Chapter 4

Buffer Solutions
Jianming Lan
College of Pharmacy ，
Fujian Medical University
E-mail:
1135373171@qq.com
 Buffer solutions
 Maintenance of pH is vital to all cells.
Cellular process such as metabolism are
dependent on the activities of enzymes, and
in turn, enzyme activity is markedly
influenced by pH. The primary protection
against harmful pH changes is provided by
buffer systems.
 Overview of acid-base chemistry
 acids and bases
 Strong acids and bases ionize (break into
ions) completely when dissolved in water.
For example: HCL ， H2SO4 ， NaOH ， KOH etc.
 Weak acids and bases are ionize (break
into ions) partially while most others
remain intact when dissolved in water.
For example: CH3COOH ， NH3.H2O etc.

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  The degree of dissociation of a weak acid in
water is described by the acid ionization
(dissociation) constant, Ka.
[ H  ][ A ]
HA  H   A Ka 
[ HA]

 The degree of dissociation of a weak base in

water is described by the base ionization
(dissociation) constant, Kb.
  [ HA][OH  ]
A  H 2O  HA  OH Kb 
[ A ]

Ka  Kb  K w [H+][OH-]= Kw= 1.00 x 10-14 at 25C

or
pH + pOH = 14
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 Definition of pKa
 As with pH, can describe Ka in more
convenient term as pKa

 The Ka and the pKa quantitatively measure

strength of an acid
 Larger Ka indicates a strong acid
 Larger pKa indicates a stronger base
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 Conjugate acid-conjugate base pair
 The Conjugate Base is the base formed by
removal of a proton from an acid
CH 3COOH  H   CH 3COO 

Conjugate acid Conjugate base

Conjugate acid-conjugate base pair

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 Which one is the conjugate base of H3PO4?

A NaH2PO4
B Na2HPO4
C Na3PO4

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 Buffer solutions
Before you start, it would be helpful to…

• Know that weak acids and bases are only partly

ionized in solution.
• Be able to calculate pH from hydrogen ion
concentration.
• Be able to construct an equation for the
dissociation constant of a weak acid or a weak
base.
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Outline
1. Composition and Action of Buffer Solutions
2. pH Value of Buffer Solutions
3. Buffer Capacity and Buffer Range
4. Preparation of Buffer Solutions
5. Significance of Buffer Solutions in Medicine

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 Preface
 Gastric juice: 0.9-1.8; Urine: 4.6-8.0; Saliva: 6.6-7.1(pH)

 Human blood pH ≈7.4 (slightly alkaline)

 Many foods and metabolic processes can add or subtract H+ or

OH- ions
Reducing blood pH to <7.35, results in acidosis

Increasing blood pH to >7.45, results in alkalosis

Both situations are life-threatening

 Health of organisms requires maintaining pH of body

fluids within narrow limits.
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 How does blood maintain a constant pH very
close to 7.4 at all times in contact with
countless cellular acid-base reactions?

The answer in each case is through the

presence of a buffer solution.

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 What is a buffer solution?
 Definition
 A buffer solution is one which can lessen
changes in concentration of H 3O+ from the
addition of a strong acid, a strong base or
dilution.

Human blood is a buffer solution

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Experiment
HCl blue pH >7.6
H2O H 2O
Bromthymol yellow pH <6
blue
NaOH green pH 6~7.6

HO
2

H O is not buffer solution

2

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Experiment

HCl NaOH H2 O

HAc+NaAc HAc+NaAc HAc+NaAc HAc+NaAc

pH ≈ 5.13 Methyl Orange: 3.1-4.4

Red ——Orange——Yellow
HAc + NaAc solution is a buffer solution

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4-1 The composition and action of buffer solutions

I. The composition of buffer solution

● a weak acid and its conjugate base

HAc/NaAc H2CO3 / HCO3-
● a weak base and its conjugate acid.
NH4+ / NH3

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4-1 The composition and action of buffer solutions
I. The composition of buffer solution
In a buffer solution, there are both anti-acid components
and anti-base components. These two components are said to
constitute the “buffer system” or “buffer pair”.

