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1 NAME:~ ~.. PERIOD: CH 13 HOMEWORK. a. Read CH 13 b. Review your notes. c. Answer the following: 1. Characterize a system at equilibrium with respect to each of the following: (a) The rates of the forward and reverse reactions. (b) The overall composition of the reaction mixture. -Jk. ~ ~ 1:;tK.t ~..~~ ~.~~ ~~!t-o ~~~.&m~.. 2. Is the following statement true or false? "Reactions with large equilibrium constants are very fast." Explain... J~ - ~ cwi ~-J ~ ~~ 1Q?1. CWt.~ In one experiment, 1.00 mol H 2 0 (g) and 1.00 mol CO (g) are put into a flask and heated to 350 C. In a second experiment, l.00 mol H2 (g) and l.00 mol CO 2 (g) are put into another flask with the same volume as the first and heated to 350 C. After equilibrium r: is reached, will there be any difference in the composition of the mixtures in the two flasks?.. I.. ;Jo) 1:k ~ 'A- rm~ AAl/t0t ~1. Jk. ~~ ~.La~. u4 ~ ~~-Jk~ ~~.~h4t 0j~~ ~ wd/l ~ C0n~ 1~J4.(kvl ~. --_._--_

2 6. Write the equilibrium expression (K) for each of the following gas-phase reactions: (a) N7 (g) + O2 (g) <-72 NO (g) - ~ K:: [NO] [tja J [Oa J (b) SiH 4 (g) + 2 Cl, (g) <-7 SiCI 4 (g) + 2 H2 (g) [S~cJ~ ] (W~ J K..: -lsll~4 JTCJ.,J d 7. At a given temperature, K = 1.3 X 10'2 for the reaction.:it N2 (g) + 3 H2 (g) <-7 'S. NH3 (g) Calculate the values of K for the following reactions at this temperature. (a) lj, N2 (g) + 3/2 H2 (g) <-7 NH3 (g) I ~ -~) y~ 1< i: 1< = (1."3 y. I 0 = (b) 2 NH3 (g) <-7 N2 (g) + 3 H2 (g) " I k :: K = (c) NH) (g) <-7 Y, N2 (g) + 3/2 H2 (g) 1<' z: (-' )Ya _ (,~) Y d ii.. I< -.ot3.: 2,), (d) 2 N2 (g) + 6 H2 (g) <-74 NH3 (g) I () bl 1\:: 1< :: ---"-'~--=-~7, (.013) t At high temperatures, elemental nitrogen and oxygen react with one another to form nitrogen monoxide: N2 (g) + O2 (g) <-7 2 NO (g) Suppose the system is analyzed at a particular temperature and the equilibrium concentrations are found to be [N2] = M, [0 2 ] = M, and [NO] = 4.7 X 10'4 M. Calculate the value ofk for the reaction. Lr-lO]J ("f.7x/o-,);j l - - (.041)(.0018') ---~~- -,-~-- ~,

3 9. At a particular temperature a 2.00 L flask at equilibrium contains 2.80 x 10-4 mol of Nj, 2.50 x 10-5 mol of O 2, and x 10-2 mol N 2 0. Calculate the value of K at this temperature for the reaction: 2 N, (g) + O 2 (g)... 2 N 2 0 (g) 11-.\"2.. 0 J z:.:..9!- L dloo =.0\ M :: (.0 \) a -4 ~,?o ' ' «.00 [0<; J s: = d. $0"1(/0 -.5 OJ. 0 V -s I. ;} S Y. 10 f'1 10. Distinguish between the terms equilibrium constant and reaction quotient.. vkrj.h=tl JI4AJ(.xlv. ~",'\IZ r~'do, I( ~.~ 7~u~t-. t) ~ ~d ~01 G.A»t vwjl ~ ~, Q1-o ~.Xc ofdta/mw Mw- ~..uti. ~. M~A~~. 11. The magnitude oftlie equilibrium constant is related to the tendency of a reaction to occur. Explain. '-.IN m~~ f( ~.f.a-ij.~ tl-.~ Iuw ~~ ~ o-t ~U a1." -0, IJ~ k' A-o krfj'~ ck ~. tj~ I(~ ~) ~~. 12. For the reaction. Hz (g) + Br2 (g)... 2 HBr (g) K, = 3.5 X 10 4 at 1495K. What is the value ofkp for the following reactions at1495k? (a) HBr (g)... Y, H2 (g) + Y, Br2 (g) I (.s: ) Yi)., Kf '" Kp = --{ 3. S X loll (b) 2 HBr (g)... H2 (g) + Br2 (g) I I I l<p = I<p = -3-. S-y..-,-O<{ (c) Y, H2 (g) + Y, Br (g)... HBr (g)

