ACID-BASE

EQUILIBRIA AND
BUFFER SOLUTIONS
CHEM 142_N LAB
THE EQUILIBRIUM CONSTANT
In a chemical reaction, chemical equilibrium is the state in which both the reactants and products are
present in concentrations which have no further tendency to change with time, so that there is no observable
change in the properties of the system.

Where the small superscript letters denote stoichiometric coefficients and each capital letter stands for the chemical
species. The symbol [A] stands for the concentration of A relative to its standard state. For solutes, the standard
state is 1M {[A]/(1M)}; for gases, the standard state is 1 bar{[D]/(1bar)}; for solids and liquids, the standard states
are the pure solid or pure liquid{[C]/(concentration of C in its std state)} would be unity (1).
THE EQUILIBRIUM CONSTANT
In a chemical reaction, chemical equilibrium is the state in which both the reactants and products are
present in concentrations which have no further tendency to change with time, so that there is no observable
change in the properties of the system.

To evaluate the equilibrium constant,

1. The concentration of solutes should be expressed as moles per liter.
2. The concentration of gases should be expressed in bars.
3. The concentration of pure solids, pure liquids and solvents are omitted because they are unity.
THE EQUILIBRIUM CONSTANT

EXAMPLE: Write the equilibrium constant for the reaction:

THE EQUILIBRIUM CONSTANT

EXAMPLE: Write the equilibrium constant for the reaction:

Hydrogen Ion Concentration: Acids and
Bases
In aqueous solutions — especially in biological systems — the concentration of hydrogen ions () is very
important. Biological systems often take great pains to make sure that their hydrogen ion concentration —
represented as [] or by the measurement of pH (the measure of acidity in a solution) — doesn’t change.
Even minor changes in hydrogen ion concentration can have dire consequences to a living organism. For
example, in human blood, only a very small range of hydrogen ions allows the body to function properly.
Hydrogen ion concentrations higher or lower than this range can cause death.
Because living organisms are so dependent on pH, we review the concepts of acids, bases, and pH in the
following sections.

Achieving Equilibrium
Achieving Equilibrium
The equilibrium of hydrogen ions is present in all aqueous solutions. Water may or may not be the major
hydrogen ion source (usually it isn’t). Water is a contributor to the hydrogen ion concentration because it
undergoes autoionization, as shown by the following equation:

You often see (aq) represented as .

The double arrow ( ) indicates that this reaction (represented by the equation) is an equilibrium; as such,
there must be an associated equilibrium constant (K). The equilibrium constant in the preceding equation is Kw.
The value of Kw is the product of the concentrations of the hydrogen ion and the hydroxide ion:
 The value of the constant Kw, like all K’s, is only constant if the temperature is constant. In the human body,
where T = 37°C, Kw = 2.4 × .

In pure water, at 25°C, [H+] = 1.0 × M (1.6 × M at 37°C). The hydroxide ion concentration is the same as the
hydrogen ion concentration because they’re formed in equal amounts during the autoionization reaction. Keep in
mind that [] = [] only in pure water.

M is a concentration term, the molarity. Molarity is the number of moles of solute per liter of solution.

Understanding the pH scale

Expressing hydrogen ion concentrations in an exponential form, such as 1.0 × 10–7, isn’t always
convenient. Thankfully, you have a way of simplifying the representation of the hydrogen ion concentration:
the pH. You can calculate the pH for any solution by using the following equation:
pH of Strong Acids and Bases
Acids and bases are classified as strong or weak, depending on whether they react “completely” or “partly”
to produce H+ or OH-. Because there is continuous range for a “partial” reaction, there is no sharp distinction
between weak and strong. However, some compounds react so completely that they are unquestionably strong
acids or bases- and everything else is defined as weak.
pH of Strong Acids and Bases
the principal components that make rainfall acidic are nitric and sulfuric acids, which are strong acids. Each
strong acid or strong base in aqueous solution dissociates completely to provide 1 mole of H+ or OH-.
Nitric acid is a strong acid, so the reaction

Goes to completion. In regard to sulfuric acid, one proton is completely dissociated, but the second is only partly
dissociated (depending on conditions):
EXAMPLES:
1. What is the pH of
a. 1x10^-3 M HBr
b. 3.2 x10^-2 mM HI
 Solutions with a pH less than 7 are acidic. Solutions with a pH greater than 7 are basic. Solutions whose pH is 7
are neutral. The pH of pure water is 7. Be careful, though: Not every solution that has a pH of 7 is pure water! For
example, if you add table salt to water, the pH remains at 7, but the resulting solution is certainly not pure water.