Buffer Proton theory Proton transfer

systems Conjugate acids Conjugate bases equilibriums

CH3COOH CH3COO-
CH3COOH- CH 3COOH  H 2O 
CH3COONa anti-base anti-acid CH 3COO   H 3O 
components components
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4-1 The composition and action of buffer solutions
I The composition of buffer solution (P76, Table 4-
1)
Anti-base component Anti-acid component
H2CO3 - NaHCO3
NH4Cl - NH3
H3PO4 - NaH2PO4

NaH2PO4 - Na2HPO4

Na HPO – Na PO
2 4 3 4

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Summary
 What is a buffer solution?
A buffer solution is one which can lessen
changes in concentration of H 3O+ from the
addition of a strong acid, a strong base or
dilution.
 Usually buffers are made with
 a WEAK ACID and its conjugate base or
 a WEAK BASE and its conjugate acid.

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Exercise
Predict whether each of the following pairs of substances could
work as a buffer system in a aqueous solution?

(a) KF/HF (b) NaCl/NaAc (c) Na2CO3/NaHCO3

(d) HCl/NH3.H2O(excess) (e) Na2HPO4/Na3PO4 (f) HCl/NaOH
 (a) HF is a weak acid and F- is its conjugate base buffer solution

 (b) NaCl is a salt not a buffer solution

 (c) CO32- is a weak base and HCO3- is it conjugate acid buffer solution
 (d) HCl react withNH3.H2O(excess) and produce NH4+ , NH4+ is a weak acid and
NH3 is it conjugate base buffer solution

 (e) HPO4 2-is a weak acid and PO4 3- is it conjugate base buffer solution

 (f) HCl is a strong acid and NaOH is a strong base not a buffer solution
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 4-1Composition and Action of Buffer Solutions
II Buffering Action

The action which resists the addition of a strong acid,

a strong base or the dilution of the buffer solution is
called buffering action.

HCl NaOH HO
2

HAc +NaAc HAc +NaAc HAc +NaAc

pH≈5.13
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 How do buffer solutions work?
 A buffer solution has to contain species
which will remove any hydrogen ions or
hydroxide ions that you might add to it,
otherwise the pH will change. Acidic and
alkaline buffer solutions achieve this in
different ways.

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 Exp 1. Solutions of a Weak Acid and a Salt of the
Weak Acid

As you know, the CH3COONa is a strong electrolyte,

dissociating completely into its constituent ions, but
CH3COOH is a weak electrolyte and only slightly ionized.

CH3COONa Na+ + CH3COO-

CH3COOH + H2O H3O+ + CH3COO-

The solution will therefore contain these important species:

● lots of un-ionized CH3COOH ;
● lots of CH3COO- from the CH3COONa;

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 adding small amounts of HCl to this solution, causing [H 3O+] to
increase, and the dissociation equilibrium of the weak acid shifts to the
left. CH3COO- accepts the proton to use up most of the added H3O+.

When a new equilibrium is established, the concentration of CH3COOH

increases and the concentration of CH3COO- decreases, but there is little
change in the pH.
Here the conjugate base (the acetate ion) is
said to be an anti-acid component.
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 HAc + NaAc solution. At equilibrium

NaAc Ac - + Na+
(common ion effect)
HAc + H2O Ac - + H3O+

HCl
Ac can help to resist the change in pH when a strong
–

acid is added, so is said to be an anti-acid component

HAc +NaAc

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 When small amounts of strong base, NaOH is added to the same
buffer solution, it is consumed by the acidic component, CH 3COOH.
The additional OH- reacts with proton and forms water, reducing the
concentration of hydronium ion. So, the equilibrium shifts to the right,
causing more CH3COOH to ionize.

When a new equilibrium is established, the concentration of CH3COOH

decreases and the concentration of CH3COO- increases, but there is little change
in the pH.

The conjugate acid (the acetic acid) is said to be an

anti-base component.
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 4-1Composition and Action of Buffer
Solutions
II Buffering Action

1. Solutions of a Weak Acid and a Salt of the Weak Acid

HAc + NaAc solution. At equilibrium

NaAc Ac - + Na+
HAc + H2O Ac - + H3O+ NaOH
+
OH-
HAc can resist the change in
pH when a strong BASE is HAc +NaAc
added , so is said to be an
2HO
anti-base component 2

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2. Solutions of a Weak Base and a Salt of the Weak Base

NH4Cl NH4+ + Cl-

NH3 + H2O NH4+ + OH-

The solution will therefore contain these important species:

● lots of unreacted ammonia;

● lots of ammonium ions from the ammonium chloride;

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 When HCl is added to this buffer solution, the OH- ion accepts the
proton and forms water. The dissociation reaction of ammonia shifts
to the right. this slightly increases the ratio [NH4+/NH3], but there is
little change in the pH.

