{ ter studying this unit you will be to: oust dynamic nature of equilibrium involved in physical ‘and chemical processes; state the law of equilibrium; explain characteristics of equilibria involved in physical ‘and chemical processes; write expressions for equilibrium constants; establish a relationship between and K; explain various factors that affect the equilibrium state of a reaction; classify substances as acids or bases according to Arrhenius, Bronsted-Lowry and Lewis concepts; classify acids and bases as weak or strong in terms of their {ionization constants; explain the dependence of degree of ionization on concentration of the électrolyte and that of the common ion; describe pH scale for Tepresenting hydrogen ion concentration; explain fonisation of water and ils duel role as acid and base; describe ionic product (Ky) and PK, for water; appreciate use of buffer solutions; Calculate solubility product constant, UNIT 7 Chemical equilibria are important in numerous biological and environmental processes. For example, equilibria invol and the protein hemoglobin play a Crucial role in the transport and delivery of O, from our TERS To our muscles~SimTar equilibria Tnvolving CO molecules and hemoglobin account for the toxicity of CO. When a liquid evaporates in a closed container, molecules with relatively higher kinetic je liguid surface into the vapour phase and number of liquid molecules from the vapour phase sttike the liquid surface , and are retained in the liquid phase. It gives rise to a conistanit because of an. equilibrium in which the number of m leaving the umber of molecules leaving the quid equals the number returning to liquid from the vapour. We say that the system. haS reached equilibrium state at this stage. However, this is at the bount uid and the vapour. Thus, at equilibrium, the Tate of eraporation ja equal-to-the rate of condensation, It may be represented by 0 () = 1.0 (vap The double half arrows indicate that the processes in both the directions are going on simultaneously. The mixture of reactants and products in the equilibrium state is called an equilibrium mixture. ‘both ic 5, The eactOT Ty Beast orsl spending on the experimental conditions and the nature of the reactants. When the reactants in a closed vessel at a particular temperature react'to give products, the concentrations of the reactants keep on decreasing, while those of products keep on increasing for some time after which there is no change in the concentrations of either of the reactants or products. This stage of the system is the dynamic equilibrium and the rates of the forward and186 J Teverse reactions become equal. It is due to this dynamic equilibrium stage that there ts no change in the concentrations of varlous_ Species in the reaction mixture, Based on the oiatio which the reactions proceed to reach the state of chemical equilibrium, these may be classified in three groups. () The reactions that proceed nearly. to completion and_ only negligible concentrations of the reactants are left. In Some cases, it may not be even possible to detect these experimentally. (ii) The reactions in which only small amounts of products are formed and most of the Teactants remain unchanged. at equilibrium stage. (iit) The reactions in which the concentrations of the reactants and_pro. e ‘comparable, when the system is in equilibrium. The extent of a reaction in equilibrium varies witli the experimental Conditions such ‘aS concentrations of reactants, temperature, etc. OpIMISATIOT OT THE operational condifions {s very important in industry and laboratory so that equilibrium is favorable in the direction of the desired product. Some important aspects of equilibrium involving physical and chemical processes are dealt in this unit along with the equilibrium involving ons in aqueous solutions which is called as ionic equilibrium. : 7.1 EQUILIBRIUM PROCESSES The characteristics of system at equilibrium are better understood if we examine sore. physical processes, The most familiar examples are phase transformation Processes, e.g., IN PHYSICAL solid = liquid liquid = gas solid = gas 7.1.1 Solid-Liquid Equilibrium Ice and water kept in a perfectly insulated thermos flask (no exchange of heat between its contents and the surroundings) at 273K J‘ Chey and the atmospheric Pressur, equilibrium state and the g, stem are & Interesting characteristic features, wr, *40n, that the mass of ice.and water do with. time and the. temperat constant. However, the equilibrium ss static. The Intense activity can be noel tffé boundary between ice and me at Molecules from the liquid water coi, ide ater, ice and adhere to it and some Molecules a % escape into liquid phase. There is no ch; leg of mass of ice and water, as the rates of rs 8 of molecules from ice into water and ofrer equal at oe transfer from water into ice are atmospheric pressure and 273 K, It is obvious that ice and water equilibrium only at particular tempe and pressure. For ani are in Tature at Le at Land liquid phases: are equilibrium is called thal selina po or normal point of the substance, The system here is in dynamic equilibrium ana we can infer the following: (i) Both the opposing processes occur — simultaneously. (ii) Both the processes occur at the same raté so that the amount of ice and watér remains constant. Po. Os 7.1.2. Liquid-Vapour Equilibrium This equilibrium can be better understood if we consider the example of a transparent box c a U-tube with mercu few hours in the box. After removing the drying agent by tilting the box on one side, a watch glass (or petri dish) containing water is quickly placed inside the box. It will be observed that the mercury level in the right limb of the manometer slowly increases and finally attains a constant value, that fs, the pressure inside the box increases and reaches a constant value, Also the volume of water in the watch glass decreases (Fig, 7.1). Initially there was no water vapour (or very less) inside the box. As water evaporated the pressure i. the box increased due to addition of water7 uiBRIUM Fig.7.1, Measuring equilibriunt molecules into the gaseous phase inside the = of evapora riSten poration is c t. box. THE rate of evaporation= rate of condensation H,0() =H,0 (vap) Atequilibrium the pressure exerted by the water_mol is called the equilibri a ressure of water (or just vapour ressure of water); . If the above experiment is repeate Tethy! alcohol, acetone and ether, it is observed that different liquids have different equilibrium vapour pressures at the same temperature, and the “If we expose three watch glasses €peat the experiment with different volumes of the liquids in a warmer room, it is observed that in all such cases the liquid eventually disappears and the time taken for complete evaporation depends on (i) the nature of the _ liquid, (i) the amount of the liquid and (iit) the temperature. When the watch glass is open to the atmosphere, the rate of evaporation remains constant but the molecules are [." ‘Anhydrous calcium chloride / 0s 5) "containing separately ImL each of ethyl alcohol, and wat josphere and - : 187 LT dish of water ur pressure of water at a constant temperature dispersed into large volume of the room. As a consequence the rate of condensation from vapour to liquid state is much less than the rate of evaporation. These are open systems Water and water vapour are in equilibrium position at atmospheric pressure (1.013 bar) and at 100°C in a closed vessel. The boiling point of water 1s100%Cat 1.013 bar pressure. For any pure liquid at one atmospheric pressure (1.013 bar), the temperature. at which the liquid jours are at of the liquid. Boiling point of the liqui . It depends on the al lace; 7.1.3 Solid - Vapour Equilibrium Let us now consider the systems where solids sublime to vapour phase. If we place solid iodine [oSed vessel, after sometime the vessel gets filled up with violet vapour and the intensity of colour increases withtine- Aer corain Gmethe Resor efor Becomes constant andat this, stage equilibrium is attained. Hence solid iodine sublimes to give iodine vapour and the iodine vapour condenses to give solid iodine. The equilibrium can be represented as, 1,plid) = 1, (vapour) “Other examples showing this kind of equilibrium are, Camphor (vapour) = NH,Cl (vapour)188 Henry % tow mn r CHEMIST, 7.1.4 Equilibrium Involving)Digsolution) pressure of the gas above the of Solid or Gast Solids in liquids We know from our experience that we can dissolve only a limited amount of salt or sugar in_a given amount of water at room in Liquids ag temperature. If we make a thick sugar syrup solution by dissolving sugar at a higher temperature, sugar crystals separate out if we _ cool the s} to mptrature. We call ta Saturated solution when no more of solute can be dissolved in it at a given temperature. The concentration of the solute in a saturated solution depends upon the temperature. In a saturated solution, a dynamic equilibrium exits between the solute molecules in the solie'state and in tion: Sugar (solution) = Sugar (solid), and — [the rate of dissolution of sugar = rate of | grystallisation of sugar. e adioa sugar. If we drop some radioactive sugar into Saturated solution of non-radioactive sugar, then after some time radioactivity is observed bo eS andin . Initially there were no Tadioactive sugar molecules in the solution but due to dynamic nature of equilibrium, there is exchange between the radioactive and non-radioactive sugar molecules between the two phases. The ratio of the radioactive to non- radioactive m the solution increases tillit attains a constant value.“ Fe) : (aur Gases in liquids eto. When a soda water bottle is opened, some of the carbon dioxide gas dissolved in it fizzes out rapidly. The phenomenon arises due to ailference in solubility of carbon-dioxide at different pressures. There 15 equilibrium beiween the molecules in the gaseous state and the molecules dissolved in the liquid under pressure 1.¢., CO,(gas) = CO,(in solution) This equilibrium is governed by enrys law, which states that the mass of a gas dissolved in a given mass of a solvent at any temperature is proportional to the amount decreases with incre’ hs temperafuire. The soda water bottle g under pressure of gas when its solupre“l water Is high. As soon as the bottle ig oo some of the dissolved carbon dioxide «* escapes to reach a new equilibrium cong, 6 required for the lower pressure, nam, dition partial pressure in the atmosphere, This, Its the soda water in bottle when left open ri air for some time, turns ‘flat’. It ca, the generalised that: n be (i) For solid = liquid equilibrium, there only one temperature (melting Point) : 1 alii (1-013 BarTal which the two phase, can coexist. If there is no exchange of hes, with the Surrouridings, the mass of the iy phases remaifisconstant.