Global Extension Systems

Lesson-3

Acid, base, salts: Hydrogen ions, modern

concept of pH and buffer

Content

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Course Name Soil and Water Chemistry
Acid, base, salts: Hydrogen ions, modern concept of pH
Lesson 3
and buffer
Course Revisor Name Dr. Rajdeep Dutta
University/College Name Assam Agricultural University, Jorhat
Course Reviewer Name T V Ramana
University/College Name Sri Venkateswara Veterinary University,Tirupati

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 Soil and Water Chemistry

Lesson 3

Objectives:
To understand the concept of acid, base and salts
To know about the modern concept of pH & buffer

Glossary of terms:
Acid: An acid is a chemical species that donates proton or hydrogen ion
and/or accepts electrons.
Base: A base is a chemical species that donates electrons, accepts protons,
or release hydroxide (OH-) ions in aqueous solution.
Salts: Salts are the compounds obtained by neutralization of acid and base.
Buffer: Buffers are aqueous systems that tend to resist changes in pH when
small amounts of acid (H+) or base (OH-) are added.

pH: pH is defined as negative logarithm of H+ ion concentration.

Neutral: A pH of 7 is referred to as a neutral pH.

Conjugate acid-base pair: A proton donor and its corresponding proton

acceptor make up a conjugate acid-base pair.

Strong Acid: Acids which completely ionised in dilute aqueous solution.

Strong Bases: Bases which completely ionised in dilute aqueous solution.

Dissociation constant: Equilibrium constants for ionization reactions are

usually called ionization or dissociation constants, often designated as Ka.

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E-lecture:
1. Acid: An acid is a chemical species that donates protons or hydrogen
ions and/or accepts electrons. Most acids contain a hydrogen atom
bonded that can release (dissociate) to yield a cation and an anion in water.
The higher the concentration of hydrogen ions produced by an acid, the
higher its acidity and the lower the pH of the solution. The word acid comes
from the Latin words acidus or acere, which mean "sour," since one of the
characteristics of acids in water is a sour taste (e.g., vinegar or lemon juice).
Arrhenius, Brønsted-Lowry, and Lewis Acids
There are different ways of defining acids. A person referring to "an acid"
is usually referring to an Arrhenius or Brønsted-Lowry acid. A Lewis acid is
typically called a "Lewis acid." The reason for the differing definitions is
that these different acids don't include the same set of molecules:

 Arrhenius Acid: By this definition, an acid is a substance that

increases the concentration of hydronium ions (H3O+) when added to
water. We may also consider increasing the concentration of
hydrogen ion (H+) as an alternative.
 Brønsted-Lowry Acid: By this definition, an acid is a material capable
of acting as a proton donor. This is a less restrictive
definition because solvents besides water are not excluded.
Essentially, any compound that can be deprotonated is a Brønsted-
Lowry acid, including typical acids, plus amines, and alcohol. This is
the most widely used definition of an acid.
 Lewis Acid: A Lewis acid is a compound that can accept an electron
pair to form a covalent bond. By this definition, some compounds
that don't contain hydrogen qualify as acids, including aluminium
trichloride and boron trifluoride.

2. Base: In chemistry, a base is a chemical species that donates electrons,

accepts protons, or releases hydroxide (OH-) ions in aqueous solution.
Bases display certain characteristic properties that can be used to help

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identify them. They tend to be slippery to the touch (e.g., soap), can taste
bitter, react with acids to form salts, and catalyze certain reactions. Types
of bases include Arrhenius base, Bronsted-Lowry base, and Lewis base.
Examples of bases include alkali metal hydroxides, alkaline earth metal
hydroxides, and soap. The word "base" came into use in 1717 by French
chemist Louis Lémery. While Lémery may have used the word "base" first,
its modern usage is generally attributed to French chemist Guillaume-
François Rouelle.

