brdy 6ed ch18 solubility
TRANSCRIPT
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Chapter 18:Solubility and
Simultaneous Equilibria
Chemistry: The Molecular Nature
of Matter, 6E
Jespersen/Brady/Hyslop
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Jespersen/Brady/HyslopChemistry:TheMolecularNatureofMatter,6E
Solubility of Salts
Precipitation reactions (C !" Exchange reactions in which one product is water
insoluble compound
CaCl2 (l! "a2C#$ (aqCaC#$ (s! 2 "aCl (aq
#nsoluble compoun$ Compound ha%ing water solubility o& less than '')
mole o& dissol%ed material per liter o& solution
S * '') +
2
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Jespersen/Brady/HyslopChemistry:TheMolecularNatureofMatter,6E
Solubility of Salts Ch ! Solubility %ules
,uidelines &or what is insoluble -oesn.t mean compound won.t dissol%e at all
Just not %ery much
No& &ant to uantitate solubilities
Explore conditions under which some compoundsprecipitate and others don.t
0pplications in separation o& ions
Especially toxic metal ions such as Hg2!1 l$!1 3$!1 etc
$
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Jespersen/Brady/HyslopChemistry:TheMolecularNatureofMatter,6E
Solubility E)uilibria Solids in equilibrium with ions in solution
hen ionic salt dissol%es in water 0ssume dissociates into separate hydrated ions
>nitially1 no ions in solution
Ca*+(s" Ca+(a)" + *-(a)" 0s dissolution occurs1 ions build up and collide
Ca+(a)" + *-(a)" Ca*+(s"
0t Equilibrium Ca*+(s" Ca
+(a)" + *-(a)"
"ow ha%e saturated solution
5
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Jespersen/Brady/HyslopChemistry:TheMolecularNatureofMatter,6E
Solubility an$ Solubility Pro$uctSolubility
0mount o& salt that dissol%es in gi%en amount o&sol%ent to gi%e saturated solution
Concentration >n&inite number o& %alues
Solubility pro$uct 6roduct o& molar concentrations o& ions in saturated
solution raised to appropriate powers Equilibrium constant #nly one %alue &or gi%en solid at gi%en temperature
Temperature $epen$ence Solubilities and thus Cspchange with
D
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Solubility of Salts Consider 0gCl in water
#nly a %ery small amount dissol%es Equilibrium exists when solution is saturated
./Cl(s" ./(a)" Cl-(a)"
Equilibrium law0sp 2./
32Cl-3
0sp solubility pro$uct constant
Solubility equilibrium :e&lects solubility o& compound
6roduct o& ion concentrations
F
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Solubility an$ Solubility Pro$uct Solubility
0mount o& salt that dissol%es in gi%en amount o&sol%ent to gi%e saturated solution
Solubility pro$uct 6roduct o& molar concentrations o& ions in
saturated solution raised to appropriate powers Temperature $epen$ence
Solubilites and thus Cspchange with temperature
Table 1841 Solubility product constants at 25 GC
+ore in able CD (0ppendix p 075
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#on Pro$uct 5s4 Solubility Pro$uct
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'ritin/ 0spE)uilibrium 9a&s
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Calculation usin/ 0span$ Molar
Solubilities
Molar solubility +oles o& salt dissol%ed in one liter o& saturated
solution
0ssume what little dissol%ed1 dissociates )''L
