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Acid-Base Equilibria and Solubility Equilibria

Chapter 16

Acid-Base Equilibria and Solubility Equilibria Chapter 16 1 Copyright © The McGraw-Hill Companies, Inc. Permission
Acid-Base Equilibria and Solubility Equilibria Chapter 16 1 Copyright © The McGraw-Hill Companies, Inc. Permission

1

Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

Consider mixture of salt NaA and weak acid HA.

 

NaA (s)

Na + ( aq ) + A - + (aq) + A -

(aq)

[H + ][A - ]

HA (aq)

H + ( aq ) + A - ( aq ) + (aq) + A - (aq)

K a =

[HA]

[H + ] = K a [HA]

     

[A

- ]

-log [H + ] = -log K a - log [HA]

 
   

[A

- ]

[A

- ]

pH = pK a + log [conjugate base] [acid]

-log [H + ] = -log K a + log

[HA]

 

pH = pK a + log [HA] [A ]

-

pK a = -log K a

 
 

3

 

HCl

H + + Cl -

 

HCl + CH 3 COO -

CH 3 COOH + Cl -

 
 
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Common ion effect:

The presence of a common ion of a weak acid or a weak base.

the ionization

Consider mixture of CH 3 COONa (strong electrolyte) and CH 3 COOH (weak acid). CH
Consider mixture of CH 3 COONa (strong electrolyte) and
CH 3 COOH (weak acid).
CH 3 COONa (s)
Na + (aq) + CH 3 COO - (aq)
CH 3 COOH (aq)
H + (aq) + CH 3 COO - (aq)
2

Buffer solution is a soln of:

 
Buffer solution is a soln of:  

1.

2.

A buffer soln has the ability to resist changes in pH upon the addition of small amounts of either acid or base.

Consider an equal molar mixture of CH 3 COOH and CH 3 COONa

Add strong acid

H + (aq) + CH 3 COO - (aq)

CH 3 COOH (aq)

 

Add strong base OH - (aq) + CH 3 COOH (aq)

CH 3 COO - (aq) + H 2 O (l)

 

4

 

Titrations

 

Titration:

Equivalence point

Indicator

Slowly add base to unknown acid UNTIL  

Slowly add base to unknown acid UNTIL

Slowly add base to unknown acid UNTIL  
 

The indicator

changes color

(

)

6

 

Alternative Method of Equivalence Point Detection

 
Alternative Method of Equivalence Point Detection     monitor pH 7   Weak Acid-Strong Base
 

monitor pH

7

 

Weak Acid-Strong Base Titrations

 

CH 3 COOH (aq) + NaOH (aq)

CH 3 COONa (aq) + H 2 O (l)

CH 3 COOH (aq) + OH - (aq)

CH 3 COO - (aq) + H 2 O (l)

At equivalence point (pH > 7):

CH 3 COO - (aq) + H 2 O (l)

CH 3 COO - ( aq ) + H 2 O ( l ) OH -

OH - (aq) + CH 3 COOH (aq)

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9

 

Acid-Base Indicators

 

HIn (aq)

HIn ( aq ) H + ( aq ) + In - ( aq )

H + (aq) + In - (aq)

 

[HIn] [In - ]

10

Color of acid (HIn) predominates

 

[HIn] [In - ]

10

Color of conjugate base (In - ) predominates

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Strong Acid-Strong Base Titrations

NaOH (aq) + HCl (aq)

H 2 O (l) + NaCl (aq)

OH - (aq) + H + (aq)

H 2 O (l)

NaOH ( aq ) + HCl ( aq ) H 2 O ( l ) +

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Strong Acid-Weak Base Titrations

HCl (aq) + NH 3 (aq) H + (aq) + NH 3 (aq)

NH 4 Cl (aq)

NH 4 Cl (aq)

At equivalence point (pH < 7):

NH 4 + (aq) + H 2 O (l)

NH 3 ( aq ) + H + ( aq ) 3 (aq) + H + (aq)

10
10

Solutions of Red Cabbage Extract

Solutions of Red Cabbage Extract pH 12

pH

Solutions of Red Cabbage Extract pH 12

12

The titration curve of a strong acid with a strong base.