3. Hydrogen ion, modern concept of pH:

3.1 Pure Water Is Slightly Ionized: Water molecules have a slight tendency
to undergo reversible ionization to yield a hydrogen ion (a proton) and a
hydroxide ion, giving the equilibrium

𝐇𝟐 𝐎 ⇌ 𝐇+ + 𝐎𝐇−

Although dissociation product of water is generally shown as H+, free

protons do not exist in solution; hydrogen ions formed in water are
immediately hydrated to hydronium ions (H3O+). Hydrogen bonding
between water molecules makes the hydration of dissociating protons
virtually instantaneous:

The ionization of water can be measured by its electrical conductivity;

pure water carries electrical current as H+ migrates toward the cathode and
OH- toward the anode. The movement of hydronium and hydroxide ions in
the electric field is anomalously fast compared with that of other ions such
as Na+, K+, and Cl-. This high ionic mobility results from the kind of “proton
hopping” shown in Fig 1. No individual proton moves very far through the
bulk solution, but a series of proton hops between hydrogen-bonded water
molecules causes the net movement of a proton over a long distance in a

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remarkably short time. As a result of the high ionic mobility of H+ (and of

OH-, which also moves rapidly by proton hopping, but in the opposite
direction), acid-base reactions in aqueous solutions are generally
exceptionally fast.

Fig. 1. Proton hopping. Short “hops” of protons between a series of

hydrogen-bonded water molecules effect an extremely rapid net
movement of a proton over a long distance. As a hydronium ion (upper
left) gives up a proton, a water molecule some distance away (lower
right) acquires one, becoming a hydronium ion. Proton hopping is much
faster than true diffusion and explains the remarkably high ionic mobility
of H+ ions compared with other monovalent cations such as Na+ or K+
(Source: Principles of Biochemistry (2008, W.H.Freeman))

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 Soil and Water Chemistry

Equilibrium constant: The position of equilibrium of any chemical reaction is given by its
equilibrium constant, Keq (sometimes expressed simply as K). For the generalized reaction
A+B ⇌ C+D
An equilibrium constant can be defined in terms of the concentrations of reactants (A and B) and
products (C and D) at equilibrium:

[C][D]
𝐾𝑒𝑞 =
[A][B]

3.2 The Ionization of Water Is Expressed by an Equilibrium Constant: The

degree of ionization of water at equilibrium is small; at 25 °C only about
two of every 109 molecules in pure water are ionized at any instant. The
equilibrium constant for the reversible ionization of water is
[H+ ][OH− ]
K eq =
[H2 O]

In pure water at 250C, the concentration of water is 55.5 M (grams of H2O

in 1 L divided by its gram molecular weight: (1,000 g/L)/ (18.015 g/mol))
and is essentially constant in relation to the very low concentrations of H+
and OH-, namely, 1x10-7M. Accordingly, we can substitute 55.5 M in the
equilibrium constant expression to yield

[H+ ][OH− ]
K eq =
55.5 M
Which on rearranging becomes
(55.5M)K 𝑒𝑞 = [H][OH]= Kw

where Kw designates the product (55.5 M)(Keq), the ion product of water
at 25 °C.

The value for Keq, determined by electrical-conductivity measurements of

pure water, is 1.8 x 10-16 M at 250C. Substituting this value for Keq in the
above gives the value of the ion product of water:
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 Soil and Water Chemistry

Kw = [H+ ][OH− ]= (5.5M) (1.8 x 10-16M)

= 1.0 x 10-14 M2
Thus the product [H+][OH-_] in aqueous solutions at 250C always
equals 1.0 x 10-14 M2. When there are exactly equal concentrations of H+and
OH-, as in pure water, the solution is said to be at neutral pH. At this pH,
the concentration of H+and OH- can be calculated from the ion product of
water as follows:
Kw = [H+ ][OH− ] = [H]2

Solving for [H+] gives

[H+ ] = √K w = √1 x 10−14 M2
[H+ ] = [OH− ] = 10−7
As the ion product of water is constant, whenever [H_] is greater than 1x10-
7
M, [OH_] must become less than 1 x 10-7 M, and vice versa. When [H+] is
very high, as in a solution of hydrochloric acid, [OH-] must be very low.

