Ions and Equilibrium

Foundations to Chemistry - adapted from "Chemistry, Matter and the Universe" Page 1 of 1
16. Ions and Equilibrium; -- Jump to --
Acids and Bases

Introduction
Acids are familiar to us because of their power as corrosive agents and
solvents, bringing into solution compounds that are insoluble in water alone
Strong acids will attack many metals, converting them to soluble ions and
liberating bubbles of hydrogen gas in the process.
Acids also will dissolve carbonates such as limestone, and certain other
minerals and inorganic compounds. The weaker acids that are safe to
taste, such as citric acid in lemons and acetic acid in vinegar, have a
characteristic mouth puckering sharp taste that we immediately recognize
and designate as "acid".
Bases also are useful for dissolving water-insoluble substances, especially

oils, greases, and other organic compounds. Sodium hydroxide, for
example, will attack the oils of the skin and turn them into soap, which is
why solutions of household lye feel slippery to the touch.
We have seen previously that there are many substances, amphoteric

oxides among them, that are insoluble in plain water but are dissolved
either by an acid or a base, or both.
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Acids and Bases

Introduction
Besides their usefulness as solvents, acids and bases are important as
catalysts. Because of their small size, mobility, and charge, H+ and OH- ions
from acids and bases can attack compounds in such a way as to make
reactions occur more easily and faster. This is the key to their catalytic
effectiveness.
If a substance provides a faster pathway for reaction but is regenerated again

at the end of the process, it is a true catalyst. If catalysts are ions or molecules
dissolved in the same solution as the reactants and products, they are known
as homogeneous catalysts. This is the type of catalysis discussed in the
postscript to this chapter.
In Chapter 15 we saw examples of heterogeneous catalysts, in which the

catalyst is a separate phase - a surface to which the gaseous or dissolved
reactants diffuse and from which the products separate.
In either type of catalysis the principle is the same: A catalyst is a substance

that accelerates a thermodynamically spontaneous reaction by providing an
alternate mechanism, without itself being consumed by the overall reaction. It
can participate in several steps of the process, as long as it is regenerated at
the end.
Acids and bases are widely used homogeneous catalysts.
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Acids and Bases

Strong Acids and Bases
When salts dissolve in water the attractive forces within the ionic lattice are
broken, and are replaced by attractive forces between individual ions and the
polar water molecules that surround them in a hydration shell.
As we saw in Chapter 12, the heat of solution is the difference between

hydration energy and crystal-lattice energy. In addition, the salt becomes more
disordered when it dissolves, so the entropy increases. If the combination of
entropy increase and heat of hydration is enough to overcome the crystal-
lattice energy, the salt will dissolve.
We can write the overall process as
Salts such as NaCI are 100% ionized in the crystal and in aqueous solution.
The symbol (aq) indicates that each ion is hydrated, or surrounded by a shell of
polar water molecules in the manner that we saw first in Chapter 5, and in the
drawing at the beginning of this chapter.
For the sake of brevity, we will not use the (aq) symbol in equations in this
chapter, but you should remember that ions in aqueous solution always are
hydrated, and that hydration energy is largely responsible for making the salt
dissolve. If there were no hydration energy to balance the loss of energy from
crystal attractions, then dissolving NaCI would be as difficult as vaporizing it,
which can be accomplished only at temperatures above 1400'C.
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Acids and Bases

Strong Acids and Bases
The behavior of strong acids and bases is similar to
that of salts. Strong acids dissociate completely in
water (below) with the liberation of a proton (hydrogen
ion):
Sulfuric acid also releases a second proton, but only

incompletely, as a weak acid.) Strong bases in
aqueous solution produce hydroxide ions:
Since these compounds dissociate completely in water,

the concentration of H+ or OH- ions produced is the
same as the overall concentration of the added acid or
base. The concentration of hydrogen ions in
a tenth-molar solution of nitric acid is 0. 10 mole per
liter.
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Acids and Bases

Weak Acids and Bases
Other acids and bases are only incompletely

dissociated into ions in solution, and exist in part as
undissociated molecules.
Dissolved hydrogen fluoride, for example, exists as an

equilibrium mixture of HF molecules and hydrated H+
and F- ions.
The equilibrium constant for this dissociation usually is

written as Ka., for acid dissociation, rather than Keq:
Hydrogen fluoride is an inorganic acid.
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Acids and Bases

Weak Acids and Bases
Acetic acid is an organic acid, but behaves in a similar way: Ammonia is an example of a weak base that reacts with water to
yield ammonium and hydroxide ions, but the reaction is far from
complete:
Because acetic acid is so common, it is often given the shorthand

representation HOAc, with Ac- symbolizing
Water is both solvent and reactant in this reaction. For moderately

dilute solutions of ammonia, the concentration of water will not
change appreciably from that of pure water:
The dissociation is then written
The acid-dissociation equilibrium constant is For simplicity, the constant H2O concentration of 55.5 moles per
liter can be brought to the left side of the equation and
incoroporated into the equilibrium constant:
In such expressions concentrations of ions and molecules are

always given in units of molarity (M), or moles per liter of solution.
The units of Ka are unmistakable, and ordinarily are omitted.
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Acids and Bases

Calculations with Equilibrium Constants
In half molar nitric acid, the concentrations of H+ and NO3- ions You can avoid the quadratic formula by using a little chemical
are each 0.5 mole per liter, since strong acids are completely common sense instead. With a dissociation constant as small as
dissociated. In 0.5-molar acetic acid, dissociation is incomplete, 0.0000176, only a small fraction of the acetic acid present will be
and the ion concentrations are much less than 0.5 mole per liter. dissociated, so y is small. Hence we should be able to neglect y in
the denominator, because it is subtracted from the much larger c,
We can find out how much less by using the acetic acid and solve a simpler equation instead:
equilibrium expression. Let the original, overall HOAc
concentration be c moles per liter before dissociation takes place,
and suppose that when equilibrium is reached, y moles per liter of
this acid have dissociated.
Then c is specified by the initial conditions of the experiment, and For half molar acetic acid, c = 0.50, and
y is the concentration of each ion, because for every dissociated
HOAc molecule, one H+ ion and one OAc- ion are formed. At
equilibrium:
You can now check the validity of the approximation:
If the acid had dissociated enough so that y was a few percent of

c, this approximation would not have been valid. Our calculation
tells us that, although the overall acetic acid concentration is 0.50
This is a quadratic equation in y, and can be solved exactly using
mole liter-1, such a small amount dissociates that the acetate and
the quadratic formula:
hydrogen ions each are present at only 0.00297 mole liter-1
concentration. This is why acetic acid is classed as a weak acid.
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Acids and Bases

Dissociation Constants
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Acids and Bases

Dissociation of Water
Water itself dissociates to a small but significant extent Because this ion product is an equilibrium constant, hydroxide
and hydrogen ion concentrations can be related in aqueous
solution. If we increase the hydrogen ion concentration by adding
acid to a solution, we will repress the dissociation of water. Some
of the added H+ will combine with OH-, and the hydroxide ion
concentration will decrease until the ion product again is 10-14 .
As with ammonia, the constant term, [H2O] = 55.5 moles per liter,
can be incorporated into the equilibrium constant: After equilibrium has been reestablished, the hydrogen and
hydroxide ion concentrations will be different than before, but their
product will be the same. Similarly, if we add hydroxide ions to a
solution, they will combine with some of the H+ originally present,
in which Kw, is the "ion product" for water. The numerical value of until the ion product once again is 10-14 .
Kw varies with temperature:
When an acid and a base are mixed, some of the H+ and OH-
ions combine to form H2O. This is called neutralization. A solution
in which [H+] and [OH-] are equal is termed a neutral solution.
In pure water or any neutral solution, the hydroxide and hydrogen

