ACID BASE

EQUILIBRIUM
Buffer and salts
OVERVIEW
 Buffers (acid buffer and base buffer)
 Hydrolysis of salts :
 Salt of strong acid and weak base
 Salt of strong base and weak acid
 Salt of weak acid and weak base
 Buffer
A buffer solution is a solution of:
1. A weak acid or a weak base and
2. The salt of the weak acid or weak base
Both must be present!

Larutan buffer :
memiliki kemampuan
mempertahankan pH
meskipun ada
penambahan asam atau
basa

16.3
 Buffer
a mixture of the weak acid (CH3COOH) and its salt
(CH3COONa) will undergo the following changes on the
addition of acid or base:
• If a base (OH) is added to the solution it will be
buffered by the following reaction with acetic acid :
CH3COOH + OH  CH3COO + H2O
so the pH will not change significantly
• If acid (H+) is added, it will be buffered by another
reaction, this time using the salt (CH3COO) :
CH3COO + H+  CH3COOH
The pH will not alter significantly because the
CH3COOH formed is a weak acid
 Which of the following are buffer systems?
(a) KF/HF
(b) KBr/HBr
(c) Na2CO3/NaHCO3

(a) HF is a weak acid and F- is its conjugate base

buffer solution
(b) HBr is a strong acid
not a buffer solution
(c) CO32- is a weak base and HCO3- is it conjugate acid
buffer solution

16.3
Which one of the following combinations
cannot function as a buffer solution?
A. HCN and KCN
B. NH3 and (NH4)2SO4
C. HNO3 and NaNO3
D. HF and NaF
E. HNO2 and NaNO2

Which one of the following is a buffer

solution?
A. 0.40 M HCN and 0.10 KCN
B. 0.20 M CH3COOH
C. 1.0 M HNO3 and 1.0 M NaNO3
D. 0.10 M KCN
E. 0.50 M HCl and 0.10 NaCl
  Will these solutions form a buffer solution?
 1.0dm3 solution containing 0.1 mol NH3 and
0.2 mol HCl

 No
 After reaction: 0.1 mol NH4Cl + 0.1 mol HCl
 Weak acid and strong acid  strongly acidic solution
 Not a weak acid-conjugate base combination
 Will these solutions form a buffer solution?
 1.0 dm3 solution containing 0.2 mol NH3 and 0.1
mol HCl

 Yes
 After reaction: 0.1mol NH3 + 0.1mol NH4Cl
 Weak acid and conjugate base
 Buffer
a mixture of the weak acid (HA) and its salt (NaA)

NaA (s)  Na+ (aq) + A- (aq)

HA (aq) ⇌ H+ (aq) + A- (aq)

[H+][A-]
Ka =
[HA]
Henderson-
Ka [HA] Hasselbalch equation
[H ] =
+
[A-]
 [HA]
-log [H ] = -log Ka - log -
+
[A ]
[A-
]
-log [H ] = -log Ka + log
+
[HA]

[conjugate base]
pH = pKa + log
[acid]

[A-]
pH = pKa + log
[HA]
 Buffer capacity
• The buffering capacity of а buffer is, definеd аs
the ability of the buffer to resist changes in pH
when an acid or base is added.

• Buffering capacity is the number of grams of

strong acid or alkali which is necessary for а
change in pH of one unit of one liter of buffer
solution.

• The buffering power is greatest when pH = pKa,

i.e. when the acid and the salt are at the same
concentration
 Berapa pH larutan yg mengandung HCOOH
0.30 M and HCOOK 0.52 M? pKa HCOOH = 3.77
Mixture of weak acid and conjugate base!

HCOOH (aq) ⇌ H+ (aq) + HCOO- (aq)

Initial (M) 0.30 0.00 0.52
Change (M) -x +x +x
Equilibrium (M) 0.30 - x x 0.52 + x

[HCOO-]
pH = pKa + log
0.30 – x  0.30 [HCOOH]
0.52 + x  0.52 [0.52]
pH = 3.77 + log = 4.01
[0.30]
 Calculate the pH of the 0.30 M NH3/0.36 M NH4Cl
buffer system. What is the pH after the addition
of 20.0 mL of 0.050 M NaOH to 80.0 mL of the
buffer solution?
pKa = 9.25 NH4+ (aq) ⇌ H+ (aq) + NH3 (aq)

[NH3] [0.30]
pH = pKa + log pH = 9.25 + log = 9.17
[NH4+] [0.36]
NH4+ (aq) + OH- (aq) H2O (l) + NH3 (aq)
start (moles) 0.029 0.001 0.024
end (moles) 0.028 0.0 0.025
final volume = 80.0 mL + 20.0 mL = 100 mL
0.028 0.025 [0.25]
[NH4 ] =
+
[NH3] = pH = 9.25 + log = 9.20
0.10 0.10 [0.28]
Hitung pH larutan A yang mengandung CH3COOH
0,25 mol dan CH3COONa 0,25 mol dalam 1 L
larutan. Berapa pH larutan akhir jika 100 mL
larutan A ditambahkan dengan 1 mL HCl pekat
(12 M) ? Diketahui Ka CH3COOH 1.8 x 10-5.
Hitung pH larutan buffer A yang mengandung
0,25 M asam benzoat (C6H5COOH) dan 0,15 M
natrium benzoat (C6H5COONa). [Ka = 6,5 × 105
untuk asam benzoat]. Berapa pH larutan akhir
jika 80 mL larutan A ditambahkan dengan 20
mL HCl 0,2 M ?
 BUFFERS IN THE BLOOD
 The pH of blood is 7.35 – 7.45
 Changes in pH below 6.8 and above 8.0 may
result in death
 The major buffer system in the body fluid is
H2CO3/HCO3-

