4 Chemical Equilibrium 41 42 43 44 45 4.6 47 The State of Equilibrium Law of Mass Action Magnitude of the EquiliGrium Constant Caleulation of Keq Value ‘The Reaction Quotient Calculating Equilibrium Concentrations Le Chatelier's Principle Most cherrical reactions do not go to completion; that is, reactants are not completely convert to products. Reactions Pat do not goto completion and that can Occur in either Grecton are caled reversible reactions. Reverse ‘reactions are represented by a double heacod arrow (=). The sow pointing to te rights the forward reaction, the reaction betwoon roaciais to fom the Products| The arrow painting to the lat Is the reverse reaction, the reaction Between products to form the reactants, When the rato ofthe forward reaction equals the rate ofthe reverse reaction ina reversible chemical system, he system is ald be ina state of chemleal equilibrium. 41. The State of Equilibrium How do we attain @ stato of equim? Consider a hypothetical reversible (gaseous reacton: A+B C+D ‘Suppose that we place a mixure of A and Bina dosed container. They wil eact to produce C and D. As the forward reacton occ the concentration of A end B braduelly decrease, causing a simultaneous decrease in the rate of te reaction, a8 shown by the top euve in fhe flowing pour. From the figure two Important observations can be made: fst the rate does not decrease fo zero, ‘and second, afte a time the rat loves of to a constant value, — 5 | (covers rte Time [A the start ofthe experiment, the reverse reaction cannct proceed since or Dis nol yet formed. AS soon as the forward reaction produces some C and 1, hnowaver, the reverse reaction bogins. As the concentrations of © and D increase, tho rale ofthe reverse reaction ineraates ae shown by the botiom ‘curve in te above-igur. As ime passes, if the forward rate ls decreasing and the reverse rate Increasing, eventually the two tates wil become equal. At this ‘Slate or condition the system is now in oxuideum. The tne requred to establish ‘equitrium depends on the rates of the forward and ravers reactions, which, "urn, depend onthe nature of the reactants andthe condone of te reacton a‘There are three conditions that are found in every equilibrium system: 1. The equiltrium is dynamic. The dvval molocues are continually reactng even though Pe overall composition ofthe reaction moture does rot change, 2 Av equllorum the concentrations of ll the substances are constant but ‘not necessariy equal 8. The oqulibrium system is “closed - ciosed in the sense that no ‘substance can enter or leave te reaction vessl 42 Low of Mass Action ‘The law of mass actian states tt ‘when 2 reversible reaction has attained ‘equilbum at 2 given temperature, the product of the molar consentations oF the redocts divided bythe product ofthe molar concentrations of he reactants with {each concerivation raised to a power equal to the cosfcen! in te balanced equation, is @ constant." This constant is refewed to as the equllbriom constant, Keq. Thus, 0 he equiloru system aArbe a= cored ‘he expression fr he equitium consent i _(cror Aner “The brackets, [in his expression inicate equilorum concentrations in moles periter ‘The thermodynamic defiriton ot the equllbrium constant involves ‘ctviies rather tan concentrations. The aciviy af a component of an Wel Iiure is the rato of its concertaion or partal pressure 10 @ standard ‘concontration (1 M) ar pressure (1 aim). Because of the use of activites, all uns ‘ance! and the equilpeum constant has no unis: the values we put into the Ke are nanercaly equal © molar concarwatons, bx are dmensonss, tat ive no units [An equlibnum sysiem may involve species in a single phase. Such system is referred to 36 homogeneous equiliorlum On the other hand. 2 ‘equiltrium system that involves species in more than ‘ona shes is called ‘quilbrium “Terms for pure saide and pure hquids in a Ineterogeneous equbrium are nat cluded in the Keq expression since the ‘sett for pure sols or aids i taken as 1 ” 4.3 Magnitude of