Modern ideas about solutions

Solutions play an important role both at animate and at inanimate nature.

Complex physicochemical processes of human body and other living organisms
proceed in solutions.
Water is the most important substance being in composition of solutions
(biological liquids), which are part of the human body. There are about 80% of
water in the body of a newborn child, and there are 60% in the adult men, and 55%
in the women.
Water performs important functions in living organism. Ability of
dissociation that causes the acid-base properties of water solutions is of great
importance. Ability of water to radiolysis and photolysis defines presence in cells
of free oxygen radicals forming prooxidant and antioxidant systems. Eventually,
the structured character of water allows some authors to put in a hypothetical order
questions about the information role of water in living systems and about presence
of structural memory at water solutions.

Solution is a homogeneous system consisting of two

and more components and products of their
possible interaction, which ratio can change.

Solutions may be classified according various signs, for example:

 An aggregate state (liquid solutions, solid solutions, gaseous solutions).
 Solvent nature (water solutions, alcoholic solutions, benzene solutions,
etc.)
 Type of substance in a solution (solutions of electrolytes, solutions of non-
electrolytes).
 Concentration of the dissolved substance (diluted and concentrated
solutions).
 Solution saturation by the dissolved substance (saturated solutions,
unsaturated solutions and supersaturated solutions).
Except cases when substance dissolution is accompanied by chemical reaction,
processes of dissolution more often represent joining of solvent molecules to
molecules or ions of dissolved substances. Such process is named solvation.
Process of joining water molecules is called hydration, and products of such
interaction are named hydrates. The number of water molecules joined to an ion of
dissolved substance depends on radius of this ion and also on structure of its atom.
The ion having a small radius, for example, ion H+ or Li+, may be surrounded by a
small number of solvent molecules closely located around it. Ions with a dib radius
(for example NH4+, K+) may attach to themselves considerable number of solvent
molecules.
There is a general rule about substances ability to dissolution: “Like dissolves
like”. It means, that substances with ionic structure or with polar molecules may be
dissolved in polar solvents, and nonpolar substances are dissolved in nonpolar
solvents.

Solution’s concentration

At chemical practice the following values expressing content of solute in

solution are more often applied:
 mass fraction of solute ω(x);
 volume fraction of solute φ(x);
 mole fraction of solute χ(x);
 molar concentration of solute (molarity) c(x);
1
 molar concentration of solute’s equivalent (normality) c(�x);
 molality b(x);
 mass concentration of solute ρ(x).

Mass fraction of solute in solution ω(x) is the ratio between mass of

component m(x) and mass of solution m(solution):

m(x)
щ(x) =
m(solution)

The mass fraction has no dimension. It may be expressed in percents, then:

m(x)
щ(x) = ∙100%
m(solution)

Volume fraction of solute in solution φ(x) is the ratio between volume of

component V(x) and volume of solution V(solution):

V(x)
j (x) =
V(solution)

The volume fraction has no dimension. It may be expressed in percents, then:

V(x)
j (x) = ∙100%
V(solution)

Mole fraction of solute χ(x) is the ratio between number of moles of

component n(x) and total number of moles of all components in solution
n(solution):

n(x)
c (x) =
n( solution)
 The mole fraction has no dimension. It may be expressed in percents, then:

n(x)
c (x) = ∙100%
n(solution)

Molar concentration of solute (molarity) c(x) is the ratio between number of

moles of component n(x) and volume of solution V(solution):

n(x) m(x)
c(x) = =
V(solution) M(x) V(solution)

where m(x) is the mass of solute x;

M(x) is the molar mass of solute x.

In laboratory practice molar concentration is measured in mol/l.

