Chapter 17

Kelarutan dan Keseimbangan

Brady and Senese

5th Edition
1

Fenomena garam sukar larut dalam air

Fakta-fakta menunjukkan terdapat sejumlah garam
yang mudah larut (... NaCl dan AgNO3, ...) dan yang
tidak larut (... AgCl dan CaCO3, ...).
Kenyataannya: pada garam-garam tidak larut, ketika
dimasukkan ke dalam air, terdapat sejumlah kecil
garam yang larut dan membentuk suatu keseimbangan
ion-ion terlarut, contoh:
AgCl(s)

Ag+(aq) + Cl-(aq)

Kajian lebih lanjut menunjukkan setiap garam tidak

larut memiliki karakteristik kelarutan masing-masing,
yang ditunjukkan oleh nilai keseimbangan Ksp.
17.1. An insoluble salt is in equilibrium with the solution around it

Fenomena garam sukar larut dalam air

Fakta-fakta menunjukkan terdapat
sejumlah garam yang mudah larut
(... NaCl dan AgNO3, ...) dan yang
tidak larut (... AgCl dan CaF2, ...).
Kenyataannya: pada garam-garam
tidak larut, ketika dimasukkan ke
dalam air, terdapat sejumlah kecil
garam yang larut dan membentuk
suatu keseimbangan ion-ion terlarut,
contoh:
CaF2(s)

Ca2+(aq) + 2F-(aq)

17.1. An insoluble salt is in equilibrium with the solution around it

Konstanta hasil kali ion terlarut

Contoh:
AgCl(s)

Ag+(aq) + Cl-(aq)

Ksp = [Ag+][Cl] = 1,8 10-10

konstanta hasil kali ion terlarut

17.1. An insoluble salt is in equilibrium with the solution around it

Kajian lebih lanjut

menunjukkan setiap
garam tidak larut
memiliki karakteristik
kelarutan masingmasing, yang
ditunjukkan oleh nilai
keseimbangan Ksp.

Arti konstanta hasil kali ion terlarut

Contoh:
AgCl(s)

Ag+(aq) + Cl-(aq)

Ksp = [Ag+][Cl] = 1,8 10-10

Kelarutan AgCl = 1,34 x 10-5 M
Nilai yang tetap pada suhu tetap
penambahan salah satu ion ke
dalam air akan mengurangi
kelarutan (efek ion senama)
Apabila dalam suatu larutan hasil kali ion-ion
terlarut (Q) melebihi Ksp garam akan diendapkan
digunakan sebagai dasar pada pemurnian
dengan cara kristalisasi

Q > Ksp lewat jenuh

Q = Ksp jenuh
Q < Ksp tidak jenuh

17.1. An insoluble salt is in equilibrium with the solution around it

Efek ion senama

Contoh:

Learning Check
Write the reactions and mass action expressions for the
dissolution of the following substances in water:
Ag2CO3

Ag2CO3(s)

2Ag+(aq) + CO32-(aq)

Ksp = [Ag+]2[CO32]
(NH4)2SO4
(NH4)2SO4(s)
2NH4+(aq) + SO42-(aq)
Ksp = [NH4+]2[SO42]
17.1. An insoluble salt is in equilibrium with the solution around it

Learning Check
What is the molar solubility of AgCl at 25 C?
AgCl(s)

Ag+(aq) + Cl-(aq)

I
C

N/A
-x

0
+x

0
+x

N/A

AgCl Ksp 1.8 10-10

x2 = 1.8 10-10
molar solubility = 1.3 10-5 M
17.1. An insoluble salt is in equilibrium with the solution around it

Learning Check
What is the molar solubility of Ca3(PO4)2 at 25 C?

