Acids and Bases
Acid and base equilibrium involves equilibrium of ions in
aqueous solution (water as a solvent)
Definitions of acids and bases
Definitions of acids and bases are based on the
Arrhenius, the Bronsted-Lowry and the Lewis theory
Arrhenius acids and bases
Acid - a substance that generates hydrogen ions (H+) in
aqueous solutions
Base - a substance that generates hydroxide ions (OH-)
in aqueous solutions
eg. Acid: HCl(aq) H+(aq) + Cl-(aq)
Base: NaOH(aq) Na+(aq) + OH-(aq)
Classification of Arrhenius acids:
Monoprotic acid - generates one H+ ion per molecule:
HCl H+ + Cl-
Diprotic acid - generates two H+ ions per acid molecule:
H2SO4 2H+ + SO 24
Triprotic acid - generates three H+ ions per molecule:
H3PO4 3H+ + PO 34
[Disadvantage: The Arrhenius definition is valid for
aqueous solutions only]
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Bronsted-Lowry acids and bases
Acid – a substance that donates a proton (H+) to
another substance
Base – a substance that accepts a proton from another
substance
A Bronsted-Lowry acid or base consists of a ‘conjugate
pair’ which differ by a proton
Consider the following acid-base equilibriums:
Conjugate pair
HF(aq) + H2O(l) H3O+(aq) + F-(aq)
Acid Base Acid Base
Conjugate pair
Forward direction: HF acid, F- conjugate base
Reverse direction: H3O+ acid, H2O conjugate base
Conjugate pair
CH3NH2(aq) + H2O(l) CH3NH 3 (aq) + OH-(aq)
Base Acid Acid Base
Conjugate pair
(Note that the acid has an extra H+ in its formula)
[The Bronsted-Lowry definition applies to a broader
range of acids and bases that need not be aqueous]
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Lewis Acids and bases
Acid - accepts an electron pair to form a covalent bond
Base - donates an electron pair to form a covalent bond
Consider the following reactions:
(Lewis acid) (Lewis base)
BF3 Lewis acid (accepts an electron pair to form a
covalent bond between B and N)
NH3 Lewis base (donates an electron pair to form a
bond)
(Lewis acid) (Lewis base)
B(OH)3 Lewis acid (accepts an electron pair to form a
covalent bond between B and O)
OH- Lewis base (donates an electron pair to form a
bond)
[Advantage: The Lewis theory allows most substances
without H+ to be defined as acids]
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The ion product constant of water, Kw
Equilibrium in aqueous solution involves water (solvent)
Consider the ionization of water at 25oC:
2H2O(l) H3O+(aq) + OH–(aq)
(H3O+ hydronium ion)
or H2O(l) H+(aq) + OH-(aq)
Since [H2O]liquid = 1and H3O+ H+, we can write the ion
product constant expression as
Kw = [H+][OH-] = 1.0x10-14
where, Kw is the ion product constant of water
[H+] = molarity of H+ in solution
[OH-] = molarity of OH- in solution
Concept of pH
The molar concentration of H+ is better expressed in
terms of pH because of its small value in solution
pH = – log [H+]
Likewise, the concentration of OH- is frequently
expressed in terms of pOH
pOH = – log [OH-]
The relationship between pH and pOH is
pH + pOH = 14
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The pH of solutions and common substances:
Acidic solution: [H3O+] > [OH-] pH < 7.0
Neutral solution: [H3O+] = [OH-] pH = 7.0
Basic solution: [H3O+] < [OH-] pH > 7.0
The strengths of acids and bases
Strengths of acids and bases may be compared in
terms of their
- ionization constants (Ka for acids and Kb for bases)
- percent or degree moles ionized per liter
= x100
of ionization moles available per liter
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Strong Acids
A strong acid completely ionizes in solution (100%
ionization or dissociation)
There are 7 strong acids:
HCl, HBr, HI, H2SO4, HNO3, HClO3, HClO3, HClO4
100% ionization is represented by a single arrow:
eg: HCl H+(aq) + Cl-(aq)
or HCl + H2O H3O+(aq) + Cl-(aq)
H2SO4 2H+(aq) + SO 24 (aq)
or H2SO4 + 2H2O 2H3O+(aq) + SO 24 (aq)
Strong Bases
A strong base completely ionizes in solution (100%
dissociation)
There are 7 strong bases:
LiOH, NaOH, KOH, RbOH, Ca(OH)2, Sr(OH)2, Ba(OH)2
The dissociation is represented by a single arrow:
eg: NaOH Na+(aq) + OH-(aq)
Ca(OH)2 Ca2+(aq) + 2OH-(aq)
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Weak Acids
A weak acid undergoes partial ionization in solution
The strength of a weak acid is determined by the acid
ionization constant, Ka
pKa = -log(Ka)
The larger the value of Ka the stronger the acid
Partial equilibrium is written with double arrows:
CH3COOH CH3COO-(aq) + H+(aq)
or CH3COOH + H2O CH3COO-(aq) + H3O+(aq)
Weak bases
A weak base undergoes partial ionization in solution
The strength of a weak base is determined by the base
