Ch.

17 Additional Aspects of Aqueous Equilibria

The Common Ion Effect:

The dissociation, (or solubility), of a weak electrolyte is decreased by the addition of a strong electrolyte that has an ion in common with the weak electrolyte

Consider the e!uilibrium established when acetic acid,

"C#"$%#, is added to water& "C#"$%#(a!) "'(a!) ' C#"$%#((a!)

)hat do you think would ha**en to the e!uilibrium if we

were to dissol+e ,aC#"$%# , (a strong electrolyte), into the solution(.emember /e Ch0telier1s *rinci*le2)

Common Ion Effect

3s e4*ected, the e!uilibrium would shift to the left
The 5"'6 would decrease by reacting with the e4tra acetate ions to
*roduce "C#"$%# The 5"C#"$%#6 increases as the e!uilibrium is re7established 8ince ,aC#"$%# is a strong electrolyte and "C#"$%# is a weak electrolyte, the 5C#"$%#(6 is based on the amount of salt added to the solution not on the weak acid1s dissociation

/et1s do a *ractice *roblem with numbers&

)hat is the *" of a 9 9:; < ",%# solution, (=a > ? ; 4 @9(?) when 9 @ < of =,%# is added- ( ",%# "' ' ,%#( ) ' (
5",%#6 5" 6 9 '4 '4 5,%# 6 Initial Change E!uilibrium 9 9:; < 4 9 9:; 4 9@< '4 9 @9 ' 4

Common Ion Effect

5",%#6 Initial Change E!uilibrium 9 9:; < 4 9 9:; 4 5"'6 9 '4 '4 5,%#(6 9 @9 '4 9 @9 ' 4

=a > ? ; 4 @9(? > 5"'65,%#6A5",%#6 > 54659 @9 ' 46A59 9:; 46

3ssuming B4C is going to be a +ery small answer& ? ; 4 @9(? > 459 @96A59 9:;6 8ol+ing for B4C&4 > 9 999$: < This is e!ual to 5"'6, so& pH > ((log59 999$:6) > 3.42
D E I F)ithout the salt, *" G # #

Common Ion Effect

The *re+ious e4am*le used the dissociation of a weak acid Hut the ioniIation of a weak base can also be decreased by the addition of a strong electrolyte& "#% ' ,"$ ,"?' ' %"( If we were to add ,"?Cl to the solution, the e!uilibrium would shift to the left, and the *" would decrease as %"( reacts with the additional ,"?' in the solution

Huffered 8olutions (a k a F BHuffersC)

The solutions we ha+e been describing can resist drastic changes in *" as a strong acid, ("'), or a strong base, (%"(), is added These ty*es of solutions are called buffers 3 buffer consists of a mi4ture of a weak acid ("J) and its conKugate base (J )& "J(aq) "'(aq) ' J(aq) 8o a buffer contains both: 3n acidic s*ecies (to neutraliIe %") and 3 basic s*ecies (to neutraliIe "')

Huffers ha+e many im*ortant a**lications in the lab and in

medicine&your blood is a buffered solution that functions in the *" range of L $; L ?; (8ee * MMN for more details2)

Huffered 8olutions (a k a F BHuffersC)

)hen a small amount of %" is added to the buffer, the %" reacts with "J to *roduce J and water& HX + OH X + H2O Hut the 5"J6A5 J6 ratio remains more or less constant, so the *" is not significantly changed )hen a small amount of "' is added to the buffer, J is consumed to *roduce "J& X + H+ HX %nce again, the 5"J6A5 J 6 ratio is more or less constant, so the *" does not change significantly

Huffers

Huffer Ca*acity
Huffer ca*acity is the amount of acid or base that can be neutraliIed by the buffer before there is a significant change in *" Huffer ca*acity de*ends on the concentrations of the com*onents of the buffer The greater the concentrations of the conKugate acid7base *air, the greater the buffer ca*acity The *" of the buffer is related to =a and to the relati+e concentrations of the acid and base&

pH = pK a

[ J ] + log = pK

[ "J]

[ base] a + log [ acid]

This e!uation is known as the "enderson7"asselbalch e!uation )hen 5base6 > 5acid6, the *" > *=a