The pH scale is an open-ended scale, meaning that a solution can have a pH greater than 14 or less than 0. For
example, the pH of a 1.0 × M solution of hydrochloric acid is –1. The 0–14 scale is a convenient part of the pH
scale for most real-world solutions — especially ones found in biochemistry. Most biological systems have a pH near
7, although significant deviations may exist (for example, the pH in your stomach is close to 1).
Calculating pOH
You can calculate pOH (related to the concentration of the hydroxide ion) in a similar manner to the pH
calculation. That is, you can use the equation pOH = –log []. You can calculate the hydroxide ion concentration from the
hydrogen ion concentration and the Kw (equilibrium constant) relationship:
EXAMPLE:
1. Calculate the pH of 1.0 x 10^-2 M KOH
2. 7.7 mM Ba(OH)2
Example:
1. Find the hydrogen ion concentration in a solution whose
a. pH= 4.44
b. pOH= 2.32
Applying the Brønsted-Lowry theory
Because the acidity (pH) of the biological medium is so very important, here we take a look at one of the most
accepted theories concerning acids and bases — the Brønsted-Lowry theory. According to this theory, acids are
proton () donors, and bases are proton acceptors.

Swapping hydrogens between acids and bases

Acids increase the hydrogen ion concentration of a solution (they lower the pH, in other words). Some acids, known as
strong acids, are very efficient at changing hydrogen ion concentration; they essentially completely ionize in
water. Most acids — particularly biologically important acids — aren’t very efficient at generating hydrogen ions; they
only partially ionize in water. These acids are known as weak acids.
Bases accept (react with) rather than donate hydrogen ions in solutions. Bases decrease the hydrogen ion concentration
in solutions because they react with these ions. Strong bases, although they can accept hydrogen ions
very well, aren’t too important in biological systems. The majority of biologically important bases are weak bases.
The Brønsted-Lowry theory helps to explain the behavior of acids and bases with respect to equilibrium. A Brønsted-
Lowry acid is a hydrogen ion () donor, and a Brønsted-Lowry base is a hydrogen ion acceptor. Acetic acid,
a weak acid found in vinegar, partially ionizes in solution, evidenced by the following equation:
 The double arrow indicates that the acetic acid doesn’t completely ionize. (For a strong acid, complete
ionization would occur, indicated by a single arrow.) The equilibrium arrow ( ) indicates that all three
chemical species are present in the solution: the acetic acid, the acetate ion, and the hydrogen ion, along with the
water solvent.

In the Brønsted-Lowry theory, you consider the acetate ion to be a base because it can accept a hydrogen ion to
become acetic acid. According to this theory, two substances differing by only one hydrogen ion (H+) — such
as acetic acid and the acetate ion — are members of a conjugate acid-base pair. The species with one additional
hydrogen ion is the conjugate acid (CA), and the species with one less hydrogen ion is the conjugate base (CB).

You can express the equilibrium from the acetate example, like all equilibria, by using a mass-action expression
— as long as a balance among the species is present. This expression is also known as a reaction quotient or an
equilibrium constant. For acetic acid, this expression is as follows:
 The a subscript means that this expression represents an acid. The square brackets refer to the molar equilibrium
concentrations of the species present. You can express the K a as a pKa. The calculation of pKa is similar to the
calculation of pH:

No variations are allowed in this equation other than the actual formulas of the conjugate acid and base.
EXAMPLE:
1. Write the acid dissociation reaction for formic acid, HCO2H.
2. What is the conjugate base of formic acid?
3. Write the Ka equilibrium expression for formic acid and look up its value.
 Like an acid, a base has a Kb value (the subscript b meaning base). A weak base, like ammonia, is part of the
following equilibrium:
 Every acid has a Ka, and its corresponding conjugate base has a Kb. The Ka and the Kb of a conjugate acid-base
pair are related by the Kw — the ionization constant for water. For a conjugate acid-base pair, K aKb = Kw = 1.0 × 10–
14. In addition, you can use the following shortcut: pK a + pKb = 14.00.

