Chapter 9

Aqueous Solutions and

Chemical
Equilibria
At equilibrium, the rate of a forward process or reaction and that of the reverse
process are equal.

9A The chemical composition of aqueous solutions

Classifying Solutions of Electrolytes

Electrolytes form ions when dissolved in solvent and thus produce solutions
that conduct electricity.
Strong electrolytes ionize almost completely in a solvent, but
weak electrolytes ionize only partially.
Among the strong electrolytes listed are acids, bases, andsalts.
A salt is produced in the reaction of an acid with a base.
Ex., NaCl (sodium chloride), Na2SO4 (sodium sulfate) and
NaOOCCH3 (sodium acetate).

Acids and bases

According to the Brønsted-Lowry theory, an acid is a proton donor, and a base
is a proton acceptor. For a molecule to behave as an acid, it must encounter a
proton acceptor (or base) and vice versa.
An acid donates protons only in the presence of a proton acceptor (a base).
Likewise, a base accepts protons only in the presence of a proton donor (an
acid).

Conjugate Acids and Bases

A conjugate base is formed when an acid loses a proton. For example, acetate
ion is the conjugate base of acetic acid. Similarly, ammonium ion is the
conjugate acid of the base ammonia. A conjugate acid is formed when a base
accepts a proton.
 acid1  base1  proton

base2  proton  acid 2

acid1  base2  base1  acid 2

Acid1 and base1 act as a conjugate acid/base pair, or just a conjugate pair.

Similarly, every base accepts a proton to produce a conjugate acid. When

these two processes are combined, the result is an acid/base, or
neutralization reaction.

This reaction proceeds to an extent that depends on the relative tendencies of

the two bases to accept a proton (or the two acids to donate a proton).

A substance acts as an acid only in the presence of a base and vice versa.
In an aqueous solution of ammonia, water can donate a proton and acts as an acid
with respect to the solute NH3.
NH₃  H₂O  NH₄ 
 OH⁻
base1 acid 2 conjugate acid1 conjugate base2

Ammonia (base1) reacts with water (acid2) to give the conjugate acid ammonium ion
(acid1) and hydroxide ion (base2) of the acid water.

On the other hand, water acts as a proton acceptor, or base, in an aqueous

solution of nitrous acid.

H₂ O  HNO₂  H₃O   NO₂ 

base 1 acid2 conjugate conjugate
acid 1 base 2

The conjugate base of the acid HNO2 is nitrite ion. The conjugate acid of water is the
hydrated proton written as H3O1. This species is called the hydronium ion, and it
consists of a proton covalently bonded to a single water molecule.
An acid that has donated a proton becomes a conjugate base capable of accepting
a proton to reform the original acid.
Similarly, a base that has accepted a proton becomes a conjugate acid that can donate
a proton to form the original base.

NO₂⁻  HN₂O  H₃ O   OH 
Base1 acid2 conjugate acid1 conjugate base2

Thus, nitrite ion, the species produced by the loss of a proton from nitrous acid, is a
potential acceptor of a proton from a suitable donor. It is this reaction that causes an
aqueous solution of sodium nitrite to be slightly basic
Figure 1: Possible structures for the hydronium ion. Higher hydrates such
as H₅O₂⁺, H₉O₄⁺ , having a dodecahedral cage structure may also appear
in aqueous solutions of protons.
Amphiprotic species

Species that have both acidic and basic properties are amphiprotic.
Ex., dihydrogen phosphate ion, H2PO4 -, which behaves as a base in the
presence of a proton donor such as H3O+ (hydronium).

H₂PO₄   H₃O   H₃PO₄  H₂O

base1 acid2 acid1
base2

Here, H3PO4 (phosphoric acid) is the conjugate acid of the original base.
In the presence of a proton
H PO₄⁻(dihydrogen acceptor,
phosphate) such as
behaves as an
hydroxide
acid and ion, however,
donates a
2
proton to form the conjugate base

H₂PO₄
acid1

 OH
base2

 +H₂ O
base1 acid2
 The simple amino acids are an important class of amphiprotic compounds that
contain both a weak acid and a weak base functional group.
When dissolved in water, an amino acid, such as glycine, undergoes a kind of
internal acid/base reaction to produce a zwitterion—a species that has both a
positive and a negative charge.

