V.N.

Karazin Kharkov National University

Medical Chemistry
Module 1. Lecture 4

Acids and bases.

pH scale. Buffer solutions.
Hydrolysis of salts
Natalya VODOLAZKAYA
[email protected]
21 December 2020 Department of Physical Chemistry
 Lecture topics
√ Acids and bases
√ Neutralization: Bases are Antacids
√ Acidity of solutions
√ Chemistry in action: antacids and the pH balance in your
stomach
√ The action of aspirin
√ Acid-base indicators
√ Hydrolysis of salts
√ Buffer solutions

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 H+
Acids and bases
Citrus fruit contains both citric acid and ascorbic acid

√ Acids and bases have been defined in a number of different ways.

In the simplest form an acid can be described as a substance that yields
hydrogen ions (H+) when dissolved in water:

and a base can be described as a substance that yields hydroxide ions (OH–)
when dissolved in water:

Bases generally taste bitter; when dissolved in water, bases have a slippery,
soapy feel.

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 Acids and bases
√ The "strength" of an acid is a measure of its tendency to lose a proton
(H+) , and the "strength" of a base is similarly a measure of its tendency
to take up a proton.

√ Acids commonly used in the laboratory practice are: hydrochloric acid

(HCl), nitric acid (HNO3), acetic acid (CH3COOH), sulfuric acid (H2SO4),
and phosphoric acid (H3PO4). The first three acids are monoprotic.
Sulfuric acid is a diprotic acid. CH3COOH is a weak acid.

√ The most commonly used strong bases in the laboratory are: sodium
hydroxide (NaOH), potassium hydroxide (KOH) and barium hydroxide
(Ba(OH)2).

√ NaOH and KOH are monobasic bases, Ba(OH)2 is dibasic. The most
commonly used weak base is aqueous ammonia solution (NH4OH).

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 Neutralization: Bases are Antacids
If equal volumes of solutions of equal concentration are mixed, the
products are sodium chloride and water. This is an example of
neutralization, a chemical reaction in which the hydrogen ions from an
acid combine with the hydroxide ions from a base to form water
molecules.

The formation of water can be represented like this.

Not only will this happen in test tubes in the laboratory,

but also in your home and in almost every ecological niche
of our planet. For example, if you put lemon juice on fish,
you run an acid–base reaction. The acids found in lemons
neutralize the ammonia-like compounds that produce the
“fishy smell.” 5
 Acidity of solutions
Quantitative representation of acidity of solutions, i.e. the content
of hydrogen ions (H+) in solution, is the рН value that equals to the
negative decimal logarithm of activity of hydrogen ions :
pH = − log aH + = − log(cH + ⋅ γ ± )
In a dilute solution activities are close to concentrations (γ± ≈ 1),
so it is possible to set the рН value of solution equals to analytical
concentration of hydrogen ion:
pH ≈ − log cH +
In liquid water solution autoionization process takes place:
H 2 O R H + + OH − , K
It can be characterized by equilibrium constant, K:
aH + ⋅ aOH −
K=
aH 2O
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 Acidity of solutions
The degree of water dissociation is very small, so the a(H2O)
value is constant and equation can be represented as follows:
aH+ ⋅ aOH − = K ⋅ aH 2O = K w
Constant Kw is known as ionic product of water. At 25 °C the Kw
value is equal to 1.008⋅10–14. Usually this constant (Kw) is
represented as the negative decimal logarithm:
pK w = − log K w pK w = 14 at 25 °C.
At 25°C if the contents of hydrogen and hydroxyl ions in a solution
are equal, aH+ = aOH− , then рН = pOH = 7, such media is called neutral.
In acidic solutions aH+ > aOH− , in alkaline media aH+ < aOH− .

pOH = –log[OH–] and pOH + pH = pKw = 14

The pH and pOH values of diluted solutions are in range 0–14.