Ca3(PO4)2(s)
I
C
E

3Ca2+(aq) + 2PO43-(aq)

N/A
-x
N/A

0
+3x
3x

0
+2x
2x

Ca3(PO4)2 Ksp 2.0 10-29

> (3x)3(2x)2 = Ksp

> molar solubility = 7.1 10-7 M
17.1. An insoluble salt is in equilibrium with the solution around it

Your Turn!
What is the molar solubility of Ba3(PO4)2?
Ksp = 1.30 10-29
A. 1.17 10-7 M
B. 2.17 10-20 M
C. 6.55 10-7 M
D. None of these

17.1. An insoluble salt is in equilibrium with the solution around it

10

Learning Check
Given solubilities, we can find Ksp
The solubility of an salt, A2B3, is found to be
3.0 10-5 M. What is the value of Ksp?
2.6 10-21
If the solubility of a salt, AB2, is found to be
2.5 10-6 M, what is its Ksp?
6.3 10-17

17.1. An insoluble salt is in equilibrium with the solution around it

11

Learning Check: Common Ion Effect

What is the molar solubility of Ca3(PO4)2 in 0.1 M
Na3PO4? Ksp= 2.0 1029
1. Na3PO4 is strong electrolyte - ionized at the start
Na3PO4 3Na+(aq) + PO43-(aq)
0.1 M 0.3 M
0.1 M
2. Ca3(PO4)2
I
C
E

N/A
-x
N/A

3Ca2+(aq) + 2PO43-(aq)
0
+3x
3x

0.1 M
+2x
0.1 + 2x 0.1

> (3x)3(0.1)2 = Ksp > molar solubility 4.2 10-10 M

17.1. An insoluble salt is in equilibrium with the solution around it

12

Learning Check: Common Ion Effect

Calculate the molar solubility of BaSO4 in 0.1 M
BaCl2. Ksp = 1.1 10-10
1. BaCl2 is a strong electrolyte.
BaCl2 Ba2+(aq) + 2Cl-(aq)
0.1 M 0.1 M
0.2 M
2. BaSO4(s)
I N/A
C -x
E N/A

Ba2+(aq) + SO42-(aq)
0.1 M
0
+x
+x
0.1 + x 0.1 x

> x(0.1) = Ksp

> 1.1 10-9 M

17.1. An insoluble salt is in equilibrium with the solution around it

13

Your Turn!
What will happen to the solubility of Ba3(PO4)2 if
solid BaCl2 is added?
A. It increases
B. It decreases
C. It does not change
D. Not enough information given

17.1. An insoluble salt is in equilibrium with the solution around it

14

Learning Check
Will the following form a precipitate?
20.00 mL of 0.1 M CaCl2 + 20.00 mL 0.01 M Na2CO4
Ca2+(aq) + C2O42-(aq)
CaC2O4(s)
Ksp = 2.3 109 = [Ca2+][C2O42]
Qsp = 0.00025

Ksp = 2.3 109

Qsp > Ksp a precipitate will form

10.00 mL of 0.1 M Pb(NO3)2 + 10.00 mL of 0.001 M CaCl2

PbCl2(s)
Pb2+(aq) + 2Cl-(aq)
Ksp = 1.7 105 = [Pb2+][Cl-]2
Qsp = 1.3 10-8

Ksp = 1.7 105

Qsp < Ksp no precipitate will form

17.1. An insoluble salt is in equilibrium with the solution around it

15

Your Turn!
Pb(NO3)2 is added to a solution of HCl until the
mixture is 0.1 M in Pb2+ and 0.005 M in Cl-. Will a
precipitate form? Ksp = 1.7 10-5
A. No
B. Yes
C. Not enough information is given

17.1. An insoluble salt is in equilibrium with the solution around it

16

Meningkatkan kelarutan garam atau oksida

Garam-garam atau oksida yang sukar larut dalam air, dapat
ditingkatkan kelarutannya dengan penambahan asam
Contoh:
Ksp (CaCO3)
1/K2 (H2CO3)

Ktotal = Ksp (CaCO3)/K2 (H2CO3)

Ksp (CaCO3) = 4,5 x 10-9
K2 (H2CO3) = 4,7 x 10-11
jauh lebih besar dari Ksp

Ktotal = 4,5 x 4,7 x 102 = 2,1 x 103

Ktotal =

kelarutan semakin besar jika

[H3O+] semakin tinggi

[Ca2+] [HCO3-]
[H3O+]