The titration curve of a strong acid with a strong base. 13

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Solubility Equilibria AgCl (s) Ag + (aq) + Cl - (aq) K sp = [Ag
Solubility Equilibria
AgCl (s)
Ag + (aq) + Cl - (aq)
K sp = [Ag + ][Cl - ]
K sp is the solubility product constant
MgF 2 (s)
Mg 2+ (aq) + 2F - (aq)
2Ag + (aq) + CO 3 2- (aq)
K sp = [Mg 2+ ][F - ] 2
Ag 2 CO 3 (s)
K sp = [Ag + ] 2 [CO 3 2- ]
Ca 3 (PO 4 ) 2 (s)
3Ca 2+ (aq) + 2PO 4 3- (aq)
K sp = [Ca 2+ ] 3 [PO 4 3- ] 2
Dissolution of an ionic solid in aqueous solution:
Q
< K sp
Q
= K sp
Q
> K sp
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Molar solubility (mol/L):

Solubility (g/L):

Molar solubility (mol/L): Solubility (g/L) : 17
Molar solubility (mol/L): Solubility (g/L) : 17
Molar solubility (mol/L): Solubility (g/L) : 17
Molar solubility (mol/L): Solubility (g/L) : 17
Molar solubility (mol/L): Solubility (g/L) : 17

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Which indicator(s) would you use for a titration of HNO 2 with KOH ?

Which indicator(s) would you use for a titration of HNO 2 with KOH ? 14

14

16

16

18

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The Common Ion Effect and Solubility

What is the molar solubility of AgBr in (a) pure water and (b) 0.0010 M NaBr?

Complex Ion Equilibria and Solubility A complex ion 2- Co 2+ (aq) + 4Cl -
Complex Ion Equilibria and Solubility
A complex ion
2-
Co 2+ (aq) + 4Cl - (aq)
CoCl 4
(aq)
The formation constant or stability constant (K f ):
2-
[CoCl 4 ]
Co(H 2 O) 6 2+
CoCl
4
stability of
K f
complex
HCl
21

2-

K f =

[Co 2+ ][Cl - ] 4

23

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pH and Solubility

The presence of a common ion decreases the solubility.

Insoluble bases dissolve in acidic solutions

 

Insoluble acids dissolve in basic solutions

 

add

remove

Mg(OH) 2 (s)

Mg 2 + ( aq ) + 2OH - ( aq )

Mg 2+ (aq) + 2OH - (aq)

At pH less than 10.45

K sp = [Mg 2+ ][OH - ] 2 = 1.2 x 10 -11

Lower [OH - ]

 

K sp = (s)(2s) 2 = 4s 3 4s 3 = 1.2 x 10 -11

OH - (aq) + H + (aq)

H 2 O (l)

Increase solubility of Mg(OH) 2

s = 1.4 x 10 -4 M

At pH greater than 10.45

[OH - ] = 2s = 2.8 x 10 -4 M pOH = 3.55 pH = 10.45

Raise [OH - ]

Decrease solubility of Mg(OH) 2

 

20

Effect of Complexation on Solubility

 

AgNO

Add NH

3
3

3

+ NaCl

AgNO Add NH 3 3 + NaCl
 

AgCl

Ag(NH 3 ) 2 +

22

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Qualitative

Analysis of

Cations

Qualitative Analysis of Cations 25
Qualitative Analysis of Cations 25
Qualitative Analysis of Cations 25
Qualitative Analysis of Cations 25
Qualitative Analysis of Cations 25
Qualitative Analysis of Cations 25
Qualitative Analysis of Cations 25
Qualitative Analysis of Cations 25

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Flame Test for Cations

Flame Test for Cations lithium sodium potassium copper 26

lithium

Flame Test for Cations lithium sodium potassium copper 26

sodium

Flame Test for Cations lithium sodium potassium copper 26

potassium

Flame Test for Cations lithium sodium potassium copper 26

copper

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