CHM101

Engineering Chemistry

UNIT I
Fundamentals of Chemistry

Lecture 7

Acid-Base Chemistry
 Acids and Bases

The earliest definition that highlighted the molecular nature of acids and bases is the Arrhenius acid-
base definition, which classifies these substances in terms of their formulas and behavior in water:
An acid is a substance with H in its formula that dissociates in water to yield H+:

_
A base is a substance with OH in its formula that dissociates in water to yield OH :

The released H+ ion is highly unstable and immediately reacts with H2O to form hydronium ion, H3O+
In the Arrhenius sense, neutralization occurs when the H+ from the acid and the OH− from the base
form H2O.
Some typical Arrhenius acids are HCl, HNO3, and HCN, and some typical Arrhenius bases are NaOH,
KOH, and Ba(OH)2.
Even though some substances do not have discrete OH− ions, they still behave as bases. For
example, NH3 and K2CO3 also yield OH− in water.
 Brønsted and Lowry Concept

In the early 20th century, J. N. Brønsted and T.M. Lowry suggested definitions that removed the
limitations of Arrhenius concept.
According to the Brønsted-Lowry acid-base definition,
 An acid is a proton donor, any species that donates an H+ ion. An acid must contain H in its formula;
HNO3 and H2PO4 − are two of many examples. All Arrhenius acids are Brønsted-Lowry acids.
 A base is a proton acceptor, any species that accepts an H+ ion. A base must contain a lone pair of
electrons to bind H+ ; a few examples are NH3, CO32−, and F−, as well as OH− itself. Brønsted-Lowry
bases are not Arrhenius bases, but all Arrhenius bases contain the Brønsted-Lowry base OH−.
From this perspective, an acid-base reaction occurs when one species donates a proton and another
species simultaneously accepts it: an acid-base reaction is thus a proton transfer process.
 Amphoteric Nature of Water
According to J. N. Brønsted and T.M. Lowry definition, an acid-base reaction occurs even when an
acid (or a base) just dissolves in water, because water acts as the proton acceptor (or donor).

Therefore, H2O is amphiprotic: it acts as a base (accepts an H+ ) in one case and as an acid
(donates an H+ ) in the other.
 Water Weakly Ionizes to Form H+ and OH−

Water dissociates very slightly into ions in an equilibrium process known as autoionization (or self-ionization):

The degree of ionization of water at equilibrium is small;

at 25oC only about two of every 109 molecules in pure
water are ionized at any instant.
Pure water can conduct electricity owing to proton
jumping/hopping (OH ̅ moves in the opposite direction).
Proton Jumping/hopping
Ionization of water is very essential for its unique and life
sustaining properties.
 Ionization of Water is Reversible and can be Quantitated using Dissociation Constant.

Dissociation constant:
( K =1.8 X10 ̅ 16 M)
Concentration of unionized water is much more
than the individual ions so that the change in
concentration can be held as constant.

Ionization constant of water:

= 10-14 M2 at 25oC Ion Product of Water

Ion product of water remains constant at
constant temperature.
It increases with increase in temperature owing
Pure water (neutral pH) contains equimolar [ H+] = [OH-] to increase in ionization of water.
concentrations of [ H+] and [OH-].
[ H+] = [OH-] = 10-7 M
 Acidic and Basic Solutions

Pure water (neutral pH) contains equimolar concentrations of

[ H+] and [OH-].
[ H+] = [OH-] = 10-7 M

So if [ H+] is more than 10-7 M, [OH-] will be correspondingly less

and vice-versa. In both cases, as long as the temperature is
constant, the value of KW is constant.
Both ions are present in all aqueous systems. Thus, all acidic
solutions contain a low [OH-], and all basic solutions contain a
low [H3O+]. The equilibrium nature of autoionization allows us to
define “acidic” and “basic” solutions in terms of relative
magnitudes of [H3O+] and [OH-]:

If [ H+] > 10-7 M, We call the solution as acidic.

If [ H+] < 10-7 M, We call the solution as basic.

If [ H+] = 10-7 M, We call the solution as neutral.

Ionic Product of Water is the Basis of pH Scale.

