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The older Arrhenius theory of acids and bases viewed them as substances which
produce hydrogen ions or hydroxide ions on dissociation. As useful a concept as
this has been, it was unable to explain why NH3, which contains no OH ions, is a
base and not an acid, why a solution of FeCl3 is acidic, or why a solution of Na2S
is alkaline.
The theory
The relationship between the Bronsted-Lowry theory and the Arrhenius theory
The Bronsted-Lowry theory doesn't go against the Arrhenius theory in any way - it just adds
to it.
Hydroxide ions are still bases because they accept hydrogen ions from acids and form
water.
An acid produces hydrogen ions in solution because it reacts with the water molecules by
giving a proton to them.
When hydrogen chloride gas dissolves in water to produce hydrochloric acid, the hydrogen
chloride molecule gives a proton (a hydrogen ion) to a water molecule. A co-ordinate (dative
covalent) bond is formed between one of the lone pairs on the oxygen and the hydrogen
from the HCl. Hydroxonium ions, H3O+, are produced.
When an acid in solution reacts with a base, what is actually functioning as the acid is the
hydroxonium ion. For example, a proton is transferred from a hydroxonium ion to a
hydroxide ion to make water.
Showing the electrons, but leaving out the inner ones:
It is important to realise that whenever you talk about hydrogen ions in solution, H+(aq), what
you are actually talking about are hydroxonium ions.
This is no longer a problem using the Bronsted-Lowry theory. Whether you are talking about
the reaction in solution or in the gas state, ammonia is a base because it accepts a proton (a
hydrogen ion). The hydrogen becomes attached to the lone pair on the nitrogen of the
ammonia via a co-ordinate bond.
If the reaction is happening in the gas state, the ammonia accepts a proton directly from the
hydrogen chloride:
Either way, the ammonia acts as a base by accepting a hydrogen ion from an acid.
Because hydronium- and hydroxide ions can move without actually
moving and thus without having to plow their way through the solution
by shoving aside water molecules as do other ions, solutions which are
acidic or alkaline have extraordinarily high electrical conductivities.
According to the Brnsted concept, the process that was previously written as a
simple dissociation of a generic acid HA ("HA H+ + A)" is now an acid-base
reaction in its own right:
HA + H2O A+ H3O+
The idea, again, is that the proton, once it leaves the acid, must end up
somewhere; it cannot simply float around as a free hydrogen ion.
Conjugate pairs
A reaction of an acid with a base is thus a proton exchange reaction; if the acid
is denoted by AH and the base by B, then we can write a generalized acid-base
reaction as
AH + B A + BH+
BH+ + A B + AH+
is also an acid-base reaction. Because all simple reactions can take place in both
directions to some extent, it follows that transfer of a proton from an acid to a
base must necessarily create a new pair of species that can, at least in principle,
constitute an acid-base pair of their own.
In fact, the reaction between HCl and water is reversible, but only to a
very minor extent. In order to generalise, consider an acid HA, and
think of the reaction as being reversible.
But there is also a back reaction between the hydroxonium ion and the
A- ion:
The reversible reaction contains two acids and two bases. We think of
them in pairs, called conjugate pairs.
When the acid, HA, loses a proton it forms a base, A-. When the base,
A-, accepts a proton back again, it obviously refoms the acid, HA.
These two are a conjugate pair.
If you are thinking about HA as the acid, then A- is its conjugate base.
If you are thinking about A- as the base, then HA is its conjugate acid.
The water and the hydroxonium ion are also a conjugate pair.
Thinking of the water as a base, the hydroxonium ion is its conjugate
acid because it has the extra hydrogen ion which it can give away
again.
The water is acting as an acid, and its conjugate base is the hydroxide
ion. The hydroxide ion can accept a hydrogen ion to reform the water.
Looking at it from the other side, the ammonium ion is an acid, and
ammonia is its conjugate base. The hydroxide ion is a base and water
is its conjugate acid.
The table below shows the conjugate pairs of a number of typical acid-base
systems.
acid base
hydrochloric
HCl Cl chloride ion
acid
dihydrogen monohydrogen
H2PO4 HPO42
phosphate ion phosphate ion
hydrogen
HSO4 SO42 sulfate ion
sulfate ion
hydrogen
carbonate
HCO3 CO32 carbonate ion
("bicarbonate")
ion
iron(III)
Fe(H2O)63+ Fe(H2O)5OH2+
("ferric") ion
If the base H2O overwhelmingly wins this tug-of-war, then the acid HA is said to
be a strong acid. This is what happens with hydrochloric acid and the other
common strong "mineral acids" H2SO4, HNO3, and HClO4:
Solutions of these acids in water are really solutions of the ionic species shown
in heavy type on the right. This being the case, it follows that what we call a 1 M
solution of "hydrochloric acid" in water, for example, does not really contain a
significant concentration of HCl at all; the only real a acid present in such a
solution is H3O+!