the Equilibrium Constant ‘The magnitude of Keq isa measure ofthe extent to which a reaction occurs. For ‘any reaction, the value of Keq + varies ont with temperature + is constant ata gwen temporature ‘is independent ofthe inital concentrations Knowing the value of Keq is important since it tls us the relative amounts of the reactants and products formed at equlibrum, and hence the yeld of the reaction ents + Alarge vale of Keg indicates that at equirum, the forward reaction @ fs favored thas, mos ofthe reactants ae converted wf progucs +A small value of Keg inccates that at equilibrium, the reverse reaction @ (ESE ation of to onctons romonn wrresced tony ‘small amounts of products are formed. 02H gen « fm ‘The numerical value ofthe equilbrium constant is determined by substtuting te squliorum concentraons, n molester. of the reactants and product into te ‘Squlibrum constant expression 446 Calculation of Keq Value Example 4:1 Consider the reversible gaseous reaction: 20; + Q; =—*2 S03 at 1500. Suppase 0.40 M of SOz and 0.20 M of O: are injected into @ closed container When equim is established, we find that 0.344 M of S02, 0.172 M of O2 and (0.058 Mot SOs are present. Caleuate the Keq for the reacion at the same temperature, Solution: ‘We re-wite the reaction, showing the equilibrium concentration of each reactant and product, and then solve forthe Keg value 2802 + Or = 2805 [fo] 034M 0.172M 0.056 (S03? (0.086)? = eet ee hs [80,7103] (0.344) (0.172)Example 4.2 For the gaseous reaction 2$0: +0; =—* 280s Keq=0.15 23) Stppose we wet the equation in fevers, what wil be is eauirian constant ‘Answer: The equiirium constant for he reverse reaction isthe recirocel ff the equlibrum constant fer the coginal reaction. Thus, forthe reverse reaction 280s ==" 2502 + Os (soy 1 Sie ey (S07 Keg au 1b) Ifthe equation forthe reaction were writen a& SO; + Oz == 80s, what willbe its equitrium constant? “Answer: If the coefficients in an equation for a reaction are increased or ‘decreased by a number, n, then the orginal value of Keq is raised to the nth power. Comparing this equation withthe orginal equation, we see thal ‘ne coofiionts are decreased by %. Thus, % {803 {802} 02)" keg! = (@.15)* = 039 Example 43, ‘At S00 K, 1.0 M of nitosy! chloride, NOCI, is introduced into a container, At fequilbrum, the NOCI is 9% dissociated. Calculate the Keq at 500 K for the ‘gaseous reaction 2NOCI ==" 2NO + Ch Solution; To help us analyze the data, we prepare = reaction summary which Consists ofthe inital concentrations], the changes in concentrations due tO Feacton [c,and the equilfrium concentrations [e). The values for tne middle row ‘are sways based on the stociometnc relatonshp among the reactants and prodtas. 2wocl == 20 + Ch uu ‘om ° ° fe =009{10)=009 +002 +a. el 19 NOP ICH] (0.097 (0.048) a aaxict Noo "(ast % 48. The Reaction Quotient, Q For the general reaction QA+ DB ge cc + aD ‘he reaction quotient, Qs given by the expression (cf (OF arier "Note thet the cesction quotient has the seme form as the Keq expression. To Calculate the , the ® taken are inserted into the 'By comparing the values of @ and Kea, \we can determine whether Or nota system is already in equilibrium, and # itis Tol, we ean also preset the ciection which a reacbon must occur to greater ‘extort inorder to estabish equim Fora gwen reaction, a= + Q eq: The reverse reaction (« —) must occur to a greater extent ‘than the forward rection for equsibeum to be established © = Keq The system is aleady in equiltrium, so no futher net Feastion scours Example 4.4 Forthe gaseous rescion 2HF =—® H, + Fr, Keq=1.0x 10" at avery Noh temperatura catain time the folowing concantaions were detected (H] = 0150 M,(He} = 1.0 x 107M, [Fa] = 40 x 10% MIs the system in equilibrium? If net, what must occur for equievium tobe established?” Solution: To answer the question, we must solve for the value of Q and compare it withthe valve of Kea, (alta cag (1.02109) 40% 10%) “eee 18x10 (os0FSince Q > Keg, the system is actin equilibrium. For