91 (a) A weak electrolyte only partially ionizes when dissolved in water. NaHCO 3 is an


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1 Chpter 9 9 ( A ek electrolyte only prtilly ionizes hen dissolved in ter. NC is n exmple of ek electrolyte. (b A Brønstedory cid is cule tht dontes proton hen it encounters bse (proton cceptor. By this definition, N cn be Brønstedory cid. (c The conjugte cid of Brønstedory bse is the ecies formed hen Brønsted ory bse ccepts proton. For exmple, the N is the conjugte cid of N. (d Neutrliztion, ccording to the Brønstedory concept, occurs hen rection involving n cid nd its conjugte bse is combined ith second rection involving bse nd its conjugte cid. Thus, N N In the exmple bove, N cts s bse ith N s its conjugte cid. cts s n cid ith  s its conjugte bse. (e An mphiprotic solvent cn ct either s n cid or bse depending on the solute. Wter is n exmple of n mphiprotic chemicl ecies. (f A zitterion is chemicl ecies tht bers both positive nd negtive chrges. Free mino cids, such s glycine, cn exist s zitterions in solution. N CC N C C glycine zitterion (g Autoprotolysis is the ct of selfioniztion of solvent to produce both conjugte cid nd conjugte bse. (h A strong cid dissocites completely such tht no undissocited cules re left in queous solution. ydrochloric cid, Cl, is n exmple of strong cid.
2 (i The e Châtelier principle sttes tht the position of n equilibrium lys shifts in such direction to relieve stress pplied to the system. (j The commonion effect is reonsible for the reduced solubility of n ionic precipitte hen one of the soluble components recting to form the precipitte is dded to the solution in equilibrium ith the precipitte. 9 ( An mphiprotic solute is chemicl ecies tht possesses both cidic nd bsic properties. The dihydrogen phohte ion, P , is n exmple of n mphiprotic solute. (b A differentiting solvent revels different strengths of cids. By this definition, nhydrous cetic cid is differentiting solvent becuse perchloric cid dissocites 000 times more thn hydrochloric cid. (c A leveling solvent is one in hich series of cids (or bses ll dissocite completely. Wter is n exmple, since strong cids like Cl nd Cl ionize completely. (d A mssction effect rises hen shift in the chemicl equilibrium occurs due to the introduction of one of the prticipting chemicl ecies (i.e., ddition of one of the rectnts or products. 9 For n queous equilibrium in hich ter is prticipnt, the concentrtion of ter is normlly so much lrger thn the concentrtions of the other rectnts or products tht it cn be ssumed to be constnt nd independent of the equilibrium position. Thus, its concentrtion is included ithin the equilibrium constnt. For pure solid, the concentrtion of the chemicl ecies in the solid phse is constnt. As long s some solid exists s second phse, its effect on the equilibrium is constnt nd is included ithin the equilibrium constnt.
3 99 Acid Conjugte Bse ( Cl Cl  (b  (c N N (d  C (e  P  C  P Bse Conjugte Acid ( (b N N (c (d  C C (e P  P  9 ( (b C C C C C C (c C N C N C N (d C C C 9 ( C N C N 0 [C N b.. [C N (b CN CN
4 b. CN [CN (c N C N C b.90 N [C N [C (d CN CN b. [CN CN..00 (e As As As As As As As As.0 (. (. (. As As As As As [As As [As As As As As β β (f C C C C C C
5 β β b b C [C C [C C C b ( (. (.9 C [C C [C C C. b b 9 ( CuI( s Cu I [Cu [I (b PbClF( s Pb Cl F [Pb [Cl [F (c PbI ( s Pb I [Pb [I (d BiI s ( Bi I [Bi [I (e gn P ( s g N P [g [N [P 99 ( [Cu [I [Cu [I (b [Pb [Cl  [F  [Pb [Cl  [F  (c [Pb /[I  [Pb [I  (( (d [Bi /[I  [Bi [I  (( (e [g [N [P  [g [N [P 
6 9 ( [Cu [e Cue ( s.0 Cu. e [Cu [e (. (. (b [Pb. Pb(I ( s (c Pb I [I [Pb [Pb (. [I (.. (.. [r rf ( s. r F [F [r [r [F (. (. (... 9 (d [Th. Th( ( s Th [Th [Th (. (.. (. 9 (.0  [Cu [e  (0.00 [e  [e (b.  [Pb [I  (0.00 [I  [I ½[I  ½(. . 
