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CHM12-3

Lecture Unit 5
 BASIC CHEMICAL AND IONIC EQUILIBRIA

1
Unit Goals

1. Chemical Equilibrium Basic Concepts


2. The Equilibrium Constant and Reaction Quotient
3. Le Chatelier‟s Principle
4. Partial Pressures and Kc –Kp Relationship
5. Ionic Equilibria Basic Concepts
6. The pH and pOH scales
7. Ionization constants for Acids and Bases
8. Solubility Product Principle

2
Basic Concepts

 Reversible reactions do not go to completion.


 They can occur in either direction
 Symbolically, this is represented as:
cC +dD
a Ag  + b Bg   g  g 

3
Basic Concepts

 Chemical equilibrium exists when two


opposing reactions occur simultaneously at
the same rate.
 A chemical equilibrium is a reversible reaction that
the forward reaction rate is equal to the reverse
reaction rate.
 Chemical equilibria are dynamic equilibria.
 Molecules are continually reacting, even though
the overall composition of the reaction mixture
does not change.

4
Basic Concepts
 Graphically, this is a representation of the
rates for the forward and reverse reactions
for this general reaction.
cC +dD
a Ag  + b Bg   g  g 

5
Basic Concepts

 One of the fundamental ideas of chemical


equilibrium is that equilibrium can be
established from either the forward or reverse
direction.

6
The Equilibrium Constant

 For a simple one-step mechanism reversible


reaction such as:

A(g)  B(g)  C(g)  D(g)
 The rates of the forward and reverse reactions
can be represented as:
Rate f  k f A B which represents the forward rate.
Rate r  k r CD which represents the reverse rate.

7
The Equilibrium Constant

 When system is at equilibrium:


Ratef = Rater
Substitute for the rate relationsh ip to give :
k f A B  k r CD
which rearranges to
k f CD

k r A B
8
The Equilibrium Constant

 Because the ratio of two constants is a


constant we can define a new constant as
follows :
kf
 Kc and
kr

Kc 
 C D
A  B
9
The Equilibrium Constant

 Similarly, for the general reaction:



a A(g)  b B(g)  c C(g)  d D(g)
we can define a constant

Kc 
C D
c d
 products

A B
a b  reactants

This expression is valid for all reactions.


10
The Equilibrium Constant
 Kc is the equilibrium constant .
 Kc is defined for a reversible reaction at a
given temperature as the product of the
equilibrium concentrations (in M) of the
products, each raised to a power equal to its
stoichiometric coefficient in the balanced
equation, divided by the product of the
equilibrium concentrations (in M) of the
reactants, each raised to a power equal to its
stoichiometric coefficient in the balanced
equation. 11
The Equilibrium Constant

 Example 17-1: Write equilibrium constant


expressions for the following reactions at
500oC. All reactants and products are gases
at 500oC.


PCl5  PCl3  Cl2

Kc 
PCl3 Cl2 
PCl5  12
The Equilibrium Constant


H 2 + I 2  2 HI
You do it!

13
The Equilibrium Constant


H 2 + I 2  2 HI

Kc 
HI 
2

H 2 I 2 
14
The Equilibrium Constant


4 NH3 + 5 O 2  4 NO + 6 H 2O
You do it!

15
The Equilibrium Constant


4 NH3 + 5 O 2  4 NO + 6 H 2O

Kc =
NO H 2O
4 6

NH3  O 2 
4 5

16
The Equilibrium Constant

 Equilibrium constants are dimensionless


because they actually involve a
thermodynamic quantity called activity.
 Activities are directly related to molarity

17
The Equilibrium Constant

 Example 17-2: One liter of equilibrium mixture from the


following system at a high temperature was found to
contain 0.172 mole of phosphorus trichloride, 0.086 mole
of chlorine, and 0.028 mole of phosphorus pentachloride.
Calculate Kc for the reaction.

PCl5  PCl3  Cl2
 Equil []‟s 0.028 M 0.172 M 0.086 M
You do it!

18
The Equilibrium Constant

Kc 
PCl3 Cl2 
PCl5 
Kc 
0.1720.086
0.028
K c  0.53
19
The Equilibrium Constant

 Example 17-3: The decomposition of PCl5


was studied at another temperature. One
mole of PCl5 was introduced into an
evacuated 1.00 liter container. The system
was allowed to reach equilibrium at the new
temperature. At equilibrium 0.60 mole of
PCl3 was present in the container. Calculate
the equilibrium constant at this temperature.

20
The Equilibrium Constant


PCl5g   PCl3g   Cl2g 
Initial 1.00 M 0 0

21
The Equilibrium Constant


PCl5g   PCl3g   Cl2g 
Initial 1.00 M 0 0
Change - 0.60 M + 0.60 M + 0.60 M

22
The Equilibrium Constant


PCl5g   PCl3g   Cl2g 
Initial 1.00 M 0 0
Change - 0.60 M + 0.60 M + 0.60 M
Equilibriu m 0.40 M 0.60 M 0.60 M

23
The Equilibrium Constant

PCl5g   PCl3g   Cl2g 
Initial 1.00 M 0 0
Change - 0.60 M + 0.60 M + 0.60 M
Equilibriu m 0.40 M 0.60 M 0.60 M

K '

0.60 0.60 
 0.90 at another T
c
0.40 24
The Equilibrium Constant

 Example 17-4: At a given temperature 0.80


mole of N2 and 0.90 mole of H2 were placed
in an evacuated 1.00-liter container. At
equilibrium 0.20 mole of NH3 was present.
Calculate Kc for the reaction.
You do it!

25
The Equilibrium Constant

N 2(g) + 3 H 2(g)  2 NH3(g)
Initial 0.80 M 0.90 M 0
Change - 0.10 M - 0.30 M + 0.20 M
Equilibriu m 0.70 M 0.60 M 0.20 M

Kc 
NH3 
2

0.20 
2
 0.26
N 2 H 2  0.700.60
3 3

26
Variation of Kc with the
Form of the Balanced Equation
 The value of Kc depends upon how the balanced
equation is written.
 From example 17-2 we have this reaction:


PCl5  PCl3  Cl2
 This reaction has a Kc=[PCl3][Cl2]/[PCl5]=0.53

27
Variation of Kc with the
Form of the Balanced Equation
 Example 17-5: Calculate the equilibrium constant
for the reverse reaction by two methods, i.e, the
equilibrium constant for this reaction.

PCl3  Cl2  PCl5
Equil. []‟s 0.172 M 0.086 M 0.028 M
The concentrations are from Example 17-2.

