugate acid — 1") Write the conjugate acids for the folowing Bronsted bases: NH, NH and HOO”. NH, NH, HCOOH (Conjugate acid = conjugate base +H") “The species: HO, FICO}, HSO; and NH, cam act both as Brdnsted acids and base, For each came give the corresponding conjogne nid nd bee, ind the conjugate a dbase forthe following Pe Conjapa a cos cof 80; SOF Ni NU No Lewis acids and Lewis bases and show how these act as ‘Lewis acid/base: (2) OH () F () H® (2) BCI, (@ OFF isa Lewis base because itcan donate an electron pai (i) Fina Lewis base because it ean donate electron pai. (i) 17 ina Lewis acid because it can accept an electron pair. () BC, is a Lewis acid because itis an electron deficient molecule and can accept an leciron pai “The concentration of hydrogen fon in a sample of soft drink is 3.8 X 10" M. What pl = —logy(tl") = —logi(88 % 10°) = 242 ‘The pH of sample of vinegar is 3.76. Calculate the concentration of hydrogen ton init. logit") = -8.76 or (H*] = antlogy(-8:76) = antilogiy%24 74 10M ‘The ionization constant of phenol is 1.0 X 10-®, What isthe concentration of phenolate ion in 0.05 M solution of phenol? What will be its degree of ionization if the solution is also 0.01 M in sodium phenolate? ws pH HOH = CHO +H Initial cone. 0.05M eee Conc.at equilibrium 005-2 x « [GoHsOTIN __ ee [GION D05—* Ke fa =1.0%10-" (given) oxi0"Since, phenols not much dissociated, 0.05 —* = 0.5, Hence, Loxin” Dos or = (O05 10% 1% = 2.24 « 10 Hence, (OHO"Tin solution = x= 2.24 x 104M Inthe presence of 0.01 M GHl,ONs ‘Suppose ys the amount of phenol disociated. Therefore, at equilibrium [GyHJOH] = 0.05 -y, [G,H,07] = 0.01 + y and (H1"] (001+ yo) "005-9 Since, in the presence ofsodium phenolate the dissociation of phenol wil get further suppressed wean take 0.01 +=0.01 and 0.05 -»=005 1.010" (given) 44, The firs ionization constant of Ha i 9.1 x 10°, Calculate the concentration of HS” ion in its 0.1 Msolution. How will this concentration be affeced ifthe solution is 0.1 M in HL also ?1f the second dissociation constant of H,Sis 1.2 X 10, ealculate the concentration of ™ under both conditions ‘Ans. Calulation of (57 HS ionises in two stages. The firs stage of tonisation i as follow HS HT + HS Init cone anaes Conc. atequilbrium (@.1-9M x K,, = 9.1 x 10° (given) According tothe law of equibrivm, tH HS) 0 THT eee on 9.10 = X= 2 oni yery sll s0 0 = 0.1) or x= (9.1 10% x 0.1)!" Hence, (HS 0.1 M solution 1m the presence of 0.1 M HCl suppose HyS dissociates to an extent ofy M. Therefore, {HS} = 041-9 04M, (H"] = 9 0.1 = 04 Mand (HS) = M (Since, in the presence of HCI, the dissociation of HS will futher get suppressed)oxy Ruy or y= 9.1% 10°M Hence, in the presence of 0.1 M HCL 9.x 10M Leo Ht +HS K,,=9.1%10% HY +S% K,=12%10-% +s Ors) ar) Kym Ko Ky 91 108 125 1 = Lc. In the absence of 1 MC Hs ant + st Ina cone anes Coneateqiliviom —Ol=v (tax) 7 5x10"M 65x 10M Hence (8°Tin the absence of 0.1 M HE Inthe presence of 0.1 MHC Suppose HS disoites oan extent of M [HS] = 0.1 May 0.1 M(H] = ay + 04101 and Ss) ohy CF x10” c 110M Hence, [S*] in the presence of 0.1 M HCL 1a x10" M 45. ‘The ionization constant of acetic ac acetic acid in is 0.05 M solution. Caleu its pH. 14 x 10, Calculate the degree of dissociation of the concentration of acetate ton nthe solution and CH,COOH —-cH,coo-+Ht Initia cone 005M a s Conc.at equilibrium ——0.05=x x x According tothe law of equilibrium, [cco] [eH,COOHTor = (eis very small or = (1.74 10x 0,05)! = 0.88 > 104M [cH,coo}, 33 104 mol L* [H"] =< = 933 x 104 mol L* pH = logy [H*] = —login(@88 « 10%) = 3.03 46, It has been found that the pH of a 0.01M solution of an organic acid is 4.15. Calculate the concentration ofthe anion, the ionization constant of the acid and its pK, [Ans.. Suppose the organic acid is HL. HAA pH = —logip [1 4.15 = ~logio(H) [HP] = antilogiy (4.15) = 7.08 x 10° M [A] = [8°] = 7.08 x 10 M aay * 10° 