Topic 5

Plan

The theory of electrolitic dissociation.

Dissosiation degree and dissosiation constant.
Ionic product of water.
pH as hydrogen index.
Activity and ionic strength.
Buffer systems, their mechanism and biological
significance

History electrolytic dissociation

Already in 1795, a charge separation of particles was
Volta after the discovery of electrochemical electricity by
Galvani contemplated by different metals. Grotthus
developed in 1805 a theory for charge separation of water
molecules. Berzelius and Daniell were concerned to salts in
water, they assumed that the salts are there separated into
positive and negative charge carriers. Faraday coined the
term of the ion, but he had not the current notion of a
localized charge on an atom or molecular moiety in
solution. Rudolf Clausius believed that the charge carriers
are not fixed, but perform oscillations. He realized even then
the possibility of dissociation of electrolytes. Since the first
stream was only obtained from electrochemical batteries and
the basic laws of electricity and electronics have been
developed with these batteries, had the question to the
electrolyte and the conductivity of the solutions a high
priority.
Basic work on the actual dissociation were, however,
only by Friedrich Wilhelm Georg Kohlrausch ( producing a
conductivity meter with AC for liquids, formulation of a law
for strong electrolytes, carbon intoxication square-root law ),
Jacobus Henricus van ' t Hoff ( Osmotic pressure as a
function of the number of particles ), Svante Arrhenius
(works on the conductivity with Kohlrausch's conductivity
meter and postulate the dissociation of salts in positive and
negative charge carriers, founder of dissociation ) and
Wilhelm Ostwald (dissemination of Arrhenius ideas,
application of the law of mass action to the dissociation and
formation of the important law for weak electrolytes,
Ostwald cal dilution law ) made
A mathematical theory of dissociation was later
developed by Peter Debye and Erich Hückel. With this
Debye- Hückel theory can be calculated mathematically
from known boundary conductivities, the degree of
dissociation of the electrolyte. However, the model is only
for low electrolyte concentrations (up to 0.01 mol / l ) are
suitable.

Arrhenius theory of electrolytic dissociation.

Arrhenius (1887) put forward the theory of electrolytic
dissociation, as a more explicit form of one he had proposed
in 1883, which forms the basis of the modern treatment of
electrolytes. Postulates of Arrhenius theory In aqueous
solution, the molecules of an electrolyte undergo
spontaneous dissociation to form positive and negative ions.
The assumption made was that when an acid, base or salt is
dissolved in water, a considerable portion becomes
spontaneously dissociated into positive and negative ions.
The Arrhenius assumption was based on degree of
ionization ,so it valid on weak electrolytes(incomplete
ionization) but it failure with respect to strong
electrolytes(complete ionization in either strong and weak
electrolytes). The decreasing of equivalent conductance at
high concentration as Arrhenius suggest belong to
decreasing of degree of ionization of electrolyte. The
Arrhenius interpretation concentrate about number of ions
and he ignore the mobility of ions. The Arrhenius suggestion
are only apply on weak electrolytes because the strong
electrolytes are completely dissociate at high concentration.
Degree of ionization (α) = Number of dissociate d molecules
/ Totoal number of moelcules of electrolyte before
dissociation At moderate concentrations, there exists an
equilibrium between the ions and undissociated molecules,
such as,

NaOH? Na+ + OH– ;

KCl? K+ + Cl–
 This equilibrium state is called ionic equilibrium.
Each ion behaves osmotically as a molecule. Factors
affecting degree of ionization 1- At normal dilution, value of
α is nearly 1 for strong electrolytes, while it is very less than
1 for weak electrolytes. 2- Higher the dielectric constant of a
solvent more is its ionizing power. Water is the most
powerful ionizing solvent as its dielectric constant is highest.
3- α ∝ 1/Con. of solution ∝ 1/wt.of solution ∝ Dilution of
solution ∝ Amount of solvent 4- Degree of ionization of an
electrolyte in solution increases with rise in temperature. 5-
Presence of common ion: The degree of ionization of an
electrolyte decreases in the presence of a strong electrolyte
having a common ion.

Dissociation. Dissociation ( dissociare from the Latin

" disconnect" ) is understood in the chemistry of the excited
or automatically running process of division of a chemical
compound into two or more molecules, atoms or ions. As a
measure of the degree of dissociation or dissociation, the
dissociation constant is used. The degree of dissociation is
the ratio of the dissociated particles for formal initial
concentration of undissociated chemical compound. The
dissociation energy is the energy that is necessary to cleave
a chemical bond.