Weak acids
Most acids, however, are able to hold on to their protons more tightly, so only a
small fraction of the acid is dissociated. Thus hydrocyanic acid, HCN, is a weak
acid in water because the proton is able to share the lone pair electrons of the
cyanide ion CNmore effectively than it can with those of H2O, so the reaction
Since a strong acid binds its proton only weakly, while a weak acid binds it
tightly, we can say that
If you are able to explain this apparent paradox, you understand one of the most
important ideas in acid-base chemistry!
Examples of proton donor-acceptor reactions
conjugate conjugate
reaction acid base
acid base
1) autoionization of water
H2O H2O H3O+ OH
H2O
2) ionization of
HCN H2O H3O+ CN
hydrocyanic acid HCN
3) ionization of ammonia
NH3 H2O NH4+ OH
NH3 in water
4) hydrolysis of
NH4+ H2O H3O+ NH3
ammonium chloride NH4Cl
5) hydrolysis of sodium
H2O CH3COO CH3COOH OH
acetate CH3COO- Na+
6) neutralization of HCl by
HCl OH H2O Cl
NaOH
7) neutralization of NH3
CH3COOH NH3 NH4+ CH3COO
by acetic acid
8) dissolution of BiOCl
(bismuth oxychloride) by 2 H3O+ BiOCl Bi(H2O)3+ H2O, Cl
HCl
9) decomposition of
2 H3O+ Ag(NH3)2+ NH4+ H2O
Ag(NH3)2+ by HNO3
This is just a re-statement of what is implicit in what has been said above about
the distinction between strong acids and weak acids. The fact that HCl is a
strong acid implies that its conjugate base Cl is too weak a base to hold onto
the proton in competition with either H2O or H3O+. Similarly, the CN ion binds
strongly to a proton, making HCN a weak acid.
The fact that HCN is a weak acid implies that the cyanide ion CN reacts readily
with protons, and is thus is a relatively good base. As evidence of this, a salt
such as KCN, when dissolved in water, yields a slightly alkaline solution:
CN + H2O HCN + OH
This reaction is still sometimes referred to by its old name hydrolysis ("water
splitting"), which is literally correct but tends to obscure its identity as just
another acid-base reaction. Reactions of this type take place only to a small
extent; a 0.1M solution of KCN is still, for all practical purposes, 0.1M in cyanide
ion.
In general, the weaker the acid, the more alkaline will be a solution of its salt.
However, it would be going to far to say that "ordinary weak acids have strong
conjugate bases." The only really strong base is hydroxide ion, OH, so the
above statement would be true only for the very weak acid H2O.
The only really strong bases you are likely to encounter in day-to-day chemistry
are alkali-metal hydroxides such as NaOH and KOH, which are essentially
solutions of the hydroxide ion.
There are actually a number of bases that are stronger than the hydroxide ion
best known are the oxide ion O2 and the amide ion NH2, but these are so
strong that they can rob water of a proton:
O2 + H2O 2 OH
This gives rise to the same kind of leveling effect we described for acids, with
the consequence that
Hydroxide ion is the strongest base that can exist in aqueous solution.
Salts of weak bases give acidic solutions
The most common example of this is ammonium chloride, NH4Cl, whose aqueous
solutions are distinctly acidic:
Because this (and similar) reactions take place only to a small extent, a solution
of ammonium chloride will only be slightly acidic.
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HCl H2O
This reaction proceeds to completion if the CO32 ions are removed by precipita-
tion with Ca2 ions to form a precipitate of calcium carbonate. In the absence of
ions that remove the CO32 ions, though, the equilibrium remains strongly in favor
of the reactants because a positively charged proton can be removed from the
H2O O2
negatively charged HCO3 ion only with difficulty.
In the BrnstedLowry theory, the strength of an acid depends on the extent to
which it donates protons to the solvent. We can therefore summarize the distinction
between strong and weak acids as follows:
Almost all the molecules of a strong acid are deprotonated in solution.
Only a small fraction of the molecules or ions of a weak acid are deprotonated OH OH
in solution.