3.3 The pH Scale Designates the H+ and OH- Concentrations: The ion
product of water, Kw, is the basis for the pH scale (Table 1). It is a
convenient means of designating the concentration of H+ (and thus of OH-
) in any aqueous solution in the range between 1.0 M H+ and 1.0 M OH-.
The term pH is defined by the expression

1
pH = log +
= −log[H+ ]
[H ]

The symbol p denotes “negative logarithm of.” For a precisely neutral

solution at 250C, in which the concentration of hydrogen ions is 1.0 x 10-7
M, the pH can be calculated as follows:

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 Soil and Water Chemistry

1
pH = log = log(1.0 x 107)
1.0 x 10−7

= log 1.0 + log 107

= 0 + 7= 7
The value of 7 for the pH of a precisely neutral solution is not an arbitrarily
chosen figure; it is derived from the absolute value of the ion product of
water at 250C, which by convenient coincidence is a round number.
Solutions having a pH greater than 7 are alkaline or basic; the
concentration of OH- is greater than that of H+. Conversely, solutions
having a pH less than 7 are acidic.
The pH scale is logarithmic, not arithmetic. To say that two solutions differ
in pH by 1 pH unit means that one solution has ten times the H+
concentration of the other, but it does not tell us the absolute magnitude
of the difference. Figure 2 gives the pH of some common aqueous fluids. A
cola drink (pH 3.0) or red wine (pH 3.7) has an H+ concentration
approximately 10,000 times that of blood (pH 7.4).

Table 1 The pH scale

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 Soil and Water Chemistry

Fig.2 The pH of some aqueous fluids (Source: Principles of

Biochemistry (2008, W.H.Freeman))

3.4 Weak Acids and Bases Have Characteristic Dissociation Constants:

Hydrochloric, sulfuric, and nitric acids, commonly called strong acids,
are completely ionized in dilute aqueous solutions; the strong bases NaOH
and KOH are also completely ionized. On the other hand, weak acids and
bases do not completely ionized when dissolved in water.

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 Soil and Water Chemistry

Acids may be defined as proton donors and bases as proton

acceptors. A proton donor and its corresponding proton acceptor make up
a conjugate acid-base pair (Fig. 3). Acetic acid (CH3COOH), a proton donor,
and the acetate anion (CH3COO-), the corresponding proton acceptor,
constitute a conjugate acid-base pair, related by the reversible reaction

CH3 COOH ⇌ H+ + CH3 COO−

Each acid has a characteristic tendency to lose its proton in an aqueous

solution. The stronger the acid, the greater its tendency to lose its proton.
The tendency of any acid (HA) to lose a proton and form its conjugate base
(A-) is defined by the equilibrium constant (Keq) for the reversible reaction
𝐻𝐴 ⇋ 𝐻 + + 𝐴−

Which is

[H+ ][A− ]
K eq = [HA]
=Ka

Equilibrium constants for ionization reactions are usually called ionization

or dissociation constants, often designated Ka. The dissociation constants
of some acids are given in Figure 3. Stronger acids, such as phosphoric and
carbonic acids, have larger dissociation constants;
weaker acids, such as monohydrogen phosphate (HPO42-), have smaller
dissociation constants.

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 Soil and Water Chemistry

Fig.3 Conjugate acid-base pairs consist of a proton donor and a proton

acceptor. Some compounds, such as acetic acid and ammonium ion, are
monoprotic; they can give up only one proton. Others are diprotic (H2CO3
(carbonic acid) and glycine) or triprotic (H3PO4 (phosphoric acid)). The
dissociation reactions for each pair are shown where they occur along a
pH gradient. The equilibrium or dissociation constant (Ka) and its
negative logarithm, the pKa, are shown for each reaction. (Source:
Principles of Biochemistry (2008, W.H.Freeman))

The values of pKa, which is analogous to pH and is defined by the

equation
1
p𝐾a = log = −log𝐾a
𝐾a
The stronger the tendency to dissociate a proton, the stronger is the acid
and the lower its pKa.