(Can you use these data and Le Chatelier's principle to predict ion concentrations are
whether the dissociation of water is endothermic or exothermic?
Check your prediction against Appendix 2.) The value of Kw that
conventionally is used in calculations is
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Acids and Bases

A simple calculation can show how small a fraction of

water molecules is dissociated. A concentration of 1.0 x
10-7 moles of H+ per liter of water means that 1.0 x 10-7
moles of H2O has dissociated per 55.5 moles of water,
or one part in 0.56 x 10-9.
Approximately two water molecules out of every billion

are dissociated into H+ and OH- ions. The animation
shows what a tiny percentage that actually is...
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Acids and Bases

A simple calculation can show how small a fraction of

water molecules is dissociated. A concentration of 1.0 x
10-7 moles of H+ per liter of water means that 1.0 x 10-7
moles of H2O has dissociated per 55.5 moles of water,
or one part in 0.56 x 10-9.
Approximately two water molecules out of every billion

are dissociated into H+ and OH- ions. The animation
shows what a tiny percentage that actually is...
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Acids and Bases

The pH Scale
Concentrations involving such extreme powers of ten, extending over 14
orders of magnitude, are clumsy to handle. In the discussion of entropy in
Chapter 13 we found it convenient to reduce a wide-ranging quantity,
probability, to more manageable numbers by taking the logarithm
In chapter 14 we saw that standard free energies convey the same information
as equilibrium constants, but in a more compact logarithmic form:
The value of logarithmic notation can be illustrated by the 10 X 10 X 10 stack

of blocks at the right. The entire stack contains 1000 blocks. One face of the
stack has 100 blocks, or 1/10 of the whole.
One edge contains 10 blocks, or 1/100 of the stack, and one corner block
represents 1/1000 of the entire ensemble. The fractions represented by the full
block, face, edge, and corner, can be represented by 1 (or 100), 10-1, 10-2 ,
and 10-3.
We also can represent these different orders of magnitude by picking out the
negative exponents: 0, 1, 2, and 3. We can label these numbers pF values if
we define pF as the negative logarithm to base ten of the fraction, F:
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Acids and Bases

The pH Scale
Instead of saying that a corner block is one thousandth of the We can write the water dissociation equilibrium expression as Kw =
complete stack, or F = 0.001, we could say that relative to the [H+] [OH-] = 10-14; then pKw = pH + pOH = 14.00. The product of
stack as a whole, a single corner block represents pF = 3. the concentrations of H+ and OH- ions is a constant, 10-14, and the
sum of pH and pOH is another constant, 14.
This is the basis of the pH scale, with ions in solution replacing Pure water has a pH of 7.00, acids have pH values less than 7,
blocks in a stack. The pH of a solution is defined as the negative and bases have pH values above 7. The pH of several commonly
logarithm to base 10 of the hydrogen ion concentration: encountered liquids are shown below.
In the same way, pOH is the negative logarithm of the hydroxide

ion concentration, pOH = -log10 [OH-], and pK is the negative
logarithm of any equilibrium constant, pK = -log10 K. The table on
page 7 gives the value of pKa as well as Ka.
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Acids and Bases

Neutralization
If a strong acid is added to a strong base, the product
of hydrogen and hydroxide ion concentrations will be
high at first. Some of these ions will recombine to form
water until the product of [H+] and [OH-] is again
brought down to 10-14 mole2 liter-2 . This is the process
of neutralization:
You can see from this that the neutralization of an acid

and a base really involves only the H+ and OH- ions,
and that other ions, Na+ and Cl- ions in this case play
only a passive role.
One mole of an acid that liberates one H+ per molecule,

or one mole of a base that produces one OH- per
molecule, are said to possess one equivalent of
neutralizing power. For H2SO4, which can release two
protons per molecule, one mole of acid produces two
acid-base equivalents. When an acid and a base have
exactly neutralized one another, the number of
equivalents of acid and base must be the same, no
matter what the concentrations of the individual
solutions.
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Acids and Bases

Neutralization
Example. How many milliliters of a 0.10-molar NaOH solution will be required
to neutralize 100 mil of 0.75-molar HCl
Solution. The amount of HCl present is
0.100 liter X 0.75 mole liter-1 = 0.075 mole HCl
Since each mole of HCI yields one mole of H+ upon complete dissociation, this
quantity is also equal to 0.075 equivalent of HCl. For neutralization, the same
number of equivalents of NaOH are required, 0.075. Again, since one mole of
NaOH yields one mole of OH- upon dissociation, 0.075 equivalent of NaOH
equals 0.075 mole. The volume of 0.10-molar NaOH required to produce this
amount is
Just as milliliters are easier to use than liters in most situations because they
replace decimal fractions with whole numbers, so millimoles (mmole) and
milliequivalents (meq) often are more convenient than moles and equivalents;
1 mole = 1000 millimoles. The previous problem could be solved using
millimoles and milliequivalents as follows:
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Acids and Bases

Neutralization
Example. How many milliliters of a 0.10-molar NaOH solution will be required
to neutralize 100 mil of 0.75-molar HCl
Solution. The amount of HCl present is
0.100 liter X 0.75 mole liter-1 = 0.075 mole HCl
Since each mole of HCI yields one mole of H+ upon complete dissociation, this
quantity is also equal to 0.075 equivalent of HCl. For neutralization, the same
number of equivalents of NaOH are required, 0.075. Again, since one mole of
NaOH yields one mole of OH- upon dissociation, 0.075 equivalent of NaOH
equals 0.075 mole. The volume of 0.10-molar NaOH required to produce this
amount is
Just as milliliters are easier to use than liters in most situations because they
replace decimal fractions with whole numbers, so millimoles (mmole) and
milliequivalents (meq) often are more convenient than moles and equivalents;
1 mole = 1000 millimoles. The previous problem could be solved using
millimoles and milliequivalents as follows:
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Acids and Bases

Neutralization
The easiest way of measuring how much of an
unknown acid or base is present in solution is to
neutralize it with just enough base or acid to bring the
pH to 7.00, as measured by an acid-base indicator or
other means.
At neutrality, the number of equivalents of acid and

base must be the same. This process of neutralization
as a means of measuring the amount of unknown acid
or base present is known as titration.
The sample to be measured and a small amount of

acid-base indicator are placed in a beaker, and the
titrating base or acid is added from a graduated burette,
as shown on the previous page, until a change of color
of the acid-base indicator in the sample solution shows
that neutralization, or the end point, has been reached.
Example. A solution of acetic acid of unknown

concentration is titrated against 0.01-molar KOH, and it
is found that 83 mil of base are required for complete
neutralization of the acid.
How many equivalents, and how many grams, of acetic

acid were present?
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Acids and Bases