0ssumes there is somesolid uantity is not important
Solid is notincluded in mass action expression
.4 i5en Solubilites, Calculate 0sp74 i5en 0sp, Calculate Solubility
))
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.4 i5en Solubilites , Calculate 0spE 140t 25 GC1 the solubility o& 0gCl is )$7 x
)';5 + Calculate the solubility product &or 0gCl./Cl (s" ./(a)" Cl- (a)"
0sp 2./32Cl-3
Csp9 ()$7 x )';5()$7 x )';5
Csp9148; 1;-1;
./Cl(s" ./ (a)" Cl- (a)"
> ''' ' ''
C
E
14
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>our Turn?he solubility o& a salt1 02B$1 is &ound to be
$'M)';5 +4 hat is the %alue o&CspN0 2D x )'@2)
B 57 x )'@K
C 27 x )'@2$
- )F x )'@2)
02B$ 20$! ! $B2@
408 9 2($' x )'@5 4B8 9 $($' x )'@5
9 40824B8$9 (D' x )'@52(K' x )'@5$
9 2D x )'@2)
)$
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74 i5en 0sp, Calculate Solubility
E4 + hat is the molar solubility o& Cu> in
waterN hat are the equilibriumconcentrations o& Cu!and >;N
Step 14 'rite balance$ e)uation for
$issociation of saltCu#(s" Cu(a)" #-(a)"
Step +4 'rite e)uilibrium la&
0sp 2Cu32#-3
Step
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E4 +Molar Solubilities from 0spStep =4 Concentration Table
Step !4 Plu/ into an$ sol5e 0spepression
Csp9 ' )';9 (x(x
x29 ' )';
9 +48
1;-= M9 calculated molar solubilityo& Cu> 2Cu3 2#-3
Conc (+ Cu#(s" Cu (a)" #- (a)"
>nitial ''' ' ''
Change
Equil.m
+x+x
xx
x
)5
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Molar Solubility an$ 0spProblems
Strategy &or sol%ing
) rite balanced equation &or dissociation o& salt
2 rite equilibrium law
$( Csp&or salt (&rom table
7 Concentration table
5aSol%e &or x 9 solubility
#r
5b ,i%en solubilities1 calculate Csp
)D
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.4 i5en Solubilites , Calculate 0spE4 < Calculate Csp&or Bi2S$ gi%en solubility is
)' x )';)5+ at 25 GCStep 14'rite balance$ e)uation for
$issociation of salt
7i+S
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.4 i5en Solubilites , Calculate 0sp
7i+S
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74i5en 0sp, Calculate Solubilities
E4 = Calculate the solubility o& Canitial ("o entries ''' '''
Change in this
Equil.m column
+
+
)K
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E4 =Molar Solubilities from 0sp
Step
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>our Turn?,i%en Csp9 )7 x )'
;F&or Cu(>#$21 calculate the
solubility o& this salt
0 52 x )'@$
B $$ x )'@$
C 2D x )'@7
- $F x )'@7
Cu(>#$2(s Cu2! ! 2>#$
@
sp9 )7 x )'@F9 s (2s2
s 9 $$ x )' 2)
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Jespersen/Brady/HyslopChemistry:TheMolecularNatureofMatter,6E
>our Turn?hat is the solubility o& 6bCl2in grams per )''' m=
at 25o
N sp9 )F x )'@5
0 '5D g
B 'F2 g
C '75 g- '$K g
6bCl2(s 6b2! ! 2Cl@
sp9 )F x )'@59 46b2!84Cl@829 s (2s2
s 9 )D2 x )'@5 +
()D2 x )'@5mol/= x (2F)) g/mol x ') = 9 '75 gin )'' m=
2$
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Jespersen/Brady/HyslopChemistry:TheMolecularNatureofMatter,6E
%elati5e Solubilities) +ust compare salts that contain the same number
o& ions >& solubility 9 x
hen 4cation8 9 4anion8 9 x
Csp9 x2
So can compare solubilities by comparing Csp.s
CaS#7* Cu> * 0g>
most soluble least soluble
largest Csp smallest Csp
solubilityCx sp ==