Here NH3 can resist a change in pH upon the addition of

a strong acid, and is said to be the anti-acid component.

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 When a strong base such as NaOH is added to the original solution, it
is neutralized by the more acidic component, NH 4+, the dissociation
reaction of the weak base shifts to the left. This slightly causes the ratio
[NH4+/NH3] to decrease, but there is little change in the pH.

So NH4+ is said to be the anti-base component.

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 4-1Composition and Action of Buffer
Solutions
II Buffering Action
2. Solutions of a Weak Base and a Salt of the Weak Base
NH3 + NH4Cl solution. At equilibrium
HCl NaOH
NH Cl NH + + Cl-
4 4
NH3+ H2O NH4+ + OH-
NH3 +NH4Cl NH3 +NH4Cl

The buffer solution consists of high concentration of

NH3 NH4+
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 II Buffering Action

Summary
changes in pH are minimized in buffer solutions
because the Basic component (anti-acid component)
can react with H3O+ions and the acidic component
(anti-base component) can react with OH- ions

These cause a small amount of one buffer

component to convert into the other. The relative
changes in buffer component are small, so the pH
value doesn’t change appreciably.

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Exercise
 Explain buffer action using hydrofluoric acid,
HF, and its salt, sodium fluoride, NaF, after
adding a small amount of strong acid or strong
base without a major change in pH.

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 4-2 The pH value of buffer solutions
The Henderson-Hasselbalch Equation
In an acid-base buffer solution, there is a proton transfer equilibrium
between a conjugate acid and its conjugate base:
Ka
HA  H 2O  H 3O   A
Weak acid Conjugate base

The dissociation constant expression of the conjugate acid is:

[H 3 O  ]  [A  ]
Κa 
[HA]

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Rearranging this equation to show the value of [H3O+], and thus the pH,
depends on the ratio of the undissociated acid concentration to the conjugate
base concentration,
 [HA]
[H 3 O ]  K a  
[A ]
Taking the negative of the log in base 10 of both side of the preceding
equation, we obtain

 [HA]
 lg[H 3O ]   lg K a  lg
[A - ]
Allow the use of pKa and pH instead of -lgKa and -lg[H3O+]

[A - ] Henderson-Hasselbalch
∴ pH  pKa  lg Equation
[HA]

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 [A - ]
∴ pH  pKa  lg
[HA]

[A-] : the equilibrium concentration of A-

[HA] : the equilibrium concentration of HA
[A - ]
: buffer ratio
[HA ]

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 In general terms,

pH = pKa(HA) + lg [ conjugate base ]

[conjugate acid]
the dissociation
constant of the concentration ratio of
conjugate acid conjugate base to its acid

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 4-2 the pH value of buffer solutions
simplify this Equation
The Henderson-Hasselbalch Equation
HA ~ NaA constitute a buffer solution HA + H O A - + H O+
3
2

[A - ]
pH  pKa  lg
[HA]
[HA] = [HA] – [HA] (dissociation) [A- ] = [A- ]initial + [HA](dissociation)
initial

[HA] ≈
[HA]initial [A-] [A-]
≈ initial

[A - ]initial
pH  pKa  lg
[HA]initial
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 The Henderson-Hasselbalch Equation
It is not always necessary to use concentrations in the calculation. Both
reagents are present in a same buffer solution, so the solution volume
cancels from the molarity ratio, for example:

[A - ]
pH  pKa  lg
[HA]
n (A - )
pH  pKa  lg V
n (HA)
V

n(A - )
pH  pKa  lg
n(HA)

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 Summary
The Henderson-Hasselbalch Equation

[A - ]
∴ pH  pKa  lg
[HA]
[A - ]initial
pH  pKa  lg
[HA]initial

n(A - )
pH  pKa  lg
n(HA)
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 EXAMPLE 4-2

Calculate the effect on pH of buffer after adding H3O+ or OH- .