Neutralisation
Solution. The base solution contains 0.01 meq per ml, since KOH yields only
one OH- ion per molecule. The 83 mil of base solution contain
83 mil X 0.01 meq per ml = 0.83 meq of base
Since the molecular weight of acetic acid is 60.05 g per mole, or 60.05 mg per
mmole, the amount of acetic acid in the sample titrated is
60.05 mg per mmole X 0.83 mmole = 44.8 mg of acetic acid
Example. In an analysis of industrial sulfuric acid, a 5.00-ml sample was

diluted to one liter, then 20 mil of the diluted acid were titrated with 0.10-molar
NaOH. What is the concentration of the original acid, if 15.0 ml of NaOH
solution are required to neutralize the acid?
Solution. The number of milliequivalents of NaOH used is
15.0 ml x 0.10 meq per ml = 1.50 meq of NaOH
This much NaOH will neutralize the same number of meq of H2SO4, 1.50 meq;
but since each mole of H2SO4, contributes two moles of protons, 1.50 meq are
obtained from only 0.75 mmole of sulfuric acid. The diluted sample had 0.75
mmole in 20 nil, or 0.0375 mmole per ml.
The original undiluted sample was more concentrated by a factor of 5/1000,
and hence had a sulfuric acid concentration of
0.0375 moles per liter x (1000/5) = 7.5 moles per liter
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Acids and Bases

The Meaning of Acids and Bases
In the view formalized for acids and bases at the turn of the century, an acid
was any substance that dissociated to give H+ ions in aqueous solution, and
a base was any substance that dissociated to give OH- ions.This definition
(proposed by Arrhenius) was fine for potassium hydroxide, but where was
the hydroxide ion in ammonia, NH4+?
Ammonia releases hydroxide ions when it dissolves, but only because the
ammonia steals a proton from a water molecule:
One could talk about "ammonium hydroxide," NH4OH, but there is no

evidence that the compound exists.
A better definition of acids and bases in aqueous solutions is: An acid is any
substance that, when added to an aqueous solution, increases the hydrogen
ion concentration; a base is any substance that, when added to an aqueous
solution, decreases the hydrogen ion concentration and increases the
hydroxide ion concentration.
Since [H+] and [OH-] are linked by the water dissociation equilibrium, when
one is increased, the other must decrease. By this definition, both NaOH and
NH3 are bases because they increase the hydroxide ion concentration, [OH-
]. In the case of NaOH, the hydroxide ions come from the crystal lattice of the
solid, and in the case of NH3 they come from dissociated water molecules
whose protons have combined with NH3 to form, NH4+. The overall effect is
the same.
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Acids and Bases

The foregoing is the most useful everyday definition of
acids and bases, applicable to aqueous solution. The
Bronsted-Lowry theory goes one step further, and frees
us from a dependence on water as a solvent. It also is
helpful in explaining the difference between strong and
weak acids.
According to Bronsted and Lowry, an acid is any

substance that releases protons in solution, and a base
is any substance that combines with protons and
removes them from solution.
Thus in the dissociation of HCl, HCl = H+ + Cl-, the

molecule of HCl is a B-L (Bronsted-Lowry) acid
because it can release a proton, and the Cl- ion is a B-L
base because it can combine with a proton. HCl and Cl-
are called a conjugate acid-base pair (see diagram on
previous page). In the two-proton dissociation of
sulfuric acid,
the bisulfate ion, HSO4-, is the conjugate base of the B-

L acid H2SO4, and at the same time is the conjugate
acid of the B-L base SO2-. The words "acid" and "base"
in the Bronsted-Lowry theory do not describe what a
molecule is, but rather what it does.
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Acids and Bases

In contrast, the cyanide ion, CN-, is a strong B-L base. It has a
great attraction for protons, and the reaction
This is the value of Ka for the ammonium ion that is given in the
is heavily shifted to the right. As a result, HCN is a very weak table on Page 8. You can either think of NH3 as a moderately
acid. strong base with a Kb of 1.76 x 10-5, or NH4+ as a very weak acid
with a Ka of 5.68 x 10-10. The results of any calculation involving
In the examples discussed so far, the acidic species has been this acid-base equilibrium always will be the same whether you use
Ka or Kb, as long as you know what you are doing.
electrically neutral and the basic species charged. This need not
always be so. Ammonia is a B-L base, and the ammonium ion is
a B-L acid, capable of releasing a proton: Water can act as both a B-L acid and a B-L base.
We can write an acid-dissociation equilibrium espression in the We can regard the hydrating water molecules around a proton in
usual way: solution as a weak B-L base
The Bronsted-Lowry theory has so influenced chemistry that two

This is related to the base-dissociation constant seen previously,
generations of chemists have written H3O+ for the hydrated form of
Kb, by
H+ and called it the "hydronium ion", even though the true
hydration state of the proton is not known, but it is probably more
like H+(H2O)4 or H9O4+.
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Acids and Bases

The difference between strong and weak acids
The hydronium ion notation is convenient in explaining
why acids are divided into two categories, strong
(complete dissociation in water) and weak (incomplete
dissociation).
Two equilibria compete for the proton when a general

acid, HA, dissociates into H+ and A-:
One can regard A- and H2O as two B-L bases in

competition for the proton, with the H2O having the unfair
advantage of being present in great excess.
If the acid anion, A-, is a stronger B-L base than the

water molecule, it will have a greater attraction for
protons. It will be able to compete successfully with
water moleules for the available protons. Most of the
acid then will exist as HA instead of A-, and we will call
HA a weak acid.
In contrast, if H2O is a stronger B-L base than is A-, the

attraction of water molecules for protons will be greater
than that of A- ions. H2O will take protons away from HA
and form hydronium ions (hydrated H+).
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Acids and Bases

Moreover, the large excess of water molecules present in an aqueous solution
will push the equilibrium
far to the right, in the direction of dissociated acid.
For strong acids such as HClO4, HNO3, HCI, and H2SO4 (or weak B-L bases
such as ClO4-, NO3-, Cl- and HSO4-), the donation of the proton by the acid to
H2O, as shown in the reaction to the left above, is effectively complete.
We refer to these as the strong acids, in contrast to the weak acids that show
only partial dissociation in aqueous solution. Although these strong acids do
have different degrees of attraction for their protons, they all appear equally
strong when water is the solvent. This is called the leveling effect of the
solvent. If we want more information about the relative strengths of these
acids, we must turn to a different solvent, which exerts less of a pulling power
on the acid protons.
Methanol, CH3OH, has a smaller attraction for protons than water does. HCl
behaves as a weak acid in methanol solution, because it is only partially
dissociated (see diagram).
One can measure dissociation constants in methanol or other nonaqueous

solvents for compounds that are completely dissociated strong acids in water
solution, and thus can make the relative strength ranking shown in the table on
Page 8.
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Acids and Bases

Whether an acid will behave as a strong or weak acid thus ACIDS WITH SEVERAL DISSOCIATING PROTONS
depends both on the acid and the solvent. Because the fluoride
ion, F-, is small, thus permitting the proton to come close to it and Sulfuric acid can lose two protons. The first dissociation is that of a
feel a strong electrostatic attraction, it is a moderately strong B-L strong acid, and is complete in aqueous solution:
base.
Even though water molecules are present in great excess, the

attraction of F- for protons is great enough that HF is only The bisulfate ion, HSO4-, is more reluctant to lose another positive
partially dissociated in aqueous solution. In contrast, the Cl- ion is ion, since it already has one negative charge. The sulfate ion is a
large, with a diffuse electron density, and does not permit the strong B-L base, and competes successfully with water molecules
proton to approach as closely. It attracts protons more weakly, for the proton. Therefore HSO4- is a weak acid with a measurable
and is a weak B-L base. dissociation constant:
So many molecules of H2O surround each Cl- ion that they

overwhelm Cl- and compete successfully for the available H+
ions, thereby pushing the dissociation equilibrium effectively to Phosphoric acid has three dissociating protons, of varying degrees
completion. Hence HCl is classed as a strong acid in water. of weakness:
In methanol, Cl- ions in similar concentration find no difficulty in

competing successfully with an excess of CH3OH molecules for
the available H+, because of the very small attraction of CH3OH
molecules for H+. Even in methanol, however, perchloric acid is a
strong acid because the perchlorate ion, ClO4-, has less
attraction for protons than methanol molecules do. HClO4 is the
strongest of all the common acids because ClO4- is the weakest
of all the B-L bases.
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Acids and Bases