152, Calculate the degree of ionization of 0.05M acetic acid if its pK, value is 4.74. How is the degree of dissociation affected when its solution also contains (00mm (i 0AM in CL? Ans. pk,=—logioK, = 4.74 1, = amlogy 4.74) = 182 x 10° Fora weak electroly For acetic acd, seam “| = B= fA con x10 In the presence of HCl the dissociation of acetic acid wil be suppressed due to common ion fect. (@ When the solution contains 0.01 M HI also: suppose the concentration of CH,COOH. decreases by = cH,cooH cHcoo + Ht Initial cone. 0.05 - if Cone.at equilibrium 0.05~x x +001 (0.01 M of H° cone. rom 0.01 M HCI) {cH,coo ut) [cH,cOOHy or 182 10% (6 Since, xs very small, ¥ + 0.01 = 0.01 and 0.05 x = 0.05), 18210005 _ 9 ig-s ERRATA <9 1x10" Amount diswciated Tita amount Degree of dissociation (a) atx 0.055. Ans. . Ans. (i) When the solution contains 0.1 M Hk: Proceeding as above, we have 18210005 x O05 9.110 21x10 a of = S10" ose x9 ‘The ionization constant of dimethylamine is 5.4 X 10. Calculate its degree of ionization in its 0.02 M solution. What percentage of dimethylamine is ionized ifthe solution is also 0.1 M. in NaOH? Dimethylamine i weak base, For a weak base, “Therefore, for dimethylamine, In presence of 0.1 M NaOH, its disociaton will get suppressed, (CHyNH + HO = (CHYNH, + OW Initial cone 0.02 z ce Come.at equilibrium —0.02= x a0 (0.1 Mof OFF come from 0.1 M NaOH) x01) _ oe Ke om ~ 002 (eis very small,x + 0.1 0.1 and 0.02-¥= 0.02) xe tt = Os or sax tot = Oe or = SAXIOT 002 og 104 of Amount dissociated Totalamount “100 8x10 002 Percent ionisation of dimethykamine= x 100= 0.548% aleulate the hydrogen ion concentration in the following biological fluids whose pH are given below: (@) Human muscle-fTuid, 6.88 (Gi) Human stomach fuid, 1.2 (i) Human blood, 7.38, (0) Human saliva, 6.4 pH = =logio(HH,0°) [4,0°] = antilog.-PH) (@) [H,0*] in human muscle uid = antilogyo(-6.85) = 147 107 mot L (8 [H,0" in stomach Maid = antlogs-1.2) X10 mot ntlogio 7.38) 1 10 mol (a (H,0°] in human blood(») [1,0°) in human salva anilog 84) 8.98 x 107 mol Lt 55, ‘The pH of mi black coe, tomato juice lemon ic and egg white are 68, 5.0, 4.2, 22 and 718 eapetively Calculate coresponding hydrogen fon concentration in each. ‘Ans. (H*] = [H,0*], (HyO°) in milk log pH) = antlogg (08) 1.58 x 107 mol L*! [H,0°) in black coffee = antilogi(=5.0) = 1.0 10° mot Lt [H1,0°] in tomato juice = antilogyg 4.2) = 631 x 10% mol 11,0" in lemon juice = amilogys 23) = 631 x 10% mol Lt [11,0*] in egg = antilog (7.8) 1.58 x 10" mol 56. 1f 0.561 g of KOH is dissolved in water to give 200 ml. of solut concentrations of potassium, hydrogen and hydroxyl ions. What ‘Ans. Molaity ofa solution is given by at 298 K. Galeulate the its pH? MxMxv 1000 se) = M%56% 200 ee, 0.561 = MO (C2 mol. mass of KOH = 56) (05611000 55% 200 Since, KOH dissociates completely in solution or Me 105M KOH —K" +0H" Ik*] = [017] = Motty of KOH = 0.05 Mt Ke _ 1007 and (1) iy gg = ROO Now, PH = —loguH"1 = Hogs x 10" login 2 + 18 log 10 == 800+ 1 57, The solubility of S(O), at 298 K is 19.23 g/L of solu strontium and hydroxyl ions and the pH of the solution. ‘Ans. Molecular mass of QOH), = 87.6 + 2 x (16 + 1) = 1216 2.70 mn. Calculate the concentrations of, Solubility of HOM, = 19.28 git = $228 govt = 0.1581 mol L* Sr(OH)» —=Se* +201 'Sr(OF) is assumed to be completely ionised, we have [5-2] = 0.1581 mol L58, Ans. 59, Ans. and [OI] = 2 x 0.1581 = 03162 mol L K, jon and pl =—logis (H,0"}= —logio 18 « 10°") = 18.50 ‘The ioniaation constant of propanoic acid is 1.82 x 10%, Calculate the degree of ionization 0x10 O3162 (H0"}= =3.16x10" ofthe acid in its 0.05 M solution and also its pH. What willbe its degree of ionization ifthe solution is 0.01 M in HEL also? CH,CH,COOH = cH,CH,coo +H Initial cone. 0.05 : 2 Cone.atequilibrium ——_005(1a) 0.050 0054 [CH,CH,COO7UH"] “ “TCH; CH;,COOHT 5, Wns xo.05a (0.050 _ ose? cat