CHAPTER 4

BASIC CONCEPT FROM EQUILIBRIUM CHEMISTRY

Limitations of Equilibrium Calculations
Equilibrium calculations cannot be expected to describe accurately the
relationship between all the various species in such a system since equilibrium
may not be attained. However, they can indicate the direction in which reactions
would tend to proceed and the extent to which reactions would go if equilibrium
were attained.
 Ion Activity Coefficients
Lewis and Randal
They introduced the concept of ionic strength (µ) as an empirical measure of the interactions
among all the ions in a solution that caused deviation from ideal behavior.
1 2
µ = ∑Ci Zi
2
µ = ionic strength
Ci = Molarity
Zi = charge on each ion in solution
Ion Activity Coefficients
Debye-Hückel
µ
Log ɣ = -0.5𝒛𝟐
1+ µ

Davies Equation
𝟐 µ
Log ɣ = -0.5𝒛 − 𝟎. 𝟐 µ
1+ µ
Solution to Equilibrium Problems
1. the equilibrium problem
2. List all of the systems that are present at the outset
3. Chemical species likely to be present after equilibrium is attained
4. Identify the concentrations of each element/ initial conditions so that appropriate mass and
change balances can be made;
5. Equilibrium relationships
6. Mass and charge balance relationships;
7. Determine the concentration of each species at equilibrium
Acids and Bases
Strong acids and bases are considered to be completely ionized in dilute solution and weak acids
and bases are only partially ionized. Acid tend to increase the hydrogen-ion concentration in
solution, while bases increase the hydroxide concentration.
pH
pH is a measure of hydrogen ion concentration, a measure of acidity of alkalinity of a solution.
1
pH = -log [H+] or pH = log +
[H ]
[H+] [OH-] = Kw
-log [H+] – log [OH-] = pKw
pH + pOH = pKw
Kw = 1 x 10-14 at 250C, pKw = 14
Acids and Bases
Titration of Strong Acids and Bases

Equivalent point
Acids and Bases
Titration of Weak Acids and Bases

Equivalent
point
Acids and Bases
Titration curves for weak bases and for salts of weak acid

Equivalent
point
Buffer
Buffer can be defined as substances in solution that offer resistance to changes in pH as acids or
bases are added to or formed within the solution. Buffer usually contains mixtures of weak acids
and their salts (conjugate bases) or weak bases and their salts (conjugate acids).
A monoprotic acid is an acid that donates only one proton or hydrogen atom per molecule to an aqueous
solution. Ex. HCl and HNO3.

A Polyprotic acid is an acid capable of donating more than one proton or hydrogen, which are called
polyprotic acids. Polyprotic acids may be further categorized according to how many protons they can
donate (diprotic = 2, triprotic = 3, etc.)
Diprotic acids:
1. Sulfuric acid, H2SO4
2. Carbonic acid, H2CO3
3. Oxalic acid, COOH-COOH

Triprotic acids:
1. Phosphoric acid, H3PO4
2. Arsenic acid, H3AsO4
3. Citric acid, CH2COOH-C(OH)(COOH)-CH2COOH