25
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Jespersen/Brady/HyslopChemistry:TheMolecularNatureofMatter,6E
%elati5e Solubilities2 Compare salts with di&&erent number o& ions
Each produces di&&erent number o& ions
Each uses di&&erent Cspexpression
"o way to predict relati%e solubility based on Csp
Bi2S$* 0g2S * CuS+ost soluble least soluble
2D
Salt 0 sp Aions CalcB$Solubility (M"
CuS 5 x )';75 2 K2 x )';2$
0g2S )D x )';7K $ $7 x )';)F
Bi2S$ )) x )';F$ 5 )' x )';)5
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Jespersen/Brady/HyslopChemistry:TheMolecularNatureofMatter,6E
Common #on Effect 3p until now all calculations in pure water
hat happens i& > add another salt to a solutioncontaining one o& the ions in our insoluble saltN
Consider Pb#+(s" Pb+(a)" +#-(a)"
Saturated solution o& 6b>2
in water
6b>2(yellow solid precipitates out
'hy =e Chatelier.s 6riniciple
0dd product >;
Equilibrium mo%es to le&t and solid 6b>2&orms 2F
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Jespersen/Brady/HyslopChemistry:TheMolecularNatureofMatter,6E
Common #on Effect Common ion
>on in solution that is supplied by more than onesolute
Common #on Effect
=owering o& solubility o& ionic compound byaddition o& common ion
2
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Jespersen/Brady/HyslopChemistry:TheMolecularNatureofMatter,6E
E4 ! Common #on Effect
0 hat is the molar solubility o& 0g2Cr#7in
')'+ 0g"#$solutionN Csp9 K' )';)2
B hat is the molar solubility o&0g2Cr#7in pure waterN
C hat is the molar solubility o&0g2Cr#7in ')'' + "a2Cr#7N
0g2Cr#7(s 20g!(aq! Cr#7
2;(aq
sp9 40g!824Cr#7
2;8 9 K' )';)2
2K
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ff
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Jespersen/Brady/HyslopChemistry:TheMolecularNatureofMatter,6E
E4 ! Common #on Effect74Solubility o& 0g2Cr#7in pure water
./+Cr=(s" +./(a)" Cr=+-(a)"> ("o entries ''' + ''' +
C in this
E column
+x+2x
x2x
Ksp= [Ag+]2[CrO4
2] = (2x)2(x) = 9.0 1012= 4x3
$ )2$)2
)'25(27
)''(K
x
=
=
? 9 Solubility o& 0g2Cr#79 )$) )';7+
4Cr#72;8 9 x 9 )$) )';7 +
40g!8 9 2x 9 2D2 )';7+ $)
ff
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Jespersen/Brady/HyslopChemistry:TheMolecularNatureofMatter,6E
E4 ! Common #on EffectC4 Solubility o& 0g2Cr#7in ')'' + "a2Cr#7N
./+Cr=(s" +./(a)" Cr=+-(a)"> ("o entries ''' + ')' +
C in this
E column
+x+2x
2x #0.10
Ksp= (2x)2(0.10) = 9.0 1012= 4x2(0.10)
)))2
)'25(27('
)''(K
x
=
=
x 9 Solubility o& 0g2Cr#79 7F )';D+
4Cr#72;8 9 x 9 7F )';D +
40g!8 9 2x 9 K5 )';D+ $2
E ! C # Eff
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Jespersen/Brady/HyslopChemistry:TheMolecularNatureofMatter,6E
E4 ! Common #on Effect
$$
C4 Solubility o& 0g2Cr#7in ')'' + "a2Cr#7N
./+Cr=(s" +./(a)" Cr=+-(a)"> ("o entries ''' + ')' +
C in this
E column + D;41;
Csp9 (2x2(')' 9 K' )';)29 7x2(')'
)))2
)'25(27('
)''(K
x
=
=
x 9 Solubility o& 0g2Cr#79 7F )';D+
4Cr#72;8 9 x 9 7F )';D +
40g!8 9 2x 9 K5 )';D+
+x+2x
> T ?
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Jespersen/Brady/HyslopChemistry:TheMolecularNatureofMatter,6E
>our Turn?hat e&&ect would adding copper(>> nitrate
ha%e on the solubility o& CuSN0 he solubility would increase
B he solubility would decrease
C he solubility would not change
$7
> T ?