4 13. The following equilibrium pressures at a certain temperature were observed for the reaction: 2 N0 2 (g)... 2 NO (g) + O 2 (g) PN02 = 0.55 atm P NO = 6.5 x 10-5 atm PQ2= 4.5 X 10-5 atm Calculate the value ofthe equilibrium constant K, at this temperature. 1«.: (P~o ) (Pez. ) ( PtJ:l. )..-~ LJ :: ~,3 X/O ~. -_. ~ At 25.0 o C, K = 3.7 X 10 9 for the reaction CO (g) + ci, (g)... COCh (g) Calculate K, at this temperature.. ~f.: I«RT)O~ 0 (3.7'<IO q )[c.okji)(.,l.qg)j-' L~. = S X At 1100 K, K, = 0.25 for the reaction 2 S02 (g) + O2 (g)... 2 S03 (g) Calculate K at this temperature. I<f.: K (RT) t> 1\. ~ S.: Kl(. o~;2 I) ( /I co) J -I 16. Write the expression for K for the following reactions: (a) P4 (s) + 5 O 2 (g)... P40 lo (s) I (b) Sg (s) + 8 O 2 (g)... 8 S02 (g) S' [SO~J S' [O~J

5 ~ Write the expression for K, for the following reactions: (a) 4 K0 2 (s) + 2 H 2 0 (g)... 4 KOH (s) + 3 O 2 (g) I<f.: (Po. ) 3 (Pt-\~())l. (b) CO 2 (g) + MgO (s)... MgCO} (s) I 18. In a study of the reaction At 1200 K it was observed that when the equilibrium partial pressure of water vapor is 15.0 torr, the total pressure at equilibrium is 36.3 torr. Calculate the value of K, for this reaction at 1200 K. Hint: apply Dalton's law of partial pressure. p I~ D P ) Uz.O': 7W =.olq13~8l(j.f ftilr s: Hzo" r I-It = IS.Ot PH1. R-I1.:.;2(.3 :. O~KOJ-"~IS9 7~O P I - h =.J I. 3 k z 4 (. OJ~oJ.~3'Sq) (.01 q 13<O~<.( ~t) '1 :: 19. The equilibrium constant, K, is 2.40 x 10 3 at a certain temperature for the reaction J.J..c...{OX 10.:: [1J1.] [Ol]. - 2 NO (g)... Nz (g) + O 2 (g) ltjo ]J. For which of the following sets of conditions is the system at equilibrium? For those that are not at equilibrium, in which direction will the system shift? (a) A 1.00 L flask contains mol NO, 2.00 mol N 2, and 4.00 mol O2, (.2.0)('-1.0) Q z: (.0;;)1./)2. t.36 X 10" (b) A 2.00 L flask contains mol NO, mol N 2, and 4.00 mol O2. (.03.J.) (t:j,o) DI Q z C. Ol~)~ :: J. SO 'f..10 Q < k (c) A 3.00 L flask contains mol NO, 2.40 mol N 2, and 1.70 mol O2. (.~O)(..sl) I. I x. I 0" (,OJ.O),;(