It is a convenient means of designating the

concentration of H+ (and thus of OH-) in any aqueous
solution in the range between 1M H+ and 1M OH-
As the [ H+] concentrations are inconveniently small
and difficult to compare, In aqueous solutions, [H3O+]
can vary from about 10 M to 10−15 M.
To handle numbers with negative exponents more
conveniently in calculations, therefore, Søren
Sørenson in 1909 applied the negative of the
common (base-10) logarithm of the number and
devised a term called pH:

Note that, the higher the pH, the lower the [H3O+].
Therefore, an acidic solution has a lower pH (higher
[H3O+]) than a basic solution.
 Conjugate Acid-Base Pairs
Whenever an acid donates a proton, the acid changes into a base, and whenever a base accepts a
proton, an acid is formed. An acid and a base which differ only by the presence or absence of a
proton are called a conjugate acid-base pair.
A Brønsted-Lowry acid-base reaction occurs when an acid and a base react to form their conjugate
base and conjugate acid, respectively:

Each reaction has an acid and a base as reactants and as products, comprising two conjugate acid-
base pairs.

For example, let’s examine the reaction

between hydrogen sulfide and ammonia:
 Relative Acid-Base Strength and the Net
Direction of Reaction

The net direction of an acid-base reaction depends on

relative acid and base strengths: a reaction proceeds to
the greater extent in the direction in which a stronger acid
and stronger base form a weaker acid and weaker base.

A strong base accepts a proton more readily than a

weaker base.
A weak acid has a strong conjugate base.
Based on many experimental evidences, conjugate pairs
have been ranked based on their relative strengths.
The strongest acid is at top left and the strongest base at
bottom right. When an acid reacts with a base farther
down the list, the reaction proceeds to the right (Kc > 1).
 Dissociation of Strong Acids and Bases

Strong acids dissociate completely into ions in water;

In a dilute solution of a strong acid,

 HA molecules are no longer present, so [HA]eq = 0.
 All HA molecules have been converted to products, so [H3O+] = [A-] ≈ [HA]init.
Since [H3O+] and [A–] are large and [HA] ≈ 0, the value of KC is extremely large:

Because the reaction of a strong acid is essentially complete, we usually don’t express it as an
equilibrium process.

Like strong acids, strong bases also dissociate completely into ions in water and thus are classified
as strong electrolytes.
 Acid-Base Reactions in Water and pH Calculations

Strong acids and bases like HCl, NaOH completely ionize when dissolved in water. Therefore,
calculating pH, [H3O+] , [OH-], and pOH for these substances is straightforward:
The equilibrium concentration of H3O+ is equal to the initial concentration of a strong acid
therefore, pH is calculates as the negative log of initial acid concentration.
Weak acids and bases do not completely ionize and their ionization depends on their respective
strengths and are of interest to biochemists.
Acid-dissociation constants of weak acids range over many orders of magnitude.
Weak acids, therefore, are weak electrolytes and vary greatly in their strength as measured by the
amount of H3O+ they produce. Equilibrium calculations are needed to quantify the extent of acid
dissociation.
Weak acid-base dissociations in water are biologically important and their course of reaction can
be tracked.
Acid-base reactions are important in biological functions, therefore, an appreciation of acid–base
chemistry is essential for understanding the chemical context of many biological processes.
 Dissociation of Weak Acids and Bases

Acid-Base reactions in water can simply be represented as:

In a dilute solution of a weak acid,

 The great majority of HA molecules are undissociated, so; [HA]eq ≈ [HA]init.
 Only a very small number of HA molecules dissociate, so [H3O+] = [A–] << [HA]init.

The above expression can also simply be written as:

The Strength of an Acid Is Specified by Its Dissociation Constant (K) in water.

 In dilute aqueous solutions, concentration of water is constant, therefore we can combine [H2O] with K and
define a new constant called acid-dissociation (acid-ionization) constant, Ka:

K =

[H+ ][ A ̅ ]
K=
[HA]
Acids can be classified according to their relative strengths, that is, their tendencies to transfer a proton to
water. The weak acids are only partially ionized in aqueous solution (K < 1). Many of the so-called
mineral acids, such as HClO4, HNO3, and HCl, are strong acids (K >> 1).
Because acid dissociation constants, like [H+] values, can be cumbersome to work with, they can be
expressed as –log expressions and are conveniently transformed to pK.