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Jespersen/Brady/HyslopChemistry:TheMolecularNatureofMatter,6E
>our Turn?he molar solubility o& 6b
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Jespersen/Brady/HyslopChemistry:TheMolecularNatureofMatter,6E
Pre$ictin/ if Precipitate &ill *orm
>n maIing a solution containing %arious ions1
will the salt precipitate at the gi%enconcentrationsN
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Jespersen/Brady/HyslopChemistry:TheMolecularNatureofMatter,6E
Pre$ictin/ if Precipitate &ill *orm
>n maIing a solution containing %arious ions1
will the salt precipitate at the gi%enconcentrationsN
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Jespersen/Brady/HyslopChemistry:TheMolecularNatureofMatter,6E
Pre$ictin/ if Precipitate &ill *orm
$
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E 6 P $i ti P i it ti
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Jespersen/Brady/HyslopChemistry:TheMolecularNatureofMatter,6E
E4 6 Pre$ictin/ Precipitation >& reaction goes essentially to completion1 what
will &inal equilibrium concentrations beN
) -o stoichiometric calculations &or precipitate&ormation
2 hen do equilibrium calculations to determine ion
concentrations in solutionStep 14 Stoichiometric Calculation
Pb+(a)" +#- (a)" Pb#+(s"
Be&orerxn
()''m=(''5''+9 5'' mmol (2''m=(')''+9 2''' mmol "o e&&ect on Csp
0&ter:xn
!4;; - !4;; ;4;; mmol
+;4;; - +(!4;;" 1; mmol
72
E 6 P e$ictin/ P ecipitation
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Jespersen/Brady/HyslopChemistry:TheMolecularNatureofMatter,6E
E4 6 Pre$ictin/ PrecipitationStep +4 System at equilibrium
Some small amount o& 6b>2redissol%es to &ormequilibrium 46b2!8
Basically a common ion problem
Pb#+(s" Pb+(a)" +#-(a)"
>nitial conc.ns ''' )''mmol/$''m=9 $$$ x )';2+
Equilibrium
conc.ns
$$$ x )';2+ ! 2xQ $$$ x )';2+
!x
Csp9 )7 )';9 46b2!84>-829 (x($$$ x )';22
86b4)'$)
)'$$$(
)'7)x 25
22
H+
==
= +
7$
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E F Pre$ictin/ Precipitation
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Jespersen/Brady/HyslopChemistry:TheMolecularNatureofMatter,6E
E4 F Pre$ictin/ Precipitation
Suppose you mix )''' m= o& '2'' + BaCl2
with 5'' m= o& ''$'' + "a2S#7 illBaS#7(sp9 )) )'
;)' precipitateN
7aS=(s" 7a+(a)" S=
+-(a)"
sp9 4Ba2!84S#7
2;8
Step 14Calculate concentrations
4Ba2!8 9 ')$$ +
m=
m=
mol
mol+
')5'
')''
BaCl)
Ba)BaCl2'''8Ba4
2
2
22
=
+
+
75
E F Pre$ictin/ Precipitation
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Jespersen/Brady/HyslopChemistry:TheMolecularNatureofMatter,6E
E4 F Pre$ictin/ Precipitation
4S#72;8 9 '')'' +
Step +4 Calculate 8sp8sp9 4Ba
2!
84S#72;
8 9 (')$$('')'' 8sp9 )$$ )'
;$
Step
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Jespersen/Brady/HyslopChemistry:TheMolecularNatureofMatter,6E
p an$ Solubility M/("+(s" M/
+(a)" +-(a)"
#H; shi&t equilibrium to le&t 0dd H! shi&t equilibrium to right
=e Chatelier.s 6rinciple
./
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Jespersen/Brady/HyslopChemistry:TheMolecularNatureofMatter,6E
>our Turn?hat is the molar solubility o& 6b>2in pure
waterN sp9 K x )'@K
0 2) x )'@$
B )F x )'@$
C 7K x )'@5
- )7 x )'@$
6b>2(s 6b2! ! 2>@
9 K) x )' 9 46b2!84>@8 9 s (2s2
s 9 )7 x )'@$+
7
>our Turn?
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Jespersen/Brady/HyslopChemistry:TheMolecularNatureofMatter,6E
>our Turn?hat is the molar solubility o& 6b>2in '2'+"a>
solutionN Csp9 FK )';K
0 $K x )'@)'
B 27 x )'@F
C D) x )'@K
- 27 x )'@F
6b>2(s 6b2! ! 2>@ 4>@8 9 '2'+
9 FK x )'@K9 46b2!84>@829 46b2!8('2'2
46b2!8 9 27 x )'@F+
+olar solubility 9 46b2!8 9 27 x )'@F+7K
>our Turn?