The Kb for the acetate ion, the conjugate base of acetic acid, would be associated with the following equilibrium
expression:
EXAMPLE:
1. Write the acid dissociation reaction for formic acid, HCO2H.
2. What is the conjugate base of formic acid?
3. Write the Ka equilibrium expression for formic acid and look up its value.
4. Write the Kb equilibrium expression for the formate ion, HCO2-
5. Find the base hydrolysis constant for formate.
 The Ka for the ammonium ion, the conjugate acid of ammonia, would be associated
with the following equilibrium expression:
 An acid may be capable of donating more than one hydrogen ion. A biologically important example of this type of
acid is phosphoric acid (H3PO4), which is a triprotic acid (meaning it can donate three hydrogen ions, one
at a time). The equilibria for this acid are
pH of Weak Acids and Bases
Example: What is the pH and composition of a solution containing 0.002 mol benzoic acid in 1.00 L of
water?
Example 2.
Example 3. A 0.0560-g quantity of acetic acid is dissolved in enough water to make 50.0 mL of solution.
Calculate the concentrations of H+, CH3COO-, and CH3COOH at equilibrium. (Ka for acetic acid =
1.8x 10-5.)
FINDING THE pKa OF WEAK ACIDS
pH of weak Bases
pH of weak Bases
Calculate the pH of 0.05M pyridine solution. The Kb of the solution is 1.7x10^-9.
BUFFERS
Which of the following couples are buffer systems? (a) KF/HF,
(b) KBr/HBr, (c) Na2CO3/NaHCO3.
Calculate the pH of the 0.20 M NH3/0.20 M NH4Cl buffer. What is the pH of the buffer after the addition of 10.0 mL of
0.10 M HCl to 65.0 mL of the buffer?
a. What is the pH of a solution prepared by dissolving 10.0 g of tris plus 10.0 g of tris HCl in 250 mL of water?
b. What will be the pH if 10.5 mL of 0.5 M HClO4 are added to a?
c. What will be the pH if 10.5 mL of 0.5 M NaOH are added to a?
Calculating How to Prepare a Buffer Solution
How many mL of 0.500 M NaOH should be added to 10.0 grams of tris HCl to give a pH=7.6 in a final volume
of 250 mL?
Preparing a Buffer in Real Life
When you mix calculated quantities of acid and base to make a buffer, the pH does not come out exactly as
expected. The main reason for the discrepancy is that pH I governed by activities of the conjugate acid-base pair,
not by the concentrations. If you really want to prepare tris buffer at pH 7.60, you should use a pH electrode to
get exactly what you need.
Suppose you wish to prepare 1.00 L of buffer containing 0.100 M tris at pH 7.60. When we say 0.100 M tris,
we mean that the total concentration of tris plus tris H+ will be 0.100 M. You have available solid tris HCl and ≈1M
NaOH. Here’s how to do it:
1. Weight out 0.100 mol tris HCl and dissolve it in a beaker containing about 800 mL of water.
2. Place a pH electrode in the solution and monitor the pH.
3. Add NaOH solution until the pH is exactly 7.60. The electrode does not respond instantly. Be sure to allow the
pH reading to stabilize after each addition of the reagent.
4. Transfer the solution to a volumetric flask and wash the beaker a few times. Add the washings to the
volumetric flask.
5. Dilute to the mark and mix.

The reason for using 800 mL of water in the 1 st step is so that the volume will be close to the final volume
during pH adjustment. Otherwise, the pH will change slightly when the sample is diluted to its final volume and
the ionic strength changes.