Huffer Calculations
)hen a small amount of strong acid or strong base is added to a buffer, we assume that it is completely consumed by the reaction with the buffer Huffer *roblems consist of # *arts: stoichiometry O e!uilibrium Practice Problem: 3 buffer is made by adding 9 $99 moles of "%3c and 9 $99 moles of ,a%3c to enough water to make @ 99 / of solution The *" of the buffer e!uals ? L? )hat is the *" after 9 9#9 moles of ,a%" is added Dirst, we use stoichiometry to determine the effect of the addition of %"( to the buffer& %"( ' "%3c "#% ' %3c( )e see that 5"%3c6 will decrease and 5%3c(6 will increase by the concentration of %"( added to the buffer
/et1s tabulate this information&

Huffer Calculations
%"( ' "%3c "#% ' %3c(
Hefore reaction: 3fter reaction: 9 9#9 mol 9 9 $99 mol 9 #:9 mol 9 $99 mol 9 $#9 mol

,ow we can use the "enderson7"asselbalch e!uation to find *"& *" > *=a ' log ( 5base6A5acid6 ) *" > (log @ : 4 @9;) ' log ( 59 $#96A59 #:96 ) *" > ? L? ' 9 9M > ? :9

3 cou*le of things to note&

@) Eou can use mole amounts in *lace of concentrations in the e!uation #) If we added 9 9#9 moles of a strong acid, then the *" would ha+e decreased by 9 9M instead

Huffer Calculations

3cid7Hase Titrations
In an acid7base titration:
3 solution of base of known concentration is added to an acid

3cid7base indicators or a *" meter are used to signal the e!ui+alence *oint&the *oint at which the moles of "' > moles of %"( The end *oint in a titration is the *oint where the indicator changes color The *lot of *" +ersus +olume during a titration is called a *" titration cur+e
/et1s look at the titration cur+e for a strong acid7strong base& ( "Cl ' ,a%" "#% ' ,aCl )

8trong 3cid78trong Hase Titration Cur+e

Things of interest: @) The initial *" is based on the 5"Cl6 at the start #) The *" rises slowly at first then Kum*s dramatically after the e!ui+alence *oint $) The e!ui+alence *oint is at a *" of L 9 ?) The final *" is based u*on the 5,a%"6 in e4cess ;) )e should choose an indicator that changes color in the *ortion of the gra*h where the *" rises ra*idly

8trong 3cid78trong Hase Titration Cur+e

"ere1s what the gra*h would look like if the strong acid were titrated into a strong base&the e!ui+alence *oint is still at a *" of L 9

)eak 3cid78trong Hase Titrations

Consider the titration of acetic acid, "C#"$%# with ,a%"& 3gain, we di+ide the titration into four general regions: (@) Hefore any base is added& the solution contains only weak acid Therefore, *" is gi+en by the e!uilibrium calculation (#) Hetween the initial *" and the e!ui+alence *oint& the strong base consumes a stoichiometric !uantity of weak acid& "C#"$%#(aq) ' %"(aq) C#"$%#(aq) ' "#%(l) 7"owe+er, there is an e4cess of acetic acid Therefore, we ha+e a mi4ture of weak acid and its conKugate base 7Thus the com*osition of the mi4ture is that of a buffer The *" is gi+en by the buffer calculation&("enderson7"asselbalch e!uation )
moles base added = moles of acid consumed = moles of acetate ion formed

)eak 3cid78trong Hase Titrations

($) 3t the e!ui+alence *oint& all the acetic acid has been consumed and all the ,a%" has been consumed 7 "owe+er, C#"$%# has been generated 7 Therefore, the *" de*ends on the C#"$%# concentration 7 The *" P L at the e!ui+alence *oint since C#"$%#( is a weak base&(3ll weak acid7strong base titrations ha+e e!ui+alence *oints at *"1s greater than L2) 7 The e!ui+alence *oint is determined by the =a of the acid (?) 3fter the e!ui+alence *oint& the *" is based on the e4cess strong base

)eak 3cid78trong Hase Titration Cur+es

<ore on choosing indicators& Q Choose the indicator with a *=a @ less than the *" at e!ui+alence *oint if you are titrating with base Q Choose the indicator with a *=a @ greater than the *" at e!ui+alence *oint if you are titrating with acid

)eak 3cid78trong Hase Titration Cur+es

Things to notice& @) Dor a weak acid7strong base titration, the initial *" rise is more stee* than the strong acid7strong base case #) Then there is a le+eling off due to buffer effects $) The e!ui+alence *oint is higher for the weaker acids ?) The sha*e of the cur+es after e!ui+alence *oint is the same because *" is determined by the strong base in e4cess