�
Molar concentration of solute’s equivalent (normality) c( � x) is the ratio
1
between moles of equivalent of component n( x) and volume of solution
�
V(solution):

n( Z1 x) m(x)
c( Z1 x) = =
V(solution) M( Z1 x) V( solution)

where m(x) is the mass of solute x;

1
M( x) is the molar mass of solute’s equivalent.
�

1
Molar mass of equivalent of substance M( x) is the mass of substance which
�
joins or displaces one atom of hydrogen in acid-base reactions. In redox reactions
it is the mass of substance which corresponds to one electron joined or lost at
1
reaction. Factor of equivalence ( � ) shows what part of the molecule is equivalent to
the atom of hydrogen or to the electron.
Molar concentration of solute’s equivalent (normality) is expressed by mol/l.
Molality b(x) is the ratio between number of moles of component n(x) and
mass of solvent m(solvent):

n(x)
b(x) =
m( solvent)

Molality is measured in mol/kg.

Mass concentration of solute ρ(x) is the ratio between mass of component
m(x) and volume of solution V(solution):
 m(x)
r (x) =
V(solution)

Mass concentration is measured in kg/m3. Also such rates as: g/m3; g/l; g/cm3;
mg/l; mg/cm3; and other may be used.

4.3. Solubility of gases in liquids

Gases may be dissolved in a liquid or may be liberated from solution. For

these opposite processes dynamic equilibrium is established. At an equilibrium
state for certain interval of time, as much gas molecules leaves a liquid, as they
pass from a gaseous phase in the liquid.
Solubility of gases in liquids depends on nature of substances, on pressure and
on temperature. Presence in a solution of other substances also has influence on
gases solubility.
Influence of substances nature on gases solubility is analogous to its influence
on solubility of solid substances or liquids, it means that: in polar solvents gases
with polar molecules are better dissolved.
Solubility of gases depends on pressure. Henry-Dalton’s law describes
dependence of gases solubility on pressure:

Solubility of gas in liquid is directly proportional to

partial pressure of this gas above the liquid.

Mathematical expression of this law:

m = k∙p,

where m is solubility of gas at fixed temperature;

p is pressure of gas (in case of gases mixture it is partial pressure of
gas);
k is constant of proportionality.
If the gaseous phase consists of several gases mixture, solubility of each one
of the gases is directly proportional to partial pressure of corresponding gas.
Increasing of gases solubility at rising of pressure is widely used, in particular, for
manufacturing of sparkling drinks saturated by CO2 under pressure.
Dependence of gases solubility on partial pressure plays an essential role in
physiological processes of oxygen and CO2 transportation by blood. In the air that
gets into the lungs, partial pressure of oxygen is higher than concentration of
oxygen corresponding to it in blood, and partial pressure of CO2 is lesser than its
concentration in blood. Therefore lungs’ oxygen is dissolved in blood and CO2 is
removed from the blood. For improvement of organism supplying with oxygen at
some kinds of anemia and other diseases, patients are placed in premises with
raised partial pressure of oxygen in air. This method of treatment leads to fine
results at treatment of gas gangrene which is caused by microbes propagated in
necrotic tissues in the depth of a wound where blood saturated with oxygen does
not reach.
Divers working at great depths may get the so-called caisson disease, if
conditions of their gradual lifting from depth on surface are disturbed. Occurrence
of caisson illness may be explained in the following way: the oxygen dissolved in
blood is consumed by an organism, and significant amount of nitrogen remains
dissolved in blood. After the end of work, the diver is raised on surface. Pressure in
the driving-suite decreases, and solubility of gases in blood also decreases (in
accordance with Henry-Dalton’s law). Surplus number of dissolved gases is
liberated from blood through lungs at breathing if the diver is raised slowly with
periodic stops accordingly to premeditated technique. Too fast ascending of the
diver from depths on surface leads to isolation of surplus part of gases dissolved in
blood in form of bubbles. Such vials of gases in blood may cork blood vessels in
different tissues and organs. It results in heavy disease (caisson disease) or even in
diver perdition if blood vessels providing with blood vital organs (as brain) became
corked. Similar pathology can arise in passengers and crew of plane or spaceship
as a result of sudden depressurization of cabin during altitude flights if air pressure
sharply drops.
For treatment of caisson disease the patient is placed in a pressure chamber
where raised pressure required for fast dissolution of gas bubbles in blood is
created. Then pressure in the pressure chamber is slowly reduced. Surplus of gases
is gradually removed from blood trough lungs without formation of gas bubbles in
the blood.
Solubility of gases in water decreases also at dissolution of polar or ionic
substances in it. This phenomenon is explained by attraction of polar or ionic
substances to polar molecules of water. As a result, the number of free molecules
of water which may participate in process of gases dissolution is reduced.
M.Sechenov has established studying solubility of gases, that presence of
electrolytes at solution reduces gases solubility:

C = C0∙e-kc,

where C is solubility of gas in electrolyte solution;

C0 is solubility of gas in pure solvent;
e is basis of natural logarithm;
k is constant depending on nature of the gas, on nature of the
electrolyte and temperature;
c is concentration of electrolyte.
Besides electrolytes, solubility of gases in blood is influenced also by other
dissolved substances (proteins, lipids). Concentration of these substances may be
changed in certain limits and accordingly it may influence on solubility of O2 and
CO2 in blood.
 4.4. Solubility of liquids
and solid substances in liquids

Solubility of liquids and solid substances in liquids depends on:

 the nature of solvent and the nature of dissolved substance;
 temperature;
 presence of other substances in solution.
Solubility of the majority of solid substances increases with rising of
temperature. For some substances solubility slightly increases with rising of
temperature (sodium chloride NaCl), or even it may decreases (calcium hydroxide
Ca(OH)2).

Distribution of the dissolved substance

between two immiscible liquids.

If into a system containing two immiscible liquids a third substance capable to

be dissolved in each of these liquids is added, the dissolved substance will be
distributed definitely between both liquids. On the basis of corresponding
experimental reaches the Nernst’s law of distribution has been formulated:

At stable temperature the ratio of concentrations of

solute between two immiscible liquids (phases) is a
constant value.

This constant (K) is called distribution coefficient:

c1 (X)
K= ,
c 2 ( X)

where c1(X) and c2(X) are concentrations of the dissolved substance in the
first and the second solvents.
Their ability to diffuse through biological membranes plays a huge role in
distribution of substances in body. However, only not ionized molecules of fat-
soluble substances easily penetrate through membranes. Ability of such substances
to be transported through membranes is approximately proportional to values of
distribution coefficients of these substances in systems “oil-water”: an olive oil-
water, chloroform-water, etc. founded in vitro (in a flask). Such laws underlie
creation by pharmacists of new effective remedies, which should be transported
through membranes. For this purpose, determination of distribution coefficients in
vitro for remedies in systems “oil-water” is carried out, instead of rather difficult
and long researches in vivo. The coefficients of distribution received
experimentally for remedies in systems “oil-water”, and also their dependence on
acidity of medium are used for forecasting the possibility of penetration of these
remedies through biological membranes in the body of patients.

Questions and tasks for self-testing

1. Solubility of gases in water at rising of temperature will:
a) decrease;
b) not change;
c) increase;
d) firstly increase and then decrease;
e) firstly decrease and then increase.
2. Where the concentration of oxygen would be higher at the same conditions (temperature and
pression):
a) in river water;
b) in sea water?
3. What is better for oxygen consumption at equal conditions (temperature and pression):
a) distilled water;
b) sea water;
c) venous blood?
4. Find out the mass of sodium chloride for formation of 100 g. of isotonic solution (ω(NaCl) =
0,9%) that is used for intravenous introduction.
a) 1,8 g; b) 18 g; c) 0,36 g; d) 9g; e) 0,9 g.
5. How much grams of sodium hydroxide is contained in 40 ml of solution with NaOH mass
fraction of 32%? Density of solution is 1,25 g/cm3.
6. 1,58 g. of potassium permanganate are contained in 800 ml of solution. Define the mass
concentration, molar concentration and equivalent molar concentration of potassium
permanganate c( 1 KMnO 4 ) .
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