NH₂ CH₂COOH  NH₃ CH₂ COO 

glyciine
zwitterion

This reaction is analogous to the acid-base reaction between a carboxylic acid and
an amine:
R′COOH + R″NH₂ = R′COO⁻ + R′NH₃⁺
acid1 base2 base1 acid2
Water is the classic example of an amphiprotic solvent that is, a solvent that can
act either as an acid or as a base, depending on the solute.

Common amphiprotic solvents include methanol, ethanol, and anhydrous acetic

acid. In methanol, for example, the equilibria analogous to the water equilibria.
NH₃ + CH₃OH ↔NH₄⁺ + CH₃O⁻
base1 acid2 conjugate acid1 base2

CH₃OH + HNO₂ ↔ CH₃OH₂ + NO₂⁻

base1 acid2 conjugate acid1 conjugate base2
Identify the acid on the left and its conjugate base on
the right in the following equations:

Acid: Conjugate Base:

(b) ) HONH₂ + H₂O ↔ HONH₃⁺ + OH⁻

Acid: H₂O Conjugate Base: OH⁻

(c) HOCl + H₂O ↔ H₃O⁺ + OCl⁻

Acid: HOCl Conjugate base: OCl⁻

TAKE NOTE:
 An acid donates protons. A base accepts protons.
 An acid donates protons only in the presence of a proton acceptor
(a base). Likewise, a base accepts protons only in the presence of a
proton donor (an acid).
 A conjugate base is formed when an acid loses a proton. For
example, acetate ion is the conjugate base of acetic acid. Similarly,
ammonium ion is the conjugate acid of the base ammonia.
 A conjugate acid is formed when a base accepts a proton.
 The hydronium ion is the hydrated proton formed when water
reacts with an acid. It is usually formulated as H₃O⁺, although
there are several possible higher hydrates, as shown in Figure 7-1.
 A zwitterion is an ion that has both a positive and a negative
charge.
 Water can act as either an acid or a base.
 Amphiprotic solvents behave as acids in the presence of basic
solutes and bases in the presence of acidic solutes.
Autoprotolysis
Autoprotolysis (also called autoionization) is the spontaneous reaction
of molecules of a substance to give a pair of ions. Autoprotolysis is yet
another example of acid-base behavior, as illustrated by the following
equations:

The extent to which water undergoes autoprotolysis at room temperature is

slight.
Thus, the hydronium and hydroxide ion concentrations in pure water are only
about 10⁻⁷ M.
Despite the small values of these concentrations, this dissociation reaction is
of utmost importance in understanding the behavior of aqueous solutions.
Write expressions for the autoprotolysis of

(a) 2H₂O.

Answer: 2H₂O ↔ H₃O⁺ + OH₂⁻

(b) 2CH₃NH₂.

Answer: 2CH₃NH₂ ↔ CH₃NH₃⁺ + CH₃NH⁻

Briefly describe or define and give an example of

(a) a strong electrolyte.

- ionizes totally when dissolved in water. HCl is
an example of a strong electrolyte.

(b) the conjugate acid of a Brønsted-Lowry base

- is the species formed when a Brønsted-Lowry
base accepts a proton. NH₄⁺ is the conjugate acid
of the base NH₃.
Briefly describe or define and give an example of

(c) an amphiprotic solute

- can act either as an acid or a base. An amino
acid is an example.

(d) autoprotolysis
- is self-ionization of a solvent to produce both a
conjugate acid and a conjugate base.
7A-5 Strengths of Acids and Bases

Figure 2 shows the dissociation reactions of a few common acids in

water.
The first two are strong acids because reaction with the solvent is
sufficiently complete that no undissociated solute molecules are left
in aqueous solution.
The rest are weak acids, which react incompletely with water to give
solutions containing significant quantities of both the parent acid
and its conjugate base.
7A-5 Strengths of Acids and Bases

