Acid-Base Equilibrium

.
-
.
.


Ka . Kb
.

.
.
.

:

 - - :
Bronsted-Lowry Theory of Acids an Bases

:
-- : :
pOH pH H3O+ .
-- : -
.
-- : -

.
-- : -
.
-- :
- .
-- :
- .
-- :
- .

:

 - -
.
- .
- ) (-
.
-
:
.
-
.
- ) (-

.

) (

- NaOH OH- Na+

OH- - :
)OH-(aq) + H3O+ (aq 2H 2O )(l

-
-
:
)1- HCN(aq) + H2O(l )H 3O+(aq) + CN-(aq

:


)2- HCOOH(aq) + H2O(l )H 3O+(aq) + HCOO-(aq


)3- F-(aq) + H2O(l )HF (aq) + OH-(aq


)H 3O+(aq) + OH-(aq )4- H2O(l) + H2O(l

.

) (
-
-
)1- CO 3(qa) + H2O(l )OH -(aq) + HCO-3(aq -

)2- Al(H2O)3+6(aq) + H2O(l )H 3O3+(aq) + Al(H2O)5(OH)2+(aq

-
-( HPO-4 H2PO2-4 :
( H2S HS- :

) (
-
)HOCl(aq) + H2O(aq )OCl -(aq) + H3O+(aq

:

 )HNO2(aq) + H2O(aq )NO -2(aq) + H3O+(aq

)HF(aq) + H2O(aq )F -(aq) + H3O+(aq

OCl- > NO-2 > F- -

- The Autoionization of Water :

:
-- : Ka Kb
Kw
.
-- :
H+ OH- .

:
- :
-
-
-

:

 - ) (-
Kw .
-
H+ OH- ) (- .
pH + pOH = 14 - :
.

) (

]pOH = - log [OH- -

pOH = - log 3 10-6
)= - ( log 3 + log 10 -6
= 6 log 3
= 6 0.48
pOH = 5.9
pH + pOH = 14 - :
pOH = 14-10.35 = 3.65 :
]pOH = - log [OH- :
[OH-] = 2.2 10-4 M :

OH-
. 2.2 10-4 M
:
=
:

 = (2.2 10-4) 2 = 4.4 10-4 NaOH
=
= (4.4 10-4) 40 = 0.0176 g NaOH

Equilibrium of weak Acids - :

:



Ka




-- :
Kb Kw
.
-- :
. Kb Ka
-- :
.
-- :
.
-- :
.
-- :

.
-- :
.

:

 -- :
.

- :
.
- H+
OH- .
-

.
- H+ H3O+ .
- :
-
- H+
-

:
-
- Ka
-

:

 - Ka

.
-
10% .
-

.
-
.
-
.
: ) (Ka
: .
- :.
:
- .
- pH 2.7
- :
CH3COOH
Ka ])[H3O+(aq pH
mol/L
3.61 10-6 1.9 10-3 2.7 1.0
0.9 10-7 0.3 10-3 3.4 0.1
1.6 10-8 1.3 10-4 3.9 0.01
:



- .
- .
- .
Ka = 1 10-6 -

) (

Kw - :
= ][OH-
][H+

[OH-] = 4 10-4 M :

= 2.6 Ba(OH)2 171 = 0.015 mol -

= 0.015 Ba(OH)2 0.5 = 0.03 M
:
)Ba(OH)2 (aq )Ba 2+(aq) + 2OH-(aq
1 mol 1 mol 2 mol
3 10-2 3 10-2 )2(3 10-2
[OH-] = 2(3 10-2) = 6 10-2 M
:
Kw
= ][H+
][OH-

:

 [H+] = 1.66 10-13 M :
]pH = - log [H+ :
pH = 12.8 :

) (

HA :
= 0.04 HA 0.4 = 0.1 M
] [H+ :
]pH = - Log[H+
[H+]= 10-pH
= 10-4.23
[H+]= 5.9 10-5 M
:
)HA(aq )H +(aq) + A-(aq
:
[H+]= [A-] = 5.9 10-3 M

][A-] [H+
= Ka
][HA

:

 :
( 5.9 X 10-5)2
= Ka 0.1

Ka = 3.510-8

- Equilibrium of weak Bases :

:
-- : Ka
Kb Kw
.
-- : Ka
.Kb
-- :
.
-- :
.
-- :
.
-- :

.

