Acid-Base Theories

Acids are characterized by a sharp sour taste, which we experience when we taste
vinegar, which contains acetic acid. Acids react with a blue vegetable dye called
litmus. Litmus will turn pink in the presence of an acid. This phenomenon is known
as the "litmus test".  This test for acids is so commonly used in chemistry that the
term litmus test is used as an expression in everyday speech by a lot of folks who
probably do not have a clue what it really means.

Bases are characterized by a bitter taste and are slippery to the touch. Soap is an
example of a basic compound.

The first acid-base theory was the Arrhenius Theory. According to this theory, acids
are defined as compounds that donate protons, H +.  Bases are compounds that
donate hydroxide ions, HO-.

Some of the most common Arrhenius acids are...

HF (aqueous) hydrofluoric acid...remember the (aq) is needed to

differentiate this compound from the gas phase.

HCl (aq) hydrochloric acid

HBr (aq) hydrobromic acid

HI (aq) hydroiodic acid

HNO3 nitric acid...the (aq) is not necessary...this is always nitric acid

whether in solution or not

H2SO4 sulfuric acid

H3PO4 phosphoric acid

HC2H3O2 acetic acid

Some of the most common Arrhenius bases are...these are still named as ionic
compounds

NaOH  sodium hydroxide

KOH  potassium hydroxide

Mg(OH)2  magnesium hydroxide

Ca(OH)2  calcium hydroxide

One of the problems with the Arrhenius theory was that it did not cover many of the
common acid-base reactions such as the reaction of an acid with ammonia, NH 3.
 Ammonia clearly does not contain a hydroxyl group but yet it reacts readily with
acids.

Br�nsted proposed a theory that alleviated this problem. The  Br�nsted

Theory still defined an acid as a proton donor but it went further to define a base as
anything that would react with a proton, namely a proton acceptor. The acids listed
as Arrhenius acids are thus Br�nsted acids but now there are other bases.

Some Br�nsted bases are...

HO- from the above bases

NH3 (ammonia)

NaHCO3

Na2CO3

CaCO3

Amphoteric Compounds

Water can react with most Br�nsted acids and some Br �nsted bases.   This dual
nature is called amphoteric. An amphoteric compound can act either as an acid or a
base.

Most acid-base reactions take place in water solutions so the amphoteric nature of
water is very important. Hydrogen chloride is a gas. When HCl is dissolved in water,
it reacts essentially completely to form the hydronium ion, H 3O+, and chloride ion.

HCl   +   H2O   D   H3O+   +   Cl-

When the gas ammonia is dissolved in water, some of the ammonia reacts with
water to form the ammonium ion, NH4+, and hydroxide ion, HO-.

NH3   +   H2O   D   NH4+   +   HO-

Concept of pH

The concept of pH was invented by a chemist named S�renson in order to simplify

describing the acidity of weak acids or dilute solutions of strong acids.

A pH value of 7 denotes a neutral solution, pH values that are less than 7 denote an
acidic solution and pH values greater than 7 denote a basic solution (one that has
excess hydroxide ions).

The pH values of some common solutions are given in the following table. You can
arrive at the hydronium ion, concentration in moles per liter by simply making the pH
the negative exponent of 10. The hydronium ion concentration in the stomach would
be about 10-1 or 0.1 molar.
 Solution pH
stomach acid (hydrochloric acid) 1.2
lemon juice (citric acid and others) 2.3
cola (phosphoric acid) 2.8
saliva 6.5
milk (lactic acid) 6.6
blood 7.4

Acid Rain

Pure unpolluted rain water has a pH of 5.6 which means that it is slightly
acidic.  Some carbon dioxide in the atmosphere dissolves in water and reacts to
form a small amount of H2CO3, carbonic acid.

CO2   +   H2O   D   H2CO3

Carbonic acid is a very weak acid and dissociates to give a hydronium ion
concentration of 2.5 x 10-6. 

H2CO3   +   H2O   D   H3O+   +   HCO3-

The pH of rainwater in most parts of the world is less than 5.6 which means extra
acidity must be coming from somewhere other than carbon dioxide. The most acidic
rain ever recorded had a pH of 2.4 and that acidity is great enough to cause serious
problems in our environment.

The source of the extra acidity in rain comes from anthropogenic sources. This
includes the combustion of fossil fuels, burning of biomass and industry. The
problem with acid-rain is centered over highly populated industrialized areas.
However, the problem is regional and acid rain can impact people who do not even
benefit from the industrialization.

The compounds responsible for the extra acidity are nitrogen oxides and sulfur
dioxide.

Conjugate Acids and Bases

If you remove a proton from any of the acids in our previous examples, you would
be left with an anion that is called the conjugate base of that acid. If you add this
proton to any of the bases given as examples, you would produce a compound that
is called the conjugate acid of that base. This dynamic process is a "tug of war" for
the proton.