bsexto" = “o5(l-a) 005 1 63 x 107 Then, {H,0°] = 0.050» 0.05 x 1.68 x 10 = 8.15 104 M pH = 8.09 Inthe presence of .1M of HC, let a be the degree of tonization, Then, {H,0%} = 001 [A] = 005 HAL = 0.05 , = 001x005 = 82x 10% = 001 a a = 132x107 ‘The pH of 0. M solution of eyanie acid (HCNO) is 2.84. Calculate the ionization constant of the acid and its degree of ionization inthe solution, Suppose the degree of ionisation of HCNO is a HCNO —= HY + cNO Initia cone 01M - = Conc.at equilibrium — 0.1(1-q) oaxa ox Given that pH of the solution is 2.54. Theselore, = logit a) = 2254 or ogi (0-1 x a) = -2.84 or 8.1 x c= amtlogig (2:54) = 0.00457 {HENOT_ (01a) x (0.18) TIGNOY “01d=a) (0.x)? _(@.1x00857)% Dane 09 10-460. Predict ifthe solutions of the following salts are neutral, acidic or basi NaCl, KBr, NaCN, NH,NO,, NaNO, and KF ‘Ans. Neutral solutions = NaCl, KBr Acidic solutions: NH,NO, Basie solution + NaGN, NaNO,, KF 61. Tonic product of water at 310 K is 2.7 x 10°, What is the pH of neutral water at this temperature? ‘Ans. Tn neutral water, H,0"} = (or K, = [H,0" OH] = [H,0"F or [HOF = Ky = 2.7 x 10" [H,0°} = 2.7 10°)" = L64 x 107 Hence, pH = —logiy [H0"] = ~logi(l 64 x 10°) 62. Caleulate the pH ofthe resultant mixtures: (@ 10 mL of 0.2 M Ca(OH), + 25 mL of 0.1 M HCL 10 mil of 0.01 M H,SO, + 10 mL of 0.01 M Ca(OH), (i) 10 mL of 0.1 MH,S0, + 10 mL. of 0.1 M KOH Ans. fl) Normality of Ca(OH) solution = 0.2 x 2 = 0.4 N and normality of HCl solution = 0.1 x 1 = 0.1 Gram equivalents of Ca(OH) taken Nxv 0x10 = "Too = “roo = 9.0 Gram equivalents of HCI aken Nx _ 01x25, Too = 1090 ~ 00025 (0.0025 gram eq, of HCI would neutralise 0,0025 gram eq, of Ca(OH) Amount of Ca(OH), left unreacted = 0,004 ~ 0.0025 = 0.0015 gram equivalents “Taal v 104 25 = 95 mb Suppose the normality of the resultant solution is N NxV 1000 ume ofthe mixture No. of gram eq. = N35 TO00 .0015%1000 _ 51000 9.0429 Yr = 00429 Lovo: 0.08 0.0015 = 233110" pH =~logyH,0"] = logy 2881 x 10 = 12.68 (i) 10m of 01 4,80, would exacly neutralise 10 mLof0.01 M Ca(OH) and the resultant solution would be neutral Hence, pH ofthe resukant mixure = 7.00(ii) Normality of H,SO, = 0.1 2= 02. ‘and Normality of KOH = 0.1 1 IN so, « NV. 02%10 sn equivalents of HS, = “Tyg = “Topp = 2.002 aon = NK 81X10 sn equivalents of NAOH. = AAV «SAA. 9 9g) 0.001 gram cq. of NAOH would neutralise 0.001 gram eq. of H,S0, ‘Total volume of the mixture = 10 + 10 = 20 ml, Ifthe normality of the resultant solution ew wx20 01 = Na » = 20011000 or w L100 = 9.05.8 {11,0"] = 7= 005 pl = —Iogy(H1,0"] = log 0.05 = 1.90 63. Determine the solubilities of silver chromate, barium chromate, ferric hydroxide, lead chloride and mercurous iodide at 298K from their solubility product constants given. Determine also the molarities of individual ion Given, Ky Ag:GrO, = 1-1 X10, Ky BaGrO, = 1.2 x 10", Ky, FAOW)s = 1.0 10, K, PbCl, = 1.6 x 10°, Ky Hegly = 45 x 10, ‘Ans: (i) For silver chromate (Ag,Cr0,) Agscr0, 6.5% 10° mol Lt [ag']= 26265 x 105 = 18 x OM and (C:OF}=9= 65x10 M. (i) For barium chromate (BaCrO,) BaCrOy, sat + CrOr ; eeu wiesueaven 1 = (y= AERO 1.05% 10°M (i) For ferric hydroxide (Fe(OH): Fe(OH), isa quaternary sa Fe(OH); —= Fe" + 30H : . oom[Fe] = = 1.99 10M [OWT] = 6 5% 1.59% 10" = 417 x 10 (io) For lead chloride (PbCI,) + It isa ternary salt 1.59% 10M coy cE] = 256 159 x 10% x 2 = 3.18 x 10 (0) For mercurous iodide (HggI,): Hgely — Hg" + 2 : sm (He) (sto saeno na ig.) os 2.24 x 10 Bs 224 10 2 = 448 x 10 64, ‘The solubility product constant of Ag,CrO, and AgBr are 1.1 x 10" and 5.0 x 10% respectively. Calculate the ‘Ans. For AgyC1O, (a ternary sal), For AgBr (a binary st), 65, Eu wi Ans. [105 cut" +2105 —cuttoys K,,Cu(10,),= [Cu ]03}*=7.4<10° givew) volumes of 0.002 M solutions of sodium iodate and cupric chlorate are mixed together. ead to precipitation of copper iodate? (For cupric iodate Ky = 7-4 X 10°). (002M and[Cu**]=0.002M (On mixing equal volumes, the concentra gets halved. 