equilibrium to be ‘established, the value of © must decrease unt equals Keq. This can happen nly i the’ product concentrations decrease and the reactant concentration inoreases. Thus the reverse reacion must occur to @ greater extent than the forward reaction 46. Calculating Equilibrium Concentrations {Gon the Kea for a particular reaction, we can calculate the concentrations of all the. species in the. equilbrum modure. In most cases, only tho inl ‘concentrations of either reactant or product or both are given, In this case, we ‘8a Use the folowing approach to determine equistium concentrations, + Wet the reaction summary. Remember that concentrations must be ‘expressed inf. ‘+ Setup the Keg expression and solve for the value of x ‘+ Caleta the equirium concentrations of ll species. Example 45 * For he gaseous eacton PC + Ch ==F PCk, Keq= 1.9. fan equilibrium rmture na flask contains 0.25 M of PCl and 0.16 M of PCS, what is the ‘auitrium concentration of CL? Solution: Pob + Ch =? Poe [el 016M 7M 025M (rota Keg = ——— (Pon (eal (025 ws (016) (0) [oy = oem Example 46 For the gaseous reaction, A + B a=t C + D, Keq= 49 at acertain temperature If 0.40 mol of each A and B are placed in 2.0-L container, what concentrations of ll species ae present at equi? Solution: First, we convert the intial concentrations of A and B, fom moles to ‘molester or Molar, then set-up the reaction summary {al = 040 movz.0L [B] = c4omei20L ‘The reaction summary is oz0m 020M A + 8 = C+D 020M 020M oo ‘a-x 0z0-x a (1 wel 00 x ee Oe (020-9 (020-») (020-xF “Tis equation has a perfect square’on both sides. We solve for x by taking the quare roots of Both aides ofthe equation and then rearranging fo x. 10 = ‘The oauiorium concentrations are {Al = [8] = 0.20-0.175 = 0.025m [C] = (0) = x= 0175MExample 47 Consider the same reaction gven in example 4.6 at the same temperature. if (0.60 mol of A and 0.20 me at 8 are mixed in a 2.04 container and alowed (o reach equilrum, what are the equbrum concerrabons of al te species? Sotution: 0.60 meu20| 0.20 mov20 030m ww 10m eee oe ere | 0 30m * o10m 070 ia 10 we 00) a =>) (030-% (0.10-%) We can simplify the calcaton it we neglect he x term in the denonator by assuming the value 0.3 x= 0.3 and 0.1 x= 0.1 Ix is legs than 8% ofthe Initial concentration from which x fs to be subtracted, then the assumption 's valid; IIs greater than 5%, the assumption is not vad 00) (0.80) (0.10) 147 x= 124 5% of 0.3 and 0.1 aro 0.015 and 0.005, respectively. Since the value of x is more than 0.015 and 0.005, and higher than the iniialeoteantaions rom which iL must be subtracted, dhe assumption is ot valid and we cannot use te _Sinpiiving method. Proceeding rom tne crignal equation. 2 4 GAD K+ 0.080 f= a0 198K4 147 488-198 x+147 = 0 ‘Since this is the quadeatic equation: x? + bx + © = 0, we can save forthe value ‘of xby using the quadratic formula fac on /F 2a Inthis case, a = 48, b= -196, ¢ 1.47, Solving fr x gives us: 0.31 _M (not possible) .000M (answer) ‘The eaullrium concentrations ace IA] = 0.30~0.099 = 0.201 m {B] = 010-0109 = 0.001 M Io} = (0) = x = 0099m 47 Le Chateliers Principle ‘Once a reacting system has reached equilbium, i remains in equirium unl it is cisturbed by some change of experimental conditions. The guing pringpla i known as Le Chatelle's Principle, which states that "fa Grange of condtons (stess) is applied to a system in equim, tho systom responds in a way that ter to ten ha abenaenbung snow sie of cqisnan To sacs tha aens he sion doo be popoalo gl wats ene Let us now see how Le Chatoie’s principle predicts and explains how 2 {system in a state of equilrium reacts to ferent svesses. There are four types (of stresses to consider: changes in concentration, changes in pressure, changes In temperature, end presence of catalysts. 