~ ~~~ (i) For liquid= vapour equilibrium, the vapour pressure is constant at a given temperature. — (ii) For dissdlution of solids in liquids, the solubility is constant at a given temperature. (iv) For dissolution of gases in liquids, the concentration of a_gas_in liquid is proportional to the _ pressure (concentrationy of the gas over the liquia~ ‘These observations are Summarisel i Table 7.1 Table 7-1 Some Features of Physical Equilibria ,aa gor Characteristics of Equ 5 General 8 of Equilib 73° avolving Physical Processes ical processes discussed above, 10 characteristics are common to the follorrn at equilibrium: ) pquilibrium is possible only in a closed t s mat a given temper 3 w oth the opposing processes occur at the same rate and there is a dynamic but stable condition. beeeeteeneee ap ul ALL measurable properties of the system remain cons () When equilibrium is attained for a physical rocess, it 18 characterised by constant yalue of one of its parameters at a given Yemperature. Table 7.1 lists such tities. 4) The magnitude of such quantities at any stage indicates the extent to which the nysical process has proceeded before reaching equilibrium. 7.2. EQUILIBRIUM IN CHEMICAL PROCESSES — DYNAMIC EQUILIBRIUM ‘Analogous to the physical systems chemical reactions also attain a state of equilibrium. ‘These reactions can occur both in fotward and backward directions. When. the rates. of the forward and reverse reactions become cau 1, ne concentrations of the the reactants.and.the products rema ‘ant. This is the stage of chemical equilibrium: This equilibrium is dynamic in nature as it consists of a forward Teaction in which the reactants give P} aridreverse reaction in which product(s) gives the original reactants. _ For a better comprehension, let us consider a general case of @ reversible reaction, A+B 2 C+D With passage of time, there is ts C and D and a. accumulation of the produc or * depletion of the reactants ‘Aand B (Fig. 7-2): rd his leads to a decrease reaction and an increase in he, rate. of Wis reverse reaction... Eventually, the two reactions occur at the 189 Concentration —> Time > eulipeium Fig. 7.2. Attainment of chemical equilibrium. same rate and the system reaches a state of equilibrium. Similarly, the reaction can reach the state of equilibrium even Ifwes ai Dy that is, no A and B being present initially, as the equilibrium. can be reached from either direction. — The dynamic_nature of chemical ‘be demonstrated in the equilibrium_can {Eytlesis of ammonia by Haber y Haber's process] In a “experiments, Haber started with Jcnown amounts of dinitrogen, and dihydrogen. maintained at high temperature and pressure and at rep termined the afmount of ammoniapresent. He was suttésstul in determining also the concentration of unreacted dihydrogen and dinitrogen. Fig. 7-4 (page 191) shows that after acertain time ‘the composition of the mixture yemains the same even thous gh some of reactants ‘This constancy in indicates that the reaction has ilibrium. In order to understand the dynamic nature of the reaction, synthesis of ammonia is carried out with exactly the same starting conditions (of partial pressure and temperature) but using D, (deuterium) in place of H,. ‘The reaction mixtures starting either with H, or D, reach equilibrium with the same composition, except that D, and ND, are present instead of H, and NH. After equilibrium ts attained, these two mixtures composition reached equiz fo um - A Student's Activity rin a physical oF in a chemical system, is alw; qmonstrated by ‘the use ‘of radioactive Isotopes. This is noe ale fe However this concept can be easily comprehended by perf ‘AStb le Howeviraty can be performed in & gFOUP Of 8 oF 6 atug forming ng eyuinders (marked as 1 and 2) and two gla eat, er of the tubes may be same or different in th, ing cylinder-1 with coloured water eet of fanganate to water) and keep secon a th der Equilibrium whethe! in a school laboratory. the following activity. Take two 100mL measurii each of 30 cm length. Diamet 3.5mm. Fill nearly half of the measur! purpose add a crystal of potassium perm (number 2) empty. Put one tube in cylinder 1 antl second in cylinder 2. Immerse one tube in 1, close its upper tip with a finger and transfer the coloured water contained 8d lower portion to cylinder 2. Using second tube, kept in 2™ cylinder, transfer the ae Its der 1. In this way keep on tran; sferring water in a similar manner from cylinder 2 to cylin coloured water using the two glass tubes from cylinder 1 to 2 and from 2 to 1 ty You notice that the level of coloured water in both the cylinders becomes constant If you continue intertransferring coloured solution between the cylinders, th : not be any further change in the levels of coloured water in two cylinders. to analogy of ‘evel’ of coloured water with ‘concentration’ of reactants and eae i ee we can say the process of transfer, which continues even after the a is indicative of dynamic nature of the process. If we repeat the ceehnes ue two tubes of different diameters we find that at equilibrium the level of aac two cylinders is different. How far diameters are responsible for change in leveaah a cylinders? Empty cylinder (2) is an indicator of no product in it at the beginning. 88 tubeBRIUM so! — Dinitrogen (reactant Motar con ‘Ammonia (product) Time —> Fig 74 Depiction of equilibrium for the reaction N, (8) + 3H, (8) = 2NH, (g) (H,, No, NH, and D,, N,, ND;) are mixed together and left for a while. Later, when this mixture is analysed, it is found that the concentration of ammonia is just the same as péfore- However, when this mixture is analysed by a mass spectrometer, it is found that ammonia and all deuterium containing forms of ammonia (NH,, NH,D, NHD, and ND.) and dihydrogen wets -mentrated Terns 0 eae ee Thus one can cot ‘Scrambling of H and D atoms in the molecules must.result_ froma cofitinuation of the forward and reverse reactions in the mixture. If the reaction had simply stopped when they reached equilibrium, then there would have been no mixing of isotopes in this way. Use of isotope (deuterium) in the formation of ammonia clearly indicates that chemical prcictions reach a state of dynamic jcvitibrium in which the rates of forward ind reverse reactions are equal and there ‘sno net change in composition. Equilibrium can_be attained from both a whether we start reaction by taking, L(g) and N,(g) and get NH,(@) or by taking ae and decomposing it into N,(g) and } N,@+3H,g = 2NH@ 191 2NH,@) = N,(@) + 3H,@) Similarly let us consider the reaction, H,@ + 1@ = 2HI(@. If we start with equal initial concentration of H, and I,, the reaction Proceeds in the forward direction and the concentration of H, and I, decreases while that of HI increases, until all of these become constant at equilibrium (Fig. 7.5). We can also start with HI alone and make the reaction to proceed in the reverse direction; the concentration of HI will decrease and concentration of H, and I, will increase until they all become constant when equilibrium is Teached (Fig.7.5). If tota] number of I atoms are same in a given volume, the same im mixture is obtained whether we = ~ oduct. start it from pure reactants or pure pro@ucl. Concentration Equilibrium Time ———> <—Time Fig.7.5 Chemical equilibrium in the reaction H,(g) + L@) = 2HIG) can be attained from either direction 7.8 LAW OF CHEMICAL EQUILIBRIUM AND EQUILIBRIUM CONSTANT -A mixture of reactants and products in the equilibrium state is called an equilibrium mixture, In this section we shall address a number of important questions about the composition of equilibrium mixtures: What is the relationship between the concentrations of reactants and products in an equilibrium mixture? How can we determine equilibrium concentrations from initial concentrations?192 exploited to alter ce ‘an equilibrium mixture? The compos particulars important when choosing conditions for synthesis of industrial chemicals such as H,, NH,, CaO ete. ‘To answer these questions, let us consider a general reversible reaction: A+B @C+D where A and Bare the reactants, C and D are the products in the balanced chemical equation. On the basis of experimental studies of many reversible reactions, the Norwegian chemists Cato and Peter, Waage proposed in 1864 that the coriGentrations in an equilibrium mixture are related by the following equilibrium What factors can be ole! | "fale (7.1) where Kris the equilibrium constant and the expression on the right side is called the equilibrium constant expression, The equilibrium. jon is also known as the law of mass action because in the_early days of chemistry, concentration was called *active mass". fer to appreciate their worl better, let us consider reaction between gaseous H, and I, carried out in a sealed vessel at 731K. H@ + 1@ = 2Hi@ q Six sets of experim: "eh conditions were performey te ™ gaseous H, and I, in a seal ting wetty in rst four experiments (1 o*2Ctlon only HI in other two experinn, and te e ee dine 1, 2,3 and 4 — 6 ang’ ng ferent concentration © Perfo and with time it was obsemyej°! yang! of the purple colour remaines, that ita equutibrium was attained, gj tant a at m the opposite direct rium ya Data obtained from aj). : experiments are given in any ot Sets oy It is evident from the e a and 4 that number of ee Lag reacted = number of moles of ea Vag ¥% (number of moles of HI { liner experiments 5 and 6 indicate tae ; 14,@.,=L,@), | Knowing the above f; | 0 facts, establish “a _ relationship M order tg | concentrations of the reactantsand wave” several combinations Products, can b consider the simple expression ate HG, / 12, Ue, ‘ It can be seen from Tabl : le 7.3 that if put the equilibrium concentrations of the | Jmol 1mol 2 mol reactants and products, the above expression Table 7.2 Initial and Equilibrium Concentrations of H,, I, and HI ‘Experiment Fe ar Initial concentration/mol L Equilibrium concentration/mol L" [big | | b@l | [k@l | tH@1 | tH@) (b@] (HI@l 2.4 x 107 ye ] | 1.38 x 10 0 114x107 | 0.12107 | 2.52%10 2.4 x 107 ja 1.68 x 10 0 0.92x 107 | 020x107 | “2.96x10 rr 3 98 x 10 0.77107 | 0.31 10° 1.76 x 107 0.92 x 107 | 0.22 10" 0.345 x 107.g Expression Involving the Equilibrium Concentration of Reactants H@) +L@ + 2H ta FWD, [#64] ae from constant. However, if we consider the expression, Hm@?,, / HO. Lel., we find that this expression gives constant value (as shown in Table 7.3) in all the six cases. It can be seen that in this expression the power of the concentration for reactants is far and products are a ie Stoichiometric nts In the equation for the chemi thus, lor the reaction H,(@) +1,@ = aiff, following equation 7.1, the equilibrium constant K, is written as, K, =[HIGN, / HA@|., He, (7.2) Generally the subscript ‘eq’ (used for equilibrium) is omitted from the concentration terms. It is taken for granted that the concentrations in the expression for K, are equilibrium values. We, therefore, write, K, = [HIP / (H,@) Ll (7.3) The subscript ‘c’ indicates that K, is expressed in concentrations of mol L**. a given temperature, the product of concentrations of the reaction products talsed to the respective stoichiometric Coefficient in the balanced chemical ‘Squation divided by the product of trations of the reactants raised to elr individual stoichiometric coefficients has a constant value. (is . on as uilibrium Law or(Law of Chemical Equilibrium: 193 The equilibrium constant for a general reaction, aA +bB=cC+dD is expressed as, K, =(cf1Dy" / lal"iB! (74) where [A], [B], [C] and [D] are the equilibrium concentrations of the reactants and products. Equilibrium constant for the reaction, 4NH,(g) + 50,(g) = 4NO(g) + 6H,Ol8) 1s written as K, = [NO}*1H,O1° / INH,|* 10,]° Molar concentration of different species is indicated by enclosing these in square ‘bracket and, as mentioned above, it is implied that these are equilibrium concentrations. While writing expression for equilibrium constant, symbol for phases (s, 1, g) are generally ignored. Let us write equilibrium constant for the reaction, H,@) +1,@ = 2HI@ (7.5) as, K.