The common strong bases include NaOH, KOH, Ba(OH2), and the
quaternary ammonium hydroxide R₄NOH, where R is an alkyl group
such as CH₃ or C₂H₅.
The common strong acids include HCl, HBr, HI, HClO₄, HNO₃ the
first proton in H₂SO₄, and the organic sulfonic acid RSO₃H.
The tendency of a solvent to accept or donate protons determines
the strength of a solute acid or base dissolved in it. For example,
perchloric and hydrochloric acids are strong acids in water. If
anhydrous acetic acid, a weaker proton acceptor than water,
is substituted as the solvent, neither of these acids undergoes
complete dissociation. Instead, equilibria such as the following
are:
CH₃COOH + HClO₄ ↔ CH₃COOH₂⁺ + ClO₄⁻
base 1 acid2 acid1 base2
- Perchloric acid is, however, about 5000 times stronger than
hydrochloric acid in this solvent.
-Acetic acid thus acts as a differentiating solvent toward the two
acids by revealing the inherent differences in their acidities.
-In a differentiating solvent, such as acetic acid, various acids
dissociate to different degrees and have different strengths.
- Water, on the other hand, is a leveling solvent for perchloric,
hydrochloric, and nitric acids because all three are completely
ionized in this solvent and show no differences in strength.

Take note: In a differentiating solvent, various acids dissociate

to different degrees and have different strengths.
In a leveling solvent, several acids are completely dissociated
and show the same strength.
7B Chemical equilibrium
Many reactions never result in complete conversion
of reactants to products. They proceed to a state of
chemical equilibrium in which the ratio of
concentrations of reactants and products is constant.
 Equilibrium-constant expressions are algebraic
equations that describe the concentration relationships
among reactants and products at equilibrium.
Among other things, equilibrium-constant expressions
permit calculation of the error in an analysis resulting
from the quantity of unreacted analyte that remains
when equilibrium has been reached.
The Equilibrium State
Consider the chemical reaction
H₃AsO₄ + 3I⁻ + 2H⁺ ↔ H₃AsO₃ + I₃⁻ + H₂O

We can follow the progress of this reaction and the extent

to which it proceeds by monitoring the intensity of the
red-orange color of the triiodide ion I₃⁻, which appears in
Figure 3 in beakers 1, 3, and 4.
All other participants in the reaction are colorless.
For example, if 1 mmol of arsenic acid, H₃AsO₄ , from
beaker 6, is added to a solution from beaker 5 containing
3 mmol of potassium iodide, the pale red-orange color of
the triiodide ion appears almost immediately in beaker 4.
Figure 3
The Equilibrium State

 A solution of identical color intensity (and hence

identical triiodide concentration) can also be
produced by adding a solution containing 1 mmol of
triiodide ion from beaker 1 to 1 mmol of arsenous
acid, H₃AsO₃ , from beaker 2.
 In the combined solution in beaker 3, the color
intensity is initially greater than in the solution in
beaker 4, but it rapidly decreases as a result of the
reaction
The Equilibrium State

 Ultimately, the color of the solutions in beaker 3 and

beaker 4 are identical, which implies that both
reactions have achieved the same equilibrium state.
 Many other combinations of the four reactants can
be combined to yield solutions that are
indistinguishable from the two just described.
 Figure 4 shows but one of myriad other possibilities.
Figure 4
Figure 5
The Equilibrium State
 Figure 5 shows the reaction of iodine and ferrocyanide.
 The results of the experiments shown in Figures 3 to 5
illustrate that the concentration relationship at chemical
equilibrium (that is, the position of equilibrium) is
independent of the route to the equilibrium state.
 This relationship is altered by applying stress to the
system, however.
 Such stresses include changes in temperature, in pressure
(if one of the reactants or products is a gas), or in total
concentration of a reactant or a product. These effects
can be predicted qualitatively from the Le Châtelier’s
principle.
The Equilibrium State
Le Châtelier’s principle- This principle states that the position of
chemical equilibrium always shifts in a direction that tends to
relieve the effect of an applied stress.
Ex., an increase in temperature of a system alters the
concentration relationship in the direction that tends to absorb heat
and an increase in pressure favors those participants that occupy a
smaller total volume.
In an analysis, the effect of introducing an additional amount
of a reactant or product to the reaction mixture is particularly
important.
The resulting stress is relieved by a shift in equilibrium in the
direction that tends to use up the added substance.
Thus, for the equilibrium we have been considering the
addition of arsenic acid (H₃AsO₄) or hydrogen ions causes an
increase in color as more triiodide ion and arsenous acid are
formed.
The Equilibrium State
 Adding arsenous acid has the reverse effect.
 An equilibrium shift brought about by changing the
amount of one of the participating reactants or
products is called a mass-action effect.
 Theoretical and experimental studies of reacting
systems on the molecular level show that reactions
among the participating species continue even after
equilibrium is achieved.
 The concentration ratio of reactants and products is
constant because the rates of the forward and reverse
reactions are precisely equal.
 In other words, chemical equilibrium is a dynamic state
in which the rates of the forward and reverse reactions
are identical.
TAKE NOTE:
 The final position of a chemical equilibrium is independent of the
route to the equilibrium state.
 Le Châtelier’s principle states that the position of an equilibrium
always shifts in such a direction as to relieve a stress that is applied
to the system.
 The mass-action effect is a shift in the position of an equilibrium
caused by adding one of the reactants or products to a system.
 Equilibrium is a dynamic process.
 Although chemical reactions appear to stop at equilibrium, in fact,
the amounts of reactants and products are constant because the
rates of the forward and reverse processes are exactly the same.
 Chemical thermodynamics is a branch of chemistry that concerns
the flow of heat and energy in chemical reactions.
 The position of a chemical equilibrium is related to these energy
changes.
Briefly describe or define and give an example of
(e) Le Châtelier’s principle.
- states that the position of an equilibrium always
shifts in such a direction to relieve an applied
stress.