28
Variation of Kc with the
Form of the Balanced Equation
Kc 
'  PCl5 

 0.028
 1.9
 PCl3 Cl2  0.1720.086
Kc  1 ' or '
Kc  1 K  10.53  1.9
Kc c
 Large equilibrium constants indicate that most of
the reactants are converted to products.
 Small equilibrium constants indicate that only
small amounts of products are formed.
29
The Reaction Quotient
 The mass action expression or reaction quotient
has the symbol Q.
 Q has the same form as Kc
 The major difference between Q and Kc is that
the concentrations used in Q are not
necessarily equilibrium values.
For this general reaction :
aA + bB  cC + dD

Q
C D
c d

A B
a b
30
The Reaction Quotient

 Why do we need another “equilibrium


constant” that does not use equilibrium
concentrations?
 Q will help us predict how the equilibrium will
respond to an applied stress.
 To make this prediction we compare Q with
Kc.

31
The Reaction Quotient

When :
Q = K c The system is at equilibriu m.
Q  K c The reaction occurs to the left to a greater extent.
Q  K c The reaction occurs to the right to a greater extent.
To help understand this think of Q and K c as fractions.

32
The Reaction Quotient
 Example 17-6: The equilibrium constant for the
following reaction is 49 at 450oC. If 0.22 mole of
I2, 0.22 mole of H2, and 0.66 mole of HI were put
into an evacuated 1.00-liter container, would the
system be at equilibrium? If not, what must
occur to establish equilibrium?

33
The Reaction Quotient
The concentrat ions given in the problem
are not necessaril y equilibriu m []' s.
We can calculate Q.
 2 HI
H 2(g)  I 2(g)  (g)

0.22 M 0.22 M 0.66 M

Q=
HI 
2

0.66
2
 9.0
H 2 I 2  0.220.22
Q  9.0 but K c  49
Q < Kc
34
Uses of the Equilibrium Constant, Kc

 Example 17-7: The equilibrium constant, Kc, is


3.00 for the following reaction at a given
temperature. If 1.00 mole of SO2 and 1.00 mole
of NO2 are put into an evacuated 2.00 L
container and allowed to reach equilibrium, what
will be the concentration of each compound at
equilibrium?
SO2(g)  NO2(g) 
 SO3(g)  NO(g)

35
Uses of the Equilibrium Constant, Kc

SO 2(g)  NO2(g) 
 SO3(g)  NO(g)
Initial 0.500 M 0.500 M 0 0

36
Uses of the Equilibrium Constant, Kc

SO 2(g)  NO2(g) 
 SO3(g)  NO(g)
Initial 0.500 M 0.500 M 0 0
Change - xM - xM +xM +xM

37
Uses of the Equilibrium Constant, Kc

SO 2(g)  NO2(g) 
 SO 3(g)  NO(g)
Initial 0.500 M 0.500 M 0 0
Change - xM - xM +xM +xM
Equilibriu m 0.500  x M 0.500  x M xM xM

38
Uses of the Equilibrium Constant, Kc

SO 2(g)  NO2(g) 
 SO 3(g)  NO(g)
Initial 0.500 M 0.500 M 0 0
Change - xM - xM +xM +xM
Equilibriu m 0.500  x M 0.500  x M xM xM

Kc 
SO3 NO  3.00  x x 
SO 2 NO2  0.500  x 0.500  x 
This equation is a perfect square .
We can take the of both sidesof the equation.

39
Uses of the Equilibrium Constant, Kc
SO 2(g)  NO2(g) 
 SO 3(g)  NO(g)
Initial 0.500 M 0.500 M 0 0
Change - xM - xM +xM +xM
Equilibriu m 0.500  x M 0.500  x M xM xM

Kc 
SO 3 NO
 3.00 
 x  x 
SO 2 NO2  0.500  x 0.500  x 
This equation is a perfect square.
We can take the of both sides.
x
1.73 =
0.500  x
0.865 - 1.73 x  x; 0.865  2.73 x; x  0.865
2.73
x  0.316M  SO 3   NO
0.500  x M  0.184M  SO 2   NO2 
40
Uses of the Equilibrium Constant, Kc

 Example 17-8: The equilibrium constant is 49


for the following reaction at 450oC. If 1.00
mole of HI is put into an evacuated 1.00-liter
container and allowed to reach equilibrium,
what will be the equilibrium concentration of
each substance?

H 2(g) + I 2(g)  2 HI (g)
You do it! 41
Uses of the Equilibrium Constant, Kc
 2 HI
H 2(g) + I 2(g)  (g)

Initial 0 0 1.00M
Change + xM + xM - 2x M
Equilibriu m xM xM 1.00 - 2 x  M

Kc =
HI 
2
= 49 =
1.00 - 2 x 
2

H 2 I 2  x x 
K = 7.0 =
1.00 - 2 x 
c
x
7.0 x  1.00  2 x; 9 x  1.00; x  0.11 M
H 2   I 2   xM  0.11 M
HI   1.00  2 x M  0.78 M
42
Le Chatelier’s Principle

 LeChatelier‟s Principle - If a change of conditions


(stress) is applied to a system in equilibrium, the
system responds in the way that best tends to
reduce the stress in reaching a new state of
equilibrium.
 We first encountered LeChatelier‟s Principle in Chapter
14.
 Some possible stresses to a system at
equilibrium are:
1. Changes in concentration of reactants or products.
2. Changes in pressure or volume (for gaseous reactions)
3. Changes in temperature. 43
Le Chatelier’s Principle

 For convenience we may express the amount of


a gas in terms of its partial pressure rather than
its concentration.
 To derive this relationship, we must solve the
ideal gas equation.

44
Le Chatelier’s Principle

PV  nRT
n
P   RT
V
n
Because   has the units mol/L,
V
P = []RT
Thus at constant T, the partial pressure of a gas
is directly proportion al to its concentrat ion.
45
Le Chatelier’s Principle

1 Changes in Concentration of Reactants and/or Products


• Also true for changes in pressure for reactions involving gases.
 Look at the following system at equilibrium at 450oC.

 2 HI
H2  I2  g 

Kc 
HI 
 49
2

H 2 I 2 
46
Le Chatelier’s Principle

1 Changes in Concentration of Reactants and/or Products


• Also true for changes in pressure for reactions involving gases.
 Look at the following system at equilibrium at 450oC.
 2 HI
H 2  I2  g 

Kc 
HI 
2
 49
H 2 I 2 
If some H 2 is added, Q < K c .
This favors the forward reaction.
Equilbrium will shift to the right or product side. 47
Le Chatelier’s Principle

1 Changes in Concentration of Reactants and/or Products


• Also true for changes in pressure for reactions involving gases.
 Look at the following system at equilibrium at 450oC.
 2 HI
H 2  I2  g 

Kc 
HI 
2
 49
H 2 I 2 
If we remove some H 2 , Q > K c
This favors the reverse reaction.
Equilbrium will shift to the left, or reactant side. 48
Le Chatelier’s Principle

2 Changes in Volume
• (and pressure for reactions involving gases)
 Predict what will happen if the volume of this system at

equilibrium is changed by changing the pressure at


constant temperature:


2 NO2g   N 2O 4g 

Kc =
N 2O 4 
NO2  2
49
Le Chatelier’s Principle

N O
2 NO2g   2 4 g 

Kc =
N 2O 4 
NO2 2
If the volume is decreased, which increases the pressure, Q < K c .
This favors product formation or the forward reaction.
The forward reaction produces fewer moles of gas.