41. Changes in concentration more of any reactant or product is added toa system in aquirium, the stress Is reieved by shifting the equllbum the direction that consumes or decease some ofthe added substance, Suppose that we have 2 system in equitorum: Hig) + 149) =F 2 Hg) {and we increase the concentration of Hy by adding more He o the system. The ‘uitrium is cstubed, and Le Chatelie's principe bogs to apply. The system ‘wil react in a way that will decrease the concentaion of Hit can do tat by Using up some ofthe Hs (and some fp a5 wel) 0 form more Hl. The poston of 8cequitbrum is said to have shifted tothe right. When equilibrium is established ‘gain, the concentration of HI wil be higher than it was italy IF the concentration of HI is increased by adding HI to the system, the postion of eculiium wil sv o the lef. in tis way some Hl wil be used up {When equilrium is astabished again, the concentrations of Hy and I, wil Be Figher than they wore italy Removal of one of te substances from an oqullxium system wil also cause the postion of equilbrum to shift If, for example, Hl could be removed, the positon of equlldrum would shit to the night. Additonal HI would be prodtced and the concentfaions of He and Is would decrease, ‘Whether equtorium is shifted to the right o ef. the value of Keq remains the same because Keq is agan satisfied by he concentrations ofthe reactants ‘and products atthe new state of equiloium sn summary Tecbinatin Sha] Steston MPI eae! oT ght ‘eoreace ra] [i [decrease (Hel or Let us now ilusrate the effects of concentration changes fo & system that \sina state of equiibrium Example 48 ‘Some hydrogen and iodine are mixed at 229 °C ina container. The reaction is fr th. a—* 2 HL When equllrum is established, the Tolowng Concentrations are present (Hs) = 0.08 M. [I] = 0.05 Mand [HI] = .50M. iran ‘adaitonal 0.20 M of HI is then added, what concentrations of Hs fa and HL ail be present when the new equilibrium is re-established? What is the new Keq vane? Solution: Hoo +k = 2H tel 006M = 008M SOM “The value of Keg from the fist st of equitrum concentrations is 2 oa al) ‘When we add 0.20 M of HI to the container, the [HI] instantaneously increases by0.30 M and he new inal concenvations ar: (0507 (0.06) (0.06) Meee ae (2H o 005M = 0.06M 80 +03=080M ‘Since we sed HI to the systom, the equltxum shits othe lef, indeating that ‘he [Hl] must decrease. The naw action summary is: Hoot bk =e 2H {row ini) 0.06 005M = osoM [change] x +x = 24 (pew eaulibrn| 0.08 +x 5 aE ‘Substitsion ofthe naw eaultrium concentration values into the Kea expression lows us to evaluate (000-247 (0.80~24)° (008 +x? ‘Ths equaton hes @ perfect square on both sides. We solve for x by taking the _square roots ofboth sides of he equation and then rearranging for x 080-2 cy (0.06 +3) (006 +x) ast = ———— (005 +5 0.4986 + 8.31% = 080-2 soa%x = 09014 x = ag2e2m ‘The new equilibrium concentrations are [Ha = 005+0czs2 = o.ossem {i}. = 006 + aaa .0882 M [hi = 080~2(0.0292) = 0.7416M ®‘Note that when HI was added tothe system which is aady at equltrium, the reactant concentrations increased, and the product concentration decreased when @ now state of equilibrium was re-established “The Keq at he now equim sate is ar (arate? [Halli (0.0882) (0.0882) ‘This value isthe same as the original Keq forthe reaction 2. Changes in pressure +68 changes in pressure do not affect conceniratons of solids and liquids but thoy signieant affect concentrations of gases In general: + An increase in (decrease in volume) shits the equiltium in {he drecton that produces the smaller numberof moles of gas. Recall that gases exert pressure, therefore, the less moles thal are preset the lass ne pressure. +A decrease in pressure (increase in volume) shins the equitrium in {he drecton tat produces the larger number of moles, + there are equal numberof moles of gaseous reactants and products ia reaction, reser (oure) change does re ale! he poston eauionn, ‘Tose changes apply only when pressure changes are due to volume changes. \When an inert gas is added, there isn effect on the equitum postion The ‘sdoton of an inert 928 Increases the fol pressure but ae np eect an the {ancontrations or partial prossures ofthe reactants