0x10" tout yoy = (292) 202) Sine ‘the ionic products less than the solubility produc, precipitation will not take place,66. Ans. 6. Ans. ‘The ionization constant of benzoic acid is 646 x 10% and Ky for silver benzoate is 2.5 x 10". How many times is silver benzoate more soluble in a buffer of pH 8.19 compared tits solubility in pure water? GHCOOAg —= CyH,COO + Age Solubility in water: 5 = R= 125107 =5.0%10" mol! Solubility ina buffer of pH = 8.19: In abuller of pH = 3.19, log H"]= 8.19 IH] = antilogi-8.19) = 657 x 107 mol Le" “The H’ ions present in bufer solution will combine with C,11,COO™ ions to form G,H,COOH, ‘but (H*) inthe soltion will remain unchanged because the solution isa butfer solution, HCOOH — G,H,coo"+Ht [C.H,COOH"] 1GH,cOOnT [C)H,COOH] _(H') _ 6457x104 °F TCeHsCOO7 645x107 2 Suppose the solubility of iver benzoate inthe buffer iss mol L* Since, almost all the GyECOO" ions get converted to benzoic acid which remains almost unionised, we have = IAT = 86001 + [6,H,COOH] =(G,H,COO7} + 8905 x [GH{COO"] (From eq.) = 10.995 68,C00"] (GH,0001 = aaa Ky = (GHCOO"HAg") or 25x10! = To exs 7 2.5 10" 10.905, or = /RBRTOP T0905 = 1.057 x10 mol 2 OSTA gay 5.0x107 Hence, silver benzoate is 3.814 times more soluble in the buffer, ‘What isthe maximum concentration of equimolar solutions of ferrous sulphate and sodium sulphide so that when mixed in equal volumes, there is no precipitation of iron sulphide? (For iron sulphide, K, = 6.3 x10"), sppone the required concentration sx ML On mining equal volumes, concentration gets halved, ‘Therefore, (re) = Sanatsh¥ Fel? 48 — FesFor the state of no precipitation, (FENIST = Ky or 3.5 63x10" or = (6.3 «10 5 4)" = 5.02 5 10° mol Zt 68. What is the minimum volume of water required to dissolve I of calcium sulphate at 208 K? (For calcium sulphate, K, is 9.1 x 10°). ‘Ans. Fora binary salt fries For Ca80,,5 = YOIRIO™=3.0%10 mol L! Solubiity of C380, in g/L = 8.0% 10° x 196 = 041 gL (Mol. mass of CaSO, = 40+ 32 + 64 =1396 ginol) “Thus, strated solution of C0, contane OAT ofthe satin UL. Hence, the volume of water requived to dissolve 1 g of CaSO, =| 1 oar 69, The concentration of sulphide ion in 0.1 M HCI solution saturated with hydrogen sulphide is 1.0 10°" M. 110 mL of this x added to'5 ml. of 0.04 M solution ofthe following: FeSO,, Mal, ZnCl, and CdCl,. In which ofthese solutions precipitation will take place? ‘Ans. Precipitation takes only when the ionic product exceeds the solubility product. nee 10 ml. ofthe solution containing S* ion is mixed with 5 ml. of the differe solutions, volume of the mixture aRer mixing in cach case = 10-+ 5 = 15 mL. 6.0710" M 5] Loco x! 1881 = Loto

K, the reation has auained equilibrium and it has tendeney o proceed. inthe backward direction toa greater extent, ‘What isthe role of HCI gas in the purification of common salt? Inthesaturated solution of NaCl, HCl gasincreases the concentration of CI ions afer dssciation and hence increases the value of tonic product than K, for NaCl and a this stage pure NaCl gets precipitatedAns. Ans. Ans. Ans. NaCl —= Nat (ap) +E ap) Ky =Na"tCr] “The ionisation of hydrochloric aci H1(aq) + H,00) —H, 0° (aq) + Crag) Label two conjugate acid-base pi cl cr Acid Conjugate base 1,0 H,0" Base Conjugate acid Tonisation constant of a weak base MOH, iM y1017] 6 =" MON tion constant of some weak bases ata particul in water is given below: INGERT Exemplar] "Arrange the bases in decreasing order ofthe extent oftheir ionisation at equilibrium. Which ofthe above base isthe strongest? INGERT Exemplar] + Order of extent oF aniston at equilibrium ss fllws Dimethslamine > Ammonia > Pyridine > Urea ‘+ Since dimeshylamine will jonise to the maximum extent itis the strongest ase out ofthe four given tases. “The value ofK, forthe reaction 2H) —= Hy(g)+ I(@)is1 