50
Le Chatelier’s Principle

N O
2 NO2g   2 4 g 

Kc =
N 2O 4 
NO2  2

If the volume is increased, which decreases the pressure, Q > K c .


This favors the reactants or the reverse reaction.
More moles of gas are produced.

51
Le Chatelier’s Principle

3 Changing the Reaction Temperature


 Consider the following reaction at equilibrium:

 2 SO + 198 kJ
2 SO 2g  + O 2g   3 g 

Heat is a product of this reaction


Increasing the reaction t emperature stresses the products.
This favors the reverse or reactant reaction.

52
Le Chatelier’s Principle

 Introduction of a Catalyst
 Catalysts decrease the activation energy of both the forward and
reverse reaction equally.

 Catalysts do not affect the position of equilibrium.


 The concentrations of the products and reactants will be the
same whether a catalyst is introduced or not.
 Equilibrium will be established faster with a catalyst.

53
Le Chatelier’s Principle

54
Partial Pressures and the Equilibrium
Constant
 For gas phase reactions the equilibrium
constants can be expressed in partial pressures
rather than concentrations.
 For gases, the pressure is proportional to the
concentration.
 We can see this by looking at the ideal gas law.
 PV = nRT
 P = nRT/V
 n/V = M
 P= MRT and M = P/RT

55
Partial Pressures and the Equilibrium
Constant
 Consider this system at equilibrium at 5000C.

 4 HCl + O
2 Cl2g  + 2 H 2Og   g  2 g 

HCl O 2 
4
PHCl  PO 
4

Kc  and K p 
PCl  PH O 
2

Cl2  H 2O
2 2 2
2
2
2

56
Partial Pressures and the Equilibrium
Constant

Kc 
   
PHCl 4 PO2
PHCl  PO 4
  
1 5

    P  P   
RT RT 2 RT
P 2 P 2 2 2 1 4
Cl2 H 2O
RT RT Cl 2 H 2O RT

Kc  K   so for this
1
p RT reaction
-1 1
K c = K p (RT) or K p = K c (RT)
L atm
Must use R  0.0821
mol K
57
Relationship Between Kp and Kc

 From the previous slide we can see that the


relationship between Kp and Kc is:

K p  K c RT  or K c  K p RT 
n  n

n = (# of moles of gaseous products) - (# of moles of gaseous reactants)

58
Relationship Between Kp and Kc

 Example 17-15: Nitrosyl bromide, NOBr, is


34% dissociated by the following reaction at
25oC, in a vessel in which the total pressure
is 0.25 atmosphere. What is the value of Kp?

2 NOBrg  
 2 NOg  + Br2g 

59
Relationship Between Kp and Kc

2 NOBrg  
 2 NOg  + Br2g 
Initial [] x atm 0 0
Change - 0.34 x atm + 0.34 x atm + 0.17 x atm
Equilibriu m x - 0.34 x atm 0.34 xatm 0.17 x atm

60
Relationship Between Kp and Kc

PTot  PNOBr  PNO  PBr2


0.25 atm = x - 0.34 x  atm  0.34 x atm + 0.17 x atm
0.25 atm = 1.17 x atm, thus x = 0.21 atm.
Because NOBr is 34% dissociate d,
it is 66% undissocia ted.

61
Relationship Between Kp and Kc

PNOBr  x - 0.34 x   0.66 x


PNOBr  0.660.21 atm   0.14 atm
PNO  0.34 x  0.340.21 atm   0.071 atm
PBr2  0.17 x  0.17 0.21 atm   0.036 atm
PNO  PBr
2
  0.071 0.036  9.3 10
2
3
Kp  2

PNOBr 2
0.14 2

62
Relationship Between Kp and Kc

 The numerical value of Kc for this reaction


can be determined from the relationship of Kp
and Kc.

K p = Kc  RT or Kc = K p  RT
n  n
n = 1
Kc  9.3  10 3
0.08212981
 38
.  10 4

63
Relationship Between Kp and Kc

 Example 17-16: Kc is 49 for the following


reaction at 450oC. If 1.0 mole of H2 and 1.0 mole
of I2 are allowed to reach equilibrium in a 3.0-liter
vessel,

H 2g   I 2g   2 HI g 
(a) How many moles of I2 remain unreacted at
equilibrium?
You do it!

64
Relationship Between Kp and Kc
H 2 g    2 HI
I 2 g   g 
Initial 0.33M 0.33M 0
Change -xM -xM + 2x M
Equilibriu m 0.33 - x M 0.33 - x M 2x M

Kc =
HI 
2
 49 
2x
2
 7.0 
2x
H 2 I 2  0.33 - x 2
0.33 - x
9 x = 2.3; x = 0.256 M
[H 2 ]  [I 2 ]  (0.33  x) M  0.074 M
HI   2 x M  0.51M
? mol I 2  3.0 L  0.074 mol L  0.21 mol 65
Relationship Between Kp and Kc

(b) What are the equilibrium partial pressures of


H2, I2 and HI?
You do it!

66
Relationship Between Kp and Kc

PH 2  PI2  MRT  0.074 mol L 0.0821 mol  


K 723 K  4.4 atm
L atm

PHI  MRT  0.51 mol L 0.0821 mol  


K 723 K  30 atm
L atm

67
Relationship Between Kp and Kc

(c) What is the total pressure in the reaction


vessel?
You do it!

68
Relationship Between Kp and Kc

PTot = PH2  PI2  PHI  4.4  4.4  30 atm = 39 atm

69
Heterogeneous Equlibria
 Heterogeneous equilibria have more than one
phase present.
 For example, a gas and a solid or a liquid and a gas.

CaCO3s  
 CaOs   CO2g  at 500 C o

 How does the equilibrium constant differ for heterogeneous


equilibria?
 Pure solids and liquids have activities of unity.
 Solvents in very dilute solutions have activities that are essentially
unity.
 The Kc and Kp for the reaction shown above are:

K c = [CO 2 ] K p = PCO 2
70
Heterogeneous Equlibria
For this reaction :
 H SO
SO 2aq   H 2 O    o
(at 25 C)
2 3aq 

H 2 O   is the solvent.
What are the forms of K c and K p?
You do it!