or products Thus the system emai at ho ongnal equabriun positon Lotus now consider he folowing gaseous system in equim 2049) ==* 30:0) ‘We can sumarize the effect of pressure changes on this system: [sree rest on (RMP pressure increase [iereasesidecresses | Tomas he Temains docoasosinecoases [rsa cozone Example 49 redist the direction of shit reauling fem pressure decroase inthe eauitium system: 280g) + Ox) == 25039) ‘Anewer. in Ye aiven reaction, the reactant side has three moles of gaseous Teaclarts (wo SC) and one 03, while the product side has two moles of SOs, To Increate the tote! numberof molecules ans hence the pressure, the aquirium ‘must shift the let o inthe reverse rection Example 4.10 Predict the cretion ofthe shift that wil cou becavee of volume increase in ‘he equium system: Palo) + Chia) ==P 2 HOI) ‘Answer: There wil be no shif because each side ane equation has two moles ‘of gaseous molecules. Example 4.14 Forthe gaseous reaction NiO, =—F2NOz at 22°C, tne Ken's 409 x 10% 2) I Gad ma of NOs were injected info a closed 1.0-L container at 22°C, haw ‘many molar of each Gea would be presen at equiitium? 1) Ite volume were halved to 0.20 Lal constant temperate, how many molar of each gas would Be Present after the naw equiliiun has been esablsned? c) What s the new Kea, value? onion: ‘3 Viewrie be ronchn sna og, : Rue Te ano, 1¢ oe . Seon woe Oe eee doe oa” aso sng te splat, we ensure at 807" 3 80. Then a aaoxt08 = a8 0.03. fasta eld) sone eat kl ‘Since 0.03 is les than 5% of 0.80, the assimption is valid. Therefore at ‘auibrum, the concertrations are: [Nog = 2=2(005) = 005m [Ni04 = 080~x= 0180-008" 077M When the volume of the reaction vessel is haved, the pressure is doubled, snd ne cxcontalans ae biog Ts, fo now mal corcantatons of NOe ‘nd NO; are 30.77) 0.06) = 42M, respectively ag, NDe Ft 2NOs bi Tom neg {new itil 150M sem th oo, “Totter he cinco nvtich re reacion mist oo 9 grat’ een crear anata ner ie cf egaon, we scctnae Bees ne kl cSrenetone noe essen aie @ Teens suey nen ers 9 hug revere * [NO3 Gig station © Tog” ae Wea thea Because Q > Keg, the reaction must proceed othe Ig to establish a now stato) of equilibrium, a (ore 3 “The new reaction summary i NO. === 2NO: evens) 154M se 1 i Se } feet a a ee od (No. eq = IN:O4 (12-297 466x109 = aa 42 0.404 + 0.0144 ARO x 08 1Shex 42-048 +0.0144 = 7:176x 10" +406% 10% ‘8 —0485¢ #7224107 =0 We can solve forthe value of x by using the quadratic formula => (Pome 2 Intiscase, @ = 4 0.485, © = 7.22410" Solving for x gies us x= 00174 M “The new equivium concentrations in the 0.504. container sre [Nod = 012-2x=0.12-20.0174) oes IN04 = 1544 440.0174 = 1.5574 ©) The now Koq value is: wor oom? “exit aa = oseiwe) GREE, (Noy 18574 : ) Ete she Tog resut sno at change in presse does not change te vain of he ‘3. Changes in temperature ‘The shit in equlinum caused by changes in temperature wil depend on “whether the reaction as writen i axatnermic or endofnenmsc Foran Teaction, heat can be considered as one of the products; therefore, when the tempera is increased. wil have the same efectos mreasing one or 078 of the products. The equirium wil shift o the left in order to voleve the toss ‘on the system,Consider the equation forthe syiness of ammonia at 25 °C, which is an ‘exothermic reaction N+ Sip sat 2NK + Ifthe temperature of the system is increased, the poston of equiltrium wil shit to the lof Ae a result the concentration of NH, wil decrease, the concentration (f Nr and Hz ill ncoase, and tho Koq value wil decrease, Iho tomperature Is creased, the equlirium wil shit to the right the concentration of NHs will inerease, the concontation of Nz and Hs wil decrease, and the Keq value will increase, Those efecs are summanzed inthe folowing tbe: ‘order to raieve the stress onthe sytem, Consider the folowing equilbrium system, which is an endothermic reactor 2 4 COr+ He s=* CO+HO Ifthe temperature ofthe system is increased, the postion of equilibrium wil shit to the right. AS a result the concentraton of CO