Acids with several dissociating protons
The pKa, values are especially convenient, because the pKa of a dissociation
reaction is just the pH at which the undissociated and dissociated forms are
present in equal amounts:
If the pH exactly equals the pKa for the acid under consideration, then
and A- and HA are present in equal amounts. If the pH falls below pKa (more
acidic), then log10 [A-]/[HA] will be negative, the ratio [A-]/[HA] will be less than
1.00, and the HA form will be favoured.
In physical terms, if the pH is lowered by the addition of H+, some of the

excess H+ combines with A- to make more of the undissociated acid. The
dissociation equilibrium is shifted to the left.
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Acids and Bases

In contrast, if the pH is greater than pKa for the acid, then log10 The approximate relative amounts of the four phosphate species at
[A-] / [HA] will be positive, [A-] / [HA] will be greater than 1.00, pH = 7 will be
and A- will be favored over HA.
Again, in physical terms, a shortage of H+ ions in a basic solution

forces more HA to dissociate and yield A-. The equilibrium shifts
to the right. For every unit of difference between pH and pKa, the This is important physiologically because of the large number of
phosphate compounds in living organisms. Adenosine triphosphate
ratio of basic [A-] to acidic [HA] forms changes by a factor of 10.
(ATP) was discussed as an energy-storage molecule in Chapter
With this in mind, we can look at the pKa values for the three 10.
phosphoric acid dissociations and say that, at physiological pH
values of around 7.0 in a living organism, any phosphate present It has four dissociable protons. The first three dissociations occur at
- pKa values around pH = 2-3, so in neutral solutions these three
would be found as H2PO4 and HPO42- in roughly equal
amounts. dissociations are essentially complete. The fourth dissociation has
pKa = 6.5, so at pH=7 the ration of ATP4- to ATP3- is the square
Since there are five pH units between the pKa of a neutral root of 10 = 3.2 to 1.
solution and that of the first H3PO4/H2PO4- dissociation (pKa1 =

2.12) , the ratio of undissociated H3PO4 to H2PO4- ion at pH = 7
will be approximately 10-5, or 1 to 100,000.
Similarly, since the third dissociation of phosphoric acid has a

pKa3 of more than 12, the ratio of HPO42- to PO 3- at pH = 7 will
4
be more than 100,000 to 1.
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Acids and Bases

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Acids and Bases

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Acids and Bases

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Acids and Bases

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Acids and Bases

Buffers and pH control
In many chemical reactions, especially in biological systems, it is important to
keep the pH or acidity within defined limits. The bloodstream of humans is kept
at pH = 7.4 + / - 0.2, and acidosis or alkalosis outside this range can be fatal.
(Those of you who read Michael Crichton's novel The Andromeda Strain may
recall that the plot hinged on the alien life form in the victims' bloodstreams
being even more sensitive to pH than the infected humans were.)
pH control also is important in rontrolling enzyme activity. Most enzymes have

an optimum pH range in which they function best, with sharply reduced
efficiency outside this range. At too high or too low pH, acidic and basic groups
on the enzyme or on its substrate molecules may pick up or lose extra protons,
thereby altering the charge distribution at the molecular surface and possibly
making a mating of enzyme and substrate difficult or impossible (see above).
Many industrial processes go most efficiently, or most rapidly, at certain pH

values. It is important to have some way of keeping pH changes to a minimum.
The answer is the use of acid-base buffers.
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Acids and Bases

A buffer is a mixture of a weak acid and its salt, or a weak base In the example on the opposite page, the buffer mixture is
and its salt, such as: symbolized by five undissociated HA molecules and five A- ions
from NaA salt. As soon as three protons are added to the buffer,
1. acetic acid (HOAc) and sodium acetate (NaOAc); they are neutralized by three of the five A- ions, and the pH of the
solution is affected very little:
2. carbonic acid (H2CO3) and sodium bicarbonate (NaHCO3);
3. potassium dihydrogen phosphate (KH2PO4) and dipotassium

hydrogen phosphate (K2HPO4); Conversely, if three OH- ions are added to this buffer mixture, as
shown at the far right, they steal protons from three of the five
4. ammonia (NH3) and ammonium chloride (NH4Cl) undissociated HA molecules and are neutralized to form three
more water molecules:
The secret of pH control with acid buffers is that, if a small amount
of strong acid is added to the buffer solution, some of the anions
from the buffer salt will combine with the added protons to form
more undissociated buffer acid. The change in pH is less than if Without the buffer, the added H+ and OH- ions would have caused
the protons from the added acid had remained uncombined. a large alteration in pH. Of course, if six H+ ions had been added
Similarly, if a small amount of extra base is added, some of the instead of three, then pH control would have broken down. This is
buffer acid reacts with it to form more buffer salt. The reactions called exceeding the buffer capacity of the solution.
are).
Buffers are designed to damp down minor perturbations in
acidicity, and the amount of buffer acid and salt must be greater
than the amount of perturbing acid or base encountered.
Page 27 of 47
Acids and Bases

Before any outside acid or base is added, the pH of a
buffer mixture of a weak acid and its salt is given by the
same expression that we derived previously from the
equilibrium constant:
The pH of the buffer solution is determined by the pKa

of the acid used and the ratio of basic form (salt, A-) to
the acidic form (acid, HA). To prepare the buffer
mixture, [A-] can be assumed to be equal to the total
concentration of the salt, and [HA] equal to the total
concentration of the weak acid used.
If the ratio of salt to acid is 1: 1, then the pH will be the

same as the pKa, but one obviously can obtain any
desired pH close to pKa by altering the salt-acid ratio of
the solution as it is made up.
Example. The second dissociation of phosphoric acid

has a pKa near 7.0:
Page 28 of 47
Acids and Bases

What should the ratio of K2HPO4 to KH2PO4 be to obtain a
solution with a pH exactly 7.00?
Solution.
The 0.01-molar acid has managed to lower the pH only by 0.01

unit. lf there had been no buffer present, addition of 0.01-molar
strong acid would have shifted the pH to 2.00, a change in acidity
similar to that between water and lemon juice. With a buffer the
effect of the addition of strong acid is negligible.
Whenever pH changes are harmful, buffers have obvious

applications. The bloodstream is buffered by carbonic acid and
bicarbonate ions:
A phosphate buffer solution at pH = 7.00 should be approximately
two parts K2HPO4 to three parts KH2PO4. This is reasonable,
because we want the solution to be a little on the acid side of the
observed pKa, and therefore we need a little more of the acid form Since the blood is to be maintained approximately one pH unit
of the buffer pair, KH2PO4. higher than the pKa for this equilibrium, the ratio of bicarbonate
ion to carbonic acid must be approximately 10: 1. The reason a
Suppose now that we begin with a buffer mixture of 1.00 mole carbonate buffer and not a phosphate buffer is used in the
liter-1 of KH2PO4 and 0.62 mole liter-1 of K2HPO4, and add to this bloodstream, even though the PKa2 of phosphate is closer to 7.4,
buffer mixture 0.01 mole liter-1 of any strong acid. How much will is apparently because CO2 is already present as a by-product of
the pH shift? The added acid will react with HPO42- and produce respiration. lt is available for use in buffering without any special
more H2PO4-, so to a good approximation we can write: supply system being needed.
Page 29 of 47
Acids and Bases