Kc =
H 2SO3 
K p is undefined
SO 2 
71
Heterogeneous Equlibria

 What are Kc and Kp for this reaction?


 2
CaF2s   Ca aq   2 Faq 
1- o
(at 25 C)
You do it!

Kc = Ca  2
F 
 2
K p is undefined

72
Heterogeneous Equlibria

 What are Kc and Kp for this reaction?



3 Fes   4 H 2Og   Fe3O4s   4 H 2g  (at 500 C)o

 P 
4

Kc =
 H2 
4
Kp 
H2

 H 2 O P 
4 4
H 2O

73
Evaluation of Equilibrium Constants at
Different Temperatures
 From the value of Ho and K at one
temperature, T1, we can use the van‟t Hoff
equation to estimate the value of K at
another temperature, T2.
K T2 H (T2  T1 )
o
ln 
K T1 R T2 T1
or
K T2 H o
1 1
ln    
K T1 R  T1 T2  74
Evaluation of Equilibrium Constants at
Different Temperatures
 Example 17-19: For the reaction in example
17-18, Ho = 114 kJ/mol and Kp = 4.3 x 10-13
at 25oC. Estimate Kp at 250oC.
2 NO2(g)  2 NO(g) + O2(g)

75
Evaluation of Equilibrium Constants
at Different Temperatures
Let T1  298 K and T2  523 K
apply the van' t Hoff equation

76
Evaluation of Equilibrium Constants
at Different Temperatures
Let T1  298 K and T2  523 K
apply the van' t Hoff equation
K T2 (1.14 10 mol )523  298
5 J
ln 
K T1 8.314 J mol K 523 K 298 K 
K T2
ln  19.795
K T1
77
Evaluation of Equilibrium Constants at
Different Temperatures
Take the antilog of both sides of equation.
K T2
 e19.80  4.0  108
K T1
Solve for K T2 & substitute the known valu e of K T1
 
K T2  4.0  108 K T1  4.0  108 4.3  10-13 
4
K T2  1.7 10 @ 250 C vs K T1  4.3  10
o -13 o
@ 25 C
The reaction is more product favored at the higher T.
78
Ionic Equilibria Basic Concept
 This details the equilibria of weak acids and
bases.
 We must distinguish weak acids and bases from strong
electrolytes.
 Weak acids and bases ionize or dissociate
partially, much less than 100%.
 In this unit we will see that it is often less than 10%!
 Strong electrolytes ionize or dissociate
completely.
 Strong electrolytes approach 100% dissociation in
aqueous solutions.

79
Ionic Equilibria Basic Concept
 There are three classes of strong electrolytes.
1 Strong Water Soluble Acids
Remember the list of strong acids from Chapter 4.

100%  
HNO3( )  H 2O (  )  H 3O (aq)  NO 3(aq)

or
100%  
HNO3( )  H (aq)  NO 3(aq)

80
Ionic Equilibria Basic Concept
10 0%  
HNO 3( )  H 2O (  )  H 3O (aq)  NO 3(aq)

or
10 0%  
HNO 3( )  H (aq)  NO 3(aq)

81
Ionic Equilibria Basic Concept
2 Strong Water Soluble Bases
The entire list of these bases was also introduced in
Chapter 4.

H 2 O 100% 
KOH(s)   K (aq)  OH -
(aq)
H 2 O 100% 2
Sr(OH) 2(s)   Sr (aq)  2 OH -
(aq)

82
Ionic Equilibria Basic Concept
3 Most Water Soluble Salts
The solubility guidelines from Chapter 4 will help you remember
these salts.

H 2 O 100% 
NaCl(s)   Na (aq)  Cl -
(aq)
H 2 O 100% 2 
Ca(NO3 ) 2s    Ca (aq)  2 NO 3(aq)

83
Ionic Equilibria Basic Concept

 The calculation of ion concentrations in solutions of


strong electrolytes is easy.
 Example 18-1: Calculate the concentrations of ions
in 0.050 M nitric acid, HNO3.
 
HNO3( )  H 2O(  ) 
 H 3O
100%
(aq)  NO
3(aq)

0.050 M 0.050 M 0.050 M

84
Ionic Equilibria Basic Concept
 Example 18-2: Calculate the concentrations of
ions in 0.020 M strontium hydroxide, Sr(OH)2,
solution.
You do it!
2
Sr(OH) 2(s) 
 Sr
H 2O
(aq)  2 OH -
(aq)

0.020M 0.020M 20.020M 


0.040M

85
The Autoionization of Water

 Pure water ionizes very slightly.


 The concentration of the ionized water is less than one-
millionth molar at room temperature.

86
The Autoionization of Water

 We can write the autoionization of water as a


dissociation reaction similar to those previously done
in this chapter.
 
H 2O( )  H 2O( )  H3O(aq)  OH(aq)
-

 Because the activity of pure water is 1, the

  
equilibrium constant for this reaction is:

Kc  H 3O +
OH
87
The Autoionization of Water

 Experimental measurements have determined that


the concentration of each ion is 1.0 x 10-7 M at 25oC.
 Note that this is at 25oC, not every temperature!
 We can determine the value of Kc from this
information.


Kc  H 3O OH 
+ 

 1.0 x 10 1.0 x 10 
-7 -7

14
 1.0 x10
88
The Autoionization of Water

 This particular equilibrium constant is called the ion-


product for water and given the symbol Kw.
 Kw is one of the recurring expressions for the remainder of
this chapter and Chapters 19 and 20.

K w  H 3O  +
OH  

14
 1.0 x10
89
The Autoionization of Water
 Example 18-3: Calculate the concentrations of
H3O+ and OH- in 0.050 M HCl.

HCl + H 2 O  H 3O +  Cl
0.050M 0.050M 0.050M
 
Thus the H 3O +  0.050M .
 
The H 3O + and K w will allow us to calculate [OH - ].

90
The Autoionization of Water

 Use the [H3O+] and Kw to determine the [OH-].


You do it!

H O OH   1.0 10


3
+  14

OH   H O   5.0 10


14 14
 1.0  10 1.0  10
+ 2
3

OH   2.0 10 M


 13

91
The Autoionization of Water

 The increase in [H3O+] from HCl shifts the


equilibrium and decreases the [OH-].
 Remember from Chapter 17, increasing the product
concentration, [H3O+], causes the equilibrium to shift to the
reactant side.
 This will decrease the [OH-] because it is a product!
The [H 3O  ] from HCl is 0.050M
H 2O  H 2O   H O  OH -
3

The [H 3O ] from K w is 2.0 10 M . -13

The overall [H 3O  ]  0.050  2.0 10-13 M  0.050 M .