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Jespersen/Brady/HyslopChemistry:TheMolecularNatureofMatter,6E
>our Turn?hat is the molar solubility o& 6b>2in '2'+
6b("#$ solutionN Csp9 FK )';K
0 7K x )'@
B $F x )'@$
C )) x )'@7
- 22 x )'@7
6b>2(s 6b2! ! 2>@ 4>@8 9 '2'+
9 FK x )'@K9 46b2!84>@829 ('2' 4>@82
4>@8 9 22 x )'@7+
+olar solubility 9 )/2 4>@8 9 )) x )'@7+5'
>our Turn?
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Jespersen/Brady/HyslopChemistry:TheMolecularNatureofMatter,6E
>our Turn?;N
0 0dding 6b2!increases the solubility o& 6b>2
more than >@
B 0dding >@decreases the solubility o& 6b>2
more than 6b2!
C 0dding 6b2!decreases the solubility o&6b>2 more than >
@
- hey both ha%e the same e&&ect on the
solubility o& 6b>2 5)
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Solubility and Simultaneous
Equilibria
6art 2
Metal i$es @n$er/o %eaction
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Metal i$es @n$er/o %eaction&ith 'ater
5$
3sually ignore reaction o& ionic solid with water >& the anion o& a salt is %ery basic1 a subsequent
reaction o& the anion with water occurs
Such is the case o& many metal oxides
0b&or #2;9 ) M)'22
So 0g2# actually dissociates to &orm 0g!and #H;
0sp%alue listed taIes this subsequent reaction into account
0g2#(s20g!(aq! #2;(aq 0sp
#2;(aq! H2# 2#H;(aq 0b
0g2#(s! H2# 20g!(aq! 2#H;(aq 0net
Metal Sulfi$es .lso @n$er/o %eaction
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Jespersen/Brady/HyslopChemistry:TheMolecularNatureofMatter,6E
Metal Sulfi$es .lso @n$er/o %eaction'ith 'ater
57
Sul&ide ion (S2;
is also %ery basic -oesn.t exist in aqueous solution
+etal sul&ides also undergo a subsequent
reaction with water0g2S(s 20g
!(aq ! S2;(aq 0sp
S2;(aq! H2# #H;(aq! HS;(aq 0b
0g2S(s! H2# 20g!(aq! #H;(aq! HS;(aq0net.ctual 0sp940g
!824#H;84HS;8
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*ormation of #nsoluble Metal Sulfi$es
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Jespersen/Brady/HyslopChemistry:TheMolecularNatureofMatter,6E
Sul&ur is below oxygen in ,roup >0
0s a result1 metal sul&ides are similar tometal oxides S2;(liIe #2; is too strong o& a base to exist in
water Sul&ides dissol%e by reacting with water
E4 "a2S(s! H2# 2"a!(aq! HS;(aq! #H;(aq
*ormation of #nsoluble Metal Sulfi$es
5D
7asic Salts .re More Soluble #n
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Jespersen/Brady/HyslopChemistry:TheMolecularNatureofMatter,6E
7asic Salts .re More Soluble #n.ci$s
5F
Subsequent reactions assist the solubility o& solids >& anion o& salt is basic1 it will react in acidic
solution to dissol%e more &ully
"et reaction o& such dissolutions is called Cspa
nS(s n2!(aq ! S2;(aq 0sp
S2;(aq! H!(aqHS;(aq 1I0a+
HS;
(aq! H!
(aq
H2S
(g 1I0a1nS(s! 2H!(aqn2!(aq ! H2S(aq 0spa
0spa(acidic an$ 0sp(basic are listed in able )2
9earnin/ ChecJ
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Jespersen/Brady/HyslopChemistry:TheMolecularNatureofMatter,6E
9earnin/ ChecJ
5
hat is the molar solubility o& BaC#$in $' +
HClN CspBaC#$9 5' x )'
UK
H2C#$ Ca) 9 7$ x )'UFa2 9 7F x )'
U))
7aC
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%eaction of Metal ions &ith S +etal sul&ides can &orm
Some metal ions are so reacti%e that they reactwith H2S directly
hese acti%e ions include Cu2!1 6b2!1 and "i2!
0 typical reaction is
Cu2!(aq! H2S(aq CuS(s! 2H!(aq
=arge %alue o& Cindicates that Equilibrium lies &ar to right
#nly &orward reaction important
Sul&ides require closer in%estigation