In the following example, the acid HBr reacts with the base Mg(OH) 2 to form
MgBr2 (a salt) and water.  Bromide, Br-, is the conjugate base of the acid HBr. Water
is the conjugate acid of the base HO-. The Mg+2 acts as a counter ion, first to the
hydroxide ion and then to the bromide ion.

2 HBr   +   Mg(OH)2   �   MgBr2   +   2 H2O
Buffer Solutions

A buffer solution is a solution that resists a change in pH when small amounts of an

acid or base are added to the solution. A buffer is the solute present in a buffer
solution that causes the solution to be pH-change-resistant.

A buffer contains a substance that reacts with and removes added base and a
substance that reacts with and removes added acid.

Buffer solutions are very important in the functioning of life processes. Body fluids
have definite pH values that must be maintained over narrow pH ranges. Buffers in
these fluids provide protection against pH change.

Relative Acidities and Basicities

The relative strengths of some common acids and bases are shown in the following
table. The acidity constants are given as Ka values...a large number denotes a
strong acid.

All anions are assumed to have a positive counter-ion such as a metal cation, which
is merely a "spectator ion" and does not participate in the reaction. It merely "hangs
out" with whatever atom has the negative charge.

All cations are assumed to have a negative counter-ion such as a non-metal anion,
which, again, is a "spectator ion".

Any conjugate base will react with any acid above it on the list.

You will be able to work out most of the acid-base reactions in question 12 of the
problem set by this method. Acids like sulfuric acid and phosphoric acid have more
 than one acidic hydrogen atom and the product should show all acidic hydrogen
atoms reacting. Helpful Hints!

Reasons for Relative Acidities and Basicities

Not all of the acids and bases can be compared with each other using the same
theoretical principles because it is analogous to comparing apples and oranges.
However, there are some theoretical principles that can be used to make decisions
about the differences in acidity or basicity among similar acids and bases.

Remember that a strong Br�nsted acid must have a weak conjugate base because
if the conjugate base was strongly attracted to the proton, the proton could not be
lost easily and you would have a weak Br�nsted acid.  The reverse statement is
also true. A weak Br�nsted acid will have a strong conjugate base.  The Br�nsted
acids in the chart all have one thing in common. They all have a hydrogen atom
attached to an element that has a greater electronegativity.  This is important
because the hydrogen atom must have some positive character in order to react
with a base In other words, the hydrogen atom must have some of the
characteristics of a proton.

The Br�nsted bases in the chart all have electron pairs that are readily available for
sharing.

Let's look at the relative acidity of the related compounds H�F, H�OH,
H�NH2 and H�CH3. Why is hydrofluoric acid the strongest acid in this group?

Hydroiodic acid is one of the strongest acids in our chart and hydrofluoric acid is a
fairly weak acid. How can we explain this relative acidity?

Sulfuric acid is a stronger acid than nitric acid, which is a stronger acid than acetic
acid. All of the hydrogen atoms are attached to oxygen atoms in these acids. We
need to draw out the electron-dot formulas for these compounds and calculate
formal charges to see the logic in this order.

How can a comparison be made between sulfuric acid and hydroiodic acid?

Why is hydroxide ion a much stronger base than fluoride ion?

Why is hydroxide ion a much stronger base than water?

Why is ammonia a stronger base than water?

Problems

1. Name the following compounds...

H2SO4

H3PO4
 HNO3

2. Write chemical formulas for the following compounds...

hydrofluoric acid

hydrobromic acid

acetic acid  

3. What is the pH of a solution, which has a hydrogen ion concentration of 0.000001 mole/liter?

4. What is the hydrogen ion concentration in moles/liter for a solution having a pH equal to 3?

5. A high pH (number larger than 7) refers to a solution that is�

6. Which of the following compounds is the strongest acid?

H2SO4

HC2H3O2

HNO3

7. Which of the following compounds is the strongest acid?

HCl

HI

HBr

HF

8. Which of the following compounds is the strongest acid?

CH4

NH3

H2O

HF

9. Which of the following compounds is the strongest base?

H3N

H2O
 HF

CH4

10. Which of the following compounds is the strongest base?

NaOH

NaNH2

NaF

11. Which of the following compounds is the strongest base?

HSO4-

C2H3O2-

NO3-  

12. Complete and balance the following acid-base reactions. If you have trouble doing these
problems, check out this link.

HCl   +   NaOH   �   answer

HF   +   NH3   �   answer

NaOH   +   HNO3   �   answer

H2SO4  +   KOH   �   answer

H3PO4   +   NaOH   �   answer

NaHCO3   +   HCl   �   answer

CaCO3   +   H2SO4   �   answer

HCl   +   NH3   �   answer

NH3   +   H2SO4   �   answer

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Copyright � January 2001 by Richard C. Banks...all rights reserved.