Acid-Base Chemistry: Manasi Mantri

Acid-base Chemistry
Manasi Mantri
Introduction
Robert Boyle
Acid
Base
Arrhenius
Acid
Base
Acid
Acid is any substance that ionizes (partially or completely) in
water to give hydrogen ions (which associate with the
solvent to give hydronium ions, H3O+)
HA + H2O H3O+ + A-
Base
A base ionizes in water to give hydroxyl ions. Weak (partially
ionized) base generally ionizes as follows
B + H2O BH+ + OH-
 While strong bases such as metal
hydroxides (e.g., NaOH) dissociate as
M(OH)n M+ + n OH-
Limitation: Arrhenius theory is evidently and grossly restricted to only water as the solvent
 Franklin introduced the solvent system concept of acids and bases.
According to this theory a solvent undergoes ionization to produce a
cation and anion
2H2O H 3O+ + OH-
2NH3 NH4+ + NH2-

Acid – It is defined as solute that yields the cation of the solvent
Base – It is defined as solute that yields anion of solvent
 Ammonium chloride (NH4Cl) serves as strong acid in liquid ammonia (NH3)
 Where as sodamide (NaNH2) behaves predominantly as a strong base in
ammonia
2C2H5-OH C2H5-OH2+ + C2H5O-
Ethanol Ethanolium ion Ethoxide ion
Sodium Ethoxide C2H5ONa behaves as strong base in

solvent ethanol
The theory of solvent systems is suitable for ionizable solvents, but it is not applicable to
acid – base reactions in nonionizable solvents such as benzene or dioxane
In 1923 Lowry – Bronsted separately described what is now known as the Lowry – Bronsted theory
Thus we can write a half reaction Acid – acid is any substance that
can accept a proton
Acid = H+ + base Base – base is any substance that
can accept proton
The acid and base of a half reaction are called conjugate pairs. Free proton do not
exists in solution, and there must be proton acceptor (base) before a proton
donner (acid) will release a proton. That is there must be a combination of two half
reactions.
CH3COOH + NH3 NH4+ + CH3COO-
Acid1 Base2 Base2 Acid2
It is apparent from the above definition that a substance can not act acid unless a
base is present to accept a protons.
Complete or partial ionization in
Basic solvents such as water,
Acids liquid ammonia, or ethanol
depending upon basicity of
solvent and strength of acid
But in neutral or inert solvents, ionization is insignificant.
However , ionization in the solvent is not a prerequisite for an acid
base reaction, because picric acid reacts with aniline in benzene
H picrate + C6H5NH2 C6H5NH3+ + picrate-
Acid1 Base2 Base2 Acid2

Definitions of acids and
bases
 Arrhenius
acid: generates [H+] in solution
base: generates [OH-] in solution
normal Arrhenius equation: acid + base <---> salt + water
example: HCl + NaOH <---> NaCl + H2O
 Bronsted-Lowery:
acid: anything that donates a [H+] (proton donor)
base: anything that accepts a [H+] (proton acceptor)
normal Bronsted-Lowery equation: acid + base <---> acid + base
example: HNO2 + H2O <---> NO2- + H3O+
Each acid has a conjugate base and each base has a conjugate acid. These
conjugate pairs only differ by a proton. In this example: HNO2 is the acid, H2O
is the base, NO2- is the conj. base, and H3O+ is the conj. acid.
 Lewis:
acid: accepts an electron pair
base: donates an electron pair
The advantage of this theory is that many more reactions can be considered
acid-base reactions because they do not have to occur in solution.
 Salts
 A salt is formed when an acid and a base are mixed and the acid releases
H+ ions while the base releases OH- ions. This process is called
hydrolysis. The pH of the salt depends on the strengths of the original
acids and bases:
Acid Base Salt pH

strong strong pH = 7
weak strong pH > 7
strong weak pH < 7
weak weak depends on which is stronger
 This is because the conjugate base of a strong acid is very weak and
cannot undergo hydrolysis. Similarly, the conjugate acid of a strong base
is very weak and likewise does not undergo hydrolysis.
 Water
 We typically talk about acid-base reactions in aqueous-phase
environments -- that is, in the presence of water. The most fundamental
acid-base reaction is the dissociation of water:
 In this reaction, water breaks apart to form a hydrogen ion (H+) and a
hydroxyl ion (OH-). In pure water, we can define a special equilibrium
constant (Kw) as follows:

 Where Kw is the equilibrium constant for water (unitless)
[H+] is the molar concentration of hydrogen
[OH- is the molar concentration of hydroxide
 An equilibrium constant less than one (1) suggests that the reaction
prefers to stay on the side of the reactants -- in this case, water likes to
stay as water. Because water hardly ionizes, it is a very poor conductor
of electricity.
 pH
 Under the Brønsted-Lowry definition, both acids and bases are related to the
concentration of hydrogen ions present. Acids increase the concentration of
hydrogen ions, while bases decrease the concentration of hydrogen ions (by
accepting them). The acidity or basicity of something therefore can be
measured by its hydrogen ion concentration.
 In 1909, the Danish biochemist Sören Sörensen invented the pH scale for
measuring acidity. The pH scale is described by the formula:
 pH = -log [H+]
 . When measuring pH, [H+] is in units of moles of H+ per liter of solution.
 For example, a solution with [H+] = 1 x 10-7 moles/liter has a pH equal to 7 (a
simpler way to think about pH is that it equals the exponent on the H+
concentration, ignoring the minus sign). The pH scale ranges from 0 to 14.
Substances with a pH between 0 and less than 7 are acids (pH and [H+] are
inversely related - lower pH means higher [H+] and a stronger acid).
Substances with a pH greater than 7 and up to 14 are bases (the higher the pH,
the stronger the base). Right in the middle, at pH = 7, are neutral substances,
for example, pure water.
 pOH gives us another way to measure the acidity of a solution. It is just
the opposite of pH. A high pOH means the solution is acidic while a low
pOH means the solution is basic.
 pOH = -log[OH-]
 pH + pOH = 14.00
 Strong Acids: These acids completely ionize in solution so they are

always represented in chemical equations in their ionized form. There
are only seven (7) strong acids:
 HCl, HBr, HI, H2SO4, HNO3, HClO3, HClO4
 To calculate a pH value, it is easiest to follow the standard "Start,
Change, Equilibrium“
 Example Problem: Determine the pH of a 0.25 M solution of HBr.
 Weak Acids: These are the most common type of acids. They follow the equation:
 HA(aq) <---> H+(aq) + A-(aq)
 The equilibrium constant for the dissociation of an acid is known as Ka. The larger the value of Ka, the
stronger the acid.
 Example Problem: Determine the pH of .30 M acetic acid (HC2H3O2) with the Ka of 1.8x10-5.
OH  

kb c
Weak Base
 B+H2O BH++OH-
kb 
 BH OH 
 
 B
Henderson- Hasselbach
Equation
 pKa=pH- log b
a

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Acid-base Chemistry

2NH3 NH4+ + NH2-

Sodium Ethoxide C2H5ONa behaves as strong base in

Acid1 Base2 Base2 Acid2

Acid Base Salt pH

 Strong Acids: These acids completely ionize in solution so they are

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