Roly*rotic 3cid Titration Cur+es

Things to notice& @) In *oly*rotic acids, each ioniIable *roton dissociates in ste*s #) Therefore, in a titration there are Bn e!ui+alence *oints corres*onding to each ioniIable *roton $) In the titration of "$R%$ with ,a%", the first *roton dissociates to form "#R%$( then the second *roton dissociates to form "R%$2

8olubility E!uilibria
3ll dissol+ing is an e!uilibrium& 8olid Sissol+ed E4am*le: Ha8%? (s) Ha'#(a!) ' 8%?(#(a!) If there is not much solid, it will all dissol+e 3s more solid is added the solution will become saturated 3t e!uilibrium, the solid will *reci*itate as fast as it dissol+es =s* > 5Ha'#6 58%?(#6 =s* is the solubility *roduct It is the molar concentration of ions raised to their stoichiometric *owers&(Ha8%? is ignored because it is a *ure solid, so its concentration is constant ) 8olubility *roduct is an e!uilibrium constant It doesn1t change e4ce*t with tem*erature

8olubility Sefinition
8olubility is not the same as solubility *roduct 8olubility is the amount (grams) of substance that dissol+es to form a saturated solution 8olubility is an e!uilibrium *osition for how much can dissol+e <olar solubility is the number of moles of solute dissol+ing to form a liter of saturated solution 3 common ion can change the solubility of a substance

.elati+e 8olubilities
=s* will only allow us to com*are the solubility of solids that fall a*art into the same number of ions The bigger the =s*, the more soluble the substance If they fall a*art into different number of *ieces you ha+e to do an e!uilibrium calculation to see which is more soluble

Con+erting 8olubility into =s*

Practice Problem: The molar solubility of CaD# is @ #? 4 @9($ < at $;T C )hat is the solubility *roduct of CaD# at $;T CCaD#(s) Ca'#(a!) ' #D((a!) =s* > 5Ca'#6 5D(6# 5Ca'#6 > @ #? 4 @9($ < 5D(6 > # 4 (@ #? 4 @9($ <) > # ?: 4 @9($ < =s* > 5@ #? 4 @9($6 5# ?: 4 @9($6# > L M$ 4 @9(N

Note: In order to calculate =s* , all concentrations must be in units of molesA/ (or molarity, <) Reminder: gramsADormula)eight > moles

8olubility and the Common Ion Effect

This is an a**lication of /e Ch0telier1s *rinci*le2 Dor e4am*le: CaD#(s)
Ca#'(aq) ' #D7(aq)

If more D( is added, (let1s say from the addition of a strong electrolyte such as ,aD), the e!uilibrium shifts away from the increase Therefore, CaD#(s) is formed and *reci*itation occurs 3s ,aD is added to the system, the solubility of CaD# decreases If the D( is remo+ed, then the e!uilibrium shifts to the right, and more CaD# dissol+es D( can be remo+ed by adding a strong acid& D7(aq) ' "'(aq) "D(aq) This means that the *" affects the solubility of CaD#2

8olubility and *"

3nother e4am*le of *" changing the solubility& <g(%")#(s) <g'#(aq) ' #%"((a!) )hat ha**ens to the e!uilibrium if we were to add a strong acid7 3gain we a**ly /e Ch0telier1s *rinci*le: If %" is remo+ed, then the e!uilibrium shifts toward the right and <g(%")# dissol+es& %"(aq) ' "'(aq) "#%(aq) 3s *" decreases, 5"'6 increases and the solubility of <g(%")# increases The effect is most significant if one or both ions in+ol+ed are at least somewhat acidic or basic

In general: @ The solubility of slightly soluble salts containing basic ions increases as *" decreases # The more basic the anion, the greater the effect

Dormation of Com*le4 Ions

8ome metal ions, (cations), can form soluble com*le4 ions when in solutions Consider the formation of 3g(,"$)#':

3g'(aq) ' #,"$(aq)

The 3g(,"$)#' is called a com*le4 ion

3g(,"$)#(aq)

,"$ (the attached /ewis base) is called a ligand The e!uilibrium constant for the reaction is called the formation constant, =f& =f > 53g(,"$)#'6A53g'6 5,"$6#

 Consider the addition of ammonia to 3gCl (white *reci*itate):

Dormation of Com*le4 Ions

The o+erall reaction is&

3gCl(s) 3g'(aq) ' Cl7(aq) 3g'(aq) ' #,"$(aq) 3g(,"$)#(aq) 3g(,"$)#(aq) ' Cl7(aq)