and HO wil increase, the concentration of CO3and H wil decrease, and the Keq value wil increase. ifthe temperature is decroased, the equitorium wil sh to the let, the concentration of (CO'and H,0 wit decrease, the concentraton of CO> and He wil ineroaae, an the Keq vale wil decrease. These effects are summarized nthe flowing taba \Witn temperature changes, note that along wih the shi in equrium the value (of Koq i also changed The equllbvum constant has a particular value only at ‘one given tomporatre; therefore, at other lemperatures, would have acfferent value Example 412 Predict the dcection of the shit because of @ temperature increase in the quis system: POk(a) ==F PCW) + Clfa) +925 Kd ‘Answer; The equllrium must shit in the reverse direction to use up, oF consume, some ofthe heat that was added, Example 413 Predict the diction of the shit because of @ temperature decrease in the ‘thermal decompostion of limestone: Cacoys) + 176kI ==F Cad[s) + COxe) Answer: Reduction in temperature is interpreted as removal of heat. The ‘equlbvitn wil shit inthe reverse direction to repace some ofthe heat removed 4. Addition of a Catalyst We know that 2 catalyst enhances the rate of 2 reaction by lowering the rwacton’s activation energy. However, a catalyst lowers the acvaton energy of the forward reaction tothe same extent asi lowers that forthe reverve reaction, “This means that both the forward and the reverse rates are affected to exactly the same degroe. Wo can therefore conclude that the prosonce of a catalyst ‘does not afer the equilerium constant nor does it shift the poston of an fequiibrum system. ‘Adding catalyst lo a reacion mixture that ie not at fequitbium wil speed up Both the forward and reveree rates to achieve on fequitcium mixture much fester. The same equilixium mixture could be attained ‘without the catalyst, but we might have fo wait much anger fer it happen ©[Sescnaumber pr a eee se ee Exercise 4.1 Keg Expressions 4. Write te equitrium constant expression, Kea, for each of the folowing feacions 8) CO) + Hug) ==E COW) + HKG) ») 2H) ==E Hua) + Bes) ©) SCOvs) E=* SOK) + COM) 9) Pég) + 305) =F PAOu®) ©) 2NOsa) == 2NOG) + Ove) 2. On the basis ofthe given oqultxium constant values, choose he reactions in ‘which te produc are favored by enoeling the leer ofthe comect answers 8) NH(eq) + HEO) ==F NHAYaq) + OFea) Koq= 18x10" b) Aviad) + 2CNaq) =F (AUCNDI oq) Keq=2x 10 ©) PDC:O46) == PEeq) + 6.009) Keg = 44 OHS tea + Hag =F Hie) Keg = 1.0107 3. On the basis ofthe equilibrium constant values, choose the reactions in which te reactants are favored by encrling the leer ofthe conect answers, 2) 1:09 =* Haq) + OFF (a9) Kog = 18x10 DIA ag === A%eq) +6 Fea) Koq= 2x10 ©)CaxPOdus) FF 3Ca%eq) + 2POM aq — Keg=1x10* ) 2Fe%eq) + 28%eq) at Feiss) Keg= 1x10 [Seat Number: | [a Exercise 4.2 ‘Determination of Keg Value ‘1. Consider the folowing equim process at 700°: 2H + Sse DHS. ‘Analysis shows that thre are 25 moles of Ha, 1.35 x 10° mole of Send 8:7 moles of HsS present at oqulbrium in a 124 flask. Calculate the equilrum ‘Constant, Keg forthe reaction. 2. The equilibrium concentrations forthe decomposition of phosgene, COCh, Coch == CO + Ci fare [COOL] = 014M, [CO}= 1.2 x 107M, [Ch] = 0.054 M. Caloulate the Kea. 3. You ae given the following reaction andits Keq ata given temperature ‘DHBr* Cl e—= 2HCI + Bry Koq= 40x 10" Celtte the value ofthe Kod fr each of he folowing a the same emperature ‘a. 4HGr+ 2Ch eae 4HCl +261, bo HBr + 4ch =e HCl + Br © 2HCI+ Ba == 2HBr+ Ch 34. At a conten temperature, 0.074 mol of PC; was inttoduced into a 1.04, Container Forthe reaction PCl; == Pl + Cl, the concentration of Cis at equilriam was 0.05 M, What isthe Koc? 5. 10.08 mol of SOs is placed in a 1.04. container at 1000 K, 36.7% ofthe S03 's dissociated when equibrum is established: 280s ==? 250: + O2 What i the Keq value at 10007 8. NO and 0; are mixed in @ container of fixed volume kept at 1000 K. Their inital concentrations are 0.020 M and 0.030 M, respectively. When the reaction 2NO +O: g—e 2NOs has come to equim the [NOx] 8 2.2x 10" M Calculate the Req forthe reaction Exercise 4.3 Qand Keq Forthe equiitium AHCI +O; ==* 20h +2 HO at 480°, og is 889. 