Module 4 in Gen Chem
Module 4 in Gen Chem
Module 4 in Gen Chem
Acids and bases are essential in sustaining biological systems, components of medicinal and household products
and play significant functions in industrial processes. Understanding how these types of substances behave will lead to
better and safer utilization of these materials. The table below shows characteristics that differentiates an acid from a base.
Acids and bases can be classified according to their extent of ionization as strong or weak.
Strong acid is a strong electrolyte that ionizes completely to produce only ions in solution. See figure
of HCl at the right. The strong inorganic acids are mostly hydrohalic acids and oxoacids. Listed below
are the acids arranged according to decreasing strength.
Acid Name
HClO4 Perchloric acid
HI Hydroiodic acid
HCl (aq)
HBr Hydrobromic acid
HCl Hydrochloric acid H+
HNO3 Nitric acid
Cl-
Here are some rules to follow on determining the relative strengths of these strong acids.
Hydrohalic acids. The strength increases down a group because as the halide increases in size, bonding with H
becomes weaker so the H+ dissociates easily.
HCl< HBr< HI
Case 1. Oxoacids having different central atoms but from the same group. The more electronegative
central atom is more acidic
Case 2. Oxoacids having different central atoms of different groups. The more electronegative central
atoms and the higher the number of oxygen atoms compared to the number of ionizable H +.
Weak acid is a weak electrolyte and does not ionize very much in solution. At a high
concentration, it only contains small number of H+ ions. Take a look at the figure of HF
ionization at the right.
HF (aq)
e.g. Inorganic acids such as H2CO3, H3BO3, H3PO4, H2S, H2SO3
and most organic acids such ascorbic acid, acetic acid, formic acid H+
There are some rules to follow on determining the relative strengths of these strong acids. F-
Hydrohalic acid HF
Case 1. Within a group. The strength increases down a group, as the non-metal increases in size, bonding
with H becomes weaker so H+ dissociates easily
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Case 2. Across a period. Non-metal hydride increases acidity strength to the right.
Case 1. When the number of O atoms equals or exceeds by one the number of ionizable H +. Acidity
increases as the number of oxygen atom increases if the central atom is the same.
Case 2. Oxoacids having different central atoms but from the same group with same number of oxygen.
The more electronegative central atom is more acidic.
Carboxylic acids (RCOOH) .The more polar the carboxylic acid, the more acidic.
Alcohols (ROH) has a pKa range: 15.5-18.0 comparable to water, pKa = 15.7. the acidity decreases as alkyl group
increases. The presence of halogens increase the acidity. Phenol is 100 million times more acidic than cyclohexanol
Strong bases completely ionize in solutions, and water soluble compounds containing O 2- or OH- ions.
Metal hydroxides and Metal oxides of Group IA. General Formula : M 2O or MOH where M (Li, Na, K, Rb, Cs)
Metal hydroxides and metal oxides of Group 2A. General Formula MO or M(OH) 2 where M (Ca, Sr, Ba)
Weak bases do not ionize completely in aqueous solution, contain electron-rich nitrogen atom.
Ammonia, NH3
conjugate acid is formed when a conjugate base is formed when an acid loses a
base accepts a proton proton
Bronsted
the acid found in the reactant, Acid the base found in the reactant, Base 2, has a
1, has a resulting base found in the resulting acid found in the product labelled as
product labelled as Base 1. The Acid 2. The base-acid pair is referred to as
acid-base pair is referred to as conjugate pairs. Acid 2 is the conjugate acid of
conjugate pairs. Base 1 is the Base 2.
conjugate base of Acid 1.
Example Reaction
Example Reaction
These three theories arise to accommodate all the substances that exhibits acidity and basicity. Just remember that
H+ of Arrhenius acid is also the acid in a form of H 3O+ in Bronsted and same as the electron acceptor in Lewis concept of
acid.
AMPHIPROTIC SPECIES
Amphiprotic species possess both acidic and basic properties.
Example:
Dihydrogen phosphate ion behaves as a base in the presence of a proton donor as shown in
the reaction
This reaction shows that H3PO4 is the conjugate acid of the original base.
On the other hand, H2PO4- can act as an acid in the presence of a proton acceptor, such as
the hydroxide ion as shown in the reaction
Simple amino acids are important class of amphiprotic compounds. In the presence of water,
the glycine undergoes an internal acid/base reaction to produce a zwitterion- a species that bears
both a positive and a negative charge.
NH2CH2COOH NH3+CH2COO-
Glycine zwitterion
Amphiprotic solvents behave as acids in the presence of basic solutes and act as base in the presence of acidic solutes.
Examples of amphiprotic solvents are methanol, ethanol and anhydrous acetic acid.
Amphiprotic solvents undergo self-ionization or autoprotolysis to form a pair of ionic species. Examples are ammonia,
methanol, formic acid and water.
Just like the substances above water is also an example of amphiprotic solvents. Water exhibits autoionization, a
substance that can undergo ionization at a small extent. Using the Bronsted definition:
+ +
Acid 1 Base 2 Acid 2 Base 1
At 25oC, Kw = [H+] [OH-] = 1.0 x 10-14. Thus, the concentration of [H+] or [OH-] in solutions can be determined.
Example:
Solution:
The pH scale is a practical measure of the hydrogen concentration in aqueous solutions. It is defined as
pH = -log [H3O+]
The pOH scale which analogous to the pH scale is expressed as pOH = -log [OH-].
There are relatively few strong acids and their ionization constants are greater than 1. Acid ionization constant,
Ka, refers to the equilibrium constant for the ionization of a weak acid.
For the reaction: HA (aq) + H2O(l) H3O+ (aq) + A- (aq), the Ka expression is
Ka = [H3O+][ A-]
[HA]
Similarly, the ionization of weak bases is treated the same way as the ionization of weak acids.
