V.N.

Karazin Kharkov National University

Medical Chemistry
Module 1. Lecture 3

Solutions. Electrolytic
dissociation
Natalya VODOLAZKAYA
[email protected]
14 December 2020 Department of Physical Chemistry
 Lecture topics
√ General properties of aqueous solutions
√ Expression of the solution composition (Solute
concentration in solution)
√ Сonvertation of the solution concentrations
√ Electrolyte solutions
√ Electrolyte power
√ Dissociation constant
√ Solubility
√ Effect of pressure on solubility of gases

2
 General Properties of Aqueous
Solutions
A solution is a homogeneous mixture of two or more
substances.
The solute is the substance present in a smaller amount, and
the solvent is the substance present in a larger amount.
A solution may be gaseous (such as air), solid (such as an alloy,
e.g. steel), or liquid (seawater, for example).

For medical purposes the most important are liquid solutions, in

particularly the aqueous solution, in which the solute initially is a
liquid or a solid and the solvent is water.

3
Drinking water or tap water is never pure (distilled) water. It
always contains other substances (the dissolved minerals and
the solutes) (Table).

Table

Table
 Our bodies are over 60% composed of water and all the
chemical reactions of the body depend upon it.

A child’s body is about 75% water,

and adult bodies are approximately 50–
65% water.
A human brain is 75% water, blood is
83% water, and lungs are approximately
90% water. Even our bones are 22%
water.

Our bodies can go days without

water. If the water in our bodies is
reduced by just 1%, thirst will develop.
When the loss reaches 5%, muscle
strength declines. At a 10% loss,
delirium and blurred vision occur, and a
20% reduction results in death.

5
 Water is a unique compound of hydrogen and oxygen held
together by polar covalent bonds (in which the electrons are not
equally shared, but rather displaced toward the more electronegative
atom).

Figure. Polar covalent bond between

hydrogen and oxygen atoms. The electrons
are displaced toward the more electronegative
oxygen atom

Figure. (a) H2O, a polar

covalent molecule with
polar covalent bonds.
(b) The charge-density
drawing shows the partial
positive and negative
charges in a water
molecule.
6
Between the water molecules there is also an attraction of the hydrogen
and the oxygen atoms. This is caused by residual small opposite charges
on the H and O atoms. The attraction between these two slightly charged
atoms causes a weak bonding between these atoms. It is usually shown
as a dotted line between the atoms. This is called ‘hydrogen bonding’.

Hydrogen bonds are electrostatic attractions between a hydrogen atom

bearing a partial positive charge in one molecule and an O, N, or F atom bearing
a partial negative charge in a neighboring molecule.

It is sufficiently strong
to join up three or four
water molecules together
to form liquid water.
 Chemical reactions in aqueous
solution
The majority of chemical reactions inside the laboratory and
also in cells occur in aqueous solutions (water is the solvent).
There are ions in aqueous solutions which are crucial for
chemical reactions in cells. For example, the sodium (Na+) and
potassium (K+) ions in solution are vital for the passage of
messages from one cell to another.
The building of cell proteins (polyamides or polypeptides)
from small units of amino acids occurs in aqueous solution.

8
 Dissolving and solubility: water is a great solvent
When a solute dissolves in a solvent then a true solution is made.
There is a complete mixing of solute in a solvent.
Generally ionic solvents will dissolve materials of similar nature,
i.e. ionic solids. Similarly, covalent solvents will dissolve covalent
organic compounds. ‘Like dissolves like’ is a useful
generalization.
Water is a slightly ionic compound and dissolves metallic salts, e.g.
NaCl, and other ionic compounds.

Figure. Dissolving sodium

chloride (NaCl) in water:

9
 Some groups in organic compounds, are water-loving, ‘hydrophilic
groups’ and help the compounds to be soluble. These are groups like OH,
COOH and SO3Na groups. When wanting to synthesize a water-soluble
drug, these groups are usually introduced.

Cell materials are either water-soluble or water-insoluble. The smaller

building blocks of cells like amino acids and glucose are water-soluble,
but the large molecules they eventually synthesize, like proteins, cell
walls, fats and long-chain carbohydrates are water-insoluble.

Examination of sucrose structure shows that the sucrose molecule

contains eight –OH groups and three additional oxygen atoms that can
participate in hydrogen bonding. These help explain the high solubility of
sugar in water.
Sucrose
 The solubility of any material in a given amount of water is a
characteristic physical property of the material and is dependent
upon the solvent used and the temperature.
The higher the temperature the more a solid dissolves in the
solvent. On cooling, the excess solid comes back out of solution,
usually in crystalline form, leaving the solution still saturated at that
particular temperature.
Because solubility depends upon the temperature of the solvent,
it is usually referenced to room temperature or 25 °C.
The solubility of gases in water is dependent upon temperature
and atmospheric pressure (see below).

Solvents used to dry-clean clothes are usually chlorinated

compounds such as tetrachloroethylene, Cl2C=CCl2, also known
as ’perc’ (perchloroethylene). Perc is a human carcinogen, a
compound capable of causing cancer.

11
 Expression of the solution composition
(Solute concentration in solution)
Concentration is the ratio of amount of solute to amount of solution, e.g.,
1 teaspoon per 1 cup per.
Solute concentrations in aqueous solutions are expressed in different
units, e.g., ways of expressing concentration: percent; parts per million; parts
per billion; molarity, etc.

√ It is common to measure the

concentration of a solution in moles per
liter. This is molarity or molar
concentration. It’s unit is mol/l or M. This
value shows the number of a solute
moles in 1 liter of a solution:
c = n/V = m/MV, where m is mass of
solute; M is molar mass of solute, g/mol;
V is solution volume.

Figure. Preparing a 1.00 M NaCl solution 12

 Expression of the solution composition
√ The molality is another value for the expressing composition of the
solutions. It is the number of moles of solute dissolved in 1 kg (1000 g)
of a solvent. The unit of molality is mol/kg. Molality is independent of
temperature.
1000 ⋅ msolute
m=
M solute ⋅ msolvent

√ The percent by mass (also called percent by weight or weight percent) is

the ratio of the mass of a solution component (solute or solvent) to the
mass of the solution, multiplied by 100 percent:
msubstance
ω= × 100%
msolution

Where m(solution) = m(solvent) + m(substance).

Percent by mass is similar to molality in that it is independent of
temperature.
 Expression of the solution composition
√ Concentrations of dissolved substances in drinking water are
normally far lower than 1%, so they are often described in terms of parts
per million (ppm, 1 part per million).
A 1-ppm solution of calcium ion in drinking water contains 1 g of
calcium ion in 1 million (1 000 000 or 106) g of that sample. The same
concentration, 1 ppm, could be applied to a solution with 2 g of calcium
ion in 2×106 g of water.
Also 1 ppm of any substance in water equals 1 mg of that substance
per 1 liter of water.

√ Some pollutants are of concern at concentrations much lower than

parts per million and are reported as parts per billion (ppb, 1 part per
billion). One part per billion of mercury (Hg) in water means 1 g Hg in 1
billion (1×109) g of water. This means 1 microgram (1×10−6 g, or 1 μg) Hg
in 1 liter of water. For example, the acceptable limit for mercury in drinking
water is 2 ppb.

14
 Expression of the solution composition

√ The mole fraction of a component of a solution (solute or

solvent) is defined as the ratio of the quantity of the component
to the quantity of the substance in solution:
ncomponent
x=
nsolution

The mole fraction and the percent by mass are unitless values, because
they equal to the ratio of two similar quantities.
Сonvertation of the solution concentrations
Sometimes it is desirable to convert one concentration unit of a solution
to another. The convertation of values of solution concentration may be
easily done if the molar masses of the components and solution density are
known.

16
Сonvertation of the solution concentrations

17
 Electrolyte Solutions
All solutes that dissolve in water can be divided in two categories: electrolytes
and nonelectrolytes.
An electrolyte is a substance that, when dissolved in water, results in a solution
that can conduct electricity (a).
A nonelectrolyte solution does not conduct electricity (b).

a b What makes salt in solution behave any

differently from sugar in solution? Aqueous
NaCl solutions conduct electricity suggests
they contain some charged species (Na+
and Cl–) capable of moving electrons
through the solution.
No such separation occurs with
covalently bonded sugar molecule, making
these liquids unable to carry electric charge.
Salt (NaCl) Sugar dissolved
dissolved in water in water
(conducting) (nonconducting)
18
 Electrolyte Solutions
For the explanation of this and some other properties of
solutions Swedish scientist S. Arrhenius proposed (1887) the
electrolytic dissociation theory.
According to this theory molecules of acids (HCl), bases
(NaOH) or salts (NaCl) undergo dissociation into ions (cations
and anions) on dissolution in water.

When an ionic compound such as

sodium chloride (NaCl) dissolves in
water, the three-dimensional network
of ions in the solid is destroyed
(Figure).

Figure. The arrangement of

Na+ and Cl– ions in a
crystal of sodium chloride
 Electrolyte Solutions
The Na+ and Cl- ions are separated from each other and undergo
hydration, the process in which an ion is surrounded by water molecules.
Each Na+ ion is surrounded by a number of water molecules orienting
their negative poles toward the cation. Similarly, each Cl- ion is surrounded
by water molecules with their positive poles oriented toward the anion
(Figure).
Hydration helps to stabilize ions in solution and prevents cations from
combining with anions.

Figure. Hydration of Na+ and Cl- ions 20

 Electrolyte Solutions
Depending on the nature of dissociated compound one molecule of
electrolyte may give different number of ions:
binary electrolyte gives two ions, for example, NaCl, CuSO4;
ternary electrolyte gives three ions, for instance, Na2SO4, BaCl2;
quaternary electrolyte gives four ions, e.g., NaH2PO4, AlCl3.

It was found that sometimes only a part of dissolved molecules

undergo dissociation, e.g.:

CH3COOH ↔ CH3COO- + H+

21
 Electrolyte Solutions
Fraction of the solute molecules which is dissociated into ions
called the degree of dissociation (α). It equals the number of
dissociated molecules (N) divided by the total number (N0) of
dissolved molecules in solution:

α = N / No

Compounds that completely dissociate is characterized by

α>30% and is called strong electrolytes.
If the degree of dissociation is α<3% than electrolyte is
called weak electrolyte.
Electrolyte characterized by 3<α<30% is medium
electrolyte.
Electrolyte Power

23
 Electrolyte Power
Degree of dissociation (α) depends on electrolyte
concentration and usually decreases with increase in
concentration.

In a solution of any electrolyte there is an equilibrium

between the free ions (cations and anions), on the one hand,
and undissociated molecules (CatAn), on the other hand, one
may write this equilibrium in the form:
CatAn ↔ Cat+ + An-

24
 Dissociation constant
Mass action law for the equilibrium dissociation process gives:

[Cat + ][An − ]
K=
[CatAn]
where [...] – denotes equilibrium concentration of a particle, K –
equilibrium constant, called the dissociation constant.

It may be shown that for a weak binary electrolyte, e.g. acetic acid
(CH3COOH), dissociation constant and degree of dissociation (α)
interconnected by the expression:
α 2c
K=
1− α
This equation is known as Ostwald's dilution law, it is applicable for
weak 1-1 electrolytes only.
25
 Solubility
√ The solubility of the solute is the maximum amount of solute that may dissolve in
a given quantity of solvent at a given temperature.
√ The solution that contains the maximum amount of a solute that may dissolve in
a given quantity of a solvent is called the saturated solution. An unsaturated
solution contains less solute than it may dissolve.
√ For most substances, temperature affects solubility. The solubility of a solid
substance increases with temperature.
√ Vitamins often are classified on the basis of solubilities; they either are lipid-
soluble or water-soluble. For example, the structural formula of vitamin A
contains carbon and hydrogen atoms almost exclusively. Thus, it is similar to
the hydrocarbons derived from petroleum. Vitamins that are not lipid-soluble
are soluble in water because these polar molecules contain several –OH
groups that form hydrogen bonds with water molecules. Vitamin C is a case in
point.

26
 Solubility
The solubility of gases in water usually decreases with
increasing temperature. Figure shows the temperature
dependence of the solubility of O2 in water at constant pressure of
the gas over the solution (1 atm).

27
 Effect of pressure on solubility
External pressure has no influence on the solubilities of liquids
and solids, but it does greatly affect the solubility of gases.
The quantitative relationship between gas solubility and
pressure is given by Henry’s law, which states that the solubility of
a gas in a liquid is proportional to the pressure of the gas over the
solution:
c = KH p
c is the molar concentration of the gas dissolved; p is the pressure of the
gas over the solution at equilibrium; KH is Henry’s constant for a given gas,
that depends only on temperature.
The units of the constant depend on the units of the pressure,
when p expressed in atm is measured in mol/L·Pa–1. Most gases
obey Henry’s law, but there are some important exceptions.

28
 For example, if the dissolved gas reacts with water, higher
solubilities can result. The solubility of ammonia (NH3) is much
higher than expected because of the reaction:

NH3 + H2O → NH3·H2O↔ NH4+ + OH–.

Carbon dioxide (CO2) also reacts with water, as follows:

CO2 + H2O ↔ H2CO3

Normally, oxygen gas is only sparingly soluble in water.
However, its solubility in blood is dramatically greater because of
the high content of hemoglobin (Hb) molecules. Each hemoglobin
molecule can bind up to four oxygen molecules, which are eventually
delivered to the tissues for use in metabolism:
Hb + 4O2 ↔ Hb(O2)4
This leads to the high solubility of molecular oxygen in blood.
29
 References
¾ Chang R. Chemistry. 10-th edition. NY: McGraw-Hill,
2010. 1170 p.
¾ Chang R. General Chemistry: The Essential Concepts. 6-
th edition. NY: McGraw-Hill, 2011. 853 p.
¾ Chemistry in context : applying chemistry to society – 6th
ed. / Lucy Pryde Eubanks ... [et al.]. NY: McGraw-Hill,
2009. 569 p.
¾ S. V. Eltsov, N. A. Vodolazkaya. Practical Medical
Chemistry: manual / Kh.: V. N. Karazin Kharkiv National
University, 2018. 196 p.

30