FIGURE 12.3 When an oxide ion is
The strength of an acid depends on the solvent, and an acid that is strong in present in water, it exerts such a strong
water may be weak in another solvent or vice versa (see Section 12.8). However, attraction on the nucleus of a hydrogen
because almost all reactions in living tissues and most reactions in laboratories take atom in a neighboring water molecule
place in water, unless otherwise specified, the solvent in this chapter is water. that the hydrogen ion is pulled out of
A Brnsted base possesses a lone pair of electrons to which a proton can bond. the molecule as a proton. As a result,
For example, an oxide ion is a Brnsted base. When CaO dissolves in water, the the oxide ion forms two hydroxide ions.
strong electric field of the small, highly charged O2 ion pulls a proton out of and
away from a neighboring H2O molecule (FIG. 12.3). In the process, a coordinate
covalent bond forms between the proton and a lone pair of electrons on the oxide
ion. By accepting a proton, the oxide ion has become protonated. Every oxide ion A coordinate covalent bond is a bond
present accepts a proton from water, and so O2 is an example of a strong base in in which both bonding electrons come
water, a species that is fully protonated. That is, the following reaction goes essen- from the same atom (Section 3.11).
tially to completion:
O2 1aq2 H2O1l2 2 OH 1aq2
Another example of a Brnsted base is ammonia. When an NH3 molecule is pres-
ent in water, the lone pair of electrons on the N atom accepts a proton from H2O:
NH3 1aq2 H2O1l2 NH4 1aq2 OH 1aq2
The fact that the NH3 molecule is electrically neutral means that it has much less
proton-pulling power than the oxide ion. As a result, only a very small proportion of
the NH3 molecules are converted into NH4 ions (FIG. 12.4). Ammonia is therefore a
weak base. All amines, organic derivatives of ammonia, such as methylamine, CH3NH2,
are weak bases in water. Because the proton transfer equilibrium in an aqueous solu- OH
tion of ammonia is dynamic, we should imagine the protons as ceaselessly exchanging
between NH3 and H2O molecules with a constant, very low concentration of NH4
and OH ions. The proton transfer to the strong base O2 is also dynamic, but the NH3
equilibrium lies so strongly in favor of products that, as for a strong acid, we represent
it just by its forward reaction with a single arrow.
We can summarize the distinction between strong and weak bases as follows:
NH4
All the molecules or ions of a strong base are protonated in solution.
Only a small fraction of the molecules or ions of a weak base are protonated
in solution.
As for acids, the strength of a base depends on the solvent: a base that is strong in
FIGURE 12.4 In this molecular
water may be weak in another solvent and vice versa. The common strong bases
portrayal of the structure of a solution
in aqueous solution are listed in Table J.1.
of ammonia in water at equilibrium, we
see that NH3 molecules are still present
A Note on Good Practice: The oxides and hydroxides of the alkali and alka-
because only a small percentage of
line earth metals are not Brnsted bases: the oxide and hydroxide ions they
them have been protonated by transfer
contain are the bases (the cations are spectator ions). However, for conve-
of hydrogen ions from water. In a typical
nience, and using the Arrhenius definitions, chemists often refer to the com-
solution, only about 1 in 100 NH3
pounds themselves as bases.
molecules is protonated. The inset at
the left shows only the solute species.
The species produced by proton transfer in aqueous solution may also donate
a proton to or accept a proton from water and thus be classified as an acid or a ANIMATION FIGURE 12.4
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base. For example, the CN ion produced when HCN is deprotonated can accept
a proton from a neighboring H2O molecule and form HCN again. Therefore,
according to the Brnsted definition, CN is a base; it is called the conjugate base
of the acid HCN. In general, a conjugate base of an acid is the species remaining
when the acid donates a proton:
donates H
Acid conjugate base
Because HCN is the acid that forms when a proton is transferred to a cyanide ion,
HCN is the conjugate acid of the base CN. In general, a conjugate acid of a
base is the species formed when the base accepts a proton:
accepts H
Base conjugate acid
Self-Test 12.1A What is (a) the conjugate acid of OH; (b) the conjugate base of
HPO42?
[Answer: (a) H2O; (b) PO43]
NH3
NH4Cl Self-Test 12.1B What is (a) the conjugate acid of H2O; (b) the conjugate base of NH3?
Related Exercises 12.112.6
The Brnsted definitions of acids and bases also apply to species in nonaque-
ous solvents and even to gas-phase reactions where there is no solvent. For exam-
ple, when acetic acid is dissolved in liquid ammonia, proton transfer takes place
and the following equilibrium is reached:
CH3COOH1am2 NH3 1l2 CH3CO2 1am2 NH4 1am2
HCl
(The label am indicates a species dissolved in liquid ammonia.) An example of
proton transfer in the gas phase is the reaction of hydrogen chloride and ammonia
gases. They produce the fine powder of ammonium chloride often seen coating
FIGURE 12.5 The white powder is surfaces in chemical laboratories (FIG. 12.5):
ammonium chloride formed by gaseous HCl1g2 NH3 1g2 NH4Cl1s2
ammonia and hydrogen chloride
gas escaping from concentrated A Brnsted acid is a proton donor and a Brnsted base is a proton acceptor.
hydrochloric acid. The conjugate base of an acid is the base formed when the acid has donated
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a proton. The conjugate acid of a base is the acid that forms when the base
has accepted a proton. A strong acid is fully deprotonated in solution; a weak
acid is only partially deprotonated in solution. A strong base is completely
protonated in solution; a weak base is only partially protonated in solution.