For the reaction B (aq) + H2O(l) HB (aq) + OH- (aq), the base ionization constant (Kb) is
Kb = [HB][ OH-]
[B]
Relationship of Acid Strength and Ka, and the strength of its conjugate Base and Kb
Hydrofluoric acid, -4 -
7.1 x 10 F 1.4 x 10-11
HF
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Nitrous Acid,
4.5 x 10-4 NO2- 2.2 x 10-11
HNO2
Hydrocyanic acid 4.9 x 10-10 CN- 2.0 x 10-5
If the [H+] is very low, it is advisable to get the pKa or the pKb value.
As the pKa value decreases. Ka value increases, the strength of the acid increases
As the pKb value decreases, Kb value increases, the strength of the base increases
Salt is an ionic compound formed by the reaction between an acid and a base. However not all salts are neutral.
Some salts undergo reaction with water to produce an acidic or a basic solution. This is known as Salt hydrolysis that is
the reaction of a cation or anion of a salt or both in water. It affects the pH of the solution.
Salts producing Neutral solutions. These are salts that Contains Group IA and IIA metal ions with a conjugate base
of a strong acid.
KNO3 + H2O K+ + NO3-
Salts producing Basic Solutions. The salt formed from a strong base and a weak acid.
CH3COONa + H2O Na+ + CH3COO-
-
CH3COO + H2O CH3COOH + OH-
Salts producing Acidic Solutions. The salt from a strong acid and a weak base.
NH4Cl + H2O NH4+ + Cl-
NH4+ +H2O H3O+ + NH3
Amphoteric oxides are compounds that can behave either as an acidic oxide or a basic oxide depending on
reaction conditions. It is usually found on the diagonal between the metal and non-metal elements. The usual product is a
salt.
As an acid Al2O3 + 2NaOH + 3H2O → 2NaAl(OH)4
As a base Al2O3 + HCl → 2AlCl3 + 3H2O
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ACID-BASE TITRATIONS
Titration is a technique used to quantitatively study acid-base
neutralization reaction using a standard solution added to an
analyte until the chemical reaction between the two solutions is
complete.
End point. It is the point in an actual titration when a physical change occurs that is associated with the condition of chemical
equivalence between the acid and a base.
Indicators. Substances that are added to the analyte solution to produce an observable physical change (end point).
Indicator changes include appearance or disappearance of distinctly different colors or turbidity in acidic and basic media.
pH reading. In the absence of indicators, the pH changes in the titration process can be monitored using the pH
meter. The pH reading and the volume of the analyte are plotted as points in a graph and the equivalence point is determined
graphically. This is known as potentiometric titration.
Titration Curves
Equivalence point for Fig 2. Titration curve of strong acid vs strong base
Linear segment curve. The vertical axis represents the instrument reading
that is proportional to the concentration of the analyte or the reagent. See
figure to determine the equivalence point.
Industrial Uses
Pickling is a process at which acids are used to remove rust and other corrosion from metals.
Mineral processing. Phosphate minerals react with sulfuric acid to produce phosphoric acid for the production of
phosphate fertilizers. Zinc is produced by dissolving zinc oxide into sulfuric acid.
Chemical industry. Acids react in neutralization reactions to produce salts. For example, nitric acid reacts with
ammonia to produce ammonium nitrate, a fertilizer. Additionally, carboxylic acids reacts alcohols to produce esters.
Acids are used as catalysts; for example, sulfuric acid is used in very large quantities in the alkylation process to
produce gasoline. Strong acids, such as sulfuric, phosphoric and hydrochloric acids also contributes to dehydration
and condensation reactions.
Acids are used as additives to drinks and foods, as they alter their taste and serve as preservatives. Phosphoric
acid, for example, is a component of cola drinks.
Biological occurrence
In humans and many other animals, hydrochloric acid is a part of the gastric acid secreted within the stomach to
help hydrolyze proteins and sugars, as well as converting the inactive pro-enzyme, pepsinogen into the enzyme, pepsin, an
enzyme that aids in the digestion process.
Some organisms produce acids for defense; for example, ants produce formic acid.
Buffer
A buffer solution has the ability to resist change in pH upon the addition of small amounts of either acid or base. It
is a solution of a weak acid and its weak salt or a weak base and its salt. Aqueous solutions of amphiprotic compounds can
act as buffers.
An example is the preparation of acetate buffer by adding comparable molar amounts of acetic acid and its salt
sodium acetate (CH3COONa) to water. This buffer solution can be written as CH 3COONa/CH3COOH or CH3COO-
/CH3COOH. The equilibrium that is occurring between the acids and the conjugate base helps in maintaining the pH of a
given system. Let us say for example:
Case 1. If an acid is added, the H+ ions will be consumed by the conjugate base in the buffer.
Case 2. If a base is added to the buffer system, the OH- ions will be neutralized by the acid in the buffer.
Buffering capacity is the effectiveness of the buffer solution. It depends on the amount of acid and conjugate base
from which the buffer is made. The greater the concentration of the weak acid and its conjugate base, the greater the buffer
capacity.
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Buffers are important in biological system. It is used to maintain the pH of the human body for proper enzyme
functions as well as in keeping balance of osmotic pressure.
Blood buffers. In order for the pH of blood which is about 7.4 to be maintained, the blood contains bicarbonates
and phosphates as buffering systems.
The blood contains bicarbonates (H2CO3/HCO3-) as buffers with a ratio of 1:10. It is a better buffer for acids. In
normal conditions, larger amounts of acidic rather than basic substances enter human blood.
The phosphate buffer made from 1.6: 1 ratio of hydrogen phosphate and dihydrogen phosphate ions [HPO 42-
]/H2PO4-].