Measuring pH: Acid-Base Indicators
So far we have said nothing about how pH is detected and Methyl orange is red in acid and yellow in base. The color tint
measured. Acids have a sharp taste, and bases have a bitter shows the different extent of delocalization of electrons in the
taste, but this method is both inexact and dangerous. two pH forms of methyl orange. The extent of delocalization
affects the wavelengths of light absorbed and the color
Bases feel slippery because they saponify, or make soap from the produced, as described in Chapter 9.
oils of your fingertips, but testing for bases in this way can be
dangerous and is strongly not recommended.
Elaborate and convenient pH meters using glass electrodes

provide the most accurate means of measuring pH. The most
common detectors, however, are the color changes of acid-base
indicators.
Page 30 of 47
Acids and Bases


indicators.
Page 30 of 47
Acids and Bases


indicators.
Page 30 of 47
Acids and Bases


indicators.
Page 30 of 47
Acids and Bases


indicators.
Page 30 of 47
Acids and Bases


indicators.
Page 30 of 47
Acids and Bases


indicators.
Page 30 of 47
Acids and Bases


indicators.
Page 30 of 47
Acids and Bases


indicators.
Page 30 of 47
Acids and Bases

An acid-base indicator is a weak acid (or a weak base) that has SOLUBILITY EQUILIBRIA
different colors in its un-ionized and ionized states. Most indicators
are aromatic molecules that have delocalized electrons, and in The most familiar salt, sodium chloride, is so soluble that we tend
Chapter 9 we saw the reason for their color changes. The to think that all salts are equally soluble. This is far from true, and
equilibrium many salts are quite insoluble in water.
Solubility is the result of competition between the mutual

attractions of ions in the crystal, and hydration of individual ions
with HIn representing the acid form of the indicator compound, is by solvent molecules. Both of these processes involve large
shifted to the left by an excess of acid, and to the right by an energies, and solubility depends on the frequently quite small
excess of base. The ratio of basic to acidic form of the indicator is difference between them. It is difficult to calculate crystal-lattice
linked to the pH by the now familiar expression energies and hydration energies accurately enough to predict
whether the difference between them will be positive or negative.
Although we understand the forces at work when a salt dissolves,
it is not easy to predict whether a given salt will dissolve or not.
in which pKa is the acid-dissociation constant for the weak

There are a few common-sense principles that help in a general
indicator acid, HIn. The eye is sensitive to color changes over way. A crystal is held together by electrostatic forces between
approximately a 1:10 to 10:1 concentration ratio, meaning that oppositely charged ions. Crystals with small ions that can be
visible color changes in an indicator occur in a pH range of around packed close together generally are harder to pull apart than
2 units, centered on the indicator's own pKa. Litmus paper crystals with large ions.
changes from red in acid to blue in base, in the pH range 5-8.
Phenolphthalein solution added in minute quantities to the solution
being tested or titrated changes from colorless (acid) to red (base)
Hence fluorides (F-) and hydroxides (OH-) tend to be less soluble
in the range of pH 8-10 because it has a pKa around 9. Other
than nitrates (NO3-) and perchlorates (ClO4-) with the same
common indicators, color changes, and useful pH ranges are
positive ion; chlorides (Cl-) are intermediate in solubility.
shown in the diagram on page 30.
Page 31 of 47
Acids and Bases

Solubility Equilibria
This rule is too simple in real situations, since small ions also As long as any solid AgCl remains in contact with the solution, it
permit a closer approach by the hydrating water molecules, which provides an infinite reservoir of more material, so the effective
favors solution. The crystal-energy factor usually dominates, so concentration of AgCl is unchanged.
salts with small ions are usually (but not always) relatively
insoluble. For similar electrostatic reasons highly charged ions This constant term, like the water concentration term in the
such as phosphates (PO43-) and carbonates (CO32-) interact denominator of the Ka equilibrium expression, might as well be
strongly with cations in the crystal and therefore are less soluble lumped together with the equilibrium constant. The resulting
than are the singly charged nitrates and perchlorates. combined constant is known as the solubility-product constant,
Ksp:
Silicates, with SiO44- and larger frameworks, are notoriously
insoluble, which is fortunate for the development of our planet.
Although real salts do seem to separate into the readily soluble This tells us that, as long as a solution of Ag+ and Cl- ions is in
and the barely soluble, "soluble" and "insoluble" really are terms equilibrium with solid AgCl, the product of the two ion
for two extremes of an equilibrium between an intact salt and concentrations in solution will be constant.
hydrated ions in solution. Silver chloride is an example of a
sparingly soluble salt in equilibrium with its solid: If more of either ion is added from the outside, then solid AgCl will
precipitate until the product of ion concentrations again equals
Ksp. If one ion is partially removed by a chemical reaction, or if the
solution is diluted so both concentrations decrease, then more
The usual equilibrium-constant expression would be written AgCl will dissolve until the ion solubility product is reached again.
Solubility-product constants, like all equilibrium constants, vary
with temperature, but values at 25'C are ordinarily used.
Page 32 of 47
Acids and Bases

Example. The solubility of AgCl in water is 0.000013 mole liter-1 The solubility-product constant will be the same as in the previous
at 25C. What is the solubility-product constant, Ksp? example; thus,
Solution. Since one mole of AgCI produces one mole each of Ag+
and Cl-, the concentration of each ion in a saturated solution is
We can guess in advance that adding more chloride ion will make
AgCl less soluble, because the product of [Ag+] and [Cl-] remains
unchanged, or that x will turn out to be less than 1.3 x 10-5 mole
Hence, liter-1. We then can neglect x in comparison with 0.01 in the sum,
and thereby avoid having to solve a quadratic equation. With this
simplification,
Example. Would AgCl be more, or less, soluble in 0.01-molar

sodium chloride than in pure water? What would its solubility be?
If you compare this result with that of the preceding example, you
Solution. The solubility-constant expression tells us that the will find that the solubility of AgCl in 0.01-molar NaCI is only one
product of concentrations of Ag+ and Cl- is fixed, no matter what 76th its solubility in pure water.
the source of the ions. Hence, if we let x be the solubility of AgCl
under these conditions, there will be 0.01 mole of Cl- ion per liter This decrease in solubility of a slightly soluble salt in the presence
from NaCI, and x moles per liter from AgCl. The total ion of another salt that shares an ion is known as the common ion
concentrations will be effect. We could have predicted it from Le Chatelier's principle:
When a system at equilibrium is subjected to a stress, the
equilibrium shifts in such a way as to partially relieve that stress.
Page 33 of 47
Acids and Bases

Thus if Ag+ and Cl- are in balance in pure water, and if
more Cl- is added from another salt, then Ag+ and Cl- will
combine and precipitate as solid AgCl until the product of
[Ag+] and [Cl-] once again is as low as Ksp for AgCl.
Solubility-constant expressions can be written for all

slightly soluble salts. Salts such as NaCI are very
soluble, and their Ksp's are effectively infinite, as far as
solubility-product calculations are concerned. Soluble
and slightly soluble salts resemble strong and weak
acids, for although in theory there is no sharp
demarcation between the two categories, in practice the
division between two kinds of behavior is useful.
Solubility-product constants for various salts are given in

the table across. Remember that these come from
equilibrium-constant expressions, so if dissociation of a
mole of a salt produces n moles of one of the ions, that
ion will appear in the Ksp expression as the nth power of
the concentration. For example,
Page 34 of 47
Acids and Bases