Autoprotolysis
From some of the examples given above, we see that water can act as an acid
CN + H2O HCN + OH
and as a base
If this is so, then there is no reason why "water-the-acid" cannot donate a proton to
"water-the-base":
Chemists still often refer to this reaction as the "dissociation" of water and use the
Arrhenius-style equation H2O H+ + OHas a kind of shorthand.
As discussed in the previous lesson, this process occurs to only a tiny extent. It does
mean, however, that hydronium and hydroxide ions are present in any aqueous
solution.
Can other liquids exhibit autoprotolysis? The answer is yes. The most well-known
example is liquid ammonia:
Each of these solvents can be the basis of its own acid-base "system", parallel to the
familiar "water system".
Ampholytes
Water, which can act as either an acid or a base, is said to be amphiprotic: it can
"swing both ways". A substance such as water that is amphiprotic is called
an ampholyte.
As indicated here, the hydroxide ion can also be an ampholyte, but not in aqueous
solution in which the oxide ion cannot exist.
It is of course the amphiprotic nature of water that allows it to play its special role in
ordinary aquatic acid-base chemistry. But many other amphiprotic substances can also
exist in aqueous solutons. Any such substance will always have a conjugate acid and a
conjugate base, so if you can recognize these two conjugates of a substance, you will
know it is amphiprotic.
For example, the triplet set {carbonic acid, bicarbonate ion, carbonate ion} constitutes
an amphiprotric series in which the bicarbonate ion is the ampholyte, differing from
either of its neighbors by the addition or removal of one proton:
If the bicarbonate ion is both an acid and a base, it should be able to exchange a
proton with itself in an autoprotolysis reaction:
Your very life depends on the above reaction! CO2, a metabolic by-product of every cell
in your body, reacts with water to form carbonic acid H2CO3 which, if it were allowed to
accumulate, would make your blood fatally acidic. However, the blood also contains
carbonate ion, which reacts according to the reverse of the above equation to produce
bicarbonate which can be safely carried by the blood to the lungs. At this location the
autoprotolysis reaction runs in the forward direction, producing H2CO3which loses water
to form CO2 which gets expelled in the breath. The carbonate ion is recycled back into
the blood to eventually pick up another CO2 molecule.
If you can write an autoprotolysis reaction for a substance, then that substance is
amphiprotic.
Amphoteric substances
You may possibly have noticed (although probably not!) that in one of the last two examples,
water was acting as a base, whereas in the other one it was acting as an acid.
A substance which can act as either an acid or a base is described as being amphoteric.
Note: You might also come across the term amphiprotic in this context. The
two words are related and easily confused.
An amphiprotic substance is one which can both donate hydrogen ions (protons)
and also accept them. Water is a good example of such a compound. The water
acts as both an acid (donating hydrogen ions) and as a base (by accepting
them). The "protic" part of the word refers to the hydrogen ions (protons) either
being donated or accepted. Other examples of amphiprotic compounds are
amino acids, and ions like HSO4- (which can lose a hydrogen ion to form sulphate
ions or accept one to form sulphuric acid).
All amphiprotic substances are also amphoteric - but the reverse isn't true. There
are amphoteric substances which don't either donate or accept hydrogen ions
when they act as acids or bases. There is a whole new definition of acid-base
behaviour that you are just about to meet (the Lewis theory) which doesn't
necessarily involve hydrogen ions at all.
A Lewis acid is an electron pair acceptor; a Lewis base is an electron pair donor
(see below).
Some metal oxides (like aluminium oxide) are amphoteric - they react both as
acids and bases. For example, they react as bases because the oxide ions
accept hydrogen ions to make water. That's not a problem as far as the definition
of amphiprotic is concerned - but the reaction as an acid is. The aluminium oxide
doesn't contain any hydrogen ions to donate! But aluminium oxide reacts with
bases like sodium hydroxide solution to form complex aluminate ions.
You can think of lone pairs on hydroxide ions as forming dative covalent
(coordinate) bonds with empty orbitals in the aluminium ions. The aluminium ions
are accepting lone pairs (acting as a Lewis acid). So aluminium oxide can act as
both an acid and a base - and so is amphoteric. But it isn'tamphiprotic
because both of the acid reaction and the base reaction don't involve hydrogen
ions.
I have gone through 40-odd years of teaching (in the lab, and via books and the
internet) without once using the term amphiprotic! I simply don't see the point of
it. The term amphoteric takes in all the cases of substances functioning as both
acids and bases without exception. The term amphiprotic can only be used
where both of these functions involve transference of hydrogen ions - in other
words, it can only be used if you are limited to talking about the Bronsted-Lowry
theory. Personally, I would stick to the older, more useful, term "amphoteric"
unless your syllabus demands that you use the word "amphiprotic".