92
The Autoionization of Water

 Now that we know the [H3O+] we can calculate the


[OH-].
You do it!
K w  [H 3O  ][OH-]  110-14
Since [H 3O  ]  0.050 M .
1  10 -14
[OH- ] 
[H 3O  ]
1  10 -14
[OH- ] 
[0.050 M ]
[OH- ]  2.0 10 13 M
93
The pH and pOH scales

 A convenient way to express the acidity and basicity


of a solution is the pH and pOH scales.

 
 The pH of an aqueous solution is defined as:

+
pH = -log H 3O

94
The pH and pOH scales

 In general, a lower case p before a symbol is read


as the „negative logarithm of‟ the symbol.
 Thus we can write the following notations.

 
pOH = -log OH -

pAg = -logAg  +

and so forth for other quantities .

95
The pH and pOH scales

 If either the [H3O+] or [OH-] is known, the pH and


pOH can be calculated.
 Example 18-4: Calculate the pH of a solution in
which the [H3O+] =0.030 M.

pH = -log H 3O  +

pH   log 3.0 10  2

pH  1.52
96
The pH and pOH scales

 Example 18-5: The pH of a solution is 4.597. What


is the concentration of H3O+?
You do it!

pH  -log[H 3O ]
4.597  -log[H 3O  ]

log[H 3O ]  -4.597
[H 3O  ]  10-4.597
[H 3O  ]  2.53 10 5 M
97
The pH and pOH scales

 A convenient relationship between pH and pOH may


be derived for all dilute aqueous solutions at 250C.
  14
[H 3O ][OH ]  1.0 10
 Taking the logarithm of both sides of this equation
gives:

 

log H 3O  log OH  14.00  

98
The pH and pOH scales

 Multiplying both sides of this equation by -1 gives:

 
- log H 3O   log OH   
  14.00
 Which can be rearranged to this form:

pH  pOH  14.00

99
The pH and pOH scales

 Remember these two expressions!!


 They are key to the next three chapters!

H O OH   1.0 10


3
  14

pH  pOH  14.00

100
The pH and pOH scales

 The usual range for the pH scale is 0 to 14.

H O   1.0 M to H O   1.0 10


3

3
 14
M
pH  0 to pH  14.00
 And for pOH the scale is also 0 to 14 but
inverted from pH.
 pH = 0 has a pOH = 14 and pH = 14 has a pOH = 0.

OH   1.0 10


 14

M up to OH  1.0M 

pOH  14.00 pOH  0
101
The pH and pOH scales

 Example 18-6: Calculate the [H3O+], pH, [OH-], and


pOH for a 0.020 M HNO3 solution.
 Is HNO3 a weak or strong acid?
 What is the [H3O+] ?
HNO 3  H 2 O   H 3O   NO3-
100%

0.020M 0.020 M 0.020M


H O   2.0 10 M
3
 2

pH  -log 2.0 10 M 


2

pH  1.70
102
The pH and pOH scales

 Example 18-6: Calculate the [H3O+], pH, [OH-], and


pOH for a 0.020 M HNO3 solution.
  
K w  H 3O  OH   1.0 10 14

OH   H O   2.0 10  5.0 10


14 14
 1.0 10 1.0 10 13
 2
M
3

pOH   log 5.0 10   12.30


13

103
The pH and pOH scales
 To help develop familiarity with the pH and pOH scale we can
look at a series of solutions in which [H3O+] varies between 1.0
M and 1.0 x 10-14 M.

[H3O+] [OH-] pH pOH


1.0 M 1.0 x 10-14 M 0.00 14.00
1.0 x 10-3 M 1.0 x 10-11 M 3.00 11.00
1.0 x 10-7 M 1.0 x 10-7 M 7.00 7.00
2.0 x 10-12 M 5.0 x 10-3 M 11.70 2.30
1.0 x 10-14 M 1.0 M 14.00 0.00

104
Ionization Constants for Weak
Monoprotic Acids and Bases
 Let‟s look at the dissolution of acetic acid, a weak
acid, in water as an example.
 The equation for the ionization of acetic acid is:
 
CH3COOH  H 2O  H3O  CH3COO-

 The equilibrium constant for this ionization is


expressed as:

Kc 
H O CH COO 
3

3

CH3COOHH 2O
105
Ionization Constants for Weak
Monoprotic Acids and Bases
 The water concentration in dilute aqueous solutions
is very high.
 1 L of water contains 55.5 moles of water.
 Thus in dilute aqueous solutions:

H2O  55.5M

106
Ionization Constants for Weak
Monoprotic Acids and Bases
 The water concentration is many orders of
magnitude greater than the ion concentrations.
 Thus the water concentration is essentially that of
pure water.
 Recall that the activity of pure water is 1.

K H O 
H O CH COO 
3

3

c 2
CH3COOH
K
H O CH COO 
3

3

CH3COOH
107
Ionization Constants for Weak
Monoprotic Acids and Bases
 We can define a new equilibrium constant for weak
acid equilibria that uses the previous definition.
 This equilibrium constant is called the acid ionization
constant.
 The symbol for the ionization constant is Ka.

Ka 
H O CH COO 
3

 1.8 10
3

5

CH3COOH
for acetic acid
108
Ionization Constants for Weak
Monoprotic Acids and Bases
 In simplified form the dissociation equation and
acid ionization expression are written as:
 
CH3COOH  H  CH3COO-

Ka 
H CH COO 

3

 1.8 10 5

CH3COOH

109
Ionization Constants for Weak
Monoprotic Acids and Bases
 The ionization constant values for several acids are
given below.
 Which acid is the strongest?
Acid Formula Ka value
Acetic CH3COOH 1.8 x 10-5
Nitrous HNO2 4.5 x 10-4
Hydrofluoric HF 7.2 x 10-4
Hypochlorous HClO 3.5 x 10-8
Hydrocyanic HCN 4.0 x 10-10

110
Ionization Constants for Weak
Monoprotic Acids and Bases
 From the above table we see that the order of
increasing acid strength for these weak acids is:
HF > HNO2 > CH3COOH > HClO > HCN
 The order of increasing base strength of the anions
(conjugate bases) of these acids is:
- - - - -
F < NO < CH3COO < ClO < CN
2

111
Ionization Constants for Weak
Monoprotic Acids and Bases
 Example 18-8: Write the equation for the ionization
of the weak acid HCN and the expression for its
ionization constant.
 
HCN  H  CN -

Ka 
H CN 
 -
 4.0 x 10 -10

HCN 

112
Ionization Constants for Weak
Monoprotic Acids and Bases
 Example 18-9: In a 0.12 M solution of a weak
monoprotic acid, HY, the acid is 5.0% ionized.
Calculate the ionization constant for the weak acid.
You do it!