= (HI) / (H,) [1] = (7.6) ‘The equilibrium constant for the reverse reaction, 2HI(g) =H,@ + L(g), at the same temperature is, : K,= (Hy) fh) / (HIP = 1/x=1/ Ke 77 Thus, K.=1/K (7.8) Equilibrium constant for the reverse reaction is the inverse of the equilibrium constant for the reaction in the forward direction. Ifwe change the stoichiometric coefficients in a chemical equation by multiplying throughout by a factor then we must make sure that the expression for equilibrium constant also reflects that change. For example, if the reaction (7.5) is written as, WH@ +419 = H@ (7.9) the equilibrium constant for the above reaction is given by Ke = (HN /(H)"701,)"? = (tem? / HJ"? axe Ki? (7.10) On multiplying the equation (7.5) by n, we get194 nH,(@) + nl,@ = 2nHI@ (7.10) ‘Therefore, equilibrium Ga une ", These fint reaction {s equal to K, ‘natngs or ‘summarised In Table 7.4. It sho uilibrium constants K, and ¢ rical values, It e important to specify the form of the balancet chemical equation when quoting the value of an equilibrium constant. Table 7.4 Relations between Equilibrium : Constants for a General Reaction and its Multiples. faA+b Beeb cC+dD t = er 3 aN em 71. Re ee % The following concentrations were obtained for the formation of NH, from N, and H, at equilibrium at 500K. IN,] = 1.5 x 102M. [H,] = 3.0 x10°M and INH,] = 1.2 x10°M. Calculate equilibrium constant. (Bxto) Solution Ute ‘The equilibrium constant for the reaction, N,@ + 3H,@) w# 2NH,(@) can be written as, 29x06 1. 5¥10" > centile Mele “cE, oe ___(1.2x107) (1.5x107)(3.0x107): = 0,106 x 10* = 1.06 x 10° 7.2 \—" At equilibrium, the concentrations of N,=3.0 x 10°M, O, = 4.2 x 10°M and NO= 2.8 x 10°M in a sealed vessel at CHEMIST 800K. What will be K, for the reactigan» N,@+0,0 = 2Nog | Solution | For the reaction equilibrium ; K,can be written as, Constant: 4 ae [Noy i «© [N2][02] (2.8x10°M )° . * (8.0x10°M)(4.2x10°M) = 0.622 7.4 HOMOGENEOUS EQUILIBRIA In a homogeneous system, all the and_pro i are in. . pagent example, in the gaseous reaction, N,(@) + 3H,(@) = 2NH,(g), reactants and products are in the homogeneous phase. Similarly, for the reactions, : CH,COOC,H, (aq) + H,0 0) = CH,COOH (aq + CH,OH faq) and, Fe* (aq) + SCN(aq) = Fe(SCN}* (aq) all the reactants and products are in homogeneous solution phase. We shall now consider equilibrium constant for some homogeneous reactions. 7.4.1 Equilibrium Constant in Gaseous Systems So far we have expressed equilibrium constant of the reactions in terms of molar concentration of the reactants and products, and used symbol, K, for it. For reactions involving gases, however, it is usually more uilibflua convenient to Express the equilil!'— consi terms of pi pressure. ‘The ideal gas ‘equation is written as. pV=nRT n => p==RT poy Here, pis the pressure in Pa, nis the number of moles of the gas, Vis the volume in and |uum sl spevemperacures® Kelvin 18 ‘nese centration expressed in mol/m* avs reeniration ¢, fs in mol/L or mol/dm?, : in bar then aw T, also write p = [gas IRT. Re 0.0831 bar litre/mol K ve ctant temperature, the pressure of ere st Ais proportional to its concentration L.e., the pelges! For reaction in equilibrium eye = 2H) a either ‘ R@lh@ * (Pal (7.12) oe Cy, (Ps) : Further, since Py, =[HI(g)]RT P,, = [12 (g)|RT Pu, = [He (8)]RT. ‘Therefore, ca PPT "ha)(e,) [A @))RT-[h (@)JRT __ [met H@lL@] " an In this example, K, = K, i.e., both ¢quilibrium constants are equal. However, this __‘Snotalways the case. For example in reaction NO + 3Hig) = 2NHYg) x= lm) (Px: )(Pa,) -—__[NH, (g)P [RTP » (.(@)]Rr[H, (@)) (RT) 195 [NH (g)PIRTI? elner or K, =K,(RT)? (7.14) Similarly, for a general reaction aA+bB = cC+dD CT ie (e+d) x, -(Pe)(P5) _ [el py (er) (px)(es) (aT BP (Rr) ICT ID on vera rere EF DE pry ‘ Tar pre (7.15) where An = (number of moles of gaseous products) - (number of moles of gaseous reactants) in the balanced chemical equation. It is necessary that while calculating the value of Ks, pres: ould be expressed in bar because standard state for pressure is 1 bar. We now fron Unt tat ————<—$_$—$—_—_——= pascal, Pa=1Nm™, and Ibar = 10° Pa K, values for a few selected reactions at different temperatures are given in Table 7.5 Table 7.5 Equilibrium Constants, K, for_a Few Selected Reactions ce Problem 7.3. : PCI,, PCI, and Cl, are at equilibrium at Iss 500 K and having concentration 1.59M PCl,, 1.59M Cl, and 1.41 M PCI,.196 Calculate K_ for the reaction, PCL, = PCI,+Cl, Solution The equilibrium constant K, for the above reaction can be written as, _[Pel, l[cl.] _(L 59)" _ PCI, ] em 7.4 value of K_ = 4.24 at 800K for the réaction, CO(g) +H,0 (g) = CO, (g) +H, (g) Calculate equilibrium conceritrations of CO,, H,, CO and H,0 at 800 K, ifonly CO and H ,O are present initially at concentrations of 0.10M each. Solution For the reaction, CO(g) + H,O(g) = CO, (g) +H, (g) Initial concentration: 0.1M 0.1M 0 0 Let xmole per litre of each of the product be formed. At equilibrium: 5 (O.1-x)M (O.1x)M xM xM where x is the amount of CO, and H, at equilibrium. Hence, equilibrium constant can be written as, K.= x?/(0.1-x? = 4.24 = 4.24(0.01 + x?-0.2x) x? = 0.0424 + 4.24x?-0.848x 3.24x?— 0.848x + 0.0424 = 0 a= 3.24, b =- 0.848, c = 0.0424 (for quadratic equation ax?+ bx +c = 0, (-b+vb" ~4ac) 2a x= 0.848+)(0.848)— 4(3.24)(0.0424)/ (3.24x2) x = (0.848 + 0.4118)/ 6.48 (0.848 — 0.4118)/6.48 = 0.067 : X, = (0.848 + 0.4118)/6.48 = 0.194 CHRIST the value 0.194 should be ny because it will give conceniags sad reactant which is more than a concentration, Hence the equilibrium concentrat ‘ lone apd {CO,1=1H, ]= x= 0.067 M bt | {CO} =1H,01=0.1- 0.067 = 0.0334, | Problem 7.5 ; For the equilibrium, 1 2NOCI(g) = 2NO(g) + Cl. (8) : the value of the equilibrium con; stant, is 3.75 x 10° at 1069 K. Calcul, ate the x. for the reaction at this temperature? Solution We know that, K,= K(RT)" te the above reaction, =(2+1)-2=1 K, = 3.75 x10° (0.0831 x 1069) Ree 0.033 9 7.5 HETEROGENEOUS EQUILIBRIA Equilibrium in a system having more than, one Phase is called Weterogencous-equllisun The equilibrium be' water vapour and liquid water in a closed container is an example of heterogeneous equilibrium. 1,00) = H,0() In this example, there is a gas phase anda liquid phase. In the same way, equilibrium between a solid and its saturated solution, mn 3 Soke and its saturated solut Ca(OH), (s) + (aq) = Ca®* (aq) + 20H (aq) is a heterogeneous equilibrium. Heterogeneous equilibria often involve pure Solids or liquids. We can simplify equilibrium “expreselomy Terie heterogeneous equilibria involving a pure liquid or a pure solid, as the molar concentration of a pure solid or liquid "Soe Taped ans pieseni] Th olitr wore oe in other words if a substance ‘X'S involved, then [X(s)] and [X(I)] are constan whatever the amoantar taken. Cont Sontraty | ; :,guiliBRium nis. (X(g)Land {X(aq)l will vary as the tof” lume Varles, ‘tus ermal dissociation of calcium carbonate pis an interesting and important example rogeneous chemical equilibrium, A. CaO (s) + CO, (g) take whiel of hete’ cac0,() (7.16) on the basis of the stoichiometric equation, we can write. _[cao(s)][CO. (g)] K. =" Taco, (s)] since [CaCO,(s)] and [CaO(s)] are both constant, therefore modified equilibrium nstant for the thermal decomposition of cefeium carbonate will be K-=1COJg)] 197 : theres a cons fe at 1100 K, the pressure of CO, in equilibrium with CaCO,(s) and CaO(s), 18 2.0 x10° Pa. Therefore, equilibrium constant at 1100K for the above reaction is: K, = Poo, = 210° Pa/10° Pa = 2.00 Similarly, in the equilibrium between nickel, carbon monoxide and nickeLcarbony! (used in the purification of nickel), Ni(s)+4CO(g) = Ni(CO),(g). the equilibrium constant is written as . _[Ni(CO), ] “(coy It must be remembered that for the existence of heterogeneous equilibrium pure solids or liquids must also be present (however small the amount may be) at equilibrium, but their concentrations or partial pressures do not appear in the expression of the equilibrium constant. In the reaction, Ag,O(s) + 2HNO,(aq) = 2AgNO,(aq) +H,O(1) _ [AgNO]? * [HNo,]*198 At equilibrium: (0.48 - xJbar 2x bar K, = Peo * Peo, K, = (2x?/(0.48-x)=3 4x? = 3(0.48 - x) 4x?= 1.44-x 4x? + 3x-1.44=0 a=4,b=3,c=-1.44 (vivo ~4ac) Qa =E3 £18) 441.4492 <4 = (8 £5.66)/8 =(-3 +5.66)/ 8 (as value of x cannot be negative hence we neglect that value) X= 2.66/8 = 0,33 The equilibrium. Partial pressures are, Poo = 2x = 2 x 0.33 = 0.66 bar Poo, = 0.48 -x = 0.48 - 0.33 = 0.15 bar —_—_—_—_—_—_—_—SSL ss 7.6 APPLICATIONS 0} EQUILIBRIUM CONSTANTS Before considering the applications of equilibrium constants, let us summarise the important features of equilibrium constants as follows: 1. Expression for equilibrium constant is applicable only when concentrations of the reactants and products have attained Onstant value at equilibrium state, —* The value of equilibrium constant is independent of initial concentrations of the reactants and products. —. 3. Equilibrium constan dependent having one valtre for particular reaction represented by a equation at a giverrtemperature, Doge equation ara gvertemperatufe 4. The equilibrium constant for the revere reaction is equal to the inverse of the equilibrium constant for the forward reaction. t is temperature Chey, 5. The equilibrium Constant K f an is related to the equilibrium rrtlon corresponding reaction, whose caus the obtained by multiplying or divans equation for the original Teaction, by le integer. Let us consider applications of tb, constant to: br * predict the extent of reaction on th, of its magnitude, basis * predict the direction of the Te ‘ction, ang * calculate equilibrium concent trations, 7.6.1 Predicting the Extent of a Reaction The numerical value of the equilibrium, constant for a reaction indicates € extent of the reaction. But itis importa te that an equilibrium constant does Not. gi ififormation about the rate a A g m. ied. The magnitude of or Ky is directly proportional to the concentrations of products (as these ay in the numerator of equilibrium constant ¢xPression) and inversely proportional to the Concentrations of the reactants (these appear in the denominator). This im lies value of Kis su tion ofproducts and vice-versa. enter “We'can make the following generalisations concerning the composition of equilibrium mixtures; . nee Proceeds ne; "the following examples: (a) The reaction of H, with O, at 500 K hasa very large equilibrium constant, K,= 2.4% 10", . Consider (>) Hg) + Clg) = 2HC1(g) at 300K has K.