The stronger the acid, the smaller its pK and weaker the acid higher its pK.
 Henderson–Hasselbalch Equation Correlates pH and pK
[H+ ][ A ̅ ]
K=
[HA]

Applying negative log on both sides

[HA]
-log [H+ ] = -log K
[A̅ ]
[A ̅ ]
= -log K + log
[HA]

[A ̅ ]
pH = pK + log Henderson–Hasselbalch equation
When [ A ̅ ] = [HA] [HA]

log1 = 0 pH = pK
When the molar concentrations of an acid (HA) and its conjugate base (A−) are equal, log
([A−]/[HA]) = log 1 = 0, then the pH of the solution is numerically equivalent to the pK of the acid.
 LEWIS ACID-BASE CONCEPT

Lewis concept highlights the role of the electron pair donation or acceptance as per this concept;
 An acid is any species that accepts an electron pair to form a bond.
 A base is any species that donates an electron pair to form a bond.
The product of a Lewis acid-base reaction is an adduct, a single species that contains a new
covalent bond;

By definition, then,
 A Lewis base must have a lone pair of electrons to donate.
 A Lewis acid must have a vacant orbital (or the ability to rearrange its bonds to form one) to
accept a lone electron pair and form a new bond.
The Lewis definition, like the Brønsted-Lowry definition, requires that a base have an
electron pair to donate, so it does not expand the classes of bases. However, it greatly
expands the classes of acids. Many species, such as CO2 and Cu2+ that do not contain
H in their formula (and thus cannot be Brønsted-Lowry acids) are Lewis acids.
 ADVANTAGES OF LEWIS ACID-BASE CONCEPT

The Lewis definition has the widest scope and includes the other two concepts also.
The defining event of a Lewis acid-base reaction is the donation and acceptance of an electron
pair to form a new covalent bond in an adduct.
Lewis bases still must have an electron pair to donate, but Lewis acids—the electron-pair
acceptors—include many species not encompassed by the other definitions, including molecules
with electron-deficient atoms or with polar double bonds, metal ions, and even H+ itself.
Many molecules act as Lewis acids. In every case, the atom accepting the electron pair has low
electron density due to either an electron deficiency or a polar multiple bond.
Many biomolecules with central metal ions are Lewis adducts. Most often, O and N atoms of
organic groups donate their lone pairs as the Lewis bases. Molecules with a polar double bond
also function as Lewis acids.
In the Lewis sense, hydration of a metal ion is itself an acid-base reaction, a metal ion acts as a
Lewis acid when it dissolves in water
 BUFFERS

Buffers are aqueous systems that tend to resist changes in pH when small amounts of acid (H+)
or base (OH-) are added.
Since even small changes in pH can dramatically affect the structures and functions of biological
molecules, maintaining a relatively constant pH is therefore of paramount importance for living
systems.
Strong acids and bases completely ionize in water.
Weak acids and bases do not ionize completely in water. They are ubiquitous in biological
systems and play important roles in metabolism and its regulation.
A mixture of a weak acid (or base) and its salt resists changes in pH caused by the addition of H+
or OH-. The mixture thus functions as a buffer.

Addition of acids and bases will adjust the equilibrium so that there is minimum change in pH.
Buffering results from two reversible reaction equilibria occurring in a solution of nearly equal
concentrations of a proton donor and its conjugate proton acceptor.
 Acid-base Titrations are used to Determine the Concentration of a Sample of Acid or Base

• A titrant solution of known concentration is

used.

• The test solution (analyte) is taken in a

conical flask.

• A proper indicator is added to the sample Burette

solution.

• Titrant is added till the indicator dye changes

color.

• Using the initial and final reading on the

burette, the amount of titrant used is
determined.

• The concentration of the test solution is

determined using normality equation
 Titration Curve Of Acetic Acid
Amount of acid present in a solution can be calculated using
titration curves.
A measured volume of the acid is titrated with a solution of a
strong base, usually sodium hydroxide (NaOH), of known
concentration.
The NaOH is added in small increments until the acid is
consumed (neutralized), as determined with an indicator dye or
a pH meter.
At the starting point, the acid form (CH3COOH) predominates.
As strong base (e.g., NaOH) is added, the acid is converted to
-
its conjugate base (CH3COO ) as the free H+ combines with
OH- to form H2O. At the midpoint of the titration, where pH =
pK, the concentrations of the acid and the conjugate base are
equal. At the end point (equivalence point), the conjugate
base predominates, and the total amount of OH− that has been
added is equivalent to the amount of acid that was present at
the starting point. The shaded band indicate the pH ranges
over which the corresponding solution can effectively function
as a buffer.
The concentration of the acid in the original solution can be Titration curve of 0.1M acetic acid with
calculated from the volume and concentration of NaOH added. 0.1M NaOH
Comparison of titration curves for acetic acid, phosphate, and
ammonia.