10+ {Ata given time the composition of reation mixture is X10 mol, (2f,] = 1 x 10° mol and [ly] = 1 x 10" mol tion will the reaction proceed? INGERT Exemplar] Ata given time the reaction quotient Q forthe reaction will be given by the expression, (atta cH = bao 1 exo $095 =25 x 107 As the value of reaction quotient is greater than the value of Ke, 1% 10° the reaction will proceed in the reverse direction, Following datas A/F [Ca0()] = ~635.1 bj mot A/F (CO,(g) = ~ 398.5 kj mot 41F [Cx€0,6)] =~ 1206.9 bf mor" Predict the effect of temperature on the equilibrium constant ofthe shove reaction. INCERT Exemplar] C206) + COx(g) A.W = A, H[CIO()] + A/ HCO, A HECACOY (9) A.M = 1783 Kj motAns. Ans. 12 Ans. 1s. Ans. 4. Ans. 1s. Ans. TThe reaction isendothermie, Hence, aecording to Le-Chatelir’s principe, reactants will proceed in forward direction on increasing temperature, Calculate the pH value of the following ( 0.001 M HCL i) 0.01 M NaOH. ( HGLisa strong acid and may be supposed to be completely ionised, Therefore, [H,0°1 = [HCI] = 0.001 N= 1.0 10° mot pH =—logidH,O"] = ogydl.0 10°) 9) ogg = 8 (-logigl0= 1) (NaOH isa strong base and may be supposed to be completely ionised. [OH] = [NaOH] = 0.01 M = 10% 10 mol ry = Ke 0x0" “ Hence, CHO") = BAT Pong THY 1 mol PH = logy HOT ~log(t.0 10") = 12 “The hydronium fon concentration ofa frit juice is 4.6 x 10 mol L", Whatis the pH ofthe Given that {H,0"] = 4.6 « 10° mo L* PH = og 0"] ogy. 8 104 = [logis 8 + log) = (06827 4) = 3.84 Hence, the pH ofthe juice = 3.34 ‘What is common ion effect? Illustrate your answer with an example. “The suppresion of diswcation ofa weak eletrolste on addition afastong detolytecontaninga common nivale omen of MI For example, when NHCl is added to a solution of NH/OH, common ion effect occurs resuling in the suppression of ‘dissociation of NH,OH and decrease inthe concentration of OH" ions ‘The aqueous solution of sugar does not conduct electricity. However, when sodium chloride is added to water it conducts electricity. How will you explain this statement on the basis of ionisation and how i it affected by concentration of sodium chloride? [NCERY Exemplar] ‘Conductance depends upon no. of ions present in the solution. Since, sodium chloride (NaC: is an ionic compound and as mixed with water it ionizes completely forming and aqueous lectroltie solution. Therefore the solution conducts electric BF, does not have proton but still acts as an acid and reacts with NH. Why is it so? What type ‘of bond is formed between the two? INCERT Exemplar] BF, does not have a proton but sill cts san acid because it aets asa electron pair acceptor and reacts with NH, by accepting its lone pair of electrons. The reaction can be represented by BR, +:NH, —= HyN-= BR, Coordinate bond is formed between BF, and NH. (On the basis of the equation pHi = -log(H1"), the pH of 10-* mol di solution of HCI should bbe 8. However, it is observed tobe les than 7.0. Explain the reason. [NCERT Exemplar] “The concentration of water cannot be neglected since the solution i very dilute. ‘Taal [H,O*] = 10° + 10 M. The value will ome close to 7 but less than 7 because the solution isa Nac, —+(n)+cr16. Ans. 7 Ans. 18. Ans. 19. Ans. 20, Ans. a. Ans. Write atleast four characterist “The four characterise of a chemical equilibria () allthe observable properties of the system acquire constant values at equilibrium and do not ‘change with time. (i) The state of equilibrium can be atained from cither side (i) Chemical equilibrium is dynamic in nature. (G0) Chemical equilibrium cannot be atained in an open ves ‘Write four characteristics of equilibrium constant (K,). “The four characterstis of equilibrium constant Kare 8 follows (0) The value of equilibrium constant for a particular reaction is constant at a particular temperature. (i) The value of the equilibrium constant does not depend upon the