HY  H + Y
+ -

Ka 
 H Y 
+ -

 HY
113
Ionization Constants for Weak
Monoprotic Acids and Bases
 Since the weak acid is 5.0% ionized, it is also 95% unionized.
 Calculate the concentration of all species in solution.

H   Y   0.05(0.12M )  0.0060M
+ 

H   Y   6.0 10 M
+  3

HY   0.95(0.12M )  0.11M

114
Ionization Constants for Weak
Monoprotic Acids and Bases
 Use the concentrations that were just determined in the
ionization constant expression to get the value of Ka.

Ka 
H Y 
 

HY 
Ka 
6.0 10 6.0 10 
3 3

0.11
K a  3.3 10  4

115
Ionization Constants for Weak
Monoprotic Acids and Bases
 Example 18-10: The pH of a 0.10 M solution of a
weak monoprotic acid, HA, is found to be 2.97.
What is the value for its ionization constant?
pH = 2.97 so [H+]= 10-pH

H   10
 2.97

H   1.110
 3
M

116
Ionization Constants for Weak
Monoprotic Acids and Bases
 Use the [H3O+] and the ionization reaction to
determine concentrations of all species.
HA 
 H+  A-

Equil. []'s 0.10 - 1.1  10-3  1.1  10-3 1.1  10-3
 0.10

117
Ionization Constants for Weak
Monoprotic Acids and Bases
 Calculate the ionization constant from this
information.

Ka 
H A  1.1 10 1.1 10 


 -3 -3

HA  0.10
K a  1.2  10 5

118
Ionization Constants for Weak
Monoprotic Acids and Bases
 Example 18-11: Calculate the concentrations of the
various species in 0.15 M acetic acid, CH3COOH,
solution.
 It is always a good idea to write down the ionization
reaction and the ionization constant expression.
CH3COOH  H 2 O 
 H 3O   CH 3COO-

Ka 
H O CH COO 
3

3
-
 1.8 10 5

CH3COOH

119
Ionization Constants for Weak
Monoprotic Acids and Bases
 Next, combine the basic chemical concepts with
some algebra to solve the problem.
CH3COOH  H 2O 
 H 3O   CH3COO-
Initial [] 0.15M

120
Ionization Constants for Weak
Monoprotic Acids and Bases
 Next we combine the basic chemical concepts with
some algebra to solve the problem
CH3COOH  H 2O 
 H 3O   CH3COO-
Initial [] 0.15M
Change - xM  xM  xM

121
Ionization Constants for Weak
Monoprotic Acids and Bases
 Next we combine the basic chemical concepts with
some algebra to solve the problem
 
CH3COOH  H 2O  H 3O  CH3COO-

Initial [] 0.15M
Change - xM  xM  xM
Equilibriu m [] ( 0.15-x)M  xM  xM

122
Ionization Constants for Weak
Monoprotic Acids and Bases
 Substitute these algebraic quantities into the
ionization expression.

Ka 
H 3 O 
CH
3 COO 

CH 3COOH

 x  x   1.8  10 5

0.15  x 

123
Ionization Constants for Weak
Monoprotic Acids and Bases
 Solve the algebraic equation, using a simplifying assumption that
is appropriate for all weak acid and base ionizations.
2
x
 1.8 10 5
0.15  x
x 2  0.15  x 1.8 10 5

124
Ionization Constants for Weak
Monoprotic Acids and Bases
 Solve the algebraic equation, using a simplifying assumption that
is appropriate for all weak acid and base ionizations.

x2
 1.8 10 5
0.15  x
x 2  0.15  x 1.8 10 5
Ka
 10 3 then make this assumption .
If

x is small enough to ignore compared to [].
x  0.151.8 10
2 5

125
Ionization Constants for Weak
Monoprotic Acids and Bases
 Complete the algebra and solve for the concentrations of the
species.
x 2  2.7 10 6
  
x  1.6 10 3 M  H 3O   CH 3COO 
CH3COOH  0.15  1.6 103 M  0.15M

126
Ionization Constants for Weak
Monoprotic Acids and Bases
 Note that the properly applied simplifying assumption gives
the same result as solving the quadratic equation does.
 x  x   1.8  10 5
0.15  X 
5 6
x  1.8  10 x  2.7  10
2
0
a b c
b b 2  4ac
x
2a

127
Ionization Constants for Weak
Monoprotic Acids and Bases

x

 1.8 10 5
  1.8 10 
5 2

 41  2.7 10 6 
21
x  1.6 10 3 and - 1.6 10-3

128
Ionization Constants for Weak
Monoprotic Acids and Bases
 Let us now calculate the percent ionization for the
0.15 M acetic acid. From Example 18-11, we know
the concentration of CH3COOH that ionizes in this
solution. The percent ionization of acetic acid is
CH3COOHionized
% ionization = 100%
CH3COOHoriginal
3
1.6 10 M
% ionization  100%  1.1%
0.15M

129
Ionization Constants for Weak
Monoprotic Acids and Bases
 Example 18-12: Calculate the concentrations
of the species in 0.15 M hydrocyanic acid,
HCN, solution.
Ka= 4.0 x 10-10 for HCN
You do it!

130
Ionization Constants for Weak
Monoprotic Acids and Bases
 H O   CN -
HCN  H 2 O  3

Initial   0.15 M
Change -xM +xM +xM
Equilibriu m 0.15 - x  M xM xM

Ka 
H  CN 



x x   4.0 10 10
HCN  0.15  x
x 2  6.0 10 11
  
x  7.7 10 6 M  H   CN  
HCN   0.15  x  M  0.15 M
131
Ionization Constants for Weak
Monoprotic Acids and Bases
 The percent ionization of 0.15 M HCN solution is
calculated as in the previous example.

% ionization =
HCN ionized
100%
HCN original
6
7.7 10 M
% ionization  100%  0.0051%
0.15M

132
Ionization Constants for Weak
Monoprotic Acids and Bases
 Let‟s look at the percent ionization of two weak
acids as a function of their ionization constants.
Examples 18-11 and 18-12 will suffice.
Solution Ka [H+] pH % ionization
0.15 M 1.8 x 10-5 1.6 x 10-3 2.80 1.1
acetic acid
0.15 M 4.0 x 10-10 7.7 x 10-6 5.11 0.0051
HCN

 Note that the [H+] in 0.15 M acetic acid is 210


times greater than for 0.15 M HCN.

133
Ionization Constants for Weak
Monoprotic Acids and Bases
 All of the calculations and understanding we have at
present can be applied to weak acids and weak
bases!
 One example of a weak base ionization is ammonia
ionizing in water.