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 Acidity of solutions

Figure. The relationship between pH and the concentration

of H+. As pH increases, [H+] decreases

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 Acidity of solutions

Figure. Common substances and their pH values

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 CHEMISTRY in Action
Antacids and the pH Balance in
Stomach
An average adult produces between
2 and 3 liter of gastric juice daily.
Gastric juice is a thin, acidic digestive
fluid secreted by glands in the mucous
membrane that lines the stomach. It
contains, among other substances,
hydrochloric acid (HCl). The pH of
gastric juice is about 1.5, which
corresponds to a hydrochloric acid
concentration of 0.03 M – a
concentration strong enough to Figure. A simplified diagram of
the human stomach
dissolve zinc metal!!!
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 Antacids and the pH Balance in
Stomach
The inside lining is made up of parietal cells, which are fused
together to form tight junctions.
The interiors of the cells are protected from the surroundings by
cell membranes. These membranes allow water and neutral
molecules to pass in and out of the stomach, but they usually
block the movement of ions such as H+, Na+, K+, and Cl–.
The H+ ions come from carbonic acid (H2CO3) formed as a
result of the hydration of CO2, an end product of metabolism:

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 Antacids and the pH Balance in
Stomach
The purpose of the highly acidic medium within the stomach is to digest
food and to activate certain digestive enzymes. Eating stimulates H+ ion
secretion. A small fraction of these ions normally are reabsorbed by the
mucosa.
About half a million cells are shed by the lining every minute, and a healthy
stomach is completely relined every three days or so.
However, if the acid content is excessively high, the constant influx of H+
ions through the membrane back to the blood plasma can cause muscle
contraction, pain, swelling, inflammation, and bleeding.

One way to temporarily reduce the H+ ion concentration in the stomach is

to take an antacid.

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 Antacids and the pH Balance in
Stomach
The major function of antacids is to neutralize excess HCl in gastric juice. The
reactions by which antacids neutralize stomach acid are as follows:

The CO2 released by most of these reactions increases gas pressure in the
stomach, causing the person to belch.
The fizzing that takes place when an Alka-Seltzer tablet dissolves in water is
caused by carbon dioxide, which is released by the reaction between citric acid and
sodium bicarbonate:

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 The Action of Aspirin
The mucosa of the stomach is also damaged by the action of
aspirin, the chemical name of which is acetylsalicylic acid. Aspirin is itself a
moderately weak acid:

In the presence of the high concentration of H+ ions in the stomach,

this acid remains largely nonionized.
A relatively nonpolar molecule, acetylsalicylic acid has the ability to
penetrate membrane barriers that are also made up of nonpolar
molecules.
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 The Action of Aspirin
However, inside the membrane are many small water pockets, and
when an acetylsalicylic acid molecule enters such a pocket, it ionizes into
H+ and acetylsalicylate ions. These ionic species become trapped in the
interior regions of the membrane. The continued buildup of ions in this
fashion weakens the structure of the membrane and eventually causes
bleeding. Approximately 2 mL of blood are usually lost for every aspirin
tablet taken, an amount not generally considered harmful.
However, the action of aspirin can result in severe bleeding in some
individuals.
It is interesting to note that the presence of alcohol makes
acetylsalicylic acid even more soluble in the membrane, and so further
promotes the bleeding.

15
 Acid-base indicators
An acid-base indicator (we will write as HIn) is a substance which
varies color of the solution according to the hydrogen ion concentration
of its environment.
Indicator, HIn, and its conjugate base, In–, must have distinctly
different colors. In solution, the acid ionizes to a small extent:

Color of the solution of the indicator is determined by the ratio of the

concentrations of the colored forms:

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 Acid-base indicators
It is thus possible to determine the pH value of a solution by observing
the color of a suitable indicator when it is placed in that solution.
In the simplest case of existing of two forms of indicator it is possible to
approximate the actual state of equilibrium between the forms (HIn ( ↔ H+ +
In–) using dissociation constant, K:

[H + ][In − ] [In − ]
K= , pH = pK + log
[HIn] [HIn]

If the pK value of indicator is known, and the ratio of In– and HIn of
the indicator in the given solution is measured, the pH of the solution can
be evaluated.
Indicators can be utilized for determination of the pH of the
solution in the range of the pH values in: pH = pK ± 1
This interval of the pH values is called the transition or useful
range of the indicator.
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 Acid-base indicators
Many acid-base indicators are plant pigments. For example, by boiling
chopped red cabbage in water we can extract pigments that exhibit many
different colors at various pHs (Figure).

Figure. Solutions containing extracts of red cabbage (obtained by boiling

the cabbage in water) produce different colors when treated with an acid
and a base. The pH of the solutions increases from left to right
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 Acid-base indicators
Table. Colors and useful ranges for some pH indicators

Determination of the pH using indicators

Due to the ability of indicators to change a color with pH of solution
they are employed for determination of the acidity of solutions.
Universal indicator is a mixture of several indicators displaying a
variety of colors over a wide pH range. Usually it is used as a test paper
that changes color in accordance with the solution pH value.

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 Acid-base indicators
Test papers of universal indicator are used only for an
approximate pH of the solution. For precise determination of
the pH value, colorimetric or potentiometric methods are
used.

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 Hydrolysis of salts
The term salt hydrolysis describes the reaction of an anion or a
cation of a salt, or both, with water. Salt hydrolysis usually affects the pH
of a solution.
(1) The salts composed of an alkali or alkaline earth metal ion and the
residue of a strong acid do not undergo hydrolysis and their solutions are
assumed to be neutral.
(2) Another situation is observed when dissolved salt is formed by a
weak acid or (and) a weak base.
For example, the dissociation of sodium acetate, that is strong
electrolyte, in water proceeds according to equation: CH3COONa →
Na+(aq) + CH3COO– (aq).
The sodium ion does not react with water. The acetate ion CH3COO–
has an affinity for H+ ions. The hydrolysis reaction of this anion is given
by equation: CH3COO– (aq) + H2O ↔ CH3COOH (aq) + OH– (aq). Due to
formation of OH– ions in this reaction the solution of sodium acetate will
be basic.
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 Hydrolysis of salts
The equilibrium constant for the hydrolysis reaction of CH3COONa is
determined by dissociation constant of acetic acid and ionic product of
water: −
[CH3COOH] ⋅ [HO ] Kw
Kh = =
[CH3COO − ] K acid
(3) When a salt derived from a strong acid and a weak base dissolves
in water, the solution becomes acidic.
For example, in solution of NH4Cl the dissociation process gives NH4+
and Cl– ions: NH4Cl → NH4+ (aq) + Cl– (aq).
The ammonium ion NH4+ is the conjugate acid of the weak base
NH3 and reacts with water molecule: NH4+ (aq) + H2O ↔ NH3 (aq) +
H3O+ (aq).
Because this reaction produces H3O+ ions, the pH of the solution
decreases. The equilibrium constant (hydrolysis constant) for this
process is given by equation:
[NH3 ] ⋅ [H3O + ] Kw
Kh = =
[NH 4+ ] Kbase 22
 Hydrolysis of salts
(4) For salts formed by a weak acid and a weak base, both the cation
and the anion hydrolyze. The hydrolysis constant in this case is
determined by both dissociation constants of the acid and the base:

Kw
Kh =
K acid ⋅ Kbase

If Kbase > Kacid then the solution must be basic because the anion
will hydrolyze to a greater extent than the cation. At equilibrium, there will
be more OH– ions than H+ ions.
If Kbase for the anion is smaller than Kacid for the cation, the solution
will be acidic because cation hydrolysis will be more extensive than anion
hydrolysis.
If Kbase is approximately equal to Kacid, the solution will be nearly
neutral.

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 Buffer solutions
Buffer solutions are solutions with ability to keep constant the рН
value at (1) dilution or (2) addition of small amounts of a strong acid or a
strong base.
Usually buffer solution consists of a weak acid (weak base) and salt
of this acid (base) which is strong electrolyte, e.g. CH3COOH +
CH3COONa – acetate buffer; NH4OH + NH4Cl – ammonia buffer, etc.
In general form it is possible to say, that the buffer solution consists
from conjugated acid and base.
The pH value of a buffer solution may be calculated using quantities
of the components forming it, for example, for acid buffer:
o
cHA
pH = pK − log o
cMeA
pK – negative decimal logarithm of the acid dissociation constant; co –
initial concentrations of the acid and its salt in the solution. This equation
is known as Henderson-Hasselbach equation.
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 Buffer solutions
Ability of buffer solutions to keep the рН value (see Figure) at
addition of a strong acid or a base is called buffer action.

Figure. A comparison of the

change in pH when 0.1 mol HCl is
added to pure water and to an
acetate buffer solution

As a measure of buffer action the buffer capacity is used.

Buffer capacity is an added amount of a strong acid or a
strong base, which addition to one liter of a buffer solution
changes the рН value to unity.
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 Buffer solutions in the organism
The pH of the blood plasma is maintained at about 7.40 by
several buffer systems but the most important is the bicarbonic buffer
system. This pH value is dependent upon two coupled reactions.
First, the equilibrium of gaseous carbon dioxide dissolved in the
blood and water producing the carbonic acid:
CO2(aq) + H2O ↔ H2CO3(aq).
The amount of carbon dioxide in the blood is coupled to the
amount present in the lungs.
Second, the equilibrium between carbonic acid and
bicarbonate ion:
H2CO3 (aq) ↔ HCO3− (aq) + H+ (aq), pK = 6.37.
These reactions lead to the presence in solution the conjugate
pair HCO3−/H2CO3 that forms the buffer system. The fact that the pH
of normal blood is 7.40 implies that [HCO3−]/[H2CO3] = 20. The
excess of an acid in the blood is fixed by interaction with
hydrocarbonate ion, the excess of a base – by interaction with
carbonic acid.
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Buffer solutions in the organism
Hydrophosphate buffer system is formed by hydrophosphate
and dihydrophosphate ions.
There is an protolytic equilibrium between these two ions:

H2PO4− ↔ H+ + HPO42−, pK = 7.21.

If рН value of the blood is 7.40, the ratio of the concentrations

of the ions [HPO42−]/[H2PO4−] is 1.55 : 1.

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 Buffer solutions
In the erythrocytes the pH is 7.25, the principal buffer systems are
bicarbonate HCO3−/H2CO3 and hemoglobin systems.
As a very rough approximation, we can treat it as a weak
monoprotic acid of the form HHb that dissociates in solution:

HHb(aq) ↔ H+(aq) + Hb–(aq),

HHb represents the hemoglobin molecule and Hb– the conjugate

base of HHb. Oxyhemoglobin (HHbO2), formed by the combination of
oxygen with hemoglobin, is a stronger acid than HHb:

HHbO2(aq) ↔ H+(aq) + HbO2– (aq).

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 References
1. Chang R. Chemistry. 10-th edition. NY: McGraw-Hill, 2010.
1170 p.
2. Chang R. General Chemistry: The Essential Concepts. 6-th
edition. NY: McGraw-Hill, 2011. 853 p.
3. Allen J.P. Biophysical Chemistry. Blackwell Publishing, 2008.
492 p.
4. Atkins P., de Paola J. Physical Chemistry for the Life
Sciences. W.H.Freeman Publishers, 2006. 624 p.
5. S. V. Eltsov, N. A. Vodolazkaya. Practical Medical Chemistry:
manual / Kh.: V. N. Karazin Kharkiv National University, 2018.
196 p.

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