ionization constant, Kb
pKb = -log(Kb)
The larger the value of Kb, the stronger the base
Their equilibrium is written with double arrows:
NH4OH NH 4 (aq) + OH-(aq)
NH3 + H2O NH 4 (aq) + OH-(aq)
(H2O must be included in the equation for bases without
OH in their formula)
Ka x Kb = Kw = 1.0x10-14
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Determining the pH of strong acids and bases
Sample problem
Determine (a) the pH of a 0.0750 M solution of HI and
(b) the pOH and pH of a 0.055 M Ca(OH)2 solution
Solution
Determining the pH of weak acids and bases
Sample problem
(a) Given Ka = 6.8x10-4, calculate the following:
(i) The pH of a 0.100 M solution of HF
(ii) The percent ionization of HF
(b) What is the pH of a 0.025m solution of hydrazine,
N2H4? Given Kb = 1.7x10-6
Solution
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Salts and hydrolysis
A salt is an ionic compound formed from the reaction of
an acid and a base
Salt hydrolysis is the reaction of an anion or cation of
a salt with water
Hydrolysis affects the pH of an aqueous salt solution
(salt dissolved in water):
Acid-base reaction Salt formed pH
Strong acid-strong base Sodium chloride Neutral
eg HCl + NaOH NaCl (pH = 7)
Weak acid-strong base Sodium acetate Basic
eg CH3COOH + NaOH CH3COONa (pH > 7)
Strong acid-weak base Ammonium chloride Acidic
eg HCl + NH3 NH4Cl (pH < 7)
Weak acid-weak base CH3COONH4 Depends
eg CH3COOH + NH3 Ammonium acetate on Ka/Kb
[Ions]Hydrolysed
% Hydrolysis = x100
[Ions]Initial
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Salt producing neutral solutions
eg NaCl Na+(aq) + Cl-(aq) (100% ionized)
The Na+ and Cl- ions have no tendency to donate
or accept H+ thus the solution remains neutral
Salt producing basic solutions (Hydrolysis of anions)
eg CH3COONa CH3COO- + Na+
(The salt ionizes completely)
CH3COO- is a conjugate base that has the
tendency to accept H+:
CH3COO- + H2O CH3COOH + OH-
(OH- is produced the solution is basic)
For a general anionic hydrolysis:
A- + H2O HA + OH-
The hydrolysis constant expression is
[HA][OH ]
Kh =
[A ]
Kw
Kh =
Ka
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Salt producing acidic solutions (Hydrolysis of cations)
eg NH4Cl NH 4 + Cl-
(The salt ionizes completely)
NH 4 is a conjugate acid and has the tendency to
donate H+:
NH 4 + H2O NH3 + H3O+
(H3O+ is produced the solution is acidic)
For a general cationic hydrolysis:
CH+ + H2O C + H 3O+
The hydrolysis constant expression is
[C][H3 O ]
Kh =
[CH ]
Kw
Kh =
Kb
Salts in which both the cation and anion hydrolyse
Both cations and anions of salts from weak acid-weak
base reactions hydrolyse in water
If Ka of the acid > Kb of the base, the solution is acidic
If Kb of the base > Ka of the acid, the solution is basic
If Ka Kb the solution is almost neutral
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eg: HCOONH4 NH 4 + HCOO-
Ka(HCOOH) = 1.8x10-4
Kb(NH3) = 1.8x10-5
Consequently, Kh is higher for NH 4 and the solution
is acidic: NH 4 + H2O NH3 + H3O+
Determining pH of salts and % hydrolysis
Sample problems
(a) Calculate the pH of 0.1 M solution of NH4Cl [Given:
Kb of NH4OH = 1.75x10-5]
(b) Given the Kh of CH3COONa as 5.6x10-10, calculate
the pH of a 0.05 M solution of the salt
Solution
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Buffer solutions
A buffer solution is a solution whose pH changes very
slightly upon addition of a small amount of strong acid or
strong base
Components of buffer solutions
An acidic buffer is a mixture of a weak acid and the
salt of its conjugate base
eg CH3COOH + CH3COONa
(weak acid) (salt of conjugate base)
NaH2PO4 + Na2HPO4
(weak acid H2PO 4 ) (salt of conjugate base HPO 24 )
A basic or alkaline buffer is a mixture of a weak base
and the salt of its conjugate acid
eg NH3 (weak base) + NH4Cl (salt of conjugate acid)
N2H4 (weak base) + N2H5Cl (salt of conjugate acid)
Sample problem
From the list given below, select pairs of substances that
form buffer solutions when mixed:
NH4Cl, HCl, H2CO3, HPO 24 , NaHCO, NH3, H2PO 4
and NaCl
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Solution
How buffers work to resist pH change
Consider the acidic buffer eg a mixture of aqueous
CH3COONa and CH3COOH
CH3COONa CH3COO- + Na+
(complete dissociation of salt)
CH3COOH H+ + CH3COO-
(partial dissociation of weak acid)
(a) If a small amount of acid (H+) is added it will be
absorbed by the CH3COO- ions:
H+ + CH3COO- CH3COOH
(Reduced) (Reduced) (Increased)
(b) If a small amount of base (OH-) is added it will be
absorbed by the CH3COOH:
OH- + CH3COOH H2O + CH3COO-
(Reduced) (Reduced) (Increased)