6 20. The equilibrium constant, K, for the reaction H2 (g) + F2 (g) r-+ 2 HF (g) Has a value of 2.1 x 10 3 at a particular temperature. When the system is analyzed at equilibrium at this temperature, the concentrations of H, (g) and F2 (g) are both found to be M. What is the concentration ofhf (g) in the equilibrium system under these conditions? f J ~ K =- Cl;!=")~ 3 (.;l.i~i03)(.ood.i)(.oo~') =LHF s: J., XI 0 3 6/.1)(10 t: [1-\;).1 [P~) {(J.t. 103) (. OOJ-I).;I. s: [HFJ ~ [t \FJ (.OOJ.I)(.OO;J.I) = [HFJ 21. A 1.00 L flask is filled with 2.00 mol gaseous S02 and 2.00 mol gaseous N0 2 and heated. After equilibrium was reached, it was found that 1.30 mol of gaseous NO was present. Assume that the reaction S02 (g) + N02 (g) r-+ S03 (g) + NO (g) occurs under these conditions. Calculate the value of he equilibrium constant, K, for this reaction. SOC! fa) + fjoz. (j);;;::5? S02.~) + ;.JOey) I J.Oo rl.oo 0 0 C /.30 f.10,10 (.30 /.30 [So:?] [#.1oJ ( 1.30) (1.30) e = [SO~J [NOd] (.70)(.70) L3 ~ At a particular temperature, 12.0 mol of S03 is placed into a 3.0 L rigid container, and the S03 dissociates by the reaction 2 S03 (g)... 2 S02 (g) + O 2 (g) J,00 'l>'\u.e SOa ~J 0:1 I C I: At equilibrium, 3.00 mol of S02 is present. Calculate K for this reaction. J S03 (j) ~;J SO;},;;) +- 0 d- ~) ~,O 0 0 -"I +)( t- ~ A/-x 'Y V I" //~ [SOB] Q.4 = 3.06 "".Q o 3.ooL :.; (,DO M (SO;}] z, \:'S03Jo? ro~) (1,0)2.(.5) ( 3, 0) ~ z:

7 I. c E 23. At a particular temperature, K = 3.75 for the reaction SOl (g) + N0 2 (g) ~ SO) (g) + NO (g) If all four gases had initial concentrations of M, calculate the equilibrium concentrations of the gases. SC.:t (~) +,JO.l.lj) ~ SO~~) + JJO fj).~.~.8.~ 1< ~ [SO.5) [NO] [SOa] [tjo] ~+ JC, 8'-"'1. :: I,9 J" l{q (to? 3 ; 3. 7~.:: + '"X.&'-+X 8-+'X = I.S4~,q33g- I.Q3ib4QI1073y. (.8+(()(.8~ '"X) (. ~-.., ) (. g - X) [S06J: [flo~j :;. ~ _. Ol.rnJIIl ~ ~ \. Sl/SI'1 I.:?Q3('4QI(,1?J'}C ::- ;7I./Qrq333<t5 X ::c. oj Ss I 3 ~ IllS 24. At a particular temperature, K = 1.00 X 10 2 for the reaction. H 2 (g) + 12 (g) +-t 2 HI (g) In an experiment, 1.00 mol H2 and 1.00 mol h and 1.00 mol HI are introduced into a 1.00 L container. Calculate the concentrations of all species when equilibrium is reached.. H,,1(j) +- 'I l. tj).-?,;j. 1-/.1 (j) I I C -Y- -~ E, -""'f l- ')<. \~ ::: [1-11) J. 10 z: - lh,.jli~j r -Y H ;;})l ~ 100 s: 10 - IO~ z: I+- ;)'lq = /Jy X= ~-y. I +.;l."'t ( I + J~) ~ (I-?(){I-/C ) lh~j:: [I~J:; 1'.06 ~ 7'S:. [~:L):: 1.-oO'r ~(.7S) : ) J.501"\-] li.s~