 Some CO2, the end product of cellular

metabolism, is carried to the lungs for elimination,
and the rest dissolves in body fluids, forming
carbonic acid that dissociates to produce
bicarbonate (HCO3-) and hydronium (H3O+) ions.
 More of the HCO3- is supplied by the kidneys.
 CO2 + H2O ⇌ H2CO3
 H2CO3 + H2O ⇌ H3O+ + HCO3-
16
CARBONATE BUFFER
H2CO3 + H2O ⇌ H3O+ + HCO3-
 Excess acid (H3O+) in the body is neutralized
by HCO3-
 H2CO3 + H2O ← H3O+ + HCO3-
 Equilibrium shifts left
 Excess base (OH-) reacts with the carbonic
acid (H2CO3)
 H2CO3 + OH- → H2O + HCO3-
 Equilibrium shifts right

17
 pH of the blood buffer
 The concentrations in the blood of H2CO3 and
HCO3- are 0.0024M and 0.024 respectively
 H2CO3/ HCO3- = 1/10 is needed to maintain
the normal blood pH (7.35 – 7.45)

[ H 3O  ][ HCO3 ]
Ka 
[ H 2CO3 ]
 [ H 2CO3 ]
[ H 3O ]  K a 

[ HCO3 ]
70.0024
 4.3 x10 x  4.3 x107 x0.10  4.3x108
0.024
pH   log(4.3x108 )  7.37
 The effectiveness of the blood buffer

+ 1 tetes HCl 0,05 M pH = 7,0

100 mL air (pH = 7,35)

+ 25 mL HCl 0,05 M pH = 7,0

100 mL blood

 With 5.5 L of blood in the average body, more

than 1300 mL of HCl would be required to make
the same change in pH.
The Hydrolysis of Salts

20
 ACID-BASE REACTIONS OF SALTS
(IONS AS ACIDS AND BASES)

Ionic compounds (salts) formed from acid-base reaction.

HA + MOH  M+A- + H2O
acid base salt

The salt (MA) could leave the resulting aqueous solution to

be neutral, acidic, or basic.

The ions of salts can have an influence on the pH of a solution

 Ions that come from a strong acid or base
do not influence the pH

WHY?

Since strong acids and bases are

100% ionized in water, the ions
are unable to reform the
molecular acid or the base in
water.

NaCl is the salt that comes from a strong acid and a strong base

HCl + H2O  H3O+ + Cl- “one way arrow”

NaOH + H2O  Na+ + OH- + H2O “one way arrow”
What would the pH of a sodium chloride solution
(25oC)?
pH = 7
What gives rise to this pH?

Auto hydrolysis of water.

H2O + H2O ⇌ H3O+ + OH–

Salts that contain ions that come from a weak acid or base :
• anion of the weak acid
• cation from a strong base

Example : KNO2

from weak acid : HNO2

from strong base : KOH

KNO2(s) + H2O  K+ + NO2– + H2O

Hydrolysis: NO2– + H2O ⇌ HNO2 + OH–

A basic solution

24
 RELATIONSHIP OF KA AND KB
Conjugate Acid and Base Reaction May Be Written in Both
Directions. For Example:

HA + H2O ⇌HO + A 3
+ –
Ka =
A– + H O ⇌ HA + OH
2
–
Kb =

 H 3O    A   HA OH  
Ka  Kb    
 H O 

 
 OH 

 HA  A 
 3

Thus:
Ka x Kb = [H+] [OH–] = Kw
Consider the dihydrogen phosphate ion,
H2PO4–. Ka = 6.2 x 10-8

1. What is its conjugate base?

2. Determine the Kb value for HPO42–
Calculate the pH of a 0.10 M KNO2 solution. Ka(HNO2) = 4.5 10-4

KNO2(s)  K+ + NO2-

Hydrolysis: NO2– + H2O ⇌ HNO2 + OH–

awal 0.10 0 0
reaksi -X +X +X
setimbang 0.10-X +X +X

KaKb = 1.0 x 10-14

Try dropping

pOH = -log[OH-] = 5.83

x =1.49 x 10-6 = [OH-] pH = 14 – 5.83 = 8.17

27
Salts that contain ions that come from a weak acid or base :
• anion of the strong acid
• cation from a weak base

Weak Base: (CH3)3N trimethylamine

(CH3)3NHCl trimethylammonium chloride

(CH3)3NHCl (s) + H2O  (CH3)3NH+ + Cl- + H2O

Hydrolysis: (CH3)3NH+ + H2O ⇌ (CH3)3N + H3O+

An acidic solution
 Calculate the pH of a 0.10 (CH3)3NHCl solution.
Kb((CH3)3N) = 7.4 10-5
(CH3)3NHCl(s) + H2O  (CH3)3NH+ + Cl- + H2O

(CH3)3NH+ + H2O ⇌ (CH3)3N + H3O+

awal 0.10 0 0
reaksi -x +x +x
setimbang 0.10-x +x +x

KaKb = 1.0 x 10-14

Try dropping

pH = -log[H+] = 5.43

x =3.68 x 10-6 = [H+]

What if both ions of a salt come from weak acid
and a weak base?

Then the Ka and Kb of the

acid or base from which the
ions come from must be
compared

NH4CN(aq) Ka(NH4+) = 5.6 x 10-10 Kb(CN-) = 2.04 x 10-5

note: Ka was calculated from Kb(NH3) and Kb from Ka HCN

Since Kb(CN-) is greater than Ka(NH4+), the solution is basic.

Will an aqueous solution of the salt be acidic,
basic, or neutral?
1) NaCl
2) NH4Cl
3) HCOONa
4) CH3COONH4