134
Ionization Constants for Weak
Monoprotic Acids and Bases
 All of the calculations and understanding we have at
present can be applied to weak acids and weak
bases!
 Example 18-13: Calculate the concentrations of the
various species in 0.15 M aqueous ammonia.
NH3  H 2 O 
 NH4  OH-
Initial [] 0.15M
Change - xM  xM  xM
Equilibriu m [] ( 0.15-x)M  xM  xM
135
Ionization Constants for Weak
Monoprotic Acids and
NH  H O 
Bases
 NH  OH  -
3 2 4

Initial [] 0.15M
Change - xM  xM  xM
Equilibriu m [] ( 0.15-x)M  xM  xM

Kb 
NH OH  

4
-
x x   1.8 10 5
NH3  0.15  x 
The simplifyin g assumption is valid.
x  0.15 thus 0.15 - x  0.15
x x  x x   1.8 105

0.15  x  0.15
x 2  (0.15)1.8 10 5
x 2  2.7 10 6 and x  1.6 10-3 M
NH   OH   1.6 10 M

4
- -3

NH   0.15  1.6 10 M  0.15M


3
-3

136
Ionization Constants for Weak
Monoprotic Acids and Bases
 The percent ionization for weak bases is calculated
exactly as for weak acids.

NH3 ionized
% ionization  100%
NH3 original
3
1.6 10 M
 100%
0.15M
 1.1%
137
Ionization Constants for Weak
Monoprotic Acids and Bases
 Example 18-14: The pH of an aqueous
ammonia solution is 11.37. Calculate the
molarity (original concentration) of the
aqueous ammonia solution.
You do it!

138
Ionization Constants for Weak
Monoprotic Acids and Bases
pH = 11.37
From pH + pOH = 14.00, we can derive the pOH.
pOH = 14.00 - pH  14.00 - 11.37  2.63
OH   10  10  2.3 10
-  pOH  2.63 3
M
NH   2.3 10 M

4
3

139
Ionization Constants for Weak
Monoprotic Acids and Bases
 Use the ionization equation and some algebra to get
the equilibrium concentration.
 
NH3  H 2O  NH4  OH -

Initial[] xM
Change - 2.3 10-3 + 2.3 10-3 + 2.3 10-3
 
Equilibriu m[] x - 2.3 10-3 M + 2.3 10-3 + 2.3 10-3

140
Ionization Constants for Weak
Monoprotic Acids and Bases
 Substitute these values into the ionization constant
expression.

Kb 
NH OH 

4

 1.8 10 5

NH3 
1.8 10 5

2.3 10 2.3 10 
3 3

x  2.3 10  3

141
Ionization Constants for Weak
Monoprotic Acids and Bases
 Examination of the last equation suggests that our
simplifying assumption can be applied.
 In other words (x-2.3x10-3)  x.
 Making this assumption simplifies the calculation.

2.3 10  3 2
 1.8 10 5

x
x  0.30M NH3
142
Solubility Product Constants

 Silver chloride, AgCl,is rather insoluble in water.


 Careful experiments show that if solid AgCl is
placed in pure water and vigorously stirred, a
small amount of the AgCl dissolves in the water.

    
Ag Cl  Ag aq   Claq 

143
Solubility Product Constants

 The equilibrium constant expression for this


dissolution is called a solubility product constant.
 Ksp = solubility product constant


K sp  [Ag ][Cl ]  1.8 10 - -10

144
Solubility Product Constants

 The solubility product constant, Ksp, for a


compound is the product of the concentrations of
the constituent ions, each raised to the power that
corresponds to the number of ions in one formula
unit of the compound.
 Consider the dissolution of silver sulfide in water.

+ 2-    H 2O
Ag2 S 
100%
 2 +
Ag + S 2-

145
Solubility Product Constants

 The solubility product expression for Ag2S is:

Ksp  Ag   S   10.  10
 2 2 49

146
Solubility Product Constants

 The dissolution of solid calcium phosphate in


water is represented as:

    
H 2O
3 2 3
2+
Ca 3 PO4  
3 Ca 2 PO4
2  s 100%

 The solubility product constant expression is:


You do it!

Ksp  Ca  2 3
 3 2
PO4  10  .  10 25

147
Solubility Product Constants

 In general, the dissolution of a slightly soluble


compound and its solubility product expression
are represented as:


M r Ys s 

H 2O
r M s
 s Y r
100%

Ksp  M   Y 
s r r s

148
Solubility Product Constants

 The same rules apply for compounds that have


more than two kinds of ions.
 One example of a compound that has more than
two kinds of ions is calcium ammonium
phosphate.

 2 1 3
CaNH4 PO 4s   Ca aq   NH4aq   PO 4aq 
  
K sp  Ca 2 NH4 PO34 
149
Determination of Solubility Product
Constants
 Example 20-1: One liter of saturated silver chloride
solution contains 0.00192 g of dissolved AgCl at
25oC. Calculate the molar solubility of, and Ksp for,
AgCl.
 The molar solubility can be easily calculated from
the data:
? mol AgCl 0.00192 g AgCl 1 mol AgCl
 
L L 143 g AgCl
5 mol AgCl
 1.34 10
L
150
Determination of Solubility Product
Constants
 The equation for the dissociation of silver chloride,
the appropriate molar concentrations, and the
solubility product expression are:

AgCl s  Ag 
 Cl 

1.34  10 M 1.34  10 M
-5 -5


Ksp  Ag 
Cl 

151
Determination of Solubility Product
Constants
 Substitution of the molar concentrations into the
solubility product expression gives:

Ksp  Ag Cl 


 

 134
.  10 134
.  10 
5 5

10
 18
.  10
152
Determination of Solubility Product
Constants
 Example 20-2: One liter of saturated calcium
fluoride solution contains 0.0167 gram of CaF2 at
25oC. Calculate the molar solubility of, and Ksp
for, CaF2.
1. Calculate the molar solubility of CaF2.

? mol CaF2 0.0167 g CaF2 1 mol


 
L 1.0 L 78.1 g
 4 mol CaF2
 2.14 10
L

153
Determination of Solubility Product
Constants
 From the molar solubility, we can find the ion
concentrations in saturated CaF2. Then use those
values to calculate the Ksp.
 Note: You are most likely to leave out the factor of 2 for the
concentration of the fluoride ion!
CaF 
CaF22 
 Ca2+2
Ca 
aq  2- F1-
+ 2F aq 
 4 4 4 4 4
.14
2.214 1010 MM2.214  10
.14 10M M 2(2(
2.214  10
.14 10M4 M
) )

K sp  Ca F 
2  2

 2.14  10 4.28  10 
4 4 2

 3.92  10 11

154
Uses of Solubility
Product Constants
 The solubility product constant can be used to
calculate the solubility of a compound at 25oC.
 Example 20-3: Calculate the molar solubility of
barium sulfate, BaSO4, in pure water and the
concentration of barium and sulfate ions in
saturated barium sulfate at 25oC. For barium
sulfate, Ksp= 1.1 x 10-10.