(f) an amphiprotic solvent.

- can act as either an acid or base. Water is an
example.

(g) a leveling solvent.

- is one in which a series of acids (or bases) all
dissociate completely. Water is an example since HCl
and HClO₄ dissociate completely
 Briefly explain why there is no term in an
equilibrium constant expression for water or for
a pure solid, even though one (or both) appears
in the balanced net ionic equation for the
equilibrium.
 For dilute aqueous solutions, the concentration of water is so
much larger than other reactants that it can be assumed to be
constant.
 Thus, its concentration is included in the equilibrium constant,
but not in the equilibrium constant expression.
 For a pure solid, the concentration of the chemical species in the
solid phase is constant.
 As long as some solid exists as a second phase, its effect on the
equilibrium is constant and is included in the equilibrium
constant.
 Equilibrium-Constant Expressions
 The influence of concentration or pressure (if the participants are
gases) on the position of a chemical equilibrium is conveniently
described in quantitative terms by means of an equilibrium-
constant expression.
These expressions are derived from thermodynamics.
They are important because they allow us to predict the direction
and completeness of chemical reactions.
An equilibrium-constant expression, however, yields no
information concerning the rate of a reaction.
In fact, we sometimes find reactions that have highly favorable
equilibrium constants but are of little analytical use because they
are so slow.
This limitation can often be overcome by the use of a catalyst,
which speeds the approach to equilibrium without changing its
position.
w moles of W react with x moles of X
wW  xX  yY  zZ
to form y moles of Y and z moles of Z.

The equilibrium-constant expression  Y  Z 

y z

K 
becomes W  X 
w x

The square-bracketed terms are:

1. molar concentrations if they represent dissolved solutes.
2.partial pressures in atmospheres if they are gas-
phase reactants or products. [Z]z is replaced with pz (partial
pressure of Z in atmosphere).
No term for Z is included in the equation if this species is a pure
solid, a pure liquid, or the solvent of a dilute solution.

Y  y

K 
W  X 
w x
 The constant K in is a temperature-dependent numerical quantity
called the equilibrium constant.

By convention, the concentrations of the products, as the equation

is written, are always placed in the numerator and the concentrations of
the reactants are always in the denominator.

 The exact equilibrium-constant expression takes the form:

a Yy a Zz
K 
w xX
aW a

where aY, aZ, aW, and aX are the activities of species Y, Z, W, and X.
Types of Equilibrium Constants in Analytical Chemistry
9B-4 Applying the Ion-Product Constant for
Water
 Aqueous solutions contain small concent- 2H 2O  H 3O  

rations of hydronium and hydroxide ions OH

as a result of the dissociation reaction.
H O 


K 
.OHH
3
 The dissociation constant can be written as 2
2

O
 The concentration of water in dilute aqueous solutions is enormous,
however, when compared with the concentration of hydronium and hydroxide
ions. As a result, [H2O]2 can be considered as constant and we write
K H2 O 
2
w 
 H O  OH
K 3

the new constant Kw is called the ion-product constant for water.
 log Kw   logH 3O
 Negative logarithm of the equation gives  logOH 