7 (c [F (d. [F 9 [r [F (0.00[F (.. [Th (. 9. ( (.0 [Cu (b [Pb. [Cu [Pb. (0.00 [e.0 [I. [Cu [Pb (c. 9 [r [F  [r (0.00 (0.00 (0.00 [r 9. (0.00
8 (d  [Th  [Th (0.00 [Th..0 ( Ag Cr ( s Ag Cr. [Ag [Cr ( [Cr. (. 9. (b [ Cr ( Al( ( s Al.0 [Al olr solubility of Al( [Al ( Becuse the is so smll, e cn ssume the solubility of Al( is not lrge. Therefore, it is resonble tht the [Al.0 X . The eqution then simplifies to (
9 (b As in prt (, [Ce [I (. ( 0.00 Ce. 00 m. 00 m 0.0 (0.0 m 0.0 m 0.0 m. (b 0.00 I.0 00 m 0.0 m.0 s Ce [Ce unrected. (.0.. ( 0.0 m 0.0 m 00 m. here is derived itertively using the eqution (. ( We strt by solving for ssuming no contribution to [Ce other thn from the dissocition of Ce(I. In this cse, equls. . No, e substitute.  bck into the eqution bove nd solve for itertive. itertive equls.99. is too lrge; e choose smller (i.e.,  nd reclculte itertive. Itertion continues until itertive. The results of this pproch re shon in the Tble belo.
10 Itertion itertive We no substitute.9  into the eqution belo, [Ce..9.0 (c 0.0 I. 0.0 m m The Ce is completely consumed; thus, s I unrected 0.0 (.. 00 m [I m (0.0.. ke the ssumption tht << 0.0. [Ce (0.0.. (0.0. (d 0.0 I. 0.0 m. 00 m
11 The Ce is completely consumed; thus, s I unrected.. 00 m [I m (0.0. (.. ke the ssumption tht << 0.0. [Ce (0.0.. ( [ [PdCl ( ( (0.0 m 0.0 m ( PdCl.0 (0.0 m 0.0 m 00 m 00 m s unrected m m. 00 m 00 m 0.00 (..0 The [ is 0.0 plus the contribution from the dissocition of the precipitte, x, or [ 0.0 x ubstituting the eqution bove into the equilibrium expression, e find x [ 0.0x [PdCl (. (0.0 x x x.0 We use n itertive pproch to solve for x. We begin by ignoring the contribution to [ from the dissocition of the precipitte.
12 x ubstituting this vlue bck into the eqution bove, e obtin itertive equl to.0 , hich is too lrge. We no proceed by choosing smller vlue of x equl  nd obtin itertive equls to We continue the itertive pproch until itertive s shon in the tble belo. Itertion x itertive ubstituting x equls  into the [ eqution, e find [ 0.0 ( (b 0.0 PdCl 00 m 0.0 m.00 The [ is determined directly from ; thus, [.0 [ [PdCl ( (
13 (c 0.00 PdCl m m The is completely consumed; thus, s PdCl unrected ( m [PdCl m Assume tht << 0.0 [PdCl.0 (0.0 [ 0.0 ( ( CuI(s Cu I  [Cu [I   AgI(s Ag I  [Ag [I .  PbI (s Pb I  [Pb [I ( BiI (s Bi I  [Bi [I ( ( CuI AgI PbI BiI PbI [Cu [I [Ag [I [Pb [Bi > BiI [I. (. (. [I > CuI > AgI in ter
14 (b CuI AgI PbI BiI PbI (c CuI AgI 0. PbI. 0.. (0.. ( > CuI > AgI > BiI in 0. NI. BiI PbI > BiI > CuI >. AgI in 0.0 solution of the solute ction 9 Bi(s Bi  [Bi Be( (s Be  [Be ( Tm( (s Tm  [Tm ( f( (s f  f (
15 ( ter. solubility in loest the hs Be(..0 f..0 [Tm..0 [Be.0.0 [Bi ( f Tm( Be( Bi (b N. 0. solubility in loest the hs f(.0 ( ( ( ( f Tm( 0 Be( 9 Bi 99 At 0ºC,. log(. log p At 0ºC,. log(.00 log p