=4.0 x 10", (c) Hg) + Br,(g) = 2HBr (g) at 300 K. K.=5.4 x 1018 Products,.e..ifK-is.very small, Proceeds.rarely. Consider the following examples:M BRU! you" composition of H,O into H, and 0, a bay Khas a very small equilibrium? atta K,=4.1 x 10% at 0,@ = 2NOw, o M08 K has K,= 4.8 x10", al . is in the range of 10-* to 103, 7 We jable concentrations of both al d products are tants and products are present. remelder the following examples: gor reaction of H, with I, to give HI, fa 25708. 0K. nso, 628 phase decomposition of N,O, to o xo, is another reaction with a value = 4.64 x 10° at 25°C which is neither too small nor too large. Hence, wuilibrium mixtures contain appreciable ancentrations of both NO, and NO,. ‘These generarlisations are illustrated in Fig. 7.6 egigtle ee! 10° 110 rexcontay Botheactars and | Raacon proceeds posed broducts are present almost to completion at equilibrium : Fig.7.6 Dependence of extent of reaction on K, 762 Predicting the Direction of the Reaction ‘The equilibrium constant helps in predicting the direction in which a given reaction will proceed at any stage. For this purpose, we calculate the reaction quotient Q. The “reaction quotient, Q (Q. with molar concentrations and Q, with partial pressures) is defined'in the same way as the equilibrium _ constant K. except that the concentrati 9, are not necessarily equilibrium valyes. Fora general reaction: @A+dB = cC+dD (7.19) S=ICHD}/ fare (7.20) Then, NQ.> K, the reacts tion of reactants (reverse reaction). "Q'S, the reaction will proceed in the Moro the products (forward reaction). n ) > & fo 199 IQ, = K,, the reaction mixture js already at equilibrium, Consider the gaseous reaction of H, Ly HQ +1, = 2HIQ); K,= 57.0 at 700 K. Suppose we have molar concentrations (H,}=0.10M, [1,], = 0.20 M and [HI], = 0.40 M. (the subscript t on the concentration symbols Means that the concentrations were measured at some arbitrary time t, not necessarily at equilibrium), ‘Thus, the reaction quotient, Q, at this stage of the reaction is by, Q.= [HI]? / [H,],[L], = (0.40)2/ (0.10)x(0.20) =8.0 Now, in this case, Q, (8.0) dees not equal K.(57.0), so the mixture of H,(g), I,(g) and Hg) is not at equilibrium; that is, more H,(g) and 1,@ will react to form more HI(g) and their concentrations will decrease till Q, = K.- The reaction quotient, Q, is useful in predicting the direction ‘of reaction by comparing the values of Q.andK. Thus, we can make the following generalisations concerning the direction of the reaction (Fig. 7.7) : Rescants—> Profits Readans and predic Regcarts €— Products met ‘eat equlbaun a ig. 7.7 Predicting the direction of the reaction * IfQ,K, net reaction goes from right to left. © 1fQ,=K.n Sj 2200 Solution For the reaction the reaction quotient 9. is given by, Q,= [BIICI/ [AP as [A] = [B] = [C] = 3 x 10“M Q, = (3 x10-9(3 x 10%) / (8 x10? = 1 as Q, > K_ so the reaction will proceed in the reverse direction. Forctoetlbaeetitten tr amen es CE 7.6.3 Calculating Equilibrium Concentrations In case of a problem in which we know thé initial concentrations but do not know any of the equilibrium concentrations, the following three steps shall be followed: Step 1. Write the balanced equation for.the_ reaction. Step 2. Under the balanced equation, make a table that lists for each substance involved in the reaction: (a) the initial concentration, (b) the change in concentration-on-going to equilibrium, and (Q) the equilibrium concentration. In constructing the table, define x as the concentration (mol/L) of one of the substances that reacts on going to equilibrium, then use the stoichiometry of the reaction to determine the concentrations of the other substances in terms of x. Step 3. Substitute the equilibrium concentrations into the equilibrium equation for the reaction and solve for x. If you are to solve a quadratic equation choose the mathematical ‘solution that makes chemical sense. Step 4. Calculate the equilibrium concentrations from the calculated value of x. Step 5. Check your results by substituting them into the equilibrium equation. lem 7.8 13.8g of N,O, was placed in a 1L reaction vessel at 400K and allowed to attain equilibrium N,0,@ = 2NO, @ OMe ‘The total pressure at equilbrium w found to be 9.15 bar. Calculate x, ¢ “8 partial pressure at equilibrium, © wand Solution We know pV = nRT Total volume (V) = 1L Molecular mass of N,O, = 92 g Number of moles = 13.88/92 g = 0.15 of the gas (n) Gas constant (R) = 0.083 bar L mot'K.1 Temperature (T) = 400 K pV=nRT px 1L = 0.15 mol x 0.083 bar L mol) x 400k p= 4.98 bar NO, = 2No, Initial pressure: 4.98bar ~ 0. _At equilibrium: (4.98-x) bar 2x bar Hence, Pius At Equilibrium = Py,o, + Pxo, 9.15 = (4.98-x) + 2x 9.15 = 4.98 + x x=9.15-4.98 = 4.17 bar Partial presstires at equilibrium are, Py,o, = 4.98 ~ 4.17 = 0.81bar Pro, = 2x = 2x 4.17 = 8.34 bar K, = (Pro, \ /Py,0, = (8.34/0.81 = 85.87 (Rn 85.87 = K (0.083 x 400)! 86 = 2.6 blem 7.9 3.00 mol 6f PCL, kept in 1L closed reaction vessel was allowed to attain equilibrium at 380K. Calculate composition of the mixture at equilibrium. K_= 1.80 Solution PCL, = PCL + Cl Initial concentration: 3.0 0 0- _guiLiBRim (3-x) ie ay = IPChICL IPCI} 1e=e/ 3-*) 4 1.8%- 5.4=0 21.8 # V1.8 = A842 2[-1.8+ 3.24 + 21.6]/2 1.8 + 4.981/2 1.8 + 4.981/2 = 1.59 5 3.0-x=3-1.59= 141M x=1.59M | x z “ [PCl.l= pcly] = !Cll = 1.7 RELATIONSHIP BETWEEN UILIBRIUM. CONSTANT K, TION QUOTIENT Q AND GIBBS ENERGY G The value of K, fora reaction does not depend on ine rate of the teaction. Ht wever, as you have studied in Unit 6, it is directly related to the thermodynamics of the reaction and in particular, to the change in Gibbs energy, AG. If, then the reaction is » AG is negative, 26 pega PSE FAH airection. tion is considered , AGis positive, then reac non-spontaneous- snstead, as reverse reaction would have a negative AG, the oducts of the forward reaction shall be P converted to the reactants. hieved equilibrium: , AGis 0, reaction has ac’ at this point, there js no longer any free energy left to ‘drive the reaction. A mathematical expression of this hermodynamic view of equilibrium can be e ¢ following equation: : dard Gibbs energy: At equilibrium, when AG = 0 ant he equation (7.21) becomes, AG ag? +RTInK=0 AG? =- RT InK InK =-AG° / RT Taking antilog of b (7.21) (7.22) oth sides, We get © IfAG® <0, then -AG°/RT is pos! dQ = Ko 201 (7.23) on (7.23), the interpreted 1 K 2e780°/RT Hence, using the ¢ : quati reaction spontaneity can be terms of the value of 4G”. 4° itive, and 780° /RT >1, making K>1, which implies a spontaneous reaction. tion wiiich proceeds in the forward direction to such ait “extent that the products-are present predominantly. «If AG?>-0; then -AG°/RT is negative, and e8G°/RT <1, that is, K<1, which implies anon-s] us reaction or a reaction which proceeds in the forward direction to Such a small degree that only a very sobeate formed. quantity of product is jem 7.10 for the phosphorylation The value of AG of glucose in glycolysis is 15.8 kJ/mol. Find the value of K, at 298 K. Solution AG? = 13.8 kJ/mol = 13.8 x 10°J/mol Also, AG? = - RT Ink, Hence, In K,= 13.8% 10°J/mol (g.314 J mol "Kx 298 K) 569 in K.= Keen 3.81 x 10° lem 7.11 Hydrolysis of sucro sucrose +H,0. = Glucose + Fructose for the reaction Equilibrium: constant K, f¢ is 2 x10" at 300K. Calculate AG® at 300K. Solution AG? =-RTInK, ae AG? =- 8.3 14J mol"K 300K x In(2x10"°) 64 x10! J mol" se gives, TING EQUILIBRIA of chemical synthesis jon of the reactants 7.8 FACTORS: AFFEC' One of the principal goals ts to maximise the convers'202 to products while minimizing the expenditure of energy. This implies maximum yield of products at mild ET a eT ihe conditions. If it does not happen. then the experimental conditions need to be adjusted. For example, in the Haber process for the synthesis of ammonia from N, and a choice of experimental conditions ts of real economic importance. Annual world production of ammonia is about hundred million tones, primarily for use as fer Equilibrium constant, K, is independent of initial concentrations. But if a system a! equilibrium is subjected to a change in the concentration of one or more of the reacting substances, then the system is no longer at equilibrium; and net reaction takes place in some direction until the system returns to equilibrium once again. Similarly, a change in temperature or pressure of the system may also alter the equilibrium. In order to decide what course the reaction adopts and make a qualitative prediction about the effect ofa change in conditions on equilibrium we use © elier's principle] It states that a shange in f the factors that determine the equilibrium conditions of a system will cause the system to cl fe in_such a manner so as to reduce or to counteract the effect of the change. This is applicable to all physical equilibria. We shall now be discussing factors which can influence the equilibrium. 7.8.1 Effect of Concentratfon Change In general, when equilibrium is disturbed by the addition/removal of any reactant/ - products, Le Chatelier’s principle predicts that: * The concentration stress of an added reactant/product is relieved by net reaction inthe direction that.co) 4 msumes the added substance. — « The concentration stress of a removed reactant/product is relieved by net reaction in the direction that replenishes the remgved. substance. = or in other words, = CHEST “When the concentration of aa reactants or products in q ro, 'Y oj the equilibrium is changed, the oo at of the a ce re changes tion t effect oj So as changes”. oe concentration Let us take the reaction, H,@ +L@ = 2HI@ If H, is added to the reaction Tix equilibrium, then the equilibrium Lure at reaction‘s disturbed. In order to reston e reaction proceeds in a direction. where the consumed, ie., more of H, and |, react tyra HI and finally the equili oe (forward) direction (Fig.7.8). This Tight accordance with-the Le Chatelier's priney hh which implies that incase of addition cr reactant/product, a new equilibrium will te set up in which the concenttation- reactant /product Should be} at was afte e than. “ was in the original mixtyre. what i ‘ ' . i Equilibrium re-established Fig. 7.8 Effect of addition of H, on change concentration for the reactants products in the — react Ha(q) + 1 @) = 2H) The same point can be explained intel of the reaction quotient, Q,. 9.