Dissociation of gases, thermal, photochemical

dissociation
The first methods for molecular weight determination
based on vapor density measurements. However, there were
sometimes discrepancies, this led to mental conclusions that
molecules must be dissociated in the gas phase.
Coined the term dissociation in 1857 by Henri Étienne
Sainte -Claire Deville. In the determination of vapor
densities of inorganic and organic compounds Cannizzaro,
Kopp and Kekulé discovered variations in the molecular
weight in the gas phase. Frequently, the gas density was
lower than expected. St. Claire Deville could determine a
lower density at the phosphorus pentachloride in the gas
phase, at the same time he observed a greenish coloration
and concluded that phosphorus pentachloride decompose
into chlorine and phosphorus trichloride be had. Pebal and
Skraup could by heating ammonium chloride in a thin tube
through which different gas velocities ( glass tube
constriction to measure the effusion, see Thomas Graham
( chemistry ) ) detected with litmus, that the ammonium
chloride is dissociated in the gas phase in the ammonia and
hydrochloric acid.
Thermal dissociation run much slower than
electrolytic dissociation in the rule. An example of a thermal
decomposition provides dinitrogen tetroxide that is present
at -10°C in the form of colorless crystals. Upon heating the
molecule dissociates into the intense brown-red colored
nitrogen dioxide:
This reaction is reversible. On cooling, the sample is
discolored because of recombination to dinitrogen tetroxide
again. Dissociations are particularly for macromolecules
already at relatively low temperatures.
Upon heating of peroxides or azo compounds, which
dissociate thermally bonds already at about 150 ° C,
radicals. Radical can be determined by electron spin
resonance spectroscopy (ESR ) spectroscopy.
Photochemical dissociation
Through the development of spectroscopic methods
and new findings on the bonds in molecules were accessible.
An important method was the IR spectroscopy. In the IR
spectroscopy, vibrations of the atoms in the molecule can be
measured by exposure to infrared light of a specific
wavelength. Molecules such as hydrochloric take at slightly
different wavelengths of energy, the binding gets into
vibrations, similar to two bodies - be moved - connected by
a wire spring. At very high vibrational energy, the distance
between the atoms is growing to be the bond between the
atoms is separated.
In addition to the IR - spectroscopy and photoelectron
spectroscopy for the detection of ionization of a molecule is
used.
By irradiation with UV light of a discrete wavelength, or
dialkyl ketones absorb energy - This leads sometimes to a
dissociation of the bond in two radicals. These radicals can
be determined with the (ESR ) spectroscopy. More recently,
the controlled dissociation of single bonds in the molecule
by electron Laserimpules and was possible