(a)The pH of a buffer solution consisting of 0.50M CH3COOH

and 0.50 M CH3COONa
(b)After adding 0.020 mol solid NaOH to 1.0 L of the buffer
solution in (a)
(c) After adding 0.020 mol HCl to 1.0 L of the buffer solution
in (a)
(d) After adding 100 mL H2O to 1.0 L of the buffer solution
in (a)

Ka of CH3COOH=1.8×10-5. (Assume the additions cause

negligible volume changes)
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 Solution

(a) The original pH: [H3O+] in the original buffer.

From equation ( 4-3 )
[CH 3 COO  ]initial
pH = pKa + lg
[CH 3 COOH]initial

We use the given concentrations of buffer components to calculate pH:

1
0.50 mol  L
pH = -lg1.8×10-5 + log
0.50mol  L1

= 4.74

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 (b) When solid NaOH is added, it reacts with CH3COOH to form more
CH3COONa, causing the concentration of CH3COO- ion to increase and
CH3COOH to decrease. Therefore:
0.50mol  0.02mol
[CH3COOH] = = 0.48 mol  L-1
1L
0.50mol  0.02mol
[CH3COO-] = = 0.52 mol  L-1
1L

Substitute the above value into equation ( 4-3 ),

0.52mol  L1
pH = 4.74 + lg 1 = 4.77
0.48mol  L

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 (c) When HCl is added, the proton from the HCl combines
with CH3COO- ion to form more CH3COOH, the concentration of CH3COO-
ion decreases and CH3COOH increases.
0.50mol  0.02mol
= 0.52 mol  L-1
[CH3COOH] = 1L

[CH3COO-] = 0.50mol  0.02mol = 0.48 mol  L-1

1L

Calculating the pH:

0.48mol  L1
pH = 4.74 + lg 1 = 4.70
0.52mol  L

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 (d) When 100mL water is added to the buffer solution,
the total volume of that buffer is 1100 mL, and
the concentration of the conjugate acid or conjugate base is:
0.50mol / L  1000mL
[CH3COOH] = = 0.45 mol  L-1
1100mL

[CH3COO-] = 0.50mol / L  1000mL = 0.45 mol  L-1

1100mL

0.45mol  L1
pH = 4.74+lg = 4.74
0.45mol  L1

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 4- 2 the pH value of buffer solutions

The Henderson-Hasselbalch Equation

Example4-2: Calculate the effect of added H O+ and OH- on buffer pH.
3

(a) Of a buffer solution consisting of 0.50 M CH3COOH and 0.50 M CH3COONa

(b) after adding 0.020 mol solid NaOH to 1.0 L of the buffer solution in (a).

(c) after adding 0.020 mol HCl to 1.0 L of the buffer solution in (a).
(d) after adding 100 mL H2O to 1.0 L of the buffer solution in (a)
Conclusions: ⑴ After adding a small amount of strong acid or base to the
buffer solution, the pH value changes very little.
⑵ After adding small amounts of H O into a buffer solution,
2

the pH value has no change.

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 EXAMPLE :

A solution is prepared by mixing 10 mL of 0.1 mol  L

-1

of NaH2PO4 solution and 10 mL of 0.2 mol  L-1

of Na2HPO4 solution.

Calculate the pH value of this

solution. Ka of H2PO4-=6.2×10-8

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 Solution
The amount of conjugate acid and conjugate base are
respectively:
×10 mL =
n(H2PO4 ) = 0.1
- mol  L -1
1.0 mmol
n(HPO42-) = 0.2 mol  L-1×10 mL = 2.0 mmol

then: 2
n (HPO 4 )
pH = pKa + lg 
n (H 2 PO 4 )

pH = 7.21 + 2.0 mmol

lg 1.0 mmol
pH = 7.51

The pH value of this buffer solution is 7.51.

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 When carrying out Henderson-Hasselbalch equation calculations,
keep the following important points in mind.

 The pH of a buffer depends mainly on pKa, as well as on buffer

ratio [Base]/[acid]
 Because dilution with water decreases both the concentration of
the weak acid and its conjugate base by the same factor, their
ratio remains constant, and therefore the pH of a buffer remains
constant when water is added.