[Ca2+] [HCO3-] = [H3O+] 2,1 x 103

17

Meningkatkan kelarutan garam atau oksida

Kelarutan CaCO3
semakin bertambah
pada kondisi larutan
yang lebih asam

18

Meningkatkan kelarutan garam

Garam-garam yang sukar larut dalam air, dapat ditingkatkan
kelarutannya dengan penambahan basa Lewis senyawa kompleks
Contoh:

AgCl
dalam
air

AgCl dalam air

dan ditambahkan NH3

19

Meningkatkan kelarutan garam

Garam-garam yang sukar larut dalam air, dapat ditingkatkan
kelarutannya dengan penambahan basa Lewis senyawa kompleks
Contoh:

20

Meningkatkan kelarutan garam

Garam-garam yang sukar larut dalam air, dapat ditingkatkan
kelarutannya dengan penambahan basa Lewis senyawa kompleks
Contoh:

21

Kelarutan oksida dan sulfida

Kelarutan oksida atau sulfida dalam air bisa terjadi karena O2- atau S2bersifat sangat basa, sehingga bereaksi dengan air membentuk OHContoh:

+
2Ag2O(s) 2 Ag (aq)
+ O(aq)

2O(aq)
+ H2O(l) 2 OH (aq)

Ksp
Kb
-

+
Ag2O(s) + H2O(l) 2 Ag (aq)
+ 2OH(aq)

Ag2S(s) 2Ag+(aq) + S2-(aq)

Knet

Ksp

S2-(aq) + H2O OH-(aq) + HS-(aq)

Kb

Ag2S(s) + H2O OH-(aq) + HS-(aq) + 2Ag+(aq) Knet

17.2. Solubility equilibria of metal oxides and sulfides involve reaction with water

22

Learning Check
What is the molar solubility of BaCO3 in 3 M HCl?
BaCO3
H2CO3

Ksp = 5.0 109

Ka1= 4.3 107

Ka2 = 4.7 1011

BaCO3(s) + 2H+(aq) H2CO3(aq) + Ba2+(aq)

I N/A
3
0
0
C -x
-2x
+x
+x
E N/A
3 - 2x
x
x
K net =

K sp

K a1 K a 2

x2

( 3 2x )

5.0 10 9

) (

4.3 10 9 4.7 10 11

= 2.47 1010

= 2.47 1010

1.50 M

17.2. Solubility equilibria of metal oxides and sulfides involve reaction with water

23

Your Turn!
What is Knet for the molar solubility of Ba3(PO4)2 in 6
M HCl?
Ba3(PO4)2(s) + 6HCl(aq) 2H3PO4(aq) + 3BaCl2(aq)
A.
B.
C.
D.

K sp
Ka 2
Ka 2
K sp
K a1 2 K a 2 2 K a 2 2
K sp
K sp
K a1 2 K a 2 2 K a 2 2
17.2. Solubility equilibria of metal oxides and sulfides involve reaction with water

24

Pengendapan garam secara selektif

Suatu ion dapat berkompetisi dalam mengendapkan suatu
garam dari campuran ion-ion karena nilai Ksp yang
berbeda-beda
Contoh: penambahan ion Cl- ke dalam campuran garam
nitrat dari Ag dan Pb, akan mengendapkan AgCl ketika nilai
Ksp-nya terlampaui

17.3. Metal ions can be separated by selective precipitation

25

Learning Check
What concentration of I- is needed to precipitate one ion but not
the other in a mixture of 0.1 M Pb2+ and 0.1 M Ag+?
AgI(s) Ag+(aq) + I-(aq)
Ksp = [Ag+][I-] = 8.3 10-17

PbI2(s) Pb2+(aq) + 2I-(aq)

Ksp = [Pb2+][I-]2 = 7.9 10-9

[I-] = 8.3 10-16 M

AgI tdk mengendap
AgI mengendap

AgI

batas konsentrasi I- jenuh

[I-] = 2.8 10-4 M
PbI2 tdk mengendap
PbI2 mengendap
batas konsentrasi I- jenuh
AgI dan PbI2 tidak
mengendap