Electrolytic dissociation
The electrolytic dissociation of the reversible
decomposition of a compound in anions and cations in a
solvent. The proportion of dissociated ions on the proportion
of undissociated and dissociated ions of the same species is
called dissociation (see also activity). It depends on the
concentration in the solvent. At very high dilution, the acetic
acid is completely dissociated in acetate and hydronium ions
at high concentration, there is still a large proportion of
undissociated acetic acid. The dissociation or more precisely
the degree of dissociation of salts or organic molecules can
by electrical conductivity measurements ( conductometric )
and are determined by pH measurements of aqueous
solutions.
Sodium chloride ( NaCl), which is dissolved in tap or
distilled water, dissolves in the form of positive sodium
cations and negative chlorine anion. These ions are
dissociated, ie, spatially separated from each other and with
an electric charge before. Such solutions are called
electrolytes. NaCl is strong electrolyte, because the ion
almost completely separated present in the solution.
Vinegar, comprising the ingredients of acetic acid and water,
is also partially in the form of ions, as an oxonium ions and
acetate anions before. Acetic acid is not completely
dissociated into ions, only about 0.3% of the acetic acid
molecule ( in 1 mol / L ) are present in dissociated form.
Acetic acid is a weak electrolyte. Depending on the type of
solute particles one finds all transitions between strong and
weak electrolytes.
In the electrolyte, the equilibrium constant of
dissociated products to undissociated precursors from the
degree of dissociation and the law of mass action (MWG)
can be determined. Wilhelm Ostwald formulated, that the
product of active mass concentrations of the dissociated
particles (with acetic acid, the Acetationkonzentration
multiplied by the Hydroniumkonzentration ) by the
concentration of undissociated mass particles ( undissociated
acetic acid) always yields a constant. This constant is called
the dissociation constant ( obsolete: affinity constant) and it
is used for example for the determination of pK a values of
acids. The equilibrium constant Ka, or as negative logarithm
( - logKA = pKa), the proportion of dissociated ions for each
concentration can be accurately determined.
It is Ka > 1 for strong electrolytes (salt in water).
In the case of acetic acid in water, the equilibrium lies to the
left. It is Ka < 1
If the gas is hydrogen chloride ( HCl ) is introduced into
water, an electrolytic solution is called hydrochloric acid
forms:
If the gas is ammonia (NH3 ) into water forms as a
cation NH4 and the anion OH
The equilibrium reactions of these last three examples
are also called proteolysis and is described there in more
detail. This behavior makes acetic and hydrochloric acid to
form acids. The behavior of ammonia makes ammonia a
base. The electrical conductivity of these solutions is the
experimental proof of the formation of free mobile anions
and cations.
A very important special case is the dissociation
equilibrium of pure, distilled water under exclusion of air.
Water dissociates to a very small share in the hydroxide and
hydronium ions. Kohlrausch and Heydweiller determined
the conductivity of distilled water in 1894 to 0.06 10-6 Ohm
-1. From the conductivity and the knowledge of the
boundary conductivities (see equivalent conductivity ) for
hydronium and hydroxide ions can be the equilibrium
constant, the ionic product of water calculated. It has a value
of CW = 10-14 mol2/L2 or pKW = 14 From a knowledge of
the concentration of the electrolyte and the corresponding
pKa values from tables can easily be determined pH and
Dissoziationgrad for each electrolyte.
When loosening of exactly 100.0 g of a 98 % sulfuric
acid in exactly 962.7 g of distilled water, the concentration
of sulfuric acid is exactly 1 mol / L. Taking of the sulfuric
acid solution 106.38 g dissolves in 900 mL of distilled this
water, this solution has a concentration of 0.1 mol / L, is
orders of 10.64 g of the first solution and dissolution in 990
mL of distilled water the concentration of 0.01 mol / L,
analogue can be prepared a 0.001 mol / L aqueous solution
of sulfuric acid. The sulfuric acid can be dissociated in
water, ie the hydrogen atoms split off as positively charged
oxonium ions from the sulfuric acid and as counter-ions to
form hydrogen sulfate ions or sulfate ions. The strength of
the dissociation is determined by the pKa value. Acids with
a negative pKa value are always completely dissociated. The
smaller the pKa, the stronger an acid is dissociated.
Suppose that 0.1 molar sulfuric acid would be
completely dissociated at this concentration, both hydrogen
atoms of the sulfuric acid would have to be split and the
Oxoniumkonzentration would have 0.2 mol / L amount. The
equivalent concentration (or normal ) of the sulfuric acid
would be: 2 * 0.1 mol / L = 0.2 mol / L. Based on 1000 g of
water molecules could from these 3.6 g of water molecules
are present as oxonium ions. The pH was thus
Analog would be obtained for
Oxoniumkonzentrationen of 0.02 mol / L: pH = 1.7 and
0.002 mol/L: pH = 2.7. However, the following pH values
were measured: 0.2 mol/L pH = 1.23, 0.02 mol/L pH = 1.94,
0.002 mol/L pH = 2.78. In fact agrees with the measured pH
halfway to 0.002 mol/L solution.
( C is the concentration in mol / l * equivalent number
) are used according to the Ostwald dilution law to
determine the pH dependency. For the sulfuric acid thus
obtained 0.2 mol/L: pH = 1.30 ( measured: 1.23 ), 0.02
mol/L: pH = 1.80 ( measured: 1.94 ). A high proportion of
sulfuric acid is consequently higher concentration than
hydrogen sulfate (over 40% in a 0.1 molar sulfuric acid )
rather than two-fold negative sulfate before and this explains
the differences in the pH measurements. For hydrochloric
acid and nitric acid, the logarithmic concentration
dependence is valid for the pH determination according to
the first relationship, for caustic soda in an analogous
manner for the hydroxide concentration. In titrations with
sodium hydroxide or with further dilution of the solution,
the Schwefelsäureteilchen are dissociated and the correct
total concentration is obtained.
 Weak acids and bases can act as a buffer (chemistry).
The pH of a solution remains fairly constant and equal to the
pKa of the corresponding acid, when a weak acid and its
anion are present in approximately the same concentration in
the solution. Important biological buffers are solutions of
carbonic acid and bicarbonate and dihydrogen phosphate
buffer, they shall see in biological systems for a constant
pH. Acid-base titration with a suitable pH indicator or a pH
electrode to be used in such solutions to determine the
concentration of this acid and base correctly.
Salts can dissociate more or less strong. Salt solutions
at a high concentration will exhibit different properties than
would be expected when the physical measurement value of
the diluted solutions would be extrapolated to solutions of
high concentration. In the physical properties, it may, for
example, the freezing point, boiling point or the electrical
conductivity. To describe a solution but now has a linear
dependence to a hypothetical concentration ( activity), the
concentration of a solution must be multiplied by a factor,
the activity coefficients. In order to describe the
concentration-dependent conductivity of the equivalent
conductivity coefficient is used according to the coal noise
law, this differs considerably from the activity coefficients.
In the so-called real or permanent electrolyte, the ions
already in the solid state ( ionic lattice ) are present. Indeed,
in the solid salt to grid Na and Cl - ions. On dissolving the
salt in water are now formed in the water freely moving
ions. In the dissociation of salts in the ion rather high lattice
energy of the crystal is applied by hydration during solution
process.
In the so-called potential electrolytes lie with the pure
substances have no ionic bonds. As a pure substance they
are insulators. During the introduction of the pure substances
(AB) in a solvent, the formation of ions by a chemical
reaction between the solute and solvent;
Prerequisite for such a reaction is a polar bond
between the parts A and B of compound ( AB) and a polar
solvent. For example, pure acetic acid is added to water
form as cations H3O , the anions H3C -COO-
 Not only in water ions are dissociated. An almost
equal high degree of dissociation is also observed in polar
organic solvents such as formamide, acetonitrile or
nitromethane. The decisive factor for the dissociation in
organic solvents is the dielectric constant, such as Walter
Nernst found out.
Dissociation in organic chemistry.
In the organic chemistry, knowledge of the
dissociation of great importance.
Many organic reactions are possible only if carboxylic acids,
hydroxy groups are present as anions, thus conversion
processes such as alkylation can be performed. Hammet
investigated the dissociation of the organic bases and the
carboxylic acid in water and various solvents. The first study
on the formation of organometallic compounds were carried
out by Conant and Wheland. In 1965, then put on a Cram
acidity scale ( MSAD scale) for different hydrocarbon
molecules, EM Arnett had 1963 intended for esters, amides,
thiols, amines, phenols dissociation constants. Because of
this Aciditätsskalen organic chemists can easily assess
which base is necessary for a substance implementation.