= HIP, (HII), guiupRIuM addition of hydrogen at equilibrium results alue of Q, beingless than K.. Thus, in order in attain equilibrium again reaction moves in e fo direction. Similarly, we can say «that regoval_of a product also boosts the forward_reaction. “and increases [fre foncentration.of the. is has ai commercial application in cases o reactions. ‘where the product is a gas or a volatile substance. In case of manufacture of ‘onia, ammonia is liquified and removed from the reaction mixture so that reaction ‘ oving in forwarddirection. Similarly, keeps me in the large scale production of CaO (used as tant building material) from_CaCo,, imetant removal of CO, from ine the reaction to completion. It ‘Stfould be remembered that continuous removal’ of a direction. pffect of Concentration - An experiment ‘This can be demonstrated by the following reaction: Fe*faq+ SCN faq) = Fe(SCN)P"aq) (7.24) yellow) colourless deep re ke [Fe(scn)” (aa)] «* [re® (aq) [ SCN" (aq) ] Areddish colour appears on adding two drops of 0.002 M potassium thiocynate solution to 1 mL of 0.2 M iron(III) nitrate solution due to the formation of [Fe(SCN))". The intensity of the red colour becomes constant on attaining equilibrium. This equilibrium can be shifted in either forward or reverse directions depending on our choice of adding a reactant or a product. The equilibrium can be shifted in the opposite direction by adding reagents that remove Fe* 4 SCN” ions. For exam alic_ac nC,0,), reacts with Fe* stable complex ion [Fe(C,0,),J*. thus Inaccordance éTéChatelier's principle, the concentration stress of removed Fe™ is Telieved by dissociation of [Fe(SCN)]”* to (7.25) 203 replenish the Fe ions. Because the concentration of [Fe(SCN)I** decreases. the intensity of red colour decreases. Fee SCN (aq) shifts the equilibrium in equation (7.24) from right to left to replenish SCN“Ions. Addition of potassium on the other hand increases the colour intensity of the solution as it shift the equi um to right 7.8.2 Effect of Pressure Change A pressure change obtained se fect the yield of products in case ofa gaseous reaction where the total ms of moles of gaseous reactants and total product maintains Q. at a'value less than iuiiber of moles of gaseous products, are and reaction continues to move in the fo1 fateliers principle -Trrapplying Le Cha To a heterogeneous equilibrium. the. effect.of pressure changes on solids and liquids can be ignored bécause the “volume (and concentration) of a solution /ligife'Is early independent of pressure. Consider the reaction, CO + 3H, = CH@ +H,08) Here, 4 mol of gaseous reactants (CO + 3H,) become 2 mol of gaseous products (CH, + 1,0). Suppose equilibrium mixture (for above reaction) kept in a cylinder fitted with a piston at constant temperature is compressed to one half of ts original volume. Then, total pressure will ‘be doubled (according to pV = constant). The partial pressure and therefore, concentration of reactants and produ Sho longer at. m. The direction in which the reaction goes to re-establish equilibrium can be predicted by applying the Le Chatelier's principle. Since pressure has.doubled,. the, equilibrium now shifts in the forward reson qsdiccah nie The auaie moles of the or pressure decreases (we know pressure proportional fo moles of the gas). This can also-be-understood by using ‘Feaétion quotient, Q.. Let [CO], (H,], [CH,] and {H,O] be the molar concentrations at equilibrium fo: fon réaction, WhenPp doubled. We 0b replacing each eq double its value. (cH. (8) H,0(€)] %- Feo(a) [H(@)T As Q, < K,. the reaction proc forward direction. Tn reaction Cls+ CO = 26016). wie ction goes.in the numberof males pressure is increased, the rea reverse direction because-the of gas increases in the forward direction. 7.83 Bffect of Inert Gas Addition it and an inert gas Ifthe volume is kept constan! ed’ which does not take such @S argon is added wl part in the reaction, the equllbaium rem undisturbed. It is because the addition ofan eeds in the inert ‘gas at constant volume does not change the partial pressures or the molar ie Sul ice invol inthe Feaction: The reaction quotient changes only if The added gas is a reactant or product involved in the reaction. Ke <1 Lvo) 7.8.4 Effect of Temperature Change Whenever an equilibrium is disturbed by a change in the concentration, pressure or volume, the composition of the equilibrium mixture changes because the reaction quotient, Q, no longer equals the equilibrium constant, K,. However, when a e in temperature re ee teeta constant, K, is changed. In gerfergi, the temperature dependence of the equitisfium constant depends on the sign of AH for the reaction. The equilibrium constant for an exothermic reaction (negative AH) decreases as the temperature increases. . « The equilibrium constant for an endothermic reaction (positive AH) iffeTeases as the temperature increases, Temperature changes affect the equilibrium constant and rates of reactors: a CHEMIST ction of ammonia according to th Producten ————= ie reaction, N@+ 3H,(@ = 2NH,@): = ~ 92.38 kJ mol is an ox ele, According 4 Le Chateller’s principle, raising the tum temperature S! decreases the equilibrium concentration ‘a ammonia. In other words, low temperatyr i favourable for eld_of ammonia. in pra vel OW, the reaction. and thus a catalyst is ysed. t of Temperature - An experiment Effec Effect of temperature on equilibrium can be demonstrated by NO, gas (brown in colour) which dimerises into N,O, gas (colourless). 2NO,(@) = N,O,@; AH = -57.2 kJ mol" prepared by addition of ¢ HNO, is collected int 5 mL test tubes (ensuring same intensity o colour.o each tube) and stopper sealed wit ee 250 mL beakers Yand 3 containing freezing mixture, water at room temperature and hot water (363K), respectively, are taken (Fig. 7.9). Both the test tubes are placed in beaker 2 for 8-10 minutes. After this one is placed in beaker 1 and the other in beaker 3. The effect of temperature on direction of'reaction is depicted very well in this experiment. At low temperatures in beaker 1, the forward reaction of formation of N,0, is preferred, as reaction is exothermic, and thus, integsity-of-broun_calgur duc to Ts decreases. While in beaker 3, high perature favours the reverse reaction of Fig. 7.9 Effect of temperature on equilibrium for the reaction, 2NO, (= N,0, @not NO, and thus, the brown colour temperature can also be seen in He egmic reactton. _ aq) + ACI (aq) = [COCL (aq) + 6H,0(1) 7 temperature, the equilibrium Tue due to (COCI,}*. When cooled ps “mixture, the colour of the mixture pal pink ave to [ColH,O),)". 7 desis est of a Catalyst atalyst increase ical 4c aon making available a newlowenergy reat ray 108 increasés the rate of forward and Or ge reactions that pass through the same Transition state and docs_not affect wansjum. Catalyst lowers fhe activation ook for the forwal ns eT The sameamount. Catalyst does not Terr the equilibrium composition.of a reseion. mixture. Tt does not appeat.in the palanced_ chemical equation Sen the _qibrivm constant eNpcessla mn. Tet us consider the formation of NH, from dinitrogen and dihydrogen which is highly exothermic reaction and proceeds with decrease in total number of moles formed as compared to the reactants. Bquilibrium constant decreases with increase in temperature. At Tow_tem erature rate decreases and it takes long time to reach at @iilibrium, whereas high temperatures gv give salstactory rates but poor NETS German chemist, Fritz Haber discovered that a catalyst consisting Ol iron. reaction To occur é : temgeratures, ‘where the equilibrium concentration of NH, is reasonably favourable. Since the number of moles formed in the action is less than those of reactants, the Yield of NH, can be improve’ ‘hepressure. um conditions of temperature and uerure for the synthesis of NH, using lyst are around 50Q2C and 290 atm. — — 205 Similarly, in manufacture of subplaas!® acid by conlaghprocess 280,(g) + 0,{g) > 280,(gh K,= 1-7 * 10% though the value of K Is suggestive of reaction , going to completion, but practical the oxidg of SO, to SO, Is very slow. Thus. pk tinum OF divanadium _penta-oxide V,0,) Is use as CaCHYSTOMTCTeASe ME TATE OT The reaction. Note: If a reaction-has an-exceet mall K, a catalyst would be of little help- 7.9 YONIC EQUILIBRIUM IN SOLUTION Under the effect of change of concentration on the direction of equilibrium, you have incidently come across with the following equilibrium which involves ions: Fe™(aq) + SCN(aq) = [Fe(SCN)P"(aq) ‘There are numerous equilibria that involve ions only. In the following sections we will study the equilibria involving ions. It is well known that the aqueous solution of sugar does not conduct electricity. However, when common salt (sodium chloride) is added to water it conducts electricity. Also, the conductance of electricity increases with an increase in concentration of common salt. Michael Faraday classified the substances into two categories based on their ability to conduct electricity. One category of substances conduct electficify in t 1elr aqueous solutions antrare called électrolytes while the other do, not~anid are thus, referred_to_as, non” electrolytes. Faraday further classified electrolytes into strong and weak electrolytes. Strong electrolytes on dissolution in water are fonized_almo: ely, while the weak Zlectrolytes are only partially dissociated. of » Or example, an a sodium chloride is comprised entirely of sodium ions and chloride ions, while that of acetic acid mainly contains unionized acetic acid molecules and only some acetate fons and hydronium ions, This is because there is almost 100% tonization in case of sodium chloride as compared to less than 5% ionization. of acetic acid which is a weak electrolyte. It should be noted that in weak electrolytes, equilibrium isoes 206 BL enJons_and the unionized is type of equilibrium involving us solution is called ionic alts come established_bi molecules. Thi ions in aqueo equilibrium. Acids, bases and s under the catego! rong or weak electrolytes. 