Different acids/bases have different titration curves and buffering

capacities depending on their ionization constants.

The titration curves shown in the picture have the following

properties;

1. The curves have similar shapes but are shifted vertically along the
pH axis depending on the pk values.
2. The pH at the midpoint of each titration is numerically equivalent to
the pK of its corresponding acid; at this point, [HA] = [A−].
3. The slope of each titration curve is much lower near its midpoint
than near its wings. This indicates that when [HA] ≈ [A−], the pH
of the solution is relatively insensitive to the addition of strong
base or strong acid. Such a solution, which is known as an acid–
base buffer, resists pH changes because small amounts of added
H+ or OH− react with A−or HA, respectively, without greatly
changing the value of log([A−]/[HA]).
 Buffering Mechanism
Buffering results from two reversible reaction equilibria
occurring in a solution of nearly equal concentrations of a
proton donor and its conjugate proton acceptor.
Whenever H+ or OH- is added to a buffer, the result is a
small change in the ratio of the relative concentrations of
the weak acid and its anion and thus a small change in
pH.
The amounts of acid and base in titrations are often
expressed in terms of equivalents, where one equivalent
is the amount of a substance that will react with, or supply,
one mole of hydrogen ions in an acid-base reaction.

The buffering capacity of these weak acids (their ability to resist pH changes on addition of acid or
base) is maximal when pH = pK. It is helpful to remember that a weak acid is in its useful buffer range
within one pH unit of its pK (e.g., the shaded regions of Fig. above). Above this range, where the
ratio [A−]/[HA] > 10, the pH of the solution changes rapidly with added strong base.

At the midpoint of the buffering region, where the concentration of the proton donor (e.g acetic
acid) exactly equals that of the proton acceptor (e.g acetate), the buffering power of the system
is maximal.
 Titration of a Polyprotic Acid.

Substances that can lose more than one proton, or

undergo more than one ionization, such as H3PO4 or
H2CO3, are known as polyprotic acids. The
titration curves of such molecules, as illustrated in
Fig. for H3PO4, are more complicated than the
titration curves of monoprotic acids such as acetic
acid.

A polyprotic acid has multiple pK values, one for

each ionization step. H3PO4, for example, has three
dissociation constants because the ionic charge
resulting from one proton dissociation
electrostatically inhibits further proton dissociation,
thereby increasing the corresponding pK values.
 Significance For Biological Systems

Cells and organisms maintain a specific and constant cytosolic and extracellular pH, usually near pH
7, keeping biomolecules in their optimal ionic state.
Most of the biological processes are pH dependent. pH of the medium in which a biological molecule
exists, determines the structure and function of the molecule in that environment.

Biological fluids, both intracellular and extracellular, are therefore

heavily buffered.
Phosphate buffer system
The phosphate and bicarbonate ions in most biological fluids are
important buffering agents because they have pKs in this range.
The phosphate buffer system, which acts in the cytoplasm of all cells,
consists of H2PO-4 as proton donor and HPO2-4 as proton acceptor’
The phosphate buffer system is maximally effective at a pH
close to its pK of 6.86 and thus tends to resist pH changes
in the range between about 5.9 and 7.9. It is therefore an
effective buffer in biological fluids.
+
 Bicarbonate Buffer System
Blood plasma is buffered in part by the bicarbonate
system, consisting of carbonic acid (H2CO3) as proton
donor and bicarbonate (HCO-3) as proton acceptor

This buffer system is more complex than other conjugate

acid-base pairs because one of its components, carbonic
acid (H2CO3), is formed from dissolved (d) carbon dioxide
and water, in a reversible reaction:

Moreover, many biological molecules, such as proteins

and some lipids, as well as numerous small organic
molecules, bear multiple acid–base groups that are
effective buffer components in the physiological pH range.