Dissociation constant
For reversible dissociations in a chemical equilibrium

AB ⇌ A + B

the dissociation constant Ka is the ratio of dissociated to

undissociated compound

where the brackets denote the equilibrium concentrations of

the species.

Dissociation degree
 The dissociation degree is the fraction of original
solute molecules that have dissociated. It is usually indicated
by the Greek symbol α. More accurately, degree of
dissociation refers to the amount of solute dissociated into
ions or radicals per mole. In case of very strong acids and
bases, degree of dissociation will be close to 1. Less
powerful acids and bases will have lesser degree of
dissociation. There is a simple relationship between this
parameter and the van 't Hoff factor( i ). If the solute
substance dissociates into ions, the.

For instance, for the following dissociation

KCl ⇌ K+ + Cl−

As n = 2 , we would have that I = 1 + α

The ionic product for water, kw

 This page explains what is meant by the ionic product
for water. It looks at how the ionic product varies with
temperature, and how that determines the pH of pure water
at different temperatures.

Kw and pKw
The important equilibrium in water
Water molecules can function as both acids and bases. One
water molecule (acting as a base) can accept a hydrogen ion
from a second one (acting as an acid). This will be
happening anywhere there is even a trace of water - it
doesn't have to be pure.
A hydroxonium ion and a hydroxide ion are formed.
 However, the hydroxonium ion is a very strong acid,
and the hydroxide ion is a very strong base. As fast as they
are formed, they react to produce water again.
The net effect is that an equilibrium is set up.

At any one time, there are incredibly small numbers of

hydroxonium ions and hydroxide ions present. Further down
this page, we shall calculate the concentration of
hydroxonium ions present in pure water. It turns out to be
1.00 x 10-7 mol dm-3 at room temperature.
You may well find this equilibrium written in a simplified
form:

This is OK provided you remember that H+(aq)

actually refers to a hydroxonium ion.

Defining the ionic product for water, Kw

Kw is essentially just an equilibrium constant for the
reactions shown. You may meet it in two forms:
Based on the fully written equilibrium . . .