7.10 ACIDS, BASES AND SALTS Acids, bases and salts find widespread occurrence in nature. Hydrochloric acid present in the gastric juice is secreted by the lining of our stomach ina significant amount of 1.2-1.5 L/day and is essential for digestive processes Acetic acid is known to be the main constituent epgar, Lemon and orange juices contain citric and ascorbic acids, and tartaric acid is found in tamarind paste. As most of the acids taste, e word “acid” ia been dere os alin act : me sour. Acids are known to turn blue litmus paper into red and liberate dihydrogen on react etals. Similarly, bases are known to turn red litmus paper blue, taste bitter and feel soa] com ofa Base is washing soda used for washing purposes. When acids and bases are mixed in the right proportion they react with each other to give salts. Some commonly known examples of salts are sodium chloride, barium sulphate, sodium nitrate. Sodium chloride (common salt ) is an important component of our diet and is formed by reaction between hydrochloric acid and sodium hydroxide. It work Friday evening discourses, Faraday was born near London into a family of very lunited means. At the age of 14 he~ was an apprentice to a kind bookbinder who allowed Faraday to read the books he was binding. Through a fortunate chance he becaine laboratory assistant to Davy, and during 1813-4, Faraday accompanted him to the Continent. During this trip he gained much from the expertence of coming into contact with many of the leading sctentists of the time. In 1825, he succeeded Davy as Director of the Royal Institution laboratories, and in 1833 he also became the first Fullerian Professor of Chemistry. Faraday’s first important work was on analytical chemistry. After 1821 much of his work was on electricity and magnetism and different electromagnetic phenomena. His ideas have led to th of moder field theory. He discovered his two laws of electrolysis in 1834. Faraday was a very modest and kind hearted person. He declined all honours and avoided scientific controversie: alone and never had any assistant. He disseminated science in a variety of ways including his which he founded at the Royal institution. He has been very famous for hls Christmas lecture on the ‘Chemical History of'a Candle’, He published nearly 450 sctentifie papers. CHEMIST ‘olid state as a cluster of Positives, y exists in Ss! m ions and negatively char, ed charged sodiu chloride tons which are held together die electrostatic interactions between opposite ly charged species (Fig.7.10). The electrostatic m a very high ‘dielectric constant of Thy when sodium chloride is dissolve water = by geparated due to hydration with. pred molecules. om r Oo 08,0, Oo? oy, oF ; aor vo? 8) or jot ind). 6,6 9 0° OF? or 200 Fig.7.10 Dissolution of sodium chloride in water. ‘Na’ and CI ions are stablised by their * hydration with polar water molecules. Comparing, the ionization of hydrochloric acid with that of acetic acid in water we find that though both of them are polar covalent Michael Faraday (1791-1867) establishment .s, He preferred (0‘According ~ substances ule former is completely ionized moronsteuent fons, while the latter is bind rtially jonized (< 5%). The extent to wht sa ond and the extent of solvation of ons LO eos ThE erms dissociation and ier Wem have earlier been used with different . Dissociation refers to the process of pearing yn of ions in water ad} ai In water already existing as Fin the 2 State of the solute, as ‘in ae meh the other hand, ionization 2 esponds to.4 process.in which a neutral sojecule splits into. charged iong_in the tion. Here, we shall not distinguish yeen the two and use the two terms 710-1 arrhenius Concept of Acids and to Arrhenius theory, acids are that dissociates in water. to give hydrogen tons “A (aq) and bases are substances that produce Rydroxyl-tons ;¢ ionization of an acid HX (aq) can oH faq). Th Ce resented by the following equations: HX (aq) 9 H'lag) +X ad) or HX(aq) + HOW > H,O'faq) +X (aq) H* is very reactive and A bare proton, ueous solutions. Thus, cannot exist freely in aq itbonds to the oxygen atom ofa solvent water indlecule to give trigon al_pyraml hydronium ion, 1,0" ((H (H,O)I") (see box). inthis chapter we shall use H(aq) and HO") interchangeably to mean the same ie, a hydrated proton. Similarly, a base molecule like MOH fonizes in aqueous solution according to the ‘equation: MOH[aq) > M*(aq) + OH (a) ‘The hydroxyl ion also exists in the hy form in the aqueous | ‘solution. Arrhenius concept of acid and base, however, suffers from the limitation of being applicable orily to aqueous solutions and also, does not account for the basicity of substances like, ammonia which do not possess @ hydroxyl group: 207 rn me Hydronium and Hydroryl Ions cee on by itself is a bare proton with ry small size (~10-* m radius) and intense electric field, binds itself with the water molecule at one of the two available lone pairs on it'giving H,O*. This.species has been 7.10.2 The Brénsted-Lowry ‘Acids and Bases ‘The Danish chemist, Johannes, Bronsted and the English chemist, Thomas. M. Lowry gave a more general definition of acids and bases. ‘According to Bronsted-Lowry theory, acid is a substance that is capable of donating. a drogen ion H* and bases are substances capable of accepting hydrogen ion, H. In short, acids are proton. donors and bases are proton acceptors. — Consider the examp! inH,O represented by the fol Je of dissolution of NH, owing equation: adds proton: NH; (aq) + OH (aq) conjugate conjugate NH,faq + #00, ’ acid base acid L— loses proton’ formed due to the ‘The basic solution is presence of yt ions. ‘irtnis reaction, water molecule ‘acis as proton donor and ammonia molecule acts a8 proton acceptor and are thus, called Lowry-Bronsted acid and base208 Svante Arrhenius (1859-1927) of chemistry. a base, respectively. In the reverse reaction, H* is transferred from NH; to OH”. In this case, NH; acts as a Bronsted acid while OH” acted as a Bronsted base. The acid-base pair that differs iscalled a conjugate acid-base pair. Therefore, OH is called'the conjugate Base of an acid HO and NH; is called conjugate acid of the base NH,. If Bronsted acid is. a strong acid’ then its versa. It may be note conjugal has one extra proton and each conjugate base has one less proton. ssh Consider the example of ionization of hydrochloric acid in water. HCl(aq) acts as an acid by donating a proton to H,O molecule which acts as a base. (“ “| HClag + 1,01 +> 0 lq + Cllaq) acid base conjugate conjugate a cid base, LE al It can be seen in the above equation, that water acts as a base because it accepts the proton. The species H,O* is produced when water accepts a proton from HCl. Therefore, CI is a conjugate base of HCI and HCl is the conjugate acid of base CI. Similarly, 1,0 is a conjugate base of an acid H,0* and H,0° is a conjugate acid of base H,O. f It is interesting to observe the dual role of js aba: with HCI water acts as a base while in case of rhenius was born near Uppsala, St Sy elearcyte colts ‘to the University of Uer la in travelled extensively and visited a number of' of physics at d rerun io 10a From 1905 untithis death he at the Nobel Institute in Stockholm. solutions. In 1899 he discussed the tenet basis ofan equation, now usually known as He worked in a variety ya fields, immunochemistry, cosmology, the origin of “ first to Genes ‘green house effect’ calling ee ied Chemistry in 1903 for his theory of electrolyte dissoctation and e. In case of reaction— aueden He, reseed is hes the newly formed University of Stockholm, ¢: was Director of physica, He continued to work for many, id made i ie, and the Teceived Nobe| p, ls use tn the deve tei pee kent ammonia it acts as an acid by donating proton, Arobiem 7.12 What will be the conjugate bases for the following Brénsted acids: HF, H,S0, and HCO; ? Solution The conjugate bases should have one proton less in each case and therefore the corresponding conjugate bases are: RA HSO; and CO? respectively, Problem 7.13 “* White the conjugate acids for the following Brénsted bases: NH;, NH, and HCOO’. Solution we WH yy 6 The conjugate acid should have one extra Proton in each case and therefore the Corresponding conjugate acids are: NH,, NH; and HCOOH respectively. _ Problem 7.14 The species: H,O, HCO,. HSO, and NH, can act both. sted acids and bases. For each case give the corresponding Conjugate acid and conjugate base. AR sn SY Solution The answer is @iven in the following Table: Species Conjugate Conjugate acid base 4,0 HO OH HCO; H,CO, coz HSo; H,So, so? is Nu NH, a a eegousoRiuM 710.3 Lewis Acids and Bases " pewis in 1923 defined an acid as a GN. "= which accepts electron pair and Base species wn leciron pair. As far gs donates an electron pair. Ag fa) wher sre concerted, there Is net mach bast ace between Bronsted. ‘an athe cases. However, in Lewis concept boo Feids do not have proton. A typical ction of electron deficient species LAN ample ist pF, with NH. RE aR does not have a proton but still acts 2 safone pair of electrons. The reaction can represented by, BF, + :NH, > BF,.NH, JectroiT CENCIOHUSPECTeSMREAICI,, Co, Mi 3 can act as Lewis acids wees Te o.NH, OF ‘etc. which ean donate a pair ofelecirons, can act as Lewis bases. assily the following speci ids and Lewis bases and oor 4 {ution ag Hydroxyl ion is a Lewis base as itcan donate an electron lone pair (OH). Flouride ion acts as a Lewis base as” it can donate any one of its electron lone pairs. se -A proton, is a Lewis acid as it can accept a lone pair of electrons from bases like hydroxyl ion and fluoride _ jon. e: * BCI, acts as a Lewis acid as accept a lone pair of ele« species like molecules, four 7.11 IONIZATION OF ACIDS AND BASES ‘Amthenius concept of acids and bases becomes usel on: ‘case of ionization of acids and bases — —i fy Toniza Bical systems occur im aqueous medium, * Strong acids like perchloric ac i AC IU" 209 hydrochloric acid (HCl), hydrobromte_acid (HEH), hyrdotodic acid (HI), nitric acid (HNO,) and sulphiuric acid (H,SO,) are termed strong because~they are almost completely dissociated into their cdnstituent fons in an aqueous medium, thereby acting as proton (H’) donors. Similarly, strong bases like lithium hydroxide (L10H), sodium hydroxide (NaOF), potassium hydroxide (KOR), caesium hydroxide {CSOH) and barium hydroxide ‘BafOH), are almost completely dissociated into fonfS in an aqueous medium giving hydroxyl ions, OH’. According to Arrhenius concept they are strong acids and bases as they are able to completely dissociate and produce H,O and OH’ ions respectively in the medium. Alternatively, the strength of an acid or base may also be care in terms of Bronsted Lara Concept of acids and bases, WHeTeMT a strongacid means a good proton donor anda strong base implies a good proton acceptor. Consider, the acid-base dissociation equilibrium of a weak acid HA, HA(aq) + H,O() = H,O%laq) + Alaqd conjugate conjugate acid base acid base Insection 7.10.2 we saw that acid (or base) dissociation equilibrium is dynamic involving a transfer.of proton in forward and reverse directions. Now, the question arises that if the equilibrium is dynamic then with passage of time which direction is favoured? What is the driving force behind it? In order to answer these questions we shall deal into the issue of comparing the strengths of the two acids (or bases) involved in the dissociation equilibrium. Consider the two acids HA and H,O* present in the above mentioned acid-dissociation equilibrium. We have to see which amongst exceeds in its tendency of donating a proton er the other sl é termed as the stronger the agid_and_t ft direction of weaker acid. Say, if HA is a stronger acid than F,O% then HA will donate protons and not H,0°, and the solution will mainly contain A and H,0° ions. The equilibrium moves in the direction of formation of weaker acid and weaker basei a 210 because the stronger acid donates a proton te. fhe stronger ase. It follows that as a strong acid dissociates completely in water, the resulting base formed would be very weak i. a) ve te bases. Strong acids like a : lorie-aeid ), hydrobramic.acid (HBr), hydroiodic.acid (HD), nitric acid (HNO,) and sulphuric.acid (H,S0,) will give conjugate base ions C10, Gl. Br... NO; and HSO,,, which are much weaker bases than H,O. Similarly a very strong basé~ would give a very weak cony jugate acid. Sn the other hand, a weak acid say HA is only partially dissociated in aqueous medium and Thus. the solution mainly contains undissociated HA molécules. Typical weak acids are nitrous acid (HINO,), hydrofluoric acid (HF) and acetic acid (CH,COOH). It should be noted that the weak acids Fidve very strong conjugate bases. For example, NH;, O” and H” are very good proton acceptors and thus, much stronger bases than H,0. Certain water soluble organic compounds like penolphunlein and bigiothymel blue behave"as weak acids and SoBe anereAt colours in thelracid (tln) and conjugate base (in) forms... Hinfaq) + H,00) = H,0%laq + In'faq) acid conjugate conjugate indicator acid base colour A colourB Such compounds are useful as indicators in acid-base titrations, and finding out H" ion concentration. . 