Example. The solubility product for aluminum hydroxide, AI(OH)3, POSTSCRIPT: ACID-BASE CATALYSIS
is Ksp = 5 X 10-33. What is the solubility of aluminum hydroxide in
pure water, in moles liter-1? One of the reasons given at the beginning of this chapter for an
interest in acids and bases was their widespread use as catalysts
Solution. Let the solubility be x. The dissociation reaction is for chemical reactions. We distinguish between heterogeneous
catalysis, in which the substrate molecules diffuse to a catalytic
surface, and homogeneous catalysis, in which the catalysts are
ions dissolved in the same solution as the reactants. H+ and OH-
and the solubility-product expression is are among the best of the homogeneous catalysts.
When rates of reaction began to be studied carefully at the end of

the last century, one of the most studied reactions was the
The two ion concentrations will be hydrolysis (literally "cleaving by water") of ethyl acetate into
ethanol and acetic acid:
Hence we can write
This is typical of many other hydrolysis reactions, including the

dissolving of fats in soapmaking, and the digestion of proteins. It
received a lot of attention because its equilibrium constant is close
to 1.00, making the accurate measurement of concentrations of
Solubility-product calculations rarely are worth carrying beyond reactants and products at equilibrium easy. Another attraction is
one or two significant figures, because of inaccuracies in Ksp. the dramatic effect that is produced on this reaction by catalysts.
They also are accurate mainly for dilute solutions, since the
equilibrium-constant expressions contain hidden assumptions that
the ions in solution do not interact with one another, and that their
behavior depends only on how many of them there are.
Page 35 of 47
Acids and Bases

Postscript: Acid-base catalysis
The reaction is slow in the absence of a catalyst; ethyl

acetate is relatively unreactive in water. The addition of
a small amount of a strong acid or a strong base has a
great effect. The rate of hydrolysis, as expected, is
proportional to the concentrations of ethyl acetate and
water. But if the catalyst is W or a similar strong acid,
then the rate is also proportional to the hydrogen ion
concentration. The experimental rate expression is
Page 36 of 47
Acids and Bases

Doubling the ethyl acetate concentration doubles the
speed of reaction, and doubling the hydrogen ion
concentration does the same thing. Lowering the pH by
one unit (a tenfold increase in [H+]) makes the
hydrolysis ten times as fast.
The rate therefore is sensitive to the concentration of a

substance that does not appear in the overall reaction
and is not represented in the equilibrum-constant
expression:
This behavior is a clue that catalysis is involved. It

occurs because the rate of the reverse reaction,
synthesis of ethyl acetate from ethanol and acetic acid,
also is proportional to hydrogen ion concentration:
Protons, or hydrogen ions, catalyze both the forward

and reverse reactions to the same degree, and proton
concentrations cancel from the overall equilibrium
expression.
Page 37 of 47
Acids and Bases


expression:


expression.
Page 37 of 47
Acids and Bases


expression:


expression.
Page 37 of 47
Acids and Bases

How do protons catalyze this reaction? The overall
process requires the pulling apart of a C-O bond in
ethyl acetate, and an O-H bond in water, and a
rejoining of the pieces in a different way.
In pure water, we might imagine the reaction to occur

via an intermediate activated complex like that at the
center in the diagram above. This activated complex, or
transition state, would be a very unstable entity, and the
reaction would have a high energy of activation, Ea.
Chemical reaction by this mechanism would be
extremely slow.
The actual proton-catalyzed reaction, as it has been

pieced together by chemists after many years of study,
is outlined on page 40. Any C-O bond is polarized to
some extent, because the oxygen atom is more
electronegative than the carbon atom and draws
electrons from the double bond to itself. (This slight
polarization of charge is represented by delta symbols,
d+ and d-, in contrast to + and -, which represent full
electron charges.)
Page 38 of 47
Acids and Bases

How do protons catalyze this reaction? The overall
process requires the pulling apart of a C-O bond in
ethyl acetate, and an O-H bond in water, and a
rejoining of the pieces in a different way.
In pure water, we might imagine the reaction to occur

via an intermediate activated complex like that at the
center in the diagram above. This activated complex, or
transition state, would be a very unstable entity, and the
reaction would have a high energy of activation, Ea.
Chemical reaction by this mechanism would be
extremely slow.
The actual proton-catalyzed reaction, as it has been

pieced together by chemists after many years of study,
is outlined on page 40. Any C-O bond is polarized to
some extent, because the oxygen atom is more
electronegative than the carbon atom and draws
electrons from the double bond to itself. (This slight
polarization of charge is represented by delta symbols,
d+ and d-, in contrast to + and -, which represent full
electron charges.)
Page 38 of 47
Acids and Bases

With its two lone electron pairs and slight excess of negative Substance e, in turn, could break down in a series of Steps f-h,
charge, the carbonyl oxygen has a natural attraction for a proton which are mirror images of Steps c-a, but with HOC2H5 playing
in acidic solution. A proton is attracted to the O atom (a), and uses the role of HOH.
one of the oxygen lone pairs to form a covalent O-H bond (b).
Since the lone pair thereby is pulled toward the H atom, a small Step g involves a protonated acetic acid molecule instead of
positive charge is created on the oxygen atom. This positive protonated ethyl acetate as in b, and the proton falls away again in
charge exerts an even greater pull on the electrons of the double the last step, h. The proton is used at the beginning and
bond, turning it into a single bond and another O lone pair (c), and regenerated at the end; thus it facilitates the reaction but is not
transferring the positive charge to the carbon. destroyed by it.
The positively charged carbon atom in turn has an attraction for Hydrogen ions help to catalyze this reaction in two ways. The
the unpaired electrons of the water molecules surrounding it. One binding of a proton in Step a places a positive charge on the
of these can form a bond to the carbon (d), thereby shifting the molecule and makes it more susceptible to attack by electron
positive charge to the incoming water oxygen. pairs of a water molecule (or any other electron-rich or negatively
charged entity).
Step d represents a short-lived intermediate in the reaction, which
cannot be isolated for study at leisure, but which is detectable by The other thing that a proton can do better than other ions in
rapid spectroscopic and magnetic resonance methods. From d the aqueous solution is to move about rapidly from one part of a
reaction can go in more than one direction. It could reverse itself molecule to another. The fast shift between Steps d and e could
through Steps c, b, and a, or one of the protons could dissociate not be accomplished by a sodium ion or any other substance. The
and take the positive charge with it. reason why proton transfer in water solution is so easy and so fast
is that protons can cascade domino fashion along a row of
One of the possibilities is a rapid proton transfer from the charged hydrogen-bonded water molecules, with each proton moving only
oxygen to the bridge oxygen (e), taking the positive charge with it. from one oxygen atom to its neighbor, and with the proton that
comes out at the end of the cascade different from the one that
went in. This is illustrated on the previous page.
Page 39 of 47
Acids and Bases