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  The concentration of A- at equilibrium is therefore
approximately equal to the amount of conjugate base originally
added to the solution.
 When the concentrations of the acid and conjugate base are
equal, their ratio is 1 and the lg1 is zero, therefore the pH=pKa.

 In a buffer solution, the ratio of concentrations is the same as

the ratio of moles.

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 4-3 Buffer Capacity () and Buffer Range
Buffer quantity of strong acid or base that must be added to
Capacity: change the pH of one liter of buffer by one pH unit

dnb dna
  
VdpH VdpH

dnb : infinitely small amount of added strong base.

dna : infinitely small amount of added strong acid.
V : volume of the buffer solution

dpH : infinitely small change in pH

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 4-3 Buffer Capacity () and Buffer Range
Buffer quantity of strong acid or base that must be added to
Capacity: change the pH of one liter of buffer by one pH unit

dnb dna
  
VdpH VdpH

The magnitude of  indicates the relative strength of buffer capacity:

The larger the value of  is, the greater the capacity of the
buffer to resist changes in pH is.

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Example
Calculate β in example 4-1, after adding a strong acid
(HCl)and a strong base(NaOH)
Solution:
(1) After adding HCl
△pH = - 0.04 △Ma =0.02 mol·L-1
M a
  - =-0.02/(-0.04) =0.50mol·L-1 pH-1
pH
(2) After adding NaOH
△pH = 0.03 △Mb =0.02 mol·L-1
M b
 = 0.02/0.03 = 0.67 mol·L-1 pH-1
pH
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 Using mathematical method, we can obtain the other form of the above equation

M (HA)  M (A  )
β= 2.3 
M (HA)  M (A  )

From this equation, we know the capacity of a buffer solution

depends on the total concentration [M(HA) + M(A-)] and the
ratio of concentrations[M (A-) / M (HA)].

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 4-3 Buffer Capacity () and Buffer Range

II Factors affecting buffer capacity

1 The total concentration affects the buffer capacity

For any given the concentration ratio, the larger

the total concentration, the greater the capacity.

Example4-3 (1) A buffer solution consists of 0.10 mol.L-1 CH COOH

3
and 0.10 mol.L-1 CH COONa
3

(2) A buffer solution consists of 0.010 mol.L-1 CH3COOH

and 0.010 mol.L-1 CH3COONa
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Example: Calculate the buffer capacity respectively
（ 1 ） 0.10mol·L-1HAc ～ 0.10mol·L-1NaAc solution ；
（ 2 ） 0.010mol·L-1HAc ～ 0.010mol·L-1NaAc

solution: (1) ctotal =c （ HAc ） +c （ Ac- ） = 0.2 mol·L-1

buffer ratio: 1 ： 1
c(HAc)  c(Ac  )
  2.3 
c(HAc)  c(Ac  )
0.10mol  L1  0.10mol  L1
 2.3 
0.10mol  L1  0.10mol  L1
 0.115mol  L1
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56
 （ 2 ） 0.010mol·L-1HAc ～ 0.010mol·L-1NaAc solution

Solution:
ctotal =c （ HAc ） +c （ Ac- ） =0.02
mol·L-1
buffer ratio:1 ： 1 1
0.010mol  L  0.010mol  L1
  2.3  1 1
0.010mol  L  0.010mol  L
 0.0115mol  L1

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 The relationship between C total and 


C ( Ac ) C ( HAc) C ( Ac  ) C total 
Buffer
solution C ( HAc )
mol·L-1 mol·L-1 mol·L-1 mol·L-1
I 0.1 0.1 1:1 0.2 0.115
II 0.01 0.01 1:1 0.02 0.0115

For any given ratio, the more concentrated the components of

a buffer, the greater the buffer capacity, and the smaller the
pH change

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 Example 4-4 illustrates the relationship between
the buffer capacity and the buffer ratio.