16 90 (..0.0 (9.0 ( ( ( Cl [Cl.0 Cl [Cl Cl Cl (b (9. ( ( ( C C C [C C C C [C. C C C [C C C C [C C C C C C C C C
17 (c... (. ( (0.0.. ( N [C N [C.. N [C N [C N C N C b (d... (. ( ( ( N [(C N [(C.. N [(C N [(C N (C N (C b
18 (e.9.. (. ( ( ( [Cl Cl..0 [Cl Cl Cl Cl b (f..0.0 (. ( ( ( C [C C [C.. C [C C [C C C C C 9 b
19 (g.9.. (. ( (0.0.. ( N N. N N N N (h... (.9 ( ( ( N C N C. N C N C N C N C 9
20 9 ( 0.0 (. ( (0.0.. ( C [ClC C [ClC. C [ClC C [ClC C ClC C ClC (b... (. ( (0.0.. ( C [ClC C [ClC.. C [ClC C [ClC C ClC C ClC b
21 (c... (. ( ( ( N [C N [C.. N [C N [C N C N C b (d. (. ( ( ( N [C N [C. N [C N [C N C N C (e. (. ( ( ( N [C N [C. N [C N [C N C N C 
22 (f I [I I I (0.00 [I I (. ( ( A buffer solution resists chnges in p ith dilution or ith ddition of cids or bses. A buffer is composed of mixture of ek cid nd its conjugte bse. 9 Buffer cpcity of solution is defined s the number of s of strong cid (or strong bse tht cuses 0 of buffer to undergo 0unit chnge in p. [N ( ( p p log log(. log. 9 [N (0.00 [N (0.00 (b p p log log(. log. 9 [N (0.0 The solutions hve identicl p vlues, but the solution in prt ( hs the greter buffer cpcity becuse it hs the higher concentrtion of ek cid nd conjugte bse.
23 9 ( Ac Ac Ac 0.0 Ac p log(. (b p log(. Ac m 0.00 log log. 00 m Ac 0 m m N 0 m m ( m Ac. 00 m m [Ac.0 00 m (c Ac p log( Ac Cl m 9. log. 00 m 00 m.9 ( m [Ac m 00 m. 0 m m
24 ince the rtios of the mounts of ek cid to conjugte bse re identicl the three solutions ill hve the sme p. They ill differ in buffer cpcity, hoever, ith ( hving the gretest nd (c the lest. 9 ( lic cid / sodium hydrogen mlte (b Cl / Cl  (c N Cl / N (d pyridine / pyridinium 9 ( C C C p.0 p log log. log. log C C C C C 0. C log C C C 0 0 C 00.0 m 0.00 C 00 m C (0.9 (0.00 C 0. CN.99 g eight CN 0. C. g C
25 9 p.00 p log. ( C C log 0. C C C C. C C C C log C C C C C C log. log C C C C C C C C. 0 0 C C 00.0 m 0.00 C C 00 m C C (. (0.00 C C 0. C CN 9.0g eight C CN 0. C. g C C 0.
26 C CCN 0.0 m 00 m 0.00 C p. p log (.0 [C CC log 0.0 [C CC C CC 0.9 C CC ( C CC x Cl 0.9 x Cl C CC CCN [C CC log [C CC [C CC [C CC log.0 log [C CC [C CC [C CC [C CC x Cl 0.9( x Cl 0.0 C CC 0.0 x Cl m volume Cl m Cl
27 C C p.00 p log. ( C C log 0. C C C C. C C x N. ( C C x N x N. ( C C x N. x N volume N 0.9 C C log C C 00 m C C C C log. log C C C C C C C C 00.0 m 0.00 C.. ( C C. ( m 9. m N.00 C 9 The sttement A buffer mintins the p of solution constnt is flse. The chnge in p of buffered solution is reltively smll ith the ddition of smll volume of cid or bse s shon in the exmple belo. p p log [NA A m of 0.00 N [NA A p
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