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4. Buffer: Buffers are aqueous systems that tend to resist changes in pH

when small amounts of acid (H+) or base (OH-) are added. A buffer system
consists of a weak acid (the proton donor) and its conjugate base (the
proton acceptor).
4.1 An excellent example of a buffer system is a mixture of equal
concentrations of acetic acid and acetate ion, found at the midpoint of the
titration curve can be seen in Figure 4, is a buffer system. The titration
curve of acetic acid has a relatively flat zone extending about 1 pH unit on
either side of its midpoint pH of 4.76. In this zone, an amount of H+ or OH-
added to the system has much less effect on pH than the same amount
added outside the buffer range. This relatively flat zone is the buffering
region of the acetic acid–acetate buffer pair.

Fig. 4 The titration curve of acetic acid. After addition of each increment
of NaOH to the acetic acid solution, the pH of the mixture is measured.
This value is plotted against the amount of NaOH expressed as a fraction
of the total NaOH required to convert all the acetic acid to its
deprotonated form, acetate. The points so obtained yield the titration

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curve. Shown in the boxes are the predominant ionic forms at the points
designated. At the midpoint of the titration, the concentrations of the
proton donor and proton acceptor are equal, and the pH is numerically
equal to the pKa. The shaded zone is the useful region of buffering power,
generally between 10% and 90% titration of the weak acid. (Source:
Principles of Biochemistry (2008, W.H.Freeman)

4.2 Buffering results from two reversible reaction equilibria occurring in a

solution of nearly equal concentrations of a proton donor and its conjugate
proton acceptor. Figure 5 shows how a buffer system works.

Fig.5 The acetic acid–acetate pair as a buffer system. The system is

capable of absorbing either H+ or OH- through the reversibility of the
dissociation of acetic acid. The proton donor, acetic acid (HAc), contains
a reserve of bound H+, which can be released to neutralize an addition of
OH- to the system, forming H2O. This happens because the product
[H+][OH-] transiently exceeds Kw (1x10-14 M2). The equilibrium quickly
adjusts so that this product equals 1x10-14 M2 (at 250C), thus transiently
reducing the concentration of H+. But now the quotient [H+][Ac-] / [HAc]
is less than Ka, so HAc dissociates further to restore equilibrium.

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 Soil and Water Chemistry

Similarly, the conjugate base, Ac-, can react with H+ ions added to the
system; again, the two ionization reactions simultaneously come to
equilibrium. Thus, a conjugate acid-base pair, such as acetic acid and
acetate ion, tends to resist a change in pH when small amounts of acid or
base are added. Buffering action is simply the consequence of two
reversible reactions taking place simultaneously and reaching their
points of equilibrium as governed by their equilibrium constants, KW and
Ka. (Source: Principles of Biochemistry (2008, W.H.Freeman))

4.3 Suggested reading: Henderson-Hasselbalch equation.

5. Salts: Salts are the compounds obtained by neutralization of acid and
base. These are composed of charged atoms or groups of atoms held
together in a crystal lettuce. When these salts are dissolved in a solvent of
high dielectric constant such as water or heated to melting point, the
crystal forces are weakened and the substances dissociate into the pre-
existing charged particles or ions. The resultant solutions are very good
conductors of electricity.
Example:
i. NaCl + H2O Na+ +Cl-
ii. KCl + H2O K+ + Cl-
5.1 Hydrolysis of salt: When salts dissolved in water, the resulting solution
will be neutral, acidic and alkaline solution depending on the nature of
salts.
Hydrolysis is the interaction between the ions of a salt and the ions of
water with the production of
i. Strong acids and strong bases-Sodium chloride
ii. Weak acids and strong bases
iii. Strong acid and weak bases
iv. Weak acid and weak base