8 25. At 2200 o C, K, = for the reaction I C E N2 (g) + O2 (g) H 2 NO (g) 110 What is the partial pressure of~ in equilibrium with N2 and O 2 that were placed in a flask at initial pressures of atm and atm, respectively?. _ 10 ± ~ bl. -~O-.c.. N~}(j)t O;}lj).;-.:?,.)/JOfj)X=,'t'C.J IC -Y- +J-y..8-~.~-y ~~ 2- (d'l-) ~ ::. O.s 0 :: (. g _ "X)(,.;)-)( ) = z: -.o s -t'.)0... 1(.os) ij_i-.f(3.q~)«oo8) ~ (.3. qs) -~ 3, Cf ~/O ~ (.0 ;))(. ~ - ~) C. d. -"):);; 4 -x. 01 tf'x-~:.00% -.oso?c +.oso "I-l..3.QS-xl +-.OSO"f- -.oo P = At 35 C, K = 1.60 x 10-5 for the reaction 2 NOCI (g) t-> 2 NO (g) + Cl 2 (g) Calculate the concentrations of all species at equilibrium for each of the following original mixtures: (a) 2.00 mol pure NOCl in a 2.00 L flask J ~OCQ 'j) -'7 ohiocj)'" cs, Cj).:;;..-- :r C - ;J.. 'i- -+ a)( +" I: I-~"t d~ 'X [NOJ2. [c.o~j K = : I.~ X/O :I- -s (d'x) ('k) [t-lotq] z " (\-a~) 2.. -,5!. (g X 10 = x'" 0.0f{" cl~: 1-.:l")C: /-.032.::.q(o~ ~ f [NO] z: [Ch) z [",oa] z O. 03;;) fy\ O. 01 to fy\. M 1.00._

9 (b) 1.00 mol NOCI and 1.00 mol NO in a 1.00 L flask,2!joel <j) ~ <2 A10[J)~ CJ~j) I 1.0 /,0 0 e. ~ J..'""f.. +;)"{. + "l- E I-;),Y. ~ = ~~ [a1-2- = ~ocjj -5 I. (P 'f..io x.= (1+.J~)ll~.L (t_d'l-)l K:: I ('X/O -$ ~'}L.(",~ j, ~ ~IO-s. ~ - (I) '2. 'j..o/,(''fiq -.$ ~ " I - ;} (1.(" 'I. / 0'S).: /Iqqi/, 1 ~ I.\ LoJ. OCl" J z: [NO]: I.OM /. o "" -$ (c) 2.00 mol NOCI and 1.00 mol Cl, in a 1.00 L flask K':. (, (, 'f. f 0 ~ #-.loa lj) ~ :) AlO ~)"I (J2.:J' I oz.e 0 /,0 C. -J.:y. +d."f +-JC 6 d-d.-y. d')l. /+' X 1< s: [NoJ C1uz.] l [NoCj J 1- s: -.$ C~) (,~~) " ~ '/.10.: (J.- d"1-)2- r. v )(/0 -s -s 1,(' '110 ;: xl.. }l.= 0.00'-1,----,.-., ".,' ---_... '., --'_._--_._--

10 27. Suppose the reaction system U0 2 (s) + 4 HF (g}<c->uf 4 (g) + 2 H 2 0 (g) has already reached equilibrium. Predict the effect that each of the following changes has on the equilibrium position. Tell whether the equilibrium will shift to the right, will shift to the left, or will not be affected. (a) Additional UOz (s) is added to the system. (b) The reaction is performed in a glass reaction vessel; HF (g) attacks and reacts with glass. (c) Water vapor is removed. 28. An important reaction in the commercial production of hydrogen is CO (g) + HzO (g) <c->hz (g) + CO 2 (g) How will this system at equilibrium shift in each of the following five cases? (a) Gaseous carbon dioxide is removed. (b) Water vapor is added. (c) The pressure is increased by adding helium gas. (d) The temperature is increased (the reaction is endothermic). (e) The pressure is increased by decreasing the volume of the container

11 29. In which direction will the position of the equilibrium 2 HI (g) +-> H2 (g) + h (g) be shifted for each ofthe following changes? (a) H2 (g) is added. (b) 12 (g) is removed. (c) HI (g) is removed. (d) some AI' (g) is added. (e) The volume ofthe container is doubled. (f) The temperature is decreased (the reaction is exothermic). 30. The reaction to prepare methanol from hydrogen and carbon monoxide is co (g) + 2 H2 (g) - CH 3 0H (g) is exothermic. If you wanted to use this reaction for the production of methanol commercially, would high or low temperatures favor a maximum yield? Explain your answer. ~ ~----~~~----

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