In Steps d and e of the catalytic mechanism, the same
proton does not have to move bodily from one oxygen
atom to the other. It can transfer to a nearby water
molecule and cause that molecule to donate one of its
protons to the bridge oxygen. Proton transfer in
aqueous solution is faster and easier than any other
kind of atom shift.
Any compound that has lone electron pairs on an

electronegative atom can attract a proton in acid
solution. This includes almost every type of organic
compound. A proton can also be attracted to the
electrons of a double bond and catalyze the addition of
HBr or some other substance across the bond:
There are few reactions of carbon compounds that acid

will not catalyze. This is why we have hydrochloric acid
in our stomach, to help enzymes digest and hydrolyze
proteins. This is also why acid catalysis is so important
in the chemical industry, from synthesis of rubbers and
organic dyestuffs to pharmaceutical compounds.
Page 40 of 47
Acids and Bases

Hydroxide ions also are good catalysts for many
organic reactions. The mechanism for base-catalyzed
hydrolysis of ethyl acetate is shown at the right. A
negatively charged hydroxide ion is attracted to the
slight positive charge on the carbon atom of a C=O
bond, and a C-O bond is formed with the hydroxyl
group. This pushes electrons in the C=O double bond
toward the other O atom, thereby giving it a negative
charge (b). This excess of electrons can be shifted
back either to the hydroxyl oxygen (a) or to the bridge
oxygen (c). As electrons in that C-O bridge bond are
pushed toward the O, the C2H5-O- group can fall away.
The steps from b to c and b to a are identical except
that they involve different C-O bonds. Once the C2H5-
O- group has departed, it can react with water to
regenerate a hydroxide ion:
As with acid catalysis, the OH- ion is involved in a

lower-energy pathway, but is regenerated intact at the
end of the process. Acids and bases are effective
catalysts because they contribute charged ions that can
push and pull electrons around in a molecule. We will
see in Chapter 24 that some of the catalytic
mechanisms used by enzymes are very similar to
mechanisms of acid-base catalysis.
Page 41 of 47
Acids and Bases

Questions
QUESTIONS 8. Why does the equilibrium-constant expression for the
dissociation of water ordinarily not have an H2O concentration
1. From where does the energy come to overcome the attractions term in the denominator? What happened to this concentration
between ions when a salt crystal dissolves? term? What is this H2O-dissociation constant commonly called?
How does its numerical value depend on temperature, and what
2. What is the distinction between a strong acid and a weak acid? value usually is used?
Give an example of each.
9. How can Le Chatelier's principle and the observed dependence
3. Are there also both strong and weak bases? If there are, give of the ion-product constant upon temperature be used to decide
examples. whether the dissociation of water is exothermic or not? Check
your prediction against information in Appendix 2.
4. For an acid that dissociates to release a single proton, what is
the general expression for the dissociation constant, Ka? 10. What is the process of counteracting an acid with a base
called? What ions are involved in this process, and how do they
5. What is the expression for the base-dissociation constant, Kb, interact? What is the product?
for a weak base?
11. What are the concentrations of H+ and OH- ions in pure
6. It often is convenient to use an acid-dissociation constant, Ka, water? How do these concentrations change when the solution is
for a weak base instead of Kb. For NH3, what is the acid form and made acidic?
what is the expression for Ka? Show that, in general, Ka x Kb =
Kw. 12. What is the pH scale, and why is it convenient in expressing
hydrogen ion concentration? What is pOH?
7. What is the method of successive approximations, and when
can it be used in solving acid-base equilibrium problems? 13. How are pH and pOH related in aqueous solution? What
values, or range of values, do they have in acidic, neutral, and
basic solutions?
Page 42 of 47
Acids and Bases

Questions
14. What is an equivalent in acid-base neutralization? How many 20. How does the Bronsted-Lowry theory explain the difference
equivalents are there per mole of the following: HCI, KOH, NH3, between strong and weak acids? In what sense is this a
H2CO3, H3PO4, HNO3? competition theory, and what entities are the competitors? For
what do they compete? How does the great excess of H2O
15. What is a milliequivalent? How many milliequivalents are molecules in aqueous solutions affect the situation?
present in a mole of H2SO4?
21. Show that when the pH of a solution is the same as the pKa of
16. What are the Bronsted-Lowry definitions of acids and bases? a dissociating solute, the concentrations of dissociated and
undissociated species are equal.
17. According to the traditional, or Arrhenius, definition of acid and
base, KOH is the base in a potassium hydroxide solution. What is 22. Show that when the pH of a solution containing an acid is one
the base in such a solution, according to the Bronsted-Lowry pH unit lower than the pKa of the acid, the undissociated acid and
theory? What is the conjugate acid of this B-L base? the acid anion are present in a 10:1 ratio.
18. What is meant by a conjugate acid-base pair in Bronsted- 23. What is a buffer? How does it help to control or stabilize pH?
Lowry theory? If the acid is strong, will the conjugate base also be What substances are combined to form a buffer solution?
strong? Give an example.
24. When acid is added to a buffer solution, what happens to the
19. Which of the following molecules or ions are Bronsted-Lowry extra protons? What happens when base is added to a buffer?
acids and which are bases? In each case, what is the conjugate
base or acid? What is the relative strength of each member of a 25. What is meant by "buffer capacity"? What happens when this
conjugate pair? buffer capacity is exceeded?
NO3-, HBr, NH3, SO42-, H3PO4, H2SO4, HSO4-, NH4+, H2O 26. What is an acid-base indicator? Why does a change in pH
lead to a color change in the solution?
Page 43 of 47
Acids and Bases

Questions
27. What is a solubility-product constant? How is it related to the PROBLEMS
equilibrium constant for the dissolving of a solid salt?
1. What is the pH of a 0.01-molar NaOH solution?
28. What factors affect the solubility of a salt in water? Why do
these factors make predictions of solubilities difficult? 2. What is the pH of a 10-10-molar HCl solution?
29. If chloride ion (e.g. from NaCI) is added to a saturated silver 3. If a 0.10-molar acetic acid solution is 1.3% ionized, what is the
chloride solution, how will this affect the concentration of silver pH of the solution? What is Ka for acetic acid? Compare your
ions? How is this similar to the ion-product equilibrium for the value with that in the table on Page 8.
dissociation of water?
4. If a 0.10-molar HF solution is 5.75% ionized, what is the pH of
30. How does acid enable the hydrolysis of ethyl acetate to the solution? What is Ka for HF? Compare your value with that in
proceed faster than it would occur in neutral solution? the table on Page 8.
31. In what ways are acid and base catalysis of ethyl acetate 5. From the data in the table on Page 8, calculate the base-
different? How are they similar? dissociation constant for ammonium hydroxide. Is undissociated
NH4OH really present in the solution? If not, what is the reaction
32. Why is the transfer of H+ much faster than that of Na+ in a for the production of ammonium ion and OH-? What is the pH of a
solution containing both ions? 0.0100-molar solution of ammonia?
6. A detergent box must bear a warning label if its contents will

form a solution that has a pH greater than 11 because strong base
degrades protein structure. Should a box bear such a label if the
H+ concentration of a solution of its contents is found to be 2.5 X
10-12 mole per liter?
Page 44 of 47
Acids and Bases