:

 -- :
.
:

-

.
- .
-

:
- Kb
- Kb
-

- . Kb

) (
:
)C17H19NO3(aq) + H2O(l )HC17H19NO+3(aq)+OH-(aq
] [H+ :
]pH = - log [H+
[H+] = 7.9 10-11M
:

 [OH-] = 1.3 10-4 M :
[HC17H19NO3+] = [OH-] = 1.3 10-4 M :
:
][HC17H19NO3+] [OH-
= Ka
][C17H19NO3
:
(1.3 10-4 )2
= Ka 0.01

Ka = 1.710-6

: :

.

H2CO3 . H3PO4
.
. H2SO4
:
)H 2 SO 4 + H 2 O H 3 O (aq .) + HSO 4- (aq .
HSO -
4 (aq .) + H 2 O ) H 3 O (aq .) + SO 4- (aq .

:

 .
Ka2 Ka1 . H2CO3
:

)1 - H 2 CO3 + H 2 O H 3O (aq.) + HCO3- (aq.

K a1 =
[H O ][HCO ] = 4.2 10
3
+ -
3 -7
at 25 C
] [H 2CO3

)2 - HCO3- (aq.) + H 2 O H 3O (aq.) + CO32- (aq.

K a2 =
[H O ][CO ] = 4.8 10
3
+ 2-
3 -11
at 25 C
] [HCO -
3

Ka1 Ka2 Ka2 < Ka1

. Ka1 Ka2 Ka2 Ka3
.
:
Ka

)H 2CO3 (aq.) + H 2O 2 H 3O (aq.) + CO32 - (aq.

Ka =
] [H O ] [HCO
3
+ 2 2-
3
] [H 2CO3

Ka Ka1 Ka2

:

 =
[H O ][HCO ] [H O ][CO ] = K
+ - + 2-
K a1.K a 2
] [HCO
3 3 3 3
] [H CO 2 3
-
3
a

Ka .2.010-17

- Hydrolysis :

:





-- :

) ( .
-- : .
-- : pH ] [H+
.
-- : .
-- : .pH
-- :
.

-
:
-
-
-
:

 - ) (
: " "V

.
- .
-

.
-
.
- :
.

) : ( .
: .
:.
- :.
:
- .
- .
-
.
-
.
:

 - :
pH

7 Cl- Na+
7 CH3COO- Na+
7 Cl- NH4+
7 CH3COO- NH4+

:
- : :
: :
- . pH
)NH4Cl (aq NH 4+(aq) + Cl-(aq) -

)NH4+(aq) + H2O (l NH 3 (aq) + )H3O+(aq

.
- :
.

:

 :
KOH > NaCN > NH4Cl > HCl -

Ka Kb KOH : NaCN
NH4Cl HCl .
-
* CH3COONH4 NH4+
CH3COO- NH4OH
H2O CH3COOH :
)CH3COONH4(aq CH3COO-(aq) + )NH4+(aq

CH3COO- OH- :
)CH3COO-(aq) + H2O(l )CH 3COOH(aq) + OH-(aq
pH
.7
NH4+ H3O+ :
)NH4+(aq) + H2O(l )NH 3(aq) + H3O+(aq
pH
.7

Ka Ka Kb :
Kb = CH3COOH NH3 CH3COONH4
.

:

 ** :
Mg2+ Mg(OH)2 Cl-
: HCl
)MgCl2(aq )Mg 2+(aq) + 2Cl-(aq

) ( Cl- Mg2+
pH . 7
NH4NO3
* -
:

][NH3] [H3O+
= Kh
][NH4+

Kb :
][NH4+] [OH-
= = Kb
][NH3

:
])Kw = [H+(aq)] [OH-(aq
:

Kw ][NH3] [H+][OH-
=
Ka ][NH4+] [OH-

:

 Kw ][NH3] [H+
=
Ka ][NH4+] [OH-
:
Kw
Kh =
Ka

** :

H2O
)NH4Br(s )NH 4+(aq) + Br-(aq
0.3 M 0.3 M
) NH4+(aq :
)NH4+(aq) + H2O(aq )NH 3(aq) + H3O+(aq
:
][NH3] [H3O+
= Kh
][NH4+

) NH4+(aq X mol/L
[NH3] = [H3O+(aq)] = X mol/L :
[NH4+] = 1.0 - X ~ 1.0 M
:

Kw 110-14
= Kh = = 5.5510-10
Ka 1.810-5

:

 ) ( :

5.5510 -10 X2
=
0.3
X2 = 1.67 10-10
X = 1.3 10-5
[H3O+] = 1.3 10-5 M :
pH = 4.9 :
pH ) NH4Br (aq 4.9

K a
Ka .
) 1 . (1 < K a
K a
PKa :

PKa = -logKa
PKa .
Kb Kb
. PKb
PKb .