 By definition of p function, we have
pKw  pH  pOH
At 25°C, the ion-product constant for water is 1.008 x 1014.
For convenience, we use the approximation that at room
temperature Kw  1.00 x 1014.
Table 9-3 shows how Kw depends on temperature.
The ion-product constant for water permits us to
easily find the hydronium and hydroxide ion
concentrations of aqueous solutions.
Using Solubility-Product Constants
Most sparingly soluble salts are completely dissociated in saturated
aqueous solution, which means that the very small amount that does go into
solution dissociates completely.
When an excess of barium iodate is equilibrated with water, the
dissociation process is adequately described as
Ba(IO ) (s)  Ba 2 (aq)  2IO 
Ba2

 
 IO
3
2

K  Ba(IO3 )2 (s)
(aq)
3 2  
 “An excess of barium iodate is equilibrated with water” means that more solid
3

barium iodate is added to a portion of water than would dissolve at the

temperature of the experiment.
Some solid BaIO3 is in contact with the saturated solution. The
concentration of a compound in its solid state is, however, constant. In other
words, the
number of moles of Ba(IO3)2 divided by the volume of the solid Ba(IO3)2 is
constant no matter how much excess solid is present. Therefore, the previous
equation can be rewritten
K[Ba(IO ) (s)]  K  Ba
3 2
in
sp
the 
form
2

IO 2
3
solubility-product constant


The equation shows that the position of this equilibrium is independent of the amount of
Ba(IO3)2 as long as some solid is present.
The Solubility of a Precipitate in Pure Water
The Effect of a Common Ion on the Solubility of a Precipitate
The common-ion effect is a mass-action effect predicted from Le Châtelier’s
principle and is demonstrated by the following examples.
The solubility of an ionic precipitate decreases when a soluble compound
containing one of the ions of the precipitate is added to the solution. This
behavior is called the common-ion effect.
The uncertainty in [IO3 -] is 0.1 part in 6.0 or 1 part in 60. thus, 0.0200 (1/60) 5
0.0003, and we round to 0.0200 M.

A 0.02 M excess of Ba+2 decreases the solubility of Ba(IO3)- by a factor of

about 5; this same excess of IO3- lowers the solubility by a factor of about
200.
Using Acid/Base Dissociation Constants
When a weak acid or a weak base is dissolved in water, partial dissociation occurs.

HNO  H O  H O   NO 
2 2 3
2

Ka is the acid dissociation constant for nitrous acid.

Ka 
 H O  NO

3 2

HNO 2


In an analogous way, the base dissociation constant for ammonia is

NH 3  H 2 O  NH 4 
OH

Kb 
NH OH 4
 

 NH 3


For both, [H2O] does not appear in the denominator because the concentration of
water is very large relative to the concentration of the weak acid or base that the
dissociation does not alter [H2O] appreciably.
Dissociation Constants for Conjugate Acid/Base Pairs
Consider the base dissociation-constant expression for ammonia and the acid
dissociation-constant expression for its conjugate acid, ammonium ion:

NH  H O  NH  OH  
K NH .OH
4


 3 2 4

 NH 3

.H O
b

H 2 O  NH 3  H  Ka 
NH 3 3


NH
3O
 
4
K K  H O OH

 

.
K w  H 3O .OH
a b 3

 


K w  K a Kb
Hydronium Ion Concentration of Solutions of Weak Acids

When the weak acid HA is dissolved in water, two equilibria produce

hydronium ions:
HA  H O  H O  

 H O
3
K  HA
A 
2 3 a
 
A
2H O  H O  OH
2 3
 K  H O OH w 3


 reaction suppress the


Normally, the hydronium ions produced from the first 

dissociation of water to such an extent that the contribution of hydronium ions

from the second equilibrium is negligible. Under these circumstances;
- one H3O+ ion is formed for each A- ion, and we write

A  H O 

3

The sum of the molar concentrations of the weak acid and its conjugate base
must equal the analytical concentration of the acid cHA
Thus, we get the mass-balance equation
 
c HA  A 


Substituting [H3O+] for [A-] yields

HA H O 



cHA
HA3
Which rearranges to
HA  c HA 
 H 3O

Thus, the equilibrium-constant expression becomes

K c   HO 3



a HA

3
 
2(Eqn...9
HH OOHOKKc18) 

Which rearranges to  3

0 2
a 3
a
HA
The positive solution to this quadratic equation is

H3O HA
 K  Ka 2  4 aK a

c
2
This can be simplified by making the additional assumption that dissociation does
not appreciably decrease the molar concentration of HA. 
Thus, if [H3O+] << CHA , - [H3O+]  CHA, and Equation 9-18 reduces to
CHA