3gCl(s) ' #,"$(aq)

Effecti+ely, the 3g'(aq) has been remo+ed from solution Hy /e Ch0telier1s *rinci*le, the forward reaction (the dissol+ing of 3gCl) is fa+ored

 Dinally, am*hoteric o4ides will dissol+e in either a strong acid or a strong base by forming com*le4 ions with se+eral hydro4ide ligands attached to the metal Dor e4am*le:

Dormation of Com*le4 Ions

)e won1t be dealing with these uni!ue solubility situations much, but I wanted you to be aware that they e4ist

8olubility Uuidelines for Common Ionic Com*ounds in )ater

%ur di+iding line between soluble and insoluble will be 9 9@ < at #; VC (8ome *eo*le use 9 @ < as a di+iding line, so you may see some discre*ancies between solubility guidelines ) 3ny substance that can form a solution with a concentration of 9 9@ < or more is soluble 3ny substance that fails to reach 9 9@ < is defined to be insoluble This +alue was *icked with a *ur*ose WE.E DE) substances ha+e their ma4imum solubility near to 9 9@ < 3lmost e+ery substance of any im*ortance in chemistry is either much <%.E soluble or much /E88 soluble In the *ast, some teachers would ha+e a third category: slightly soluble Dor the most *art, that category has been cast aside

8olubility Uuidelines for Common Ionic Com*ounds in )ater

(@)3ll alkali metal&(Urou* @3 >lithium, sodium, *otassium, rubidium, and cesium) and ammonium com*ounds are soluble. (#) 3ll acetate, *erchlorate, chlorate, and nitrate com*ounds are soluble ($) 8il+er, lead, and mercury (I) com*ounds are insoluble (?) Chlorides, bromides, and iodides are soluble (;) Carbonates, o4ides, *hos*hates, chromates, fluorides, and silicates are insoluble (M) "ydro4ides and sulfides are insoluble (EJCERT for Ca'#, Ha'#, and 8r'# ) (L) 8ulfates are soluble (EJCERT for Ca'#, Ha'#, and 8r'#)
7 These rules are to be a**lied in the order gi+en Dor e4am*le, Rb8%? is insoluble because .ule $ comes before .ule L In like manner, 3gCl is insoluble because .ule $ takes *recedence o+er .ule ? 7 Rlease be aware that these rules are guidelines only Dor e4am*le, there are

"ere are some of these guidelines shown in a table format&

Rreci*itation of Ions
)e can use our knowledge of =s* and e!uilibrium to determine if a *reci*itate will form when solutions are mi4ed Dor e4am*le& Ha8%?(s)

Ha#'(aq) ' 8%?#7(aq)

3t any instant in time, X > 5Ha#'658%?#76 If Q P Ksp, *reci*itation occurs until Q > Ksp. If Q > Ksp, e!uilibrium e4ists If Q Y Ksp, solid dissol+es until Q > Ksp ()e1ll look at a *ractice *roblem in a little bit ) Hased on our solubility guidelines, ions can be selecti+ely remo+ed from solutions .emo+al of one metal ion from a solution is called selecti e precipitation The te4tbook goes into detail about the *rocedure, but we won1t

 Xualitati+e analysis is designed to detect the *resence of metal ions Xuantitati+e analysis is designed to determine how much metal ion is *resent

Dorming Rreci*itates
Practice Problem: )ill 3g#8%? *reci*itate when @99 m/ of 9 9;9 < 3g,%$ is mi4ed with a @9 m/ solution of 9 9;9 < ,a#8%?3g#8%?(s) # 3g' ' 8%?# =s* > @ ; 4 @9; > 53g'6# 58%?#6
Hefore we can find the concentrations of the ions in the mi4ture, we need to determine the moles of each ion in the solutions be!ore they were mi4ed together&(.eminder: moles > /iters 4 <olarity)
moles 3g' > @99 m/ 4 (@ / A@999 m/) 4 ( 9 9;9 molesA/) > 9 99; moles moles 8%?(# > @9 m/ 4 (@ / A@999 m/) 4 ( 9 9;9 molesA/) > 9 999; moles

"!ter the solutions are mi4ed, the total +olume is @@9 m/ or 9 @@ /, so:
53g'6 > 9 99; molesA9 @@ / > 9 9?; < 58%?(#6 > 9 999; molesA9 @@ / > 9 99?; <