. . . or on the simplified equilibrium:

 You may find them written with or without the state
symbols. Whatever version you come across, they all mean
exactly the same thing!
You may wonder why the water isn't written on the
bottom of these equilibrium constant expressions. So little of
the water is ionised at any one time, that its concentration
remains virtually unchanged - a constant. Kw is defined to
avoid making the expression unnecessarily complicated by
including another constant in it.

The value of Kw
Like any other equilibrium constant, the value of Kw
varies with temperature. Its value is usually taken to be 1.00
x 10-14 mol2dm-6 at room temperature. In fact, this is its
value at a bit less than 25°C.
The units of Kw: Kw is found by multiplying two
concentration terms together. Each of these has the units of
mol dm-3.
Multiplying mol dm-3 x mol dm-3 gives you the units
above.

pKw
The relationship between Kw and pKw is exactly the
same as that between Ka and pKa, or [H+] and pH.

The Kw value of 1.00 x 10-14 mol2 dm-6 at room

temperature gives you a pKw value of 14. Try it on your
calculator! Notice that pKw doesn't have any units.

The pH of pure water

Why does pure water have a pH of 7?
That question is actually misleading! In fact, pure water only
has a pH of 7 at a particular temperature - the temperature at
which the Kw value is 1.00 x 10-14 mol2 dm-6.
This is how it comes about:
To find the pH you need first to find the hydrogen ion
concentration (or hydroxonium ion concentration - it's the
same thing). Then you convert it to pH.
In pure water at room temperature the Kw value tells you
that:

[H+] [OH-] = 1.00 x 10-14

But in pure water, the hydrogen ion (hydroxonium

ion) concentration must be equal to the hydroxide ion
concentration. For every hydrogen ion formed, there is a
hydroxide ion formed as well.
That means that you can replace the [OH -] term in the
Kwexpression by another [H+].
[H+]2 = 1.00 x 10-14
Taking the square root of each side gives:

[H+] = 1.00 x 10-7 mol dm-3

Converting that into pH:

 pH = - log10 [H+]
pH = 7

That's where the familiar value of 7 comes from.

The variation of the pH of pure water with temperature

The formation of hydrogen ions (hydroxonium ions)
and hydroxide ions from water is an endothermic process.
Using the simpler version of the equilibrium:

The forward reaction absorbs heat.

According to Le Chatelier's Principle, if you make a
change to the conditions of a reaction in dynamic
equilibrium, the position of equilibrium moves to counter
the change you have made.

Buffer Solution
 A buffer solution is an aqueous solution of a weak
acid and its conjugate base, or a weak base and its conjugate
acid. Its pH changes very little when a small amount of
strong acid or base is added to it. Buffer solutions are used
as a means of keeping pH at a nearly constant value in a
wide variety of chemical applications.
Many life forms thrive only in a relatively small pH range,
so they utilize a buffer solution to maintain a constant pH.
One example of a buffer solution found in nature is blood.
The body's acid–base balance is normally tightly regulated,
keeping the arterial blood pH between 7.38 and 7.42.
Several buffering agents that reversibly bind
hydrogen ions and impede any change in pH exist.
Extracellular buffers include bicarbonate and ammonia,
whereas proteins and phosphates act as intracellular buffers.
The bicarbonate buffering system is especially key, as
carbon dioxide (CO2) can be shifted through carbonic acid
(H2CO3) to hydrogen ions and bicarbonate (HCO3-):

H2O+CO2↔H2CO3↔H++CO3−
 Acid–base imbalances that overcome the buffer
system can be compensated in the short term by changing
the rate of ventilation. This alters the concentration of
carbon dioxide in the blood and shifts the above reaction
according to Le Chatelier's principle, which in turn alters the
pH.
The bicarbonate buffer system is an acid-base
homeostatic mechanism involving the balance of carbonic
acid (H2CO3), bicarbonate ion ( ), and carbon
dioxide (CO2) in order to maintain pH in
the blood and duodenum, among other tissues, to support
proper metabolicfunction. Catalyzed by carbonic anhydrase,
carbon dioxide (CO2) reacts with water (H2O) to form
carbonic acid (H2CO3), which in turn rapidly dissociates to
form a bicarbonate ion ( ) and a hydrogen ion (H+) as
shown in the following reaction:
 As with any buffer system, the pH is balanced by the
presence of both a weak acid (for example, H2CO3) and its
conjugate base (for example, ) so that any excess acid
or base introduced to the system is neutralized.
Failure of this system to function properly results in acid-
base imbalance, such as acidemia (pH<7.35)
and alkalemia (pH>7.45) in the blood.