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Example: Calculate the buffer capacity of the following solutions
（ 1 ） 0.10mol·L-1HAc -0.10mol·L-1NaAc solution ；
（ 2 ） 0.15mol·L-1HAc -0.050mol·L-1NaAc solution ；
or 0.05mol·L-1HAc -0.150mol·L-1NaAc solution
（ 3 ） 0.020mol·L-1HAc -0.180mol·L-1NaAc solution ；
or 0.18mol·L-1HAc -0. 02mol·L-1NaAc solution

Solution: ctotal =0.20 mol·L-1 。

（ 1 ） buffer ratio:
1:1
0.10mol  L1  0.10mol  L1
  2.3 
0.10mol  L1  0.10mol  L1
1
 0.115mol  L
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60
 （ 2 ） buffer
ratio:1:3
0.15mol  L1  0.050mol  L1
  2.3 
0.15mol  L1  0.050mol  L1
 0.086mol  L1
（ 3 ） buffer ratio:
9:1
0.020mol  L1  0.18mol  L1
  2.3 
0.020mol  L1  0.18mol  L1
 0.041mol  L1

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 For any given ctotal,
the buffer ratio is closer to 1:1, buffer capacity is greater.

The relationship between buffer ratio and the 

C total C ( Ac  ) C ( HAc ) C ( Ac  ) 
Buffer
solution mol·L-1 mol·L-1 mol·L-1 mol·L-1
C ( HAc)

I 0.2 0.18 0.02 9:1 0.041

II 0.2 0.15 0.05 3:1 0.086
III 0.2 0.10 0.10 1:1 0.115
IV 0.2 0.05 0.15 1:3 0.086
V 0.2 0.02 0.018 1:9 0.041
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II Factors affecting buffer capacity
2 The ratio of concentration affects the buffer capacity

(1) When the buffer ratio is 1:1, β is at a maximum.

- -

βmax =0.575( [HA]+ [A-])

Under this condition. pH=pKa

(2) When the buffer ratio is ＜ 0.1 or ＞ 10,

β is significantly reduced.

Conclusion ：
The total concentration and buffer ratio affect β

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 4-3 Buffer Capacity () and Buffer Range
III Buffer Range
 The buffer range is the pH range over which
the buffer acts effectively.
1
When the buffer ratio is < 10 or > 10 , the  is notably reduced.

1
 buffer ratio  10 Buffering action
10

pH  pKa  1 is called buffer range

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 1
buffer ratio  pH  pKa - 1
10

buffer ratio  10 pH  pKa  1

1 Buffer action
 buffer ratio  10
10

pKa  1  pH  pKa  1

Or : pH=pKa±1
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 In buffer range （ pH=pKa±1 ） ， buffer
solution
has buffering action.

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 4-3 Buffer Capacity () and Buffer Range
III Buffer Range
For example:
⑴ HAc~Ac- buffer solution, Ka(HAc) = 1.76×10-5, then
the buffer range is ?
pKa(HAc) = 4.75 , the buffer range is 3.75~5.75.

⑵H PO -~ HPO 2-buffer solution, pKa (H PO -) = 7.21, then

2 4 4 2 4
the buffer range is ?
the buffer range is 6.21~8.21.

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Summary
M (HA)  M (A  )
 Buffer capacity β= 2.3 
M (HA)  M (A  )

Buffer capacity(β) depends on the total concentration [M(HA) +

M(A-)] and the ratio of concentrations[M (A-) / M (HA)].

For any given the concentation ratio, the larger

the total concentration is, the greater the
capacity is.
For any given ctotal,
the buffer ratio is closer to 1:1, buffer capacity is greater.
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 Buffer Range
The buffer range is the pH range over which
the buffer acts effectively.

1 Buffer action
 buffer ratio  10
10

pKa  1  pH  pKa  1 buffer range

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In a buffer solution, [HA] =[A-], and Kb=1.0×10-9,
the pH of the buffer solution is?
a. 14 b. 9 c. 6 d. 5

What is the buffer range of the above solution?

a. 5~7 b. 8~10 c. 4~6 d. 9~11

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What is the buffer range of this buffer system
HA-A- if the Kb(A-)=1.0×10-6?
 A. 6~8 B. 7~9 C. 5~7 D. 8~10

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Which one has the largest buffer capacity
of the following buffer solutions?

 A. M(HAc)=0.01mol.L-1, M(Ac-)=0.03mol.L-1
 B. M(HCO3-)=0.03mol.L-1, M(CO32-)=0.01mol.L-1
 C. M(H2PO4-)=0.015mol.L-1, M(HPO42-)=0.015mol.L-1
 D. M(NH3)=0.02mol.L-1, M(NH4+)=0.02mol.L-1

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