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5.2 Classes of salts:

Class 1 Salt
• Strong acid and strong bases solution remain neutral
• H2O H+ + OH- (Equilibrium between H+ and OH- ions
in water)
• In the strong electrolytes of both acid and base neither anions have
tendency to combine with neither hydrogen ions nor the cat ions
with hydroxyl ions of water
Class 2 Salts
• The salt will completely dissociated in water
Eg. MA M+ + A-
• A salt ‘MA’ derived from a weak acid (HA) and a strong base (BOH).
• The equilibrium reaction can be written as A- + H2O OH- + HA

Class 3 Salts
• The initial high concentration of cat ions (M+) will be reduced by
combining with the hydroxide ions of water to from a little
dissociated base MOH until establishing equilibrium state
Eg. M+ + OH- MOH
Class 4 salts:
• In which both acid and base are weak. Two reactions will occur
simultaneously
Eg. i. M+ + H2O MOH + H+
ii.A- + H2O HA+OH-
--------------------------------------------------
M+ + A- + H2O MOH + HA
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5.3 Hydrolysis constant (Kh) of a salt: Hydrolysis constant of a salt can be

expressed as:
(OH-) x (HA)
Kh = --------------------------------------- or
(A-)

(Base) x (Acid)
Kh = --------------------------------------
Un hydrolyzed salt
5.4 Degree of hydrolysis: It is the fraction of each molecule of hydrolyzed
salt at equilibrium. The degree of hydrolysis is largely influenced by
 Changes in temperature
 Conc. of reactants.

Law of Mass action or Law of chemical equilibrium: It is the velocity of a chemical reaction which
is proportional to the product of the active masses of the reacting substances.

Hypothetical chemical reaction: A + B C+D

• The velocity with which A x D react is proportional to their
concentrations.
(C) x (D) K1
---------- = ---- = K
(A) x (B) K2
Where K is a equilibrium constant, K1 x K2 velocity coefficients

5.5 Types of Salts: 1. Simple salts ,2. Double salts,3. Complex salts, 4. Mixed
salts
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1. Simple salts
• Salts produced by Acid – base neutralization are called simple salts
i. Normal salt:
• Salts formed by the loss of all replaceable hydrogen (H+) are called
normal salts
Eg. i. Sodium hydroxide ii. Sodium nitrate iii. Sodium chloride
etc

ii. Acid salt:

• Salts formed by incomplete neutralization of acids. These salts still
contain replaceable hydrogen (H+).
Eg : i. NaHCO3 (Sodium bicarbonate)
ii. NaHSO4 ( Sodium bi-sulphate)
iii. Basic Salts:
Salts formed by incomplete neutralization of acid, polyacidic bases.
Salts still contained in one or more hydroxyl groups (OH-).
2. Double Salts: Eg : Potash, Aluminum
3. Complex Salts: Eg. K4Fe (CN)6
4. Mixed Salts
Eg: i) Bleaching powder Ca(ClO)2
ii. Rochell salt – Sodium potassium tartrate

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(NECESSARY PERMISSION MAY BE TAKEN BY THE AUTHORITY FOR

COPYING AND INCORPORATING THE FIGURES)

References:
Helmenstine, Anne Marie, Ph.D. "Base Definition in Chemistry."
ThoughtCo, Aug. 27, 2020, thoughtco.com/definition-of-base-604382
Helmenstine, Anne Marie, Ph.D. "Acid Definition and Examples."
ThoughtCo, Aug. 29, 2020, thoughtco.com/definition-of-acid-and-
examples-604358.
Lehninger, A., Nelson, D.L., Cox, M.M. (2005) Principles of
Biochemistry, 4th Ed, W.H.Freeman, USA

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