Ka
H O3
2
H O
3

KacH
 cHA

A


Figure 9-3 Relative error resulting from the assumption that [H3O+] << cHA
The method of Succesive
approximations
Hydronium Ion Concentration of Solutions of Weak Bases

Aqueous ammonia is basic as a result of the reaction

NH  H O  NH   OH 
3 2
4

The equilibrium constant of the reaction is Kb 

NH OH

4


 NH 3


9C Buffer solutions
A buffer solution resists changes in pH when it is diluted or when acids or
bases are added to it.
Bsolutions are prepared from a conjugate acid/base pair.
Buffers are used in chemicalapplications whenever
it is important to maintain the pH of a solution
at a constant and predetermined level.

Calculating the pH of Buffer Solutions

A solution containing a weak acid, HA, and its conjugate base, A2, may be
acidic, neutral, or basic, depending on the positions of two competitive
equilibria:

HA  H 2 O  H 3 O  A 
Ka
H O 

AHA
 3

 


 OH 
K
A   H 2 O  OH   HA Kb
 HA  Kw
a

A 


These two equilibrium-constant expressions show that the relative

concentrations of the hydronium and hydroxide ions depend not only on the
magnitudes of Ka and Kb but also on the ratio between the concentrations of
the acid and its conjugate base.

The equilibrium concentrations of HA and NaA are expressed in terms of

their analytical concentrations, cHA and cNaA.
HA  cH A  H 3 O  OH  

A  

c  H O 

OH NaA 3



HA A 

 cNHa AA
The dissociation-constant expression can then be expressed as:

H O 
3


a
cHA
K c NaA

The hydronium ion concentration of a solution containing a weak acid and its
conjugate base depends only on the ratio of the molar concentrations of
these two solutes.

Furthermore, this ratio is independent of dilution because the concentration

of each component changes proportionally when the volume changes.
Properties of Buffer Solutions

Figure 9-4 The effect of dilution

of the pH of buffered and unbuffered
solutions.

The Effect of Added Acids and Bases

Buffers do not maintain pH at an absolutely constant value, but changes in
ph are relatively small when small amounts of acid or base are added.
The Composition of Buffer Solutions as a Function of pH: Alpha Values
The composition of buffer solutions can be visualized by plotting the
relative equilibrium concentrations of the two components of a conjugate
acid/base as a function of the pH of the solution.

These relative concentrations are called alpha values.

If cT is the sum of the analytical concentrations of acetic acid and sodium

acetate in a typical buffer solution, we can write:

cT
 cHOAc  cNaOAc
0 the fraction of the total concentration of acid that is  0  HOAc
undissociated is cT

1 
OAc 

1, the fraction dissociated is

cT

Alpha values are unitless ratios whose sum must equal  0  1 

unity. These values depend only on [H3O+] and Ka. 1

K a HOAc
[OAc  ] 
 H3 O


cT  HOAc OAc 

 HOAc H
K H O 



HOAc HOAc( K H
a 3
cT )
 
 
O 3
O 3
The re-arranged equation becomes HOAc
c
  3
 H O 
H O 

T 3 a
K

[HOAc]/cT = 0 Thus,  HOAc
H O 

0 
c

HO 
T 3

3 a
K
Similarly,

OAc 
Ka
1 
c T

 
H3 O  a
K
Figure 9-5 Graph shows the variation in a with pH.
Note that most of the transition between a0 and a1 occurs within 1 pH unit
of the crossover point of the two curves.
The crossover point where 0 = 1 = 0.5 occurs when pH = pKHOAc = 4.74.
The buffer capacity, b, of a solution is defined as the number of moles of a
strong acid or a strong base that causes 1.00 L of the buffer to undergo a
1.00-unit change in pH.

Mathematically, dc dca
 dpH b   dpH
where dcb is the number of moles per liter of strong base, and
dca is the number of moles per liter of strong acid added to the buffer.

Since adding strong acid to a buffer causes the pH to decrease, dca/dpH is

negative, and buffer capacity is always positive.

The pKa of the acid chosen for a given application should lie within 1 unit of
the desired pH for the buffer to have a reasonable capacity.
Figure 9-6 Buffer capacity as a function of the logarithm of the ratio cNaA/cHA.
Preparation of Buffers
• Suggested problems to solve from Ch:9
• 9.1, to 9.30
• You are advised to solve each question at the
ends of the chapter 9.