Questions
7. The ionization constant for arsenous acid (HAsO2) is 6.0 x 10- 12. Hydrazine is a weak base that dissociates in water according
10. What is the PH of a 0.10-molar solution of arsenous acid? to the equation
What is the pH of a 0.10-molar solution of NaAsO2?
N2H4 + H2O = N2H5+ + OH-
8. A solution of ammonia has a hydrogen ion concentration of 8.0
x10-9 mole per liter. What is the pOH of this solution? The equilibrium constant for this dissociation at 25'C is 2.0 X 10-6.
Write the equilibrium-constant expression for this reaction. If the
9. What is the CN- ion concentration and the pOH in a 1.00-molar initial hydrazine concentration is 0.010 molar, what is the
aqueous solution of HCN? concentration of hydrazinium ion, N2H5+ ? What is the pH?
10. Pyridine is an organic base that reacts with water as follows: 13. What is the pH of a 0.18-molar solution of ammonium
chloride?
C5H5N + H O = C5H5NH+ + OH-
2
14. What is the pH of a 0.025-molar solution of sodium acetate?
The base-dissociation constant for this reaction, Kb, is 1.58 x 10-8.
What is the concentration of C5H5NH+ ion in a solution that was 15. What is the pH of a 1.0-molar solution of sodium cyanide?
initially 0.10 molar in pyridine? What is the pH of the solution?
16. A buffer solution is made with 0.30-molar sodium cyanide and
11. What is the equilibrium concentration of NO2- ion in a 0.22- 0.30-molar HCN. What is the pH of the buffer solution?
molar aqueous solution of nitrous acid? What is the pH? What is
the percent ionization of HNO2? 17. What is the pH of a buffer prepared to be 0.20 molar in NH3
and 0.40 molar in NH4Cl?
18. A buffer solution is made from equal volumes of 0.10-molar

acetic acid and 0.10-molar sodium acetate. What is the pH of the
buffer?
Page 45 of 47
Acids and Bases

Questions
19. What is the pH of a solution made from equal volumes of 0.20- (b) At the end point of the titration, the solution behaves just like a
molar propionic acid and 0.20-molar sodium propionate? solution of 0.010-molar NvcH+NO3-. What is the pH of this
solution? (c) The indicator bromcresol green has a pKa of 5.0. Is
20. A solution is 0.10 molar in formic acid and 0.010 molar in this indicator suitable for the titration?
sodium formate. What is the pH of the solution?
24. The solubility of silver phosphate, Ag3PO4, in water is 0.0065 g
21. If 0.010 mole of HCl gas is dissolved in one liter of pure water, liter-1 at 20'C. What is the solubility product (Ksp) for this salt?
what is the final pH? If the same amount of HCl is dissolved What is the solubility of silver phosphate in moles liter-1 in a
instead in one liter of the buffer solution of Problem 19, what is the solution that contains a total of 0.10 mole liter-1 of Ag+?
final pH?
25. If a solution containing 0.16 mole liter-1 of Pb2+ is made 0.10
22. If 20 mI of a solution of 0.6-molar ammonia are mixed with 10 molar in chloride ion, 99.0% of the Pb2+ is removed as PbCl2.
ml of a 1.8-molar ammonium chloride solution, what is the final What is Ksp for PbCl2?
pH? If 1 mI of a 1.0 molar HCl solution is added, what will the pH
become? If the buffer solution had been prepared from 0.06-molar Data in the table on Page 34 will help you solve the following
ammonia and 0.18-molar ammonium chloride, would the same problems.
HCl solution change the pH more, or less, than in the first
situation? Why? 26. Calculate the solubility in moles liter-1 of MgF2 in pure water.
What is the solubility in 0.050-molar NaF?
23. Novocain (Nvc) is a weak organic base that reacts with water
as follows: 27. What is the solubility of CoS in pure water in moles liter-1?
What is the solubility of CoS in 0.10-molar sodium sulfide solution?
Nvc + H2O = NvcH+ + OH-
28. What is the silver ion concentration in a solution of silver
The base-equilibrium constant for this reaction is Kb = 9.0 x 10-6. chromate in pure water? In 0.10-molar chromate solution?
Suppose that a 0.010-molar solution of Novocain is titrated with
nitric acid. (a) What is the pH of the Novocain solution at the
beginning of titration, before any acid has been added?
Page 46 of 47
Acids and Bases

Questions
29. Calculate the calcium ion concentration in a saturated solution
of calcium fluoride.
30. A solution is made 0.10 molar in Mg2+, 0.10 molar in NH3, and
1.0 molar in NH4Cl. Will Mg(OH)2 precipitate?
31. In the precipitation of metal sulfides, selective precipitation can

be achieved by adjusting the hydrogen ion concentration. At what
pH does ZnS begin to precipitate from a 0.077-molar solution of
H2S containing 0.08-molar Zn2+? (Necessary data are in the
tables of Ka and Ksp on Pages 8 and 34.)
32. What is the solubility of AgOH in a buffer at pH 13?
33. In a water solution saturated with H S, [H+]2 [S2-] = 1.3 x 10-

21 2
. Calculate the solubility of FeS at pH = 9 and at pH = 2. Can
you see how this behavior might be useful in analytical
separations?
34. Calculate the solubility of Mg(OH)2 in aqueous solution at pH =

2 and pH = 12. How is this behavior useful in chemical
separations?
Page 47 of 47

Ions and Equilibrium

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Foundations to Chemistry - adapted from "Chemistry, Matter and the Universe" Page 1 of 1

16. Ions and Equilibrium; -- Jump to --

Acids and Bases

Bases also are useful for dissolving water-insoluble substances, especially

We have seen previously that there are many substances, amphoteric

16. Ions and Equilibrium; -- Jump to --

Acids and Bases

If a substance provides a faster pathway for reaction but is regenerated again

In Chapter 15 we saw examples of heterogeneous catalysts, in which the

In either type of catalysis the principle is the same: A catalyst is a substance

Acids and bases are widely used homogeneous catalysts.

16. Ions and Equilibrium; -- Jump to --

Acids and Bases

As we saw in Chapter 12, the heat of solution is the difference between

We can write the overall process as

16. Ions and Equilibrium; -- Jump to --

Acids and Bases

Sulfuric acid also releases a second proton, but only

Since these compounds dissociate completely in water,

16. Ions and Equilibrium; -- Jump to --

Acids and Bases

Other acids and bases are only incompletely

Dissolved hydrogen fluoride, for example, exists as an

The equilibrium constant for this dissociation usually is

Hydrogen fluoride is an inorganic acid.

16. Ions and Equilibrium; -- Jump to --

Acids and Bases

Because acetic acid is so common, it is often given the shorthand

Water is both solvent and reactant in this reaction. For moderately

In such expressions concentrations of ions and molecules are

16. Ions and Equilibrium; -- Jump to --

Acids and Bases

You can now check the validity of the approximation:

If the acid had dissociated enough so that y was a few percent of

16. Ions and Equilibrium; -- Jump to --

Acids and Bases

16. Ions and Equilibrium; -- Jump to --

Acids and Bases

In pure water or any neutral solution, the hydroxide and hydrogen

16. Ions and Equilibrium; -- Jump to --

Acids and Bases

A simple calculation can show how small a fraction of

Approximately two water molecules out of every billion

16. Ions and Equilibrium; -- Jump to --

Acids and Bases

A simple calculation can show how small a fraction of

Approximately two water molecules out of every billion

16. Ions and Equilibrium; -- Jump to --

Acids and Bases

The value of logarithmic notation can be illustrated by the 10 X 10 X 10 stack

16. Ions and Equilibrium; -- Jump to --

Acids and Bases

In the same way, pOH is the negative logarithm of the hydroxide

16. Ions and Equilibrium; -- Jump to --

Acids and Bases

You can see from this that the neutralization of an acid

One mole of an acid that liberates one H+ per molecule,

16. Ions and Equilibrium; -- Jump to --

Acids and Bases

Solution. The amount of HCl present is

0.100 liter X 0.75 mole liter-1 = 0.075 mole HCl

16. Ions and Equilibrium; -- Jump to --