155
Uses of Solubility
Product Constants
 Make the algebraic substitution of x‟s into
solubility product expression and solve for x,
giving the ion concentrations.

x x   1.110 10

5
x  1.0 10 M
Ba   SO   1.0 10
2 2
4
5
M

156
Uses of Solubility
Product Constants
 Finally, to calculate the mass of BaSO4 in 1.00 L
of saturated solution, use the definition of
molarity.
5
? g BaSO 4 1.0 10 mol 234 g
 
L L mol
3 g BaSO 4
 2.3 10
L
157
Uses of Solubility
Product Constants
 Example 20-4: The solubility product constant
for magnesium hydroxide, Mg(OH)2, is 1.5 x
10-11. Calculate the molar solubility of
magnesium hydroxide and the pH of a
saturated magnesium hydroxide solution at
25oC.
You do it!

158
Uses of Solubility
Product Constants
 Be careful, do not forget the stoichiometric
coefficient of 2!

 2 
Mg(OH) 2  Mg aq   2 OH  aq 
xM  xM 2 xM
Ksp  Mg  2
OH  2

159
Uses of Solubility
Product Constants
 Substitute the algebraic expressions into the
solubility product expression.
 x 2 x   15
2
.  10 11

11
4 x  15
3
.  10
12
x  3.75  10
3

4
x  1.6  10  molar solubility
160
Uses of Solubility
Product Constants
 Solve for the pOH and pH.
 x 2 x   15
2
.  1011
.  1011
4 x 3  15
12
x  3.75  10
3

4
x  16
.  10  molar solubility
OH   2  M  3.2  10
- 4
M
pOH  3.49 pH  10.51
161
The Common Ion Effect in Solubility
Calculations
 Example 20-5: Calculate the molar
solubility of barium sulfate, BaSO4, in
0.010 M sodium sulfate, Na2SO4, solution
at 25oC. Compare this to the solubility of
BaSO4 in pure water. (Example 20-3).
(What is the common ion? How was a
common ion problem solved in Chapter
19?)

162
The Common Ion Effect in Solubility
Calculations
1. Write equations to represent the equilibria.

2
Na 2SO 4 
 2 Na  SO
1 0 0% +
4

0.010 M 2(0.010 M ) (0.010 M )


BaSO 4s  
 Ba 2
 SO 2
aq  4 aq 

xM xM xM

163
The Common Ion Effect in Solubility
Calculations
2. Substitute the algebraic representations of the
concentrations into the Ksp expression and
solve for x.
  
K sp  Ba 2 SO 24  1.110 10
  x 0.010  x 
The simplifyin g assumption can be applied.
0.010  x   0.010
0.010 x = 1.110-10
x  1.110 8  molar solubility of BaSO 4
164
The Common Ion Effect in Solubility
Calculations
 The molar solubility of BaSO4 in 0.010 M Na2SO4
solution is 1.1 x 10-8 M.
 The molar solubility of BaSO4 in pure water is 1.0 x 10-
5 M.

 BaSO4 is 900 times more soluble in pure water than in


0.010 M sodium sulfate!
 Adding sodium sulfate to a solution is a fantastic method to
remove Ba2+ ions from solution!
 If your drinking water were suspected to have lead ions
in it, suggest a method to prove or disprove this
suspicion.
165
The Reaction Quotient in
Precipitation Reactions
 The reaction quotient, Q, and the Ksp of a
compound are used to calculate the
concentration of ions in a solution and
whether or not a precipitate will form.
 Example 20-6: We mix 100 mL of 0.010 M
potassium sulfate, K2SO4, and 100 mL of
0.10 M lead (II) nitrate, Pb(NO3)2 solutions.
Will a precipitate form?

166
The Reaction Quotient in
Precipitation Reactions
1. Write out the solubility expressions.

H 2O 100% 2
K2SO4  
 2 K  +
SO4
Pb NO3 2   H 2 O 100%
 Pb 2+
2 -
NO3
Will PbSO4 precipitate?

167
The Reaction Quotient in
Precipitation Reactions
 Calculate the Qsp for PbSO4.
 Assume that the solution volumes are additive.
 Concentrations of the important ions are:

100 mL 0.10


100 mL 0.10MM
M Pb2+2+  00.050
.050MMPb
Pb2+2+
200
200mL
mL
100 mL  0.010 M
MSO2-   0.0050 M SO4 2-
4
200 mL

168
The Reaction Quotient in
Precipitation Reactions
 Finally, calculate Qsp for PbSO4 and compare it to
the Ksp.

Qsp  Pb 2
 2
SO4 
  0.050 0.0050
4
 2.5  10
8
Ksp  18
.  10 for PbSO 4
Qsp  Ksp therefore solid forms

169
The Reaction Quotient in
Precipitation Reactions
 Example 20-7: Suppose we wish to remove
mercury from an aqueous solution that contains
a soluble mercury compound such as Hg(NO3)2.
We can do this by precipitating mercury (II) ions
as the insoluble compound HgS. What
concentration of sulfide ions, from a soluble
compound such as Na2S, is required to reduce
the Hg2+ concentration to 1.0 x 10-8 M? For
HgS, Ksp=3.0 x 10-53.
You do it!
170
The Reaction Quotient in
Precipitation Reactions
 HgS
Hg 2  S2 
  
K sp  Hg 2 S2  3.0 10 53
solve for S 
2

S   Hg 
2
K sp
2

3.0 10 53
1.0 10 8
 3.0  10  45
M

If enough S2- , in the form of Na 2S, is added to just


slightly exceed 3.0 10  45 M the mercury wi ll precipitat e.

171
The Reaction Quotient in
Precipitation Reactions
 Example 20-8: Refer to example 20-7. What
volume of the solution (1.0 x 10-8 M Hg2+ )
contains 1.0 g of mercury?
2
2 1 mol Hg 1.0 L
? L  1.0 g Hg  2

201 g Hg 1.0 10 8 mol Hg 2
 5.0 105 L  125,000 gal

172
End of Lecture Unit 5

 This chapter was long but essential to your


understanding of Chemistry!
 Make sure you understand this chapter‟s
concepts!

173
Unit Goals

1. Chemical Equilibrium Basic Concepts


2. The Equilibrium Constant and Reaction Quotient
3. Le Chatelier‟s Principle
4. Partial Pressures and Kc –Kp Relationship
5. Ionic Equilibria Basic Concepts
6. The pH and pOH scales
7. Ionization constants for Acids and Bases
8. Solubility Product Principle

174
CHM12-3
Lecture Unit 5
 BASIC CHEMICAL AND IONIC EQUILIBRIA

175

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