7.11.1 The Ionization Constant of Water and its Ionic Product Some substances like water are unique in their ability of acting both as an acid and a base. We have seen this in case of water in section 7.10.2. In presence of an acid, HA it accepts a and acts as the base while in the presence of a base, B it acts as an acid by nating a proton. In pure water, one TO eieeie donates proton. and acts as an acid and ano olecules accepts a proton acts as a base at the same time. The a ving equilibrium exists: proton Cr TF ~And, as dissociation of water produces eq ow CHEMIstpy 1,00) + 1,00 = H,0%@q) + OFfaq) acid base conjugate co) acid pega The oe it 1s represented by, K=[H,07 [0111 / 4,0) (729 The concentration of water ts omitted from the denominator as water isa Pureliguig its concentration remains constant. 10] incorporated within the-eguilibrium constan to give a new cons ichis calledaee ionic prodact of Ky= [HOH] (7.27) ‘The concentration of H” has been found out experimentally as 1 0” Mat 298 k ‘number of Hand OH” ions,-the concentration. of hydroxyl ions, [OH] = [H"]= 1.0. x.107M__, Thus, the value of K, at 298K, K, =[H,0°104 OH] = (1 x 10° = 1 x 10 Me (7.28) The, mperatu as if an equilibrium constant. The density of pure water is 1000.g LL and its méla¥ Tass 1818.0 g /mol. From this thé molarity of pure water can be given as, [H,0) = (1000 g /L)(1 mol/18.0 g) = 55.55 M. Therefore, the ratio of dissociated water to that of undissociated water can be given as: 107 / (65.55) = 1.8 x 10° or We can distinguish acidic, neutral and basic aqueous solutions by the relative values of the H,O* and OH concentrations: Acidic: [H,0*] > [OH] Neutral: [H,0°] = [OH] Basie : [H,0°] < [OH] 7.11.2 "The pH Seale Hydronium ion conicentration in molarity is more conveniently expressed on a logarithmic scale known as the pH scale, The pH of a solution is defined as the negative logari to base 10 of the activity of hydrogenpo quis nature solutions (< 0.01 MQ. activity of son gen ion (Hs equal in_may a f represented by [H'l. It should =jhat activity has no units and is das m pe Taree oe alt / mol L* } I = the definition of pH, the following pe written, 2 - log ay, =~ log 1H") / mol L*) qhus. an acidic solution of HCl (10? M) ve a pH = 2. Similarly, a basic solution NaOH having [OH] =10 * M and (H,0"} = to M will have a pH = 10. At 25 °C, pure water has 2 concentration of hydrogen ions, iH'T= 10” M. Hence, the pH of pure water is oem : pH= -log107) = Acidic solutions possess a concentration of hydrogen ions, {H"] > 107 M, while basic solutions possess a concentration of hydrogen jons, [H']< 10” M. thus, we can summarise that Acidic solution has pH <7 Basie solution has pH > 7 Neutral solution has pH = 7 Now again, consider the equation (7.28) at 298K K,=[H,0°1[0H ] = 10"* Taking negative logarithm on both sides of equation, we obtain ~log K, = - log (H,0°] [OH D ~ log [H,O*] - log [OH] =~ log 10°" PK, = pH +° pOH = 14 (7.29) ange with qempetature fons in pH wl Tature aré-so small that we ofte PK, is a very important quantity for “dueous solutions and controls the relative ‘oneentrations of hydrogen and hy tons % their product is a constant, It should be that as the pH scale is logarithmic, a aut change in pH by just one unit also means change in |H'] by a factor of 10. Similarly, when the hydrogen jon concentration, [H*] changes by.a factor of 100, the value of pH changes by 2 units. Now you can realise why the change in pH with temperature is often Ignored, Measurement of pH of a solution is very essential as its value should be known when dealing with biological and cosmetic applications. The pH of a solution can be found som ly with the help of pH paper that has different colour in solutions of different pH. Now-a-days pH paper is available with four strips on it. The different strips have different colours (Fig. 7.11) at the same pH. The pH in the range of J-14 can be determined with an accuracy of-0.5)using pH paper" wn 1213 14 Fig.7.11 pH-paper with four strips that may have different colours at the same pH For greater accuracy pH meters are used. pH ileterisa device that measures-the pF ent electric tential-of the test solution within 0.001 precision. pH meters of the size ofa wilting pen are now available in the market. The pH of some very common substances are given in Table 7.5 (page 212). blem 7.16 ; The concentration of hydrogen ion in a sample of soft drink is 3.8 x 10°M. what is its pH? Solution pH =~ logi3.8 x 10°) =— flog(3.8] + logl 10°} =~ {(0.58) + (-3.0)} =-{- 2.42} = 2.42 ~ Therefore, the pH of the soft drink is 2.42 _and it can be inferred that it is acidic. Calculate pH of a 1.0 x 10° M solution _ of HCl.C) 212 Table 7.5 The pH of Some Common Substances Name of the Fluid e water | Milk of magnesia Lemon Juice Egg white, sea water Gastric juice Human blood mh saliva Name of the Fluid Black Coffee ‘Tomato juice Soft drinks and vinegar _ Solution 2H,0 () = H,0* (aq) + OF faq) K, = (0H ][H,0°] = 10% Let, x= [OH] = [H,0'] from HO. The H,0° concentration is generated (i) from the ionization of HCl dissolved i.e., HCl(aq) + H,0() = 130" (aq) + Cl (aq), and (ii) from ionization of H,O. In these _ very dilute solutions, both sources of H,O* must be considered: [H,0°*] = 10° +x ay K,= (10% +x) = 108 * orx?+ 10°x-10%=0 [OH] =x=9.5x 10° So, pOH = 7.02 and pH = 6.98 7.11.3 Ionization Constazits $f Weak Acids onstanite 5 Consider a weak acid AX that {s partially ionized in the aqueous solution. The equilibrium can be expressed by: HX(aq) + H,0l) = H,O"(aq) + X faq) Initial concentration (M) 0 c Let ao be the extent of ionization Change (M) -ca +c0, +ca. Equilibrium concentration (M) c-ca CoH co Here, c = initial concentration of.the undissociated acid, HX at time, t= 0. o.= extent up to which HX is ionized into ions. Using these notations, we can derive the equilibrium constant for the above discussed acid. dissociation equilibrium: = ea? / c(1-a) = co? / 1-0 K is called the dissociation or ionization is caret a mor onization constant ace It-can-be represented ematively in terms of molar concentration as follows, K, =H IX] / [HX] (7.30) @ Biven temperature T, Kis a i.e., larger the value of K_, the stronger is state concentration of all species is IM- —<$<$<—<$<$<$<$$ $n The values of the ionization constants of some selected weak acids are given in Table 7.6. Table 7.6 The Ionization Constants of Some Selected Weak Acids (at 298K) Ionization Constant, K, 3.5 x 10% 4.5 x 10% 1.8 x 10¢ 1.5 x 10° 1.74 x 10° 6.5 x 10° 3.0 x 10° | Hydrofluoric Acid (HF) | Nitrous Acid (HNO,) ! Formic Acid (HCOOH) | Niacin (C,H,NCOOH) Acetic Acid (CH,COOH) Benzoic Acid (C,H,COOH) Hypochlorous Acid (HCIO) | Hydrocyante Acid (HCN) 101 (CgHsOH) _ ‘ihdloes 1.3 The pH scale for the hydrogen ioP concentration has been so useful that besides pK,, it has been extended to other species anigQUILIBRIUM quantities. Thus, we have: 6 (7.31) ing the ionization constant, K of . al acid and its initial concentration. c’ it ¢ possible to calculate the equilibrium’ centration of all species and also the of onization of the acid and the pH fae solution. A general step-wise approach can be adopted to evaluate the pH of the weak electrolyte as follows: step 1. The species present before dissociation are identified as Brénsted-Lowry * acids / bases. . Step 2. Balanced equations for all Possible reactions i.e., with a species acting both as acid as well as base are written. . Step 3. The reaction with the higher Kis igentlled a5 the puimany reaction wbulsthe ofher is.a subsidiary.tegction. Step 4. Enlist in a tabular form the following values for each of the species in the primary reaction (a) Initial concentration, c. (b) Change in concentration on proceeding to equilibrium in terms of a, degree of ionization. (Q Equilibrium concentration. Step 5. Substitute equilibrium concentrations into equilibrium constant equation for principal reaction and solve for a. Step 6. Calculate the concentration of species in principal reaction. Step 7. Calculate pH = - log{H,O*] The above mentioned methodology has been elucidated in the following examples. ee _Phoblem 7,18 The ionization constant of HF is 3.2 x 10. Calculate the degree of dissociation of HF in its 0,02 M solution. Calculate the concentration of all species Present (H,O*, F- and HF) in the solution and its pH. & 213 Solution ‘The following proton transfer reactions are Possible: DHF +H,O = H,O* + F- K, = 3.2 x 104 2)H,0 + H,0 = H,0' + OH” = 1.0.x 10 As K, >> K,, [1] is the principle reaction. HF + HO HOt + F Initial concentration (M) 0.02 0 0 Change (M) 0.020. +0.020, +0.020 Equilibrium concentration (M) 0.02-0.020 0.024 0.020 Substituting equilibrium concentrations in the equilibrium reaction for principal reaction gives: K, = (0.020)? / (0.02 - 0.020) = 0.02 o? / (1-0) = 3.2 x 104 We obtain the following quadratic equation: o? + 1.6 x 10a - 1.6 x 107=0 The quadratic equation in @ can be solved and the two values of the roots are: a@ = + 0.12 and - 0.12 _ The negative root is not acceptable and hence, a=0.12 This means that the degree of ionization, a= 0.12, then equilibrium concentrations of other species viz., HF, F- and H,O* are given by: {H,0*] = [IF] = co = 0.02 x 0.12 =2.4x 10°M [HF] = c(1 - a) = 0.02 (1 - 0.12) =17.6x 10°M ~ logiH"] = -log(2.4 x 10°) = 2.62 _- Problem 7.19 The pH of 0.1M monobasic acid is 4.50. | Calculate the concentration of. species H’,214 A and HAat equilibrium. Also, determine the value of K, and pK, of the monobasic acid. Solution PH = - log [H"] Therefore, [H*] = 10 = 104 =3.16 x 10% [fH] = [A] = 3.16 x 10° Thus, K, = (H°1IA) / [HA] THA] rc, = O-1 - (3.16 x 105) = 0.1 K, = (8.16 x 10°)? / 0.1 = 1.0 x 10 PK, = - log(10*) = 8 Alternatively, “Percent dissociation” is another useful method for measure of strength of a weak acid and is given as: Percent dissociation = [HA]. / THAI, as % 100% lem 7.20 Calculate the pH of 0.08M solution of hypochlorous acid, HOCI. The ionization constant of the acid is 2.5 x 10°. Determine the percent dissociation of HOCI. Solution HOCI{aq) + H,0 () = H,O"laq) + ClO‘aq) Initial concentration (M) 0.08 Oo 0 Change to reach equilibrium concentration (™) -x ot + equilibrium concentartion (M) 0.08 - x x {[H,O*I[C1O)] / [HOCI)} = x? / (0.08 -x) As x << 0.08, therefore 0.08 - x = 0.08 x? / 0.08 = 2.5.x 10% x? = 2.0 x 10°, thus, x = 1.41 x 10° [fH] = 1.41 10°M. Therefore, (7.32) * of concentration in equilibri lowing equation: {k, [M‘][0H] / [MOH] y (7.33) CHEMISTRY Percent dissociation = HOC ypasentea / FHOCH us 100 ‘ = 1.41 x 10% x 10*/ 0.08 = 1.76 %, | pH = -log(1.41 x 10%) = 2.85. 