ii) The value of equilibrium constant ells the extent to which a reaction proceeds in the forward cor backward direction, (G0) The value of equilibrium constant does not change by the presence of a catalyst ‘What qualitative information can you obtain from the magnitude ofthe equilibrium constant? (i) We can predict the extent of a reaction (i) We ean predict the direction ofthe reaction. (i) We can cateulate eq ial concentration of at 25°C Calculate solubility of AgC! in pure water. = 1.673 x 10 mottive (On the bass of Le Chateier principle explain how temperature and pressure canbe adjusted to increase the yield of ammonia inthe following reato Ni)+ 3H (@) —2NH What will be the effect of addition of argon to the above reaction mixture at constant volume? INGERT Exemplar] ‘According to Le Chatters principle, raising the temperature shifts the equilibrium to left and decreases the equilibrium concentration of ammonia a itis an exothermic reaction. There will bbemo change in equilibria on addon of argontAr) A sparingly soluble salt having general formula. 4x'*; By* and molar solubility $ is in equilibrium with its saturated solution. Derive a relationship between the solubility and solubility produet for such salt INGERT Exempler| AE + BE — AP (ag) + 9B (og) SS moles of A B dissolve to give x S moles of A and y S mole of BY Ky = WT BYP = OSHS? asoBeau S ak en Se Ens 1. Find out the value of for each of the following equilibrium from the value of Ky. ( 2NOCKs) —=2NO|)+ Chi Ky=1.8%10 at 500K i) CaCOs() — C20) + COLE}, Ky =167 aLIOTBK ‘Ans. (0) For 2NOCIs) —= 2NO |g) + Ch (eh Ky = 18 X 107 at 500K, By using = KART aes -28 oe 1.8107 a Ke Tap" oss xson) "44x10 (8) For CaCO) — C2049) + C046), Ky = 167 8 TSK. For the reaction, areal Ke * en® Dass rxa973} K 90 2, Ata certain temperature equilibrium constant K, is 16 forthe reaction, 50, (g) + NOs(@) — $0444) + NO) Ifwe take 1 mole ofeach ofall the four gases in I litre cont ‘concentration of NO() and NO,(? er, what would be the equilibrium ‘Ans. Let moles of NO¥@) be reacted at equilibrium. Then SOxig) + NOsi—) — SOs) + NOW) Ii 0.0 ok 1 ' nea ‘tego oo kx (en dene) Ateqliviumconeninioninmott pt ios I Lt P=1Soeqiviom cone, Tee te {SOs}{NO} BSOINO Lente 1 = (rata) dee and [NO] at equilibrium i) The valu of equilibrium constant forthe reaction Gu (ag) +2246) — Cut) + Zn" ag) is.5.0% 10°, In which direction is the reaction expected to proceed to greater extent?Ans. Ans. Ans. Ans. (i) State Ostwala’s dilution law. (ii) Conjugate acid of a weak base is always stronger. What will be the decreasing order of basic strength ofthe following conjugate bases? (1, RO", CH,COO™ , cI INCERT Exemplar] (@ Forward direction asthe larger value of K indicates thatthe reaction proceeds to a greater ‘extent in the forward direction. (i) According to Ostwald’ dilution law, the degree of dissociation of a weak electrolyte is inversely proportional to the square root ofits concentration. in gee eee {i) RO“ > OFT > CH,COO™ > ‘Equal volumes of 1 x 10° M CaCl, and 4.0 x 10 M sodium sulphate solutions are Show whether product will be formed or not? (Given: Ky of CaSO, = 2.4 X 10") The condition of precipitation of any salt occurs when ionic produet exceeds the solubility product. On mixing equal volumes of CaCl, and Na,SO,, the concentration of each is reduced to hall xed. 1 19% =05x107 x10 =05x10M, Concentration of CaC, and Goncentation of NaS0, = cdo #2x10°M Tonic product of 80, = (Ca?