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Consider the alkaline buffer eg a mixture of aqueous
NH3 and NH4Cl
NH4Cl NH 4 + Cl- (salt dissociates completely)
NH3 + H2O NH 4 + OH-
( weak base dissociates partially)
(a) If a small amount of acid (H+) is added it will be
absorbed by NH3:
H+ + NH3 NH 4
(Reduced) (Reduced) (Increased)
(b) If a small amount of base (OH-) is added it will be
absorbed by the NH 4 ions:
OH- + NH 4 H2O + NH3
(Reduced) (Reduced) (Increased)
pH determination of buffer solutions
The Henderson-Hasselbalch equation is used in
calculating the pH of a buffer solution
[base]
pH = pKa + log
[acid]
where, pH = -log[H+], pKa = (-log Ka) of the acid
[Base] is the molarity of a base (conjugate base)
[Acid] is the molarity of an acid (conjugate acid)
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The Henderson-Hasselbalch equation is derived from
the Ka expression:
HA H+ + A-
(Acid) (Conjugate base)
[H ][ A ] [ Acid]
Ka = [H+] = Ka x
[HA ] [Base]
[ Acid]
-log[H ] = -logKa x (-log
+ )
[Base]
[Base]
pH = pKa + log(
[ Acid]
Therefore, the Ka expression can also be used to calculate
pH of a buffer solution
Calculating pH of a buffer solution
Sample problem
Calculate the pH of a buffer solution which consists of 25
g of NaF in 120 mL of 2.0 M HF (Ka for HF = 6.8 10-4)
Solution
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pH of buffer after the addition of acid or base
Sample problem
Calculate the pH of the HF-NaF buffer solution given in
the previous example
(a) if 2.50 mL of 2.0 M NaOH solution is added to it
(b) after 5 mL of 1.5 M HCl is added to it
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Acid-base titration
Titration - Neutralization of an acid or base solution with
a known standard to determine the concentration of the
acid or base
Equivalence point - the point when the moles of
base/acid is equal to the moles of acid/base in solution
The equivalence point can be visualized by using an
indicator or a pH meter
Indicator - A weak acid which changes color over a
specific pH range in solution
Examples:
Indicator pH Range (Acidic to Basic)
Bromophenol blue 3.0 – 4.6 Yellow to blue
Methyl orange 3.2 – 4.4 Red to yellow
Methyl red 4.8 – 6.0 Red to yellow
Bromothymol blue 6.0 – 7.6 Yellow to blue
Phenolphthalein 8.2 – 10.0 Colorless to pink
The end point is the point in a titration at which the
indicator changes color
Consider the equilibrium of phenolphthalein:
HIn H+(aq) + In– (aq)
Colorless Pink
If OH– is added to the solution it reacts with H+ and the
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result is a decrease of H+ followed by a shift to the right
(Color changes from colorless to pink)
Using a pH meter
Technique - pH is measured after each addition of a
small amount of base to a fixed amount of acid
Titration curve - a plot of pH versus volume of base
added
The equivalence point is indicated by a sharp change
in pH with volume added (steepest part of the curve)
Titration curves
Strong acid-strong base titration curve
Choice of indicators: Any indicator that changes color
between pH 3.5 to 10.5 (eg phenolphthalein or methyl
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red)
Strong acid-weak base titration curve
Choice of indicators: Any indicator that changes color
between pH 3.0 to 7.0 (eg methyl orange)
Features of the curve:
Beginning - only the strong acid is present in solution
pH is based on the concentration of the acid
Before the equivalence point – the solution contains
buffer solution the pH is based on the buffer
At the equivalence point – the solution contains salt
the pH is based on hydrolysis of the salt (cation)
After the equivalence point – the pH is calculated
using the Kb of the base
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Weak acid-strong base titration curve
Choice of indicators: Any indicator that changes color
between pH 6.5 to 10.5 (eg phenolphthalein and
bromothymol blue)
Features of the curve:
Beginning - only the weak acid is present in solution
the pH is based the Ka of the weak acid
Before the equivalence point – the solution contains a
buffer solution the pH is based on the buffer
At the equivalence point – the solution contains salt
the pH is based on hydrolysis of the salt (anion)
After the equivalence point – the pH is based on the
concentration of the strong base
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Sample problem
Consider the titration of 25.0 mL of 0.100 M acetic acid
with 0.10 M NaOH.
Given Ka (HC2H3O2) = 1.8 10–5, calculate the pH at the
equivalence point
Solution
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