7.11.4 Ionization of Weak Bases ‘The ionization of base MOH can be representeg by equation: : MOH(aq) = M*(aq) + OH faq) In a weak base there is partial ionization of MOH into Mt and OH, the case is similar to that of acid-dissociation equilibrium. The equilibrium constant for base ionization is called base ionization constant and is represented by K,- Expressed in terms molarity of various species Alternatively, if c = initial concentration of base and a= degree of ionization of base i.e. the extent to which the base ionizes. When equilibrium is reached, the equilibrium constant can be written as: K, = (co)? / (1-0) = eo? / (1-0) The values of the ionization constants of some selected weak bases, K, are given in Table 7.7. Table 7.7. The Values of the Ionization Constant of Some Weak Bases at 298 K 5.4.x 107 6.45 x 10° 1.77 x 10° 1.10 x 10° 1.77 x 10° 4.27 x 10° Dimethylamine, (CH,),NH Triethylamine, (C,H,),N Ammonia, NH, or NH,OH Quinine, (A plant product) Pyridine, C,H,N Aniline, CgH,NH, Urea, CO (NH,),Kye Cyt p.oot youtspnrm Lp! 218 _oune all behave as v ak bases due { picourey small Ke “Aimonla produces thy, Ry Alo aPy ide } b cous solution: NH, + H0 @ NI + NH,(aq) + 4,00) = NH;(aq) + OH"(aq) Initial concentration (M) en qhe pH scale for the hydrogen ion _ 0.10 0.20 tee concentration has been extended to get: Change to reach ies ph 208 (kK) (7.34) equilibritim (M) ke 7.24 ~* ae we ‘me pl of 0.004M hydrazine solution jg | MP eauibrtuma () ae | 9,7. Calculate {ts fonization constant K, 0,10-x. 0.20+x, x } and pK, K, = [NH,OH1/ (NH) | solation = (0:20 + x\fx) / (0.1 = 9) = 1.77 x 10° H+ HO = . - “As K, is small, we can neglect x fn Nia Noes, oe comparison to 0.1M and 0.2M. Thus, | prom the pH we can calculate the | hydrogen fon concentration, Knowing (OH = x= 0.88 x 10° hydrogen ion concentration and the ionic ‘Therefore, |H‘] = 1.12 x 10° duct of water we can calculate the 1H == logiHi'] = 8.95. concentration of hydroxyl ions. Thus we eee : ¥ = have: 7.11.5 Relation between K, and K, {H‘] = antilog (-pH) As seen earlier in this chapter, K, and Ky = antilog (-9.7) = 1.67 x10 represent the strength of an acid and a base. 42K. /{H1=1%104/1.67x 1019. TesPectively. In case of a conjugate acid-base Oo Le) = 5,98 x ie as pair, they are related in a simple manner so that ifone is known, the other can be deduced. Considering the example of NH{ and NH, we see, NH;(aq) + H,0(1) = H,O*laq) + NH,(aq) ‘The concentration of the corresponding hydrazinium ion is also the same as that of hydroxyl ion. The concentration of both - these ions is very small so the | concentration of the undissoctated base K,=1H,O°I NHJ / INH,'] = 5.6 x 10° | can be taken equal to 0.004M. NH, (aq) + H,0() = NH,‘(aq) + OH faq) | Thus, , K, =| NH,'l OH] / NH, = 1.8 x 10% K,=(NH,NH,10H] / (NH,NH, Net: 2 H,O(l) = H,O°(aq) + OH faq) = (5.98 x 10°} / 0.004 = 8,96 x 107 K, =[H,O'll OH] = 1.0 x 10"M pK, = logk, = -log(8.96 x 107) = 6.04, Where, K, represents the strength of NH? as | anacid ambt-represents the strengih of Nii,” lem 7,22 ~ Caleulate the pH of the solution in which It can be seen from the net reaction that 0.2M NH, CI and 0.1M NH, are present, ‘The the equilibrium constant is equal to the PK, of armmonta solution is 4.75, product of equilibrium constants K, and K, | Solution for the reactions added. Thus, | NH, + HO = NAY + OH” = K,*K,=((H,OUNH,/ INH; ))x{(NH;] | Thetonization (NEL (OH / INH} | ition constant of NH, | e{HOLOHT = K, 3 UK antilog (-pK,) i.e. = (5.6x1079) x (1.8 x 10°) = 1.0x 104MAN > Qo This can be extended to make @ generalisation. ‘The equilibrium constant for a net _reaction- obtained after adding two (or more) reactions. equals. the product of 216 the equilibrium. constants for individyal reactions: Kyer = KK, (3.35) Similarly, in case of a con, jugate, acid-base, pair. ’ Ughowing one, the other can be obtained. It should be noted that a strong acid will have a weak conjugate base and vice-versa, ‘Alternatively, the above expression K, = K, x K,, can also be obtained by considering the base-dissociation equilibrium reaction: . Blaq) + HOU) = BH*{aq) + OH (aq) K,= [BH*IOH | / (B] ‘As the concentration of water remains constant it has been omitted from the denominator and incorporated within the dissociation constant. Then multiplying and dividing the above expressiori by [H'], we get: K,=(BHJOH 1H’) / (BIH) = OHH IBH') / (BIH) =K,/K, or Kx K,=K, It may be noted that if we take negative logarithm of both sides of the equation, then pK values of the conjugate acid and base are related to each other by the equation: (PK, + PK, T4\(at 298K) _ Problem 7.23 Determine the degree of ionization and pH of a 0.05M of ammonia solution. The ionization constant of ammonia can be taken from Table 7.7. Also, calculate the ionization constant of the conjugate acid of ammonia, Solution The ionization of NH, in water is represented by equation CHEMIST NH, + H,0 = NH, + oF We use equation (7.33) to calculate hydroxyl ton concentration, [OH 1 =c a = 0.05 ot K, = 0.05 a / (1 >a) The value of o is small, therefore the quadratic equation can be simplified by neglecting o in comparison to | in the denominator on right hand side of the equation, Thus, K,=¢0? or a= V(1.77 x 10°/ 0.05) = 0.018. {OH ]=ca=0.05 x 0.018 = 9.4 x 10%M, [Ht1=K, / [OH] = 107 / (9.4 x 10°) = 1.06 x 10" pH = -log(1.06 x 107") = 10.97. Now, using the relation for conjugate acid-base pair, K,xK,=K, . using the value of K, of NH, from Table 7.7. We can determine the concentration of conjugate acid NH; K,=K, /K,= 10" / 1.77 x 10° 64 x 10°. 7.11.6 Di- and Polybasic Acids and Di- and Polyacidic Bases Some of the acids like oxalic acid, sulphuric acid and phosphoric acids have more than one ionizable proton per molecule of the acid. Such acids are known as polybasic of polyprotic acids. — "The lonization reactions for example for @ dibasic acid H,X'are represented by the equations: . H,X(aq) = H’(aq) + HX taq) HX (aq) = H'(aq) +X" (aq) And the corresponding equ! constants are given below: K,, = QH'IHXD /(H,Xland ilibriumEQUILIBRIUM K,, = CHIX*) / (HX d K,, are call Here, M., and ,, led the first and jonization constants Tespectively of the aa 7 X. Similarly, for tribasic acids lke Hp. ti hnave three‘fonization constan value ts. The value the jonization constants for es of some commoy polyprotic acids are given in Table 7.8, ” gable 7.8 The Ionization Co; Common Polypro stants of Some tic Acids (298K) 64x 10° 16x10? | 64x 10% 12x10? 5.6 x 10" 17x 10° 6.2x 10% 4.0107 42x10 It can be seen that higher or ion constants (K,,.K.. are smaller than the lower ode? fontzation constant i of a polyprotic acid. The reason for this isthatit is more difficult to remove a ‘ged fe This can be séen in the case of. Temor a proton from the uncharged H,CO, as compared from a negatively charged HCO;. Similarly, it is more difficult to remove a proton from a doubly charged HPO? ‘anion as compared to H,PO;. /Polyprotic acid solutions contain a mixture of acids like HA, HA’ and A” in case of a diprotic acid. H,A being a strong acid, the ximary reaction involves the dissociation of HA, and HO" in the solution comes mainly” fomrthe- first association Step — . 741.7 Factors Affecting Acid Strength Having discussed quantitatively the strengths of acids and bases, we come to a stage where we can calculate the pH of a given acid Solution. But, the curiosity rises about why should some acids be stronger than others? What factors are responsible for making them Stronger? The answer lies in its being a complex phenomenon. But, broadly speaking we can say that the extent of dis; of an acid depends on the str ity oftre H-Abond. ~~ But it_sho: oted that while g element he same group of the 217 In general, when strength of H-A bond decreases, that is, the ie energy a juired to break te bond decreases, HA becomes a ‘stronger acid, 4180, when the H-A bond becomes more Polar i.e. the electron ice between the atoms H and A increases and there is marked charge separation, cleavage becomes easier Thereby increasing ne (Ciable. FA bong arene us polar nature. As the-eize-ofA-mncreases ‘own the group, H-A bond str group, rength decreases and” so, acid strength increases. For example, Size increases 2 HF << HCl << HBr << HI Acid strength increases Similarly, H,S is stronger acid than H,O. But, when we discuss elements in the same row of the periodic table, H-A bond. polarity becomes deciding factor for determining nana ee ee CPeases Tres: . trength of the acid also increases. For example, Electronegativity of A increases CH, CH,COO-(aq)+ Na‘(aq) Acetate ion thus formed undergoes hydrolysis in water to give acetic acid and OH" fons CH,COO"(aq)+H,00) |= CH,COOHIaq)+OH (aq) Acetic _acid_being-—o-—weale acid (k,= 1.8% 109) remains mainly unfonised in sults in increase-oLOH.jon solution. This Similarly, NH,Cl formed from wa NH,OH and strong acid, HCl, in water dissociates completely. NHCllaq) > NH; (aq) +CT (aq) ions undergo hydrolysis with Water to form NH,OH and H* ions NH; (aq) + H,0 (1) <2 NH,OH(aq) +H" (aa) Ammonium hydroxide is a weak base (K,= 1.77 x 109) and therefore remains almost Unionised in solution. This results in 219 increased of H* ton concentration in solution making the solution acidic. Thus, the PH of NH,Cl solution in water is less than 7. Consider the hydrolysis of CH,COONH, salt formed from weal acid and weak Base. The fons formed undergo hydrolysis as follow: CH,COO"+NH; + H,O 4; CH,COOH + NH,OH CH,COOH and NH,OH, also remain into Partially dissociated form: CH,COOH 4+ CH,COO” + H* NH,OH 45 NH; + OH 4 HO <> Ht+ OH Beh Without going into detailed calculation, it can be said that degree of hydrolysis is Independent of concenirguon os wes: gE 7.25 “The pK, of aceticvacid and pK, of ide are 4.76 and 4.75 © respectively. Calculate the pH of - ammonium acetate solution. ” Solution se 4 [pH = 79 MIBK “pK (2744 14.76- 4.75) 57+ 10.01) =7 + j Fo pie 8 005 7.005 7.12 BUFFER SOLUTIONS Many body fluids ¢.g.,_b] yy. ly g.. blood or. urine have de! H_and any deyiation_in. their. pH indicates malfunctioning.of the body. Te control of pH is also very important in many chemical and biochemical processes. Many medical and cosmetic formulations require that these be kept and administered at a particular pH. The solutions which, realst change in mn of ounts of are called Buffer Solutions. Buffer solutions St aero oe ri 5)