*}{SO%] = (0.5 x 10°)L2 x 1074] = 1 10% Since, the fonie producti les than the solubility product, hence CaSO, will not be precipitated, 5. reaction between ammonia and boron trifluoride is given below: 1H, + BE} — HN: BE, Identify the aid and base in this rection. Which theory explains it? What isthe hybridisation of B and Nin the reactants? INCERT Exemplar] “though BF, does not have a proton but acts as Lewis ci sits electron deficient compound Te reacts with Ny by accepting the lone par of elecons from NH and completes its ott the reaction can be represented by BR, +:NH, — BE, ~:NHy Leis electronic theory of acids and bases expan it Bin BF, isp hybriised while N in NH isp? Iybridised. “The value ofK, for dissociation of 2HI—= H, + I, is 1.84107 If the equilibrium concentration of His 0.4789 mole litre", calculate the cone. of HT at For, HI — H+ 1, an = 2-280 K, Kane en’ Kk, = 180107 2H Hat by il concentration 2 00 Av equilibrium We) ox xAns. Ans. Ans. Given at equilibrium concentration of ere Ba-0F Hi, = 0.4789 mollis bane 478904789 21») = 3.53 molltre So, concentration of HL at equi jum is 3.58 mollitre pH of a solution of a strong acid is 5.0, What will be the pH of the solution obtained after dng the given solution #100 times? INCERT Exemplar] ven ph TH] = 10° mol L* (On calculating the pH using the equation pl = -log(H"), value of pH comes out to be 7 Is not possible. This indicates that soluion is very dilute. Hence, ‘Toa hydrogen ion concentration [H] 1° ons from acid + (Hons from water = 107 +107 pH = 2x 107 = 7-log 2? = 7-0:3010 = 6.6900 ‘pH10f0.08 mol dm HOI solution is 2.85, Calculate its ionisation constant. [CERT Exemplar] Given, pH of HOCL = 285 Now, pH = log( 1") “25 = log (11°) > Bi5=logttt"] > UH] = antilog 3.13 = IH) = 1412 x 10 mold For weak mono basic acid (11"1= VK, XC x, WEE Gus13 10%) Erte cree cereisae 0 ‘concentration of Cis 0.60 mol litre". Caleul ive 80 mol hire* A+bB—=c+D Av equilibrium; [©] = [D] = 0.60 mol lize"! AA oti EGE ae: Initially cone. 0.80 0.80 ° 0 Avequilibrium 0.8-x 080-» x xa1 anal a 0.600.60. *DR-DOS=o ~ TH=0.60)x(0.80-0.00) 10, How can you predict the following stages ofa reaction by comparing the value of K, and Q.? {) Net reaction proceeds in the forward direction. (ii) Net reaction will proceeds in the backward direction. (i) No net reaction occurs. INGERT Exemplar] ‘Ans. (@ IQ, < Kg, the reaction proceeds in the forward direction. (i) I1Q2> Ke, the reaction will proceed inthe direction of reaetants (reverse reaction), (ii) HQ. = Ky no net reaction occurs. NTPs (iris 1. Calculate the volume of water required to dissolve 0.1 g lead (1) chloride to get a saturated solution. (Ky oF PHCL, = 3.2 10" atomic mass of Pb = 207 w) (NGERT Exemplar] Ans. Ky of PoCh = 522% 10% Les be the slubily of PC () — Pb* (aq) +261 (a9) Concentration of speciesatt=0 1 o ° es Concentration of various species at equilibrium SBI ol Lot = 810 mol LZ! 5 = VETO" = 2510 mol) 35 = 25 10% mo Lt 27 Dew gL 555% 10% gL = 0.556 gL" cy is dissolved in I water Solubility of POC, in g L “To get saturated solution, 0.556 g of Pt ie ou a 0.1 g PECL is solved in ALL = 0.17984. wa 2. Calculate the pH of solution formed by mixing equal volumes of two solutions A and B of = strong acid having pHY = G and pH = 4 respectively. INCERT Exemplar] [HOTS] Ans, pH of solution A = 6 ‘Therefore, concentration of (H"] io in solution A = 10" mol L* pH of solution “Therefore, concentration of {H*] ion in solution B = 10 mol L* (On mixing one litre of each solution, total volume = IL + IL = 2b,concentration * Volume V = 10" mol IL, Amount of H® ions in HL of solution B= 10" mol HL. Total amount of H? ions in the solution formed by mixing solutions A and B is (U0 mol + 107 mol) Amount of H* ions in {of solution A- “This amount is present in 2L soltion. 