PKb = -logKb
:

 PKb
.
PH
.

- Solubility Product :

:
-- : Ksp
.
-- :
.
-- : .

:
-
:
-
-
-
- : .
- )
(

:

 -
.
.
-
-
.
- .
- ) (-
:
-
- Ksp
-
-
- . Ksp
- .

) (

])Ksp = [Ag+(aq) ]2 [CrO42-(aq -

])Ksp = [Fe2+(aq) ] [CO32-(aq
])Ksp = [Cu2+(aq)] [S2-(aq -
)= (8.910-19) (8.9 10-19
Ksp = 7.9 10-37
-
:
:

 )Pb(NO3)2(aq) + Na2SO4(aq )pbSO4 (s) + 2NaNO3(aq
:
)Pb(NO3)2 (aq )pb 2+(aq) + 2NO3-(aq
[pb2+] = [Pb(NO3)2] = 0.003 M
:
)Na2SO4(aq )2Na +(aq) + SO42-(aq

[SO42-] = [Na2SO4] = 0.04 M

:
)pbSO4(aq )pb 2+(aq) + SO42-(aq
0.003 M 0.04 M

) ( .
]Ksp = [pb2+] [SO42-
)= (0.0015)(0.02
Ksp = 3 10-5 :

Ksp
< . Ksp ][pb2+] [SO42-

:

 - The Common Ion Effect :

:
-- : .
-- :
.
-- :
.
-- : pH .

-

.
- .
- ) ( .
) (

.
-
.
- pH
.

:

 - pH
.
) : ( .
: .
:.
- :.

:
- .
- .
-
.
-
.
- :
pH
2-3 )CH3COOH(aq
3-4 ) CH3COOH(aq )CH3COONa(aq
8-10 )NH3(aq
7-9 ) NH3(aq )NH4Cl(aq

:
- - . pH
- .
:

 - pH NH4+
OH- . H+
- pH HCl
.

) (

: pH :
:
)CH3CH2COOH (aq )CH 3CH2COO-(aq) + H+(aq
X mol/L
[CH3CH2COO-] = [H+] = X mol/L :
[CH3CH2COOH] = 0.41 X ~ 0.4M
:
-
][CH3CH2COO ] [H+
= Ka
][CH3CH2COOH

X2
:
= 1.3 10-5
0.41
X2 = 5.33 10-6

:
X= 2.3 10-3 M
:

 [CH3CH2COO-] = [H+(aq)] = 2.3 10-3 M :
])pH = - log [H+(aq :
pH = 2.64 :

: pH :

0.041
= = 0.27 M
0.15

1.2
= 0.0125 mol
=
96

0.0125
= = 0.083 M
0.15

]Ka [CH3CH2COOH

= ][H+
][CH3CH2COONa

(1.3 10-5) 0.27

= ][H+ = 4.23 10-5 M
0.083

pH = 4.37

:

 - Buffers :

:
-- :
pH .
-- : pH .
-- :
.
-- :
pH .
-- : pH
.
-- : pH .

:
-
: pH

- ) (-
.
- ) (
pH .
- ) ( ) (

:


:

- .
- pH
.

) : (
: .
:.
- :.
:
- .
- .
-
.
-
.
- :

:

 NaOH HCl
1 2 NaCl
7 5

:
- .
- .
- :
pH
.

) (
- .
- :
- .
- .
- HF :
)HF(aq )H +(aq) + F-(aq
0.01
NaF :
)NaF(aq )Na +(aq) + F-(aq
0.01 0.01

:

 + :
][H ] [F-
= Ka
][HF

:
)[H+] (0.01
= 6.6 10-4
0.01
[H+] = 6.6 10-4 M
]pH = - log [H+ :
pH = 3.18 :

- pH
.
:

H2PO4- / HPO4- .
:
-
. .
- . 1
10 0.1 .
= 1

:
:

 PH=PKa 1
] [ =10
][ ). PKa+1=(PH
:
PH=PKa-1
" "
.
:
PH NH3 NH4Cl 0.35M
0.15M Ka . 5.610-10 = NH4+ . 25
:
= PK + log
] [NH 3 .
PH a
] [NH +
4

0 . 15
PH = 9 . 25 + log = 9 . 25 - 0 . 37
0 . 35
PH = 8 . 88

- ) : ( XA) + ( HA
]Ka = [ H3O+ ] [A-] /[HA

] [ H3O+ ] = Ka [HA ] / [A-
A-

:
]+HA [ ] / Ka = [ H3O+ ] [A--

:

 ] +HA] / [A-- [ [ H3O+ ] = Ka
:
] HA [] / Ka = [ H3O+ ] [A- +

] -HA] / [A-+ [ [ H3O+ ] = Ka

- ) : (BX) + ( BOH
] Kb = [OH- ] [ B+ ]/ [BOH

] [OH- ] = [BOH ] Kb / [ B+
B+
:
] + BOH [ -B+ ]/ [ ] Kb = [OH-

] - B+ [ + BOH ] Kb / [ = ] [OH-
:
] - BOH [ +B+ ]/ [ ] Kb = [OH-

] + B+ [ - BOH ] Kb / [ = ] [OH-

:

 - :

:
-- : .
-- : .
-- : .

:
-
.
-
.

:


:
-( .
-( ). H2AsO-4(aq
-( . 5.7510-10
. -( )NaCN(aq
-. 1.610-5 (-
. -( 6.610-13
-( .
-( . 1.8210-3
. -(
-( . Ag+
-( / .
-( ) HSO4-(aq ). H2SO3(aq
-( ]). [H+(aq)] [C2H3O2-(aq)] < [HC2H3O2(aq
-( )HF(aq) HCO2H(aq) HC2H3O2(aq) HClO(aq) HCN(aq
-( ). KCl(s
. -( 2.510-9
-( pH .
. -( 510-3

:

 :
-( H3O+
] [H3O+
. Ka
(
K+ Cl- . pH
(

.
( :
)NaCl(s)+H2O(l )Na +(aq)+OH-(aq)+H+(aq) +Cl-(aq
:









)CH3COONH4(s)+H2O(l )CH3COOH(aq)+NH4OH(aq
(
) ( :
)AgCl(s )Ag +(aq) + Cl-(aq
)HCl(aq )H +(aq) + Cl-(aq
( NaHSO4 )
(
) (pH = 7 NaHSO3 )
( ).( pH > 7
( H+ .
-( )( H+ OH-
.
:

 ( H+ OH-
pH .
- HCl H+

] [H+ pH
.
)HCl(aq )H +(aq) + Cl-(aq
CH3COO-(aq) + H+(aq )CH3COOH(aq
NaOH
OH- H+
] [OH-
H+ pH
.
)NaOH(aq )Na +(aq) + OH-(aq
)H +(aq) + OH-(aq )H2O(a

:
]pH = - log [H+ - :
[H+] = 1.6 10-9 M :
[OH-] = 6.25 10-6 M :
)C6H5NH2(aq) + H2O(l )C6H5NH3+(aq) +OH-(aq

:

 :

][C6H5NH3+] [OH-

= Kb
][C6H5NH2

[OH-] = [C6H5NH3+] :
:
(6.25 10-6)2
= Kb
0.1

Kb = 3.9 10-10 :
- :
= 0.02 mol/L H8C9O4
X mol/L
[C9H7O4-] = [H3O+] = X mol/L :
[HC9H7O4 ] = 0.02 X ~ 0.02 M
:
][C9H7O4-] [H3O+
= Ka
][HC9H7O4

X2
:
= 3.27 10-4
0.02

:

 X2 = 6.5 10-6
X = 2.55 10-3
[H3O+] =2.55 10-3 M :
]pH = - log [H+ :
pH = 2.6 :

= 515+460 =975mL - HCOOH HCOOK

M1V1 =M2V2
:
[HCOOH] =5150.005/975 = 2.6410-3M
[HCOOK]= 4600.001/975 = 4.710-4 M

)HCOOH(aq )H +(aq) + HCOO (aq

2.6410-3M
)HCOOK(aq )K +(aq) + HCOO (aq
4.710-4 M
]Ka[HCOOH
= ][ H +
] [ HCOO -

1.8 10 -4 2.64 10 -3
= ][ H +
4.7 10 -4

:

 [ H +] = 1.01 10 -3 M
pH = - log [ H +] = - log 1.01 10 -3 = 2.995
[HCl] = 8.50.002 /983.5
= 1.72 10 -5 M
] [ H + HCl
]HCl HCl + HCOOH] / [HCOO - -[ = Ka
= ] 1.810 -4 [1.7210 -5 +2.6410 -3]/[4.710 -4 1.7210-5
10.56 10 -4 M
pH = - log [ H +] = - log 10.56 10 -4 = 2.976

)CaCl2(aq )Ca2+(aq) + 2 Cl (aq -

0.00016 M 0.00016 M

)Na2SO4(aq )2Na +(aq + SO42-

0.00023M 0.00023M

= 255 +456 = 711 mL

[Ca2+] = (2550.00016)/ 711 = 0.057310-3
[ SO4 2-] = (4560.00023)/711= 0.147510-3
[Ca2+][ SO4 2-] = 0.057310-3 0.147510-3 M
= 0.0085 10 6 = 0.0008510 5 M
Ksp
.

:

 :
-( < atropine < erythromycin .morphine

( pH
.
:
pH = 11.25)(atropine
pH = 10.45)(morphine
pH = 10.9)(erythromycin
-( . 7.4
]pH = - log [H+ ( :
[H3O+] =3.9 10-8 M :
[H3O+] [OH-] = 1 10-14 :
[OH-] = 2.6 10-7 M :
- :
)C5NH4COOH(aq )C5NH4COO-(aq) + H+(aq
:
= 0.96 mol/L C5NH4COOH
X mol/L
[C5NH4COO-] = [H+] = X mol/L :
[HC9H7O4 ] = 0.96 X ~ 0.96 M

:

 :
][C5NH4COO-] [H+
= Ka
][C5NH4COOH

X2
:
= 1.4 10-5
0.96

X2 = 1.34 10-5
X = 3.7 10-3
[H+] =3.7 10-3 M :
pH = 4.55 - :
[H+] = 2.8 10-5 M :
0.01
= ][H2CO3 = 0.033 mol/L
0.3

][Na2CO3] [H+ :
= Ka
][H2CO3

]Ka [H2CO3
+
= ] [H
][Na2CO3

:

 )(4.2 10-7) (0.033
= 2.8 10-5
][Na2CO3

[Na2CO3] = 4.95 10-4 M :

= (4.95 10-4) (0.3) = 1.2 10-4mol Na2CO3

= (1.2 10-4) (106) = 0.0127 g Na2CO3 :

:
-( : Ka : HA
:

][H+] [A-

= Ka
][HA

][A-] = [H+ :
:
(7 10-6)2
= Ka
0.1

Ka = 4.9 10-10 :

:

 : Ka : HB
] [H+ :
]pH = - log [H+
[H+] = 1 10-4 M :
:

][H+] [B-

= Ka
][HB

][H+] = [B- :
:

(1 10-4)2
= Ka
0.1

Ka = 1 10-7 :
( D- Ka
.
( pH H+ .
HC + NH3 C- + NH +4 (

-( :
)NaHCO3 (s )Na+(aq) + HCO3-(aq

:

 :
)H2CO3(aq) + H2O(aq )HCO 3-(aq) + H3O+(aq
4 10-7
:
[ H3O+] = [ HCO3-] = 4 10-7 M
HCO3-
:
[H2CO3] = 4 10-7 M
:

][HCO3-] [H3O+
= Ka
][H2CO3
:
(4 10-7)2
= Ka
4 10-7

Ka = 4 10-7 :

( HCO3-

-(
)1- (C6H5)3C-(aq) + C4H4NH(aq (C6H5)3CH(aq) + C4H4N-
. ) (aq .

:

 )2- HC2H3O2(aq) + HS-(aq )H 2S(aq) + C2H3O2-(aq
. .

)3- O2-(aq) + (C6H5)3CH(aq )(C6H5)3C-(aq) + OH-(aq

. .

)4- C4H4N-(aq) + H2S(aq )C4H4NH(aq) + HS-(aq

. .

: : : . :
. :
( .

-(
= ] [H+ )(0.037) (4.210-7
= 1.25 10-4 M

= ] [H+ )(0.037) (4.810-11

= 1.33 10-6 M

)[H+] = (1.25 10-4) + (1.33 10-6 : (

= 12.633 10-5 M

pH = 3.89 :
: