Physical Pharmacy

2nd stage

Febreuary/2011

Dr.Dhafir Qahtan

Electrolyte solutions
The first satisfactory theory of ionic solutions was that proposed by Arrhenius in 1887,
who was able to bring together the results of diverse investigations into broad
generalization known as the theory of electrolytic ion. Although the theory proved quite
useful for describing weak electrolytes, it was soon found unsatisfactory for strong and
moderately strong electrolytes.
Accordingly, many attempts were made to modify or replace Arrhenius's ideas with
better ones, and finally, in 1923, Debye and Hckel put forth a new theory. It is based on
the principles that strong electrolytes are completely dissociated into ions in solutions of
moderate concentration and that any deviation from complete dissociation is due to
interionic attractions.
Properties of solutions of electrolytes
Electrolysis
When, a direct electric current (dc) of several volts flows through an electrolytic cell
(Figure 6-1), a chemical reaction occurs. The process is known as electrolysis. Electrons
enter the cell from the battery or generator at the cathode (road down); they combine
with positive ions or cations in the solution, and the cations are accordingly reduced.
The negative ions, or anions, carry electrons through the solution and discharge them at
the anode (road up), and the anions are accordingly oxidized.
Reduction is the addition of electrons to a chemical species, and oxidation is removal of
electrons from a species. Reduction occurs at the cathode, where electrons enter from
the external circuit and are added to a chemical species in solution. Oxidation occurs at
the anode, where the electrons are removed from a chemical species in solution and go
into the external circuit.
In the electrolysis of a solution of ferric sulfate in a cell containing platinum electrodes,
a ferric ion migrates to the cathode, where it picks up an electron and is reduced:
Fe 3 e Fe 2

The sulfate ion carries the current through the solution to the anode, but it is not easily
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oxidized; therefore, hydroxyl ions of the water are converted into molecular oxygen,
which escapes at the anode, and sulfuric acid is found in the solution around the
electrode. The oxidation reaction at the anode is:
OH

1
1
O2 H 2 O e
4
2

Platinum electrodes are used here because they do not pass into solution to any extent.
When attackable metals, such as copper or zinc, are used as the anode, their atoms tend
to lose electrons, and the metal passes into solution as the positively charged ion.
In the electrolysis of cupric chloride between platinum electrodes, the reaction at the
cathode is:
1
1
Cu 2 e Cu
2
2

Where as at the anode, chloride and hydroxyl ions are converted, respectively, into
gaseous molecules of chlorine and oxygen, which then escape. In each of these two
examples the net result is the transfer of one electron from the cathode to the anode.
It should be noted that the flow of electrons through the solution from right to left in
Figure 6-1 is accomplished by the movement of cations to the right as well as anions to
the left. The fraction of total current carried by the cations or by the anions is known as
the transport or transference number t+ or t
t

Current carried by cations

Total current

Current carried by anions

Total current

The sum of the two transference number is obviously equal to unity:

t t 1

The transference numbers are related to the velocities of the ions, the faster-moving ion
carrying the greater fraction of current. The velocities of the ions in turn depend on
hydration as well as ion size and charge. Hence, the speed and the transference numbers
are not necessarily the same for positive and for negative ions. For example, the
transference number of the sodium ion in a 0.10 M solution of NaCl is 0.385. Because it
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is greatly hydrated, the lithium ion in a 0.10 M solution of LiCl moves more slowly than
the sodium ion and hence has a lower transference number, 0.317.
Electrical units
According to Ohm's law, the strength of an electric current I in amperes flowing through
a metallic conductor is related to the difference in applied potential or voltage E and the
resistance R in ohms, as follows:
I

E
R

The current strength I is the rate of flow of current or the quantity Q of electricity
(electronic charge) in coulombs flowing per unit time:
I

Q
t

Quantity of electriccharge ,Q Current,I Time,t

The quantity of electric charge is expressed in coulombs (1 coulombs = 3109 electrostatic

unit of charge or esu) the current in amperes, and the electric potential in volts.
Electric energy E Q

Faradays laws
Faradays laws of electricity states that the passage of 96500 coulombs of electricity
through a conductivity cell produces a chemical change of 1 g equivalent weight of any
substance. The quantity 96500 is known as the faraday,F. the best estimate of the value
today is 9.6484104 coulomb/gram equivalent.
A univalent negative ion is an atom to which a valence electron has been added; a
univalent positive ion is an atom from which an electron has been removed. Each gram
equivalent of ions of any electrolyte carries Avogadros number (6.0210 23) of positive
or negative charges. Hence, from Faradays laws, the passage of 96500 coulombs of
electricity results in the transport of 6.021023 electrons in the cell. The passage of 1
faraday of electricity causes the electrolytic deposition of the following number of moles
of various ions: 1 AGg+ , 1Cu+ , Cu+2 , Fe+2 , 13 1/3 Fe+3 . Thus, the number of
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Physical Pharmacy

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Dr.Dhafir Qahtan

positive charge carried by 1 g equivalent of Fe +3 is 6.021023 , but the number of positive

charges carried by 1 g atom or 1 mole of ferric ions is 36.021023 .
Faradays laws can be used to compute the charge on an electron in the following way:
because electrons are associated with 96500 coulombs of electricity, each electron has a
charge, e of:
e

96500 coulomb
1.6 10 19 coulomb
23
6.02 10

1coulomb 3 10 9 esu
e 4.8 10 10

electrostatic unit of charge

Electrolytic conductance
The resistance, R, in ohms of any metallic or electrolytic conductor is directly
proportional to its length, l, in cm and inversely proportional to its cross-sectional area,
A, in cm2.
R

l
A

Where is the resistance between opposite faces of a 1 cm cube of the conductor and is
known as the specific resistance.
The conductance, C, is the reciprocal of resistance,
C

1
R

And hence, the conductance can be defined as a measure of the ease with which current
can pass through the conductor. It is expressed in reciprocal ohms or mhos
C

1
1 A

R l

The specific conductance,

, is the reciprocal of specific resistance and it is the

conductance of a solution confined in a cube 1 cm on an edge expressed in mhos/cm:

The relationship between specific conductance and conductance or resistance is obtained

by combining equation 1 &2
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l
1 l

A R A

The quantity l/A , the ratio of distance between electrodes to the area of the electrode,
has a definite value of each conductance cell, which is known as the cell constant, K.
The equation thus can be written as:
KC

K
R

The specific conductance of several standard solutions has been determined in carefully
calibrated cells. For example, a solution containing 7.45263 g of potassium chloride in
1000 g of water has a specific conductance of 0.012856 mho/cm at 25C. A solution of
this concentration contains 0.1 mole of salt per cubic decimeter (100 cm 3) of water and
is known as a 0.l-demal solution. When such a solution is placed in a cell and the
resistance is measured, the cell constant can be determined by use of the previous
equation (6-19).
Example: A 0.1-demal solution of KCl was placed in a cell whose constant, K was
desired. The resistance, R was found to be 34.69 ohms at 25C. When the cell was filled
with 0.01N Na2SO4 solution, it had a resistance of 397 ohms. What is the specific
conductance?
K/R
K R 0.012856 mho / cm 34.69 ohm 0.446 cm 1

K 0.446 cm 1

1.1234 10 3 mho / cm
R
397 ohm

Equivalent conductance
Equivalent conductance, is defined as the conductance of a solution of sufficient volume
to contain 1 gram equivalent of the solute when measured in a cell in which the
electrodes are spaced 1 cm apart.
To study the dissociation of molecules into ions, independent of the concentration of the
electrolyte, it is convenient to use equivalent conductance rather than specific
conductance. All solutes of equal normality produce the same number of ions when
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completely dissociated, and equivalent conductance measures the current-carrying

capacity of this given number of ions. Specific conductance, on the other hand, measures
the current-carrying capacity of all ions in a unit volume of solution, and accordingly
varies with concentration.
The equivalent conductance c at a concentration of c gram equivalents per liter is
calculated from the product of the specific conductance k and the volume V in cm3 that
contains 1 gram equivalent of solute. The cell may be imagined as having electrodes 1
cm apart and to be of sufficient area so that it can contain the solution.
V

1000 cm 3 / liter 1000

cm 3 / Eq
c Eq / liter
c

The equivalent conductance is obtained when , the conductance per cm3 of solution
(i.e., the specific conductance), is multiplied by V, the volume in cm3 that contains 1
gram equivalent weight of solute. Hence, the equivalent conductance, c, expressed in
units of mho cm2/Eq, is given by the expression:
c V

1000
mho cm 2 / Eq
c

If the solution is 0.1 N in concentration, then the volume containing 1 gram equivalent
of the solute will be 10,000 cm3, and, according to previous equation, the equivalent
conductance will be 10,000 times as great as the specific conductance. This is seen in
the following example.
Example: The measured conductance of a 0.1 N solution of a drug is 0.0563 ohm at
25C. The cell constant at 25C is 0.520 cm 1. What is the specific conductance and
what is the equivalent conductance of the solution at this concentration?
KC 0.0563 0.52 0.0293mho / cm
c

1000 1000 0.0293

293 mho cm 2 / Eq
c
0.1

Equivalent conductance of strong and weak electrolyte

As the solution of a strong electrolyte is diluted, the specific conductance decreases
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Physical Pharmacy

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Febreuary/2011

Dr.Dhafir Qahtan

because the number of ions per unit volume of solution is reduced. Conversely, the
equivalent conductance of a solution of a strong electrolyte steadily increases on
dilution. The increase in with dilution is explained as follows: The quantity of
electrolyte remains constant at 1 gram equivalent according to the definition of
equivalent conductance; however, the ions are hindered less by their neighbors in the
more dilute solution and hence can move faster. The equivalent conductance of a weak
electrolyte also increases on dilution, but not as rapidly at first.
Colligative properties of electrolytic solutions
As stated in the previous chapter, Van't Hoff observed that the osmotic pressure, , of
dilute solutions of nonelectrolytes such as sucrose and urea, could be expressed
satisfactorily by the equation:
RTc

Where R is the gas constant, T is the absolute temperature, and c is the concentration in
moles/liter, Van't Hoff found, however, that solutions of electrolytes gave osmotic
pressures approximately two, three, and more times larger than expected from this
equation, depending on the electrolyte investigated. Introducing a correction factor i to
account for the irrational behavior of ionic solutions.
iRTc

The i factor is plotted against the molal concentration of both electrolytes and
nqnelectrolytes in Figure 6-5. For nonelectrolytes, it is seen to approach unity, and for
strong electrolytes, it tends toward a value equal to the number of ions formed upon
dissociation. For example, i approaches the;, value of 2 for solutes such as NaCl and
CaSO4, 3 for K2S04 and CaCl2, and 4 for K3Fe(C)6 and FeCl3.
Example: What is the osmotic pressure of a 2 mole/liter solution of sodium chloride at
20C? The i factor for such solution is 1.9
iRTc
1.9 0.028atm.liter/mole.degree 293degree 2mole/liter 91.3atm

Arrhenius's theory of electrolytic dissociation

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When electrolytes are dissolved in water, the solute exists in the form of ions in the
solution, as seen in the following equations:
H 2O Na Cl Na Cl H 2O

[Strong electrolyte - ionic compound]

H 2 O HCl H 3O Cl

[Strong electrolyte - covalent compound]

H 2O CH 3COOH CH 3COO H 3O

[Weak electrolyte - covalent compound]

The solid form of sodium chloride is marked with plus and minus signs to indicate that
sodium chloride exists as ions even in the crystalline state. If electrodes are connected to
a source of current and are placed in a mass of fused sodium chloride, the molten
compound will conduct the electric current because the crystal lattice of the pure salt
consists of ions. The addition of water to the solid dissolves the crystal and separates the
ions in solution.
Hydrogen chloride exists essentially as neutral molecules rather than as ions in the pure
form, and does not conduct electricity. When it reacts with water, however, it ionizes .
H3O+is the modern representation of the hydrogen ion in water and is known as the
hydronium or oxonium ion.

Inter molecular forces are the forces between molecule and another molecule in the
system. These forces causes molecules to exist as aggregates in gas, liquid and solid.
intermolecular bonding is largely governed by electron orbital interaction. Cohesion (the
attraction of like molecules) and adhesion (the attraction of unlike molecules) are
examples of intermolecular forces. Balance of attractive and repulsive forces between
molecules (equilibrium) will indicates the intermolecular distances and intermolecular
conformations of such molecules. This equilibrium is important for understanding not
only properties of gases liquids and solids but also interfacial phenomena, flocculation
in suspensions, stabilization of emulsions, compactions of powders in capsules,
dispersions of granules to form tablets. Also these properties have strong influence on
bio molecules (like DNA and protein). The stability of these products during production,
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formulation and storage is affected by such properties.

Repulsive and attractive forces
When molecules interact, both repulsive and attractive forces operate. The opposite
charges and binding forces between two molecules will attract one anther. When the
molecules are brought so close that the negatively outer charged electron clouds will
repeal each other. Thus attractive forces are necessary for molecules to cohere where as
repulsive forces act to prevent the molecules from interpenetrating and overcoming each
other.