CHEMISTRY 1B

SOLUTIONS TO EXAM #2 STUDY GUIDE PROBLEMS

1] a) We need to know the molarity of the original acid solution. The first end point happens at 30mL of base added. First step of neutralization: H2A + OH ! H2O + HA " 0.240 M NaOH %" 30.0 mLbase %" 1 moleH 2 A %" % 1 $ '$ '$ '$ ' = 0.360 M H 2 A L base # &# &# 1moleNaOH &# 20.0 mLacid & Now, we can calculate Ka1 using the pH shown on the graph when 20 mL of base have been added. 20.0 mL is in the buffer region before the first end point. rxn: H2A + OH ! HA + H2O initial mmols 7.20 4.80 0 change -4.80 -4.80 +4.80 final mmols 2.40 0 4.80 final M (V=40.0mL) 0.0600 0 0.120 equilibrium: H2A ! H+ + HA pH = 4.00, so [H+] = 1.0 x 104 [ H + ][ HA" ] (1.0 x10"4 )(0.120 + 1.0 x10"4 ) K a1 = = = 2.0 x10"4 "4 [ H 2 A] (0.0600 " 1.0 x10 ) b) We can calculate Ka2 using the pH shown on the graph when 40 mL of base have been added. second step of the neutralization: HA + OH ! A2 + H2O 40.0 mL of base added is 10.0 mL past the first equivalence point (2.40 mmoles of base added to HA) rxn: HA + OH ! A2 + H2O initial mmols 7.20 2.40 0 change -2.40 -2.40 +2.40 final mmols 4.80 0 2.40 final M (V=60.0mL) 0.0800 0 0.0400 equilibrium: HA ! H+ + A2 pH = 8.00, so [H+] = 1.0 x 108 [ H + ][ A 2" ] (1.0 x10"8 )(0.0400 + 1.0 x10"8 ) Ka2 = = = 5.0 x10"9 " "8 [ HA ] (0.0800 " 1.0 x10 ) c) At 0.0 mL of base added, the only principal specie is H2A, with a concentration of 0.360 M. equilibrium: H2A ! H+ + HA [ H + ][ HA" ] ( x )( x ) K a1 = = = 2.0 x10"4 x = [H+] = 8.5 x 10-3; pH = 2.07 [ H 2 A] (0.360 " x ) d) At 10.0 mL of base added, we are in the first buffer region. rxn: H2A + OH ! HA + initial mmols 7.20 2.40 0 change -2.40 -2.40 +2.40 final mmols 4.80 0 2.40 final M (V=30.0mL) 0.160 0 0.0800 equilibrium: H2A ! H+ + HA [ H + ][ HA" ] ( x )(0.0800 + x ) K a1 = = = 2.0 x10"4 x = [H+] = 4.0 x 10-4; pH = 3.40 [ H 2 A] (0.160 " x ) H2O

e) At 30.0 mL of base added, we are at the first equivalence point. The only principal specie is HA. two equilibria: HA ! H+ + A2 HA + H2O ! H2A + OH Since this is an amphoteric specie, we can use the relationship: pH = 1 2 (3.70 + 8.30) = 6.00
pH = 1 2 ( pK a1 + pK a 2 )

f) At 50 mL of base added we are 20.0mL past the first equivalence point, in the second buffer region. ! rxn: HA + OH ! A2 + H2O initial mmols 7.20 4.80 0 change -4.80 -4.80 +4.80 final mmols 2.40 0 4.80 final M (V=70.0mL) 0.0343 0 0.0686 equilibrium: HA ! H+ + A2 x = [H+] = 2.5 x 10-9; pH = 8.60

[ H + ][ A 2" ] ( x )(0.0686 + x ) Ka2 = = = 5.0 x10"9 " [ HA ] (0.0343 " x )

g) At 60 mL of base added we are at the second equivalence point. The only principal specie is A2, which will hydrolyze (only the first step is significant for finding pH). equilibrium: A2 + H2O HA + OH

[ HA" ][OH " ] Kw 1.0 x10"14 = = = 2.0 x10"6 [ A 2" ] K a forHA" 5.0 x10"9 7.20 mmols ( x )( x ) [ A 2" ] = = 0.0900 M 2.0 x10"6 = 80.0 mL 0.0900 " x Kb = !
!
x = [OH] = 4.24 x 10-4; pOH = 3.37; pH = 10.63

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h) At 70 mL of base added, we are 10 mL past the second equivalence point. The pH is determined by the excess 2.40 mmols of base added. 2.40 mmols pOH = 1.57; pH = 12.43 [OH " ] = = 0.0267 M 90.0 mL 2] First, we need to calculate the molarity of the base(B). The endpoint occurs at 25.0 mL of acid added. " 0.100 M HCl %" 25.0 mLacid %" 1 moleB %" % 1 $ '$ '$ '$ ' = 0.125 M B # L acid &# &# 1moleHCl &# 20.0 mLbase & Second, we need to calculate Kb for this base using the pH shown at 10 mL of acid added. rxn: B + H+ ! HB+ initial mmols 2.50 1.00 0 change -1.00 -1.00 +1.00 final mmols 1.50 0 1.00 final M (V=30.0mL) 0.0500 0 0.0333

equilibrium:

B + H2O

HB+ + OH

[ HB + ][OH " ] (0.0333 + 5.9 x10"9 )(5.9 x10"9 ) Kb = = = 3.9 x10"9 "9 [ B] (0.0500 " 5.9 x10 )
a) At 0 mL of acid added, the only principal specie is 0.125M B. [ HB + ][OH " ] ( x )( x ) Kb = = = 3.9 x10"9 x = [OH] = 2.2 x 10-5; pOH = 4.65; pH = 9.35 [ B] (0.125 " x ) b) At 20 mL of acid added, we are in the buffer region before the end point. rxn: B + H+ ! HB+ initial mmols 2.50 2.00 0 change -2.00 -2.00 +2.00 final mmols 0.50 0 2.00 final M (V=40.0mL) 0.0125 0 0.0500 [ HB + ][OH " ] (0.0500 + x )( x ) Kb = = = 3.9 x10"9 x = [OH] = 9.75 x 10-10 ; pOH = 9.01; pH = 4.99 [ B] (0.0125 " x ) c) At 25 mL of acid added, we are at the equivalence point. The only principal specie is HB+, which will hydrolyze.. 2.50 mmols [ HB + ] = = 0.0556 M 45.0 mL equilibrium: HB+ ! B + H+

[ H + ][ B] Kw 1.0 x10"14 Ka = = = = 2.6 x10"6 + "9 [ HB ] K b forB 3.9 x10 ( x )( x ) x = [H+] = 3.8 x 10-4; pH = 3.42 Ka = = 2.0 x10"6 0.0556 " x
d) At 30 mL of acid added, we are 5 mL past the equivalence point. The pH is determined by the 0.500 mmoles of excess acid. 0.500 mmols pH = 2.00 [H + ] = = 0.0100 M 50.0 mL 3] a) PbS and SnS have the same type of Ksp expression, so their solubilities can be compared directly by looking at the Ksp values. PbS has a lower Ksp so it will PPT first (at a lower [S2]). Calculate the [S2] at which SnS would begin to PPT: equilibrium: SnS(s) ! Sn2+ + S-2
[ S 2" ] = 1.0 x10"25 = 1.0 x10"24 0.10

!
!

Ksp = 1.0 x 10-25 = [Sn2+][S2] ; [Sn2+] is given as 0.10M

As long as [S2] stays below 1.0 x 1024, no SnS will PPT.

b) Lets say we keep the [S2] at 9.9 x 1025.

equilibrium: PbS(s) ! Pb2+ + S-2 8.0 x10"28 Ksp = 8.0 x 10-28 = [Pb2+][S2] [ Pb 2 + ] = = 8.1x10"4 9.9 x10"25 (8.1x10"4 )(100%) % Pb 2 + remainingin solution = = 0.81% 0.10 So, more than 99% of the original Pb2+ in the solution has precipitated. !
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4] The Cd2+ will react with the CN to form the complex ion.
"1.50 gCd ( NO3 ) 2 %" 1moleCd ( NO3 ) 2 % (3 2+ $ '$ ' = 6.35 x10 molsof Cd initially # &# 236.4 gCd ( NO3 ) 2 &

rxn: Cd2+ + initial mmols 6.35 change -6.35 final mmols 0 final M (V=500mL) 0 So, [CN] = 0.45 and [Cd(CN)42] = 0.0127 equilibrium: Cd2+ + 4 CN !

4 CN 250 -25.4 225 0.45

Cd(CN)42 0 +6.35 6.35 0.0127

[Cd(CN)4]2 [Cd2+] = 4.4 x 10-18

[Cd (CN ) 4 2" ] (0.0127) Kf = = 7.1x1016 = 2+ " 4 [Cd ][CN ] [Cd 2 + ](0.45) 4

5. The Cu2+ will react with the added ammonia to form the complex ion. Let Q = the mmoles of NH3 at equilibrium. rxn: Cu2+ + 4 NH3 ! Cu(NH3)42+ initial mmols 30.0 Q+120 0 change -30.0 -120 +30.0 final mmols 0 Q 30.0 final M (V=300mL) 0 Q/300 0.100 equilibrium: Cu2+ + 4 NH3 ! [Cu(NH3)4]2+ We want [Cu2+] = 1.0 x 10-8 Q = 11 mmols

(0.100) 4 "8 # Q & (1.0 x10 )% ( $ 300 ' initial NH3 = Q + 120 = 131 mmols !

[Cu( NH 3 ) 4 2 + ] Kf = = 5.0 x1012 = 2+ 4 [Cu ][ NH 3 ]