10*+0.0) _ 10110 Toul (1 mol LZ! 05 x 104 mol = 5% 10 mol logltt"] = “log(s x 10%) = [log 5 + C5 togt0n) log 5+ 5 = 5—log 5 5 =0.6900 = 4.9010 = 43 3. Armixture of 3 moles of Hy and 1 mole of N, react at constant pressure of 100 atmosphere. ‘At equilibrium 0.5 mole of ammonia is formed. Calculate the value of K, for the equilbrs pH 32H, + 12N, —=NH, Ans. Ne + 3Hp —= 2NHy Initially 1 3 ° Atequilibrium 1x 8-39) Es Initially no. of moles (n) = 1+3=4 Pressure = 100 atm A equilibrium ‘Toa number of moles, nj = (13) + (8~Se) 4 v= 4-2 Pressure = 100 atm From ideal gas law, PV = nkT Ac constant temperature Pan To 100 = 21.42 225 22 100 = 64.28 ota ciies Fp x100 = 1428 Poy PR Pit, 128x148 "Bran @aasye ~ 000089 a0Ans. Ans. |. A sparingly soluble salt gets precipitated only when the product of concentration of isi 5. The solubil Sued For the reacion Ha * 5; ay (0.000035) 005 atm in the solution (Q,) becomes greater than its solubility product, Ifthe solubility of BaSO, in water 8 x 10" mol dim, caleulate its solubility in 0.01 mol dm of H,SO, [NCERT Exemplar] (HOTS) B30 (0) — Ba** (ag) + S0¥ (og) Ara ' 0 o ‘Av equilibrium in water Ins o o ‘Ac equilibrium in the presence Ios 5 +001) of sulphur acid K, for BaSO, in water = [B38* [SOF] But ¢= 8 x10" mol dn Kya Ox 10% = 6b) “The expression for Kin the presence of sulphuric acid will bea ellos: Ky= 606+ 000) wi) Since, value of Ky will not change in the presence of sulphuric acid “Therefore, fom (1) and (2) we have, (916+ 001) = 64x 10" #4 001s = 64% 10% 3400164 170 tots VOOTF + (4 64x10) = os VOUT saxon 10°) 0.01 = V0 F B56 IO™) Xs} ots 1011 25610) 2 0.0810" +0256) z 101+ L012719) z 5 x 10012719 = 64 x 10%moL dmv? product of AIH) is 2.7 x 10°" ‘out pl of this solution. (Atomie mass of Al Let be the solubility of KOH), Calculate its solubility in gL and also find 0). (NCERT Exemplar] AM(OH1s — Al*(ag)+ 80H (ag) 1 o o A concentration of species t¢ Concentration of species at equilibrium — 11 : se Ky = [APTHOHT = 689" = 2734ta Ke 27x10 Ba xI0 spo 52110 mol LZ! (0, Soluitty of KOH), Molar mass of ANOH),is 7g. Therefore, EET = 1x 10x TA gL! = 78H 10 gL = 78 Oe gL (i pH ofthe solaons: «= 110° mol Sx 1x 105=3 x10" 3g’ 14 pOH = 11 + bg = 114771 Write a relation between AG and Q and define the meaning ofeach term and answer the following (Why x renin proceeds forvard when Q< Kan no net reaction ocurs when @ = K: i) Explain the effect of increase in pressure in terms of reaction quotient Qfor the reaction: CO(g) +34 (¢) — CH, (g)+11,0(«) INGERT Exemplar] cP-+RTINQ ‘Ans. @ Aswe know that a¢ eq a ib cg io eth wet deen (i) On increasing the pressure, volume decreases. Lette pressure is doubled, then the volume willbe halved but the molar concentrations will be doubled, Therefore, Fea 21C01. 21H.) 1 {CHINO} _ 1, Ficomy 4 “Thuis, the equilibrium shift in the forward direction as Q < K. UESTIONS FOR PRACTICE 1. In Bronsted and Lowry concept wate justify this statement 2. AL a certain temperature, the hydronivm ion concentration in pure water i found to be LTE > 107 mol L, What is the value of Kat this temperature? 3. Write the expression of solubility products for the following sal AgsC10,, Cay(PO))e State the unit oF Ky and K, for the reaction: BNO) + Orig) —= 2NOK) 5. Why is HO regarded asa Lewis base? 6. From the following data (at 208 K) predict which oxide of nitrogen is most table? 2NO gig) — Neg) + 20,4): K = 67 x 10" 2NOI— Naw) + Oye): K= 22 10 is regarded as an amphoteric substance, Ci ‘examples to2N,0q)— 2Nag) + Oh: K= 95% 10 2N,0, = 2Ns) + 50x): K = 12 10" “The ionic product of water is 0.1L 10°! at 275 Ky 1.0.10" at 208 K and 51% 10°" at 87S K. Deduce from this data whether the ionisation of water to hydrogen and hydroxide tons is ‘exothermic or endothermic ‘Comment on the statement: All bronsted bases are also lewis bases but all bronsted acids are not Lewis acids, 4, ‘win doyovundersandy conjunc pind hecnjgue nite fe floing oa HINO, CN", HCIO,, F>, OH”, COF ands 10, Forde reaion Redes oo ail ca ln te ec le a capes INO MOI 6 ANOS — NHL iy 28449 09 — ANI fa a iaade a meetup as aes ae Gracies veuien nese Gienamorene ee ocopees pt sso aed saa a iy aha meee eceagecw alec aetna sa 12, Wee eri forth oqo naa. Koren fe long oon 1) N1s0040) + 80,4104) —= N04) COG) (ii) PbIy(s) -Pb"* (ag) + 21-(aq) (i) Co) C0,4)— 2000) ‘Answers 2, 2.06 x 10" 10, () 0.024 (iy 6.4 Gi 1.68 x 10"