10.090 mol of HCI, 0.620 mol of O>, 0.080 mol of Cl. and 0.070 mol of H20 are mixed in @.04 container, in what direction wil the reaction proceed? For the equiltrium CHe + Hs == CO + 3H) at 1500°C, eq is 5.67 I 0.020 mol of CH, 0.080 tol of H.0, 0.030 mol of CO, and (0.50 mol of Hare mixed In 7.04 container, in what drecon wile reaction proceed? For the equiitriun Nz + Os =—t 2NO at 1800 K, the equlriam ‘constant, Keq is 1.2 x 10H 0.060 mol of Ns, 0.075 mot of Os, and 0.00025 mol of NO are mixad in a .0-L Nask. in what dracon wil the reaction proceed? 9sExprcise 4.4 Determining Reactant and Product Concentrations 14, The equitrium constant Keqiorthe reacion He + Bre == 2HBris 2.18 x 10% at 730 °C. Starting with 320 mol HBr in a 12.01 reacton vessel ‘aleulate the concentrations of Hs Bre, and HBr at equim, 2. The dissociation of molecular odin into acne atoms is resent 2s os 2 [A 1000 K. the Keq forthe reaction is 3.80 x 10°. I you stat with 020456 mol of Taina 2.204 flask at 1000 KC whet are the concentrations of Ts molecules and I atoms at equibium? 7 3. Forthereacton Hy + £0, Z=* H:0 + CO Kea is 42 0 1650°C. Inia, 0.80 mot Hy and 0.80 mot COs are jected ino a 5.04 flask. Calciaie ‘hs concentration of each species at equliboun, 4 Forthereacion He + Iss 2HI the Keqis S43 420°C. Athe start of te reaction there are 0.714 mol of Ha, 0.954 mel of ly end 0.886 ma of Hin & 240+ reacten chanber Calcsate the concenrains of he gases st ‘uit,[Scathunbor ED ieee cece Bagrcise 4.5 Le Chateliers Principle Kaaba toe can crt) urcon tama econ wt follows. 2 NaHCOye) Na,COss) + COz + H:0. Would we Shain more COs and 120 by dking entra bang soda tote easton Mtre 2) 2 dosed veseal. ban open vessel? Explan your chee 2. Consider the following equilrium systom™ SO + Cle ==* $0:Ciz Precit how the equlxium position would change, at constant temperate, 3) Clewore added toe system ) 80:0 wore removed fam he system 1) SO: wore removed fom the systom $3. Heating sold NaHCOs ina closed vessel stabishos the folowing equirium: 2NeHCOys) =F _NaxCOns) + CO, + H:O. What would happon to the ‘quilerium posivon fat constam tempera, 2) some ofthe CO, were tmoved fm the systom ») some Solid Na.CO, wore added othe sysiom 4, Forthe aquirium Nz +O; == 2NO_Koqis 4.08. 10~ st 2000 ‘and 3.60. 10" at 250K. the reacian a6 wien exothermic or enaotheric? 5, Forthe system NiQW CO =F Nie) + COs Kegis 4543 10° ‘8998 K and 1.58 x 10" at 1125 K. is fo reaction as writon exothermic oF ‘endothermic? 6. Thereacton CH + 2H:S =F OS) + 42 feanentothermic process. What wil happen to 2) [HS] l tomers is increased? B) [Hil CS; is romoved? 6) ICH) pressure increased 7. Theresction NiO) + CO = Nig) + CO; isan exothormic process ‘How would each of the following changes affect the positon of fault? 1} decroasa the temperature ) decrease the pressure ©) add NO. 1) ad a catalyst Problems on Le Chatelir's Principle Exercise 4.6 4. Consdr the fon aaultrum proces a6 °C 1 eee ores ger ee so caution creates fhe racing seties ae (CO) [Ha] = 0.045 M, (CO;] = 0.085 M, and (H.0} ®: iat 050 M, (040 M. 2) Calculate Keq for he reaction. b) ithe concentration of CO; were raised to 0.50 M by the adton of CO, what would be the concentratons of all the gases when equlibim reestobished? 2 Given A+B 3% C+D. a) Atequilbrium 21.04 container was found to conan 1.6 moles of C, 1.6 moles of D, Od mole ofA, and 0.4 mole Of B, Caleuate the Koq forthe reac, 'b) i 0.2 mole of B and 0.2 male of C are added to this system, whal wil be the new equliorium concentrations of A? 2 Given: A ==> C+D. a) Whenthe system s in equiltrium at 200 6, the conesrirations are found o be: [A] = 0.30 M, (C}= 020M. and [D}= (020M Calculate Keg. b) Ifthe volume ofthe container in which the eystam ie in equiivium is suddenly doubled at 200°C, what will bo the new equilibrium concentrations”?