AgI mengendap
PbI2 tdk mengendap

AgI dan PbI2

mengendap

PbI2

Learning Check
At what pH will one ion ppt but not the other in a mixture of
0.1 M Mn2+, 0.1 M Fe3+?
Fe(OH)3(s) Fe3+(aq) + 3OH-(aq)
Ksp = [Fe3+][OH-]3 = 1.6 10-39

Fe: pH = 1.40

Mn(OH)2(s) Mn2+(aq) + 2OH-(aq)

Ksp = [Mn2+][OH-]2 = 1.6 10-13

Mn: pH = 8.10
pH

17.3. Metal ions can be separated by selective precipitation

27

Your Turn!
When a solution containing 0.1 M Ca2+ and 0.01 M
Mg2+, what concentration of CO32- will precipitate
one but not the other?
A. 5 10-8
Ksp
B. 5 10-7
CaCO3
4.8 10-9
C. 5 10-6
MgCO33H2O 4.0 10-5
D. All of these will do
E. None of these will do

17.3. Metal ions can be separated by selective precipitation

28

Learning Check
What pH will prevent the precipitation of any metal ions
in 0.1 M H2S, 0.1 M Cu2+, and 0.1 M Pb2+?
Cu2+(aq) + H2S(aq) 2H+(aq) + CuS(s)
Kspa = 6 1016
6 1016

Cu 2+ [ H 2S]

=
2
H+

Pb2+(aq) + H2S(aq) 2H+(aq) + PbS(s)

Kspa = 3 107
3 10

Pb 2+ [ H 2S]

=
2
H+

CuS pH= -6.61

PbS pH= -2.26

pH

17.3. Metal ions can be separated by selective precipitation

29

Complexation and Kinst

Complex ions are charged particles in which a
metal ion is surrounded by anions or molecules
called ligands, L
Complex ions are soluble, hence complexation is a
means of dissolving some solids
Complexes are governed by the instability
constant, Kinst
M(L)nm+(aq) Mm+(aq) + nL(aq)
When we reverse an equation, we invert K, thus
Kform = 1/Kinst.
17.4 Complex ions participate in equilibria in aqueous solutions

30

Aqueous Metal Ions are Complex Ions

In the solvation of ionic compounds, ions are
dissolved in water through ion-dipole interactions
Water acts as a ligand, the Lewis base that forms a
coordinate covalent bond with the metal

17.4 Complex ions participate in equilibria in aqueous solutions

31

Learning Check
What is the concentration of Cu2+ available when
10.0 mL 0.1 M Cu2+ are combined with 10.0 mL of
0.01 M NH3?
Kform = 1.1 1013

Cu2+(aq) + 4NH3(aq)

[Cu(NH3)4]2+(aq)

0.048 M

17.4 Complex ions participate in equilibria in aqueous solutions

32

Learning Check
Calculate the molar solubility of Ag2S in 2 M NH3.
Ag2S Ksp = 6.0 10-51

Ag2S(s) + 4NH3(aq)

[Ag(NH3)2+] Kinst= 6.3 108

2[Ag(NH3)2]+ + S2-(aq)

1.8 10-12 M

17.5 Complex ion formation increases the solubility of a salt

33

Your Turn!
What is the molar solubility of Co2S3 in 6.0 M NH3
A. 1.8 10-11 M Co S + 12NH 2Co(NH ) 3+ + 3S22 3
3
3 6
-57
B. 4.6 10 M (2x)2 (3x)3 Ksp
57
=
=

5.37
10
2
C. 2.3 10-3 M
(6 12x)12 Kinst
D. None of these 108x 5
57
12

= 5.37 10

x = 1.61 10-10
[Co(NH3)6]3+
Co2S3

Kinst = 2.2 10-34

Ksp = 2.6 10 -124

17.5 Complex ion formation increases the solubility of a salt

34