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abc-ELECTROCHEMISTRY
Part II
2. Ionic solutions
2.1 Electroneutrality
2.10 Summary
1
2. Ionic solutions
Solutions of electrolytes (especially aqueous solutions) are the most important
members of the class of ionic conductor. We will discuss the behaviour of
dissolved ions and their thermodynamic properties
2.1 Electroneutrality
Electrolyte - substance when dissolved (in water or some other liquid)
or melted produces ions and so enhances the electrical conductivity of the liquid.
An electrolyte can be solid (NaCl), liquid (H2SO4) or gas (NH3).
Solid electrolyte - solids that possesses their own ionic conductivity.
Dinitrogen pentoxide reacts completely with water - strong electrolyte
Strong electrolyte:
Some non-ionized dissolved ammonia remains in equilibrium with its ionic
products - weak electrolyte
Weak electrolyte:
2
Electroneutrality principle
The forces of interaction between dissolved cations and anions are so large that it is
virtually impossible to prepare solution that contains significantly unequal numbers
of positive and negative charges- electroneutrality principle of electrochemistry.
Example:
Solution of K2SO4 in water contains exactly twice as many K+(aq) ions as
SO42- (aq) ions.
For solution containing only two kinds of ions (one - positively and one - negatively
charged) holds the equality
For solution of any composition holds the general electroneutrality relationship:
Electric field
The absence of electroneutrality leads to electric field gradients. The relationship
between the field strength and the charge is given by Gausslaw of electrostatics.
When applied to an isolated charge Q surrounded by a medium of permitivity
law states that the field strength at a distance r from the charge is:
, this
from the
because
is in units C m-3
is obtainable:
Where:
II
by the relationship:
The work required to carry the ion of charge Qi from a region of potential
to
one of potential
is simply the product
of the charge and the
potential difference
.
Since Qi = ziQe = ziF/NA we have
The product
of Avogadros and Boltzmanns constants is itself a
constant known as gas constant R
R=
Therefore
Important equation - the equilibrium ion distribution law - relates the
disparity of the equilibrium concentrations of an ion between two regions
to the electrical potential difference between those regions
(for example the low predict a 48% enrichment in the concentration of a
singly charged anion by a 10.0 mV difference).
10
From
can be obtained (after multiplication by Fzi):
If
is small compared with the above value, as is often the case, it
is legitimate to expand the exponential function in 2:2:9, using
Ignoring all but the first two terms this leads to:
11
After summing over all the ions and using for charge density
we obtain
12
It clearly shows the role of the ionic strength - it determines the extend to
which a potential differences induces a charge density difference.
In very large regions of the electrolyte solution electro-neutrality is guaranteed.
If I is such a electroneutral region, than = 0. If we agree to measure
potential elsewhere with respect to the average potential in region I, so that we
may set = 0.
The equation 2:2:14 reduces (the subscript II is redundant) to:
is small compared
13
2.3 Activities
Activity - useful notion in electrochemistry
To every chemical distinct species can be assigned an activity - reflecting its
immediate environment.
Activity of a species in a certain location reflects its restlessness there.
The greater the activity, the more eager is the species to leave.
Three ways to display restlessness of a species:
- to move to adjacent location where its activity is lower (diffusion to region
of lower concentration)
- travel to a joining phase (precipitation from solution)
- the amount of species may diminish by virtue of a chemical (or
electrochemical) reaction
In each of the above cases, the activity determines not only the extend to which the
species disappear but also the rate of its disappearance.
The activity is manifested both thermodynamically and kinetically.
14
Standard state - the activity of a species measures its restlessness in some state of
interest compared to its restlessness in a standard state.
Activities are pure numbers (no dimensions or units) - they are ratios.
Activities are affected by temperature and to a lesser extent by the total pressure.
Because the influence of these variables is not a major constants in electrochemistry - at
first approximation we will ignore such effects - treat only systems at constant temperature
and pressure (298.15 K, 100,000 Pa).
Gases
The activity
pressure
rather high pressures.
The standard state for a gas is chosen to be pure gas at pressure of 100,000 pascals (1
bar). Because the domain of proportionality generally extends to much higher pressures
than this, the relationship
holds accurately for gases in the pressure range of general interest in electrochemistry
15
Liquids
The standard state for species in a liquid state is the pure liquid.
The activity of the solvent remains close to unity even for solutions of quite high
concentrations (aH2O = 1.004 in aqueous KCl solution of concentration 2000 mol m-3).
Solid
The standard state for a species in a solid phase is the pure solid.
In electrochemistry the solids are mostly pure elements or compounds and their
activities are equal to unity.
Examples:
Activity of Ag in a piece of pure silver metal is one (aAg = 1).
In silver-gold alloy, however, aAg is less than one.
Activities of very thin layers of metals, such as newly electrodeposited films,often differ
from unity
16
Solutes
Activity of a solute depends on its concentration, being proportional to concentration at
sufficient dilution.
The region of linearity of ai versus ci graph is rather
limited especially for ionic solutes.
The standard state is chosen as a hypothetical state it corresponds to what the behaviour of the solute would
have been at the standard concentration c0 if the linear
relationship had been maintained up to that
concentration. The activity of the solute therefore is:
where
the departure from the linearity. The activity coefficient i of a solute at any
concentration ci equals to its actual activity ai divided by the ideal activity ci/c0.
The concentration of an ideal solution in which the solute activity equals ci/c0 is
often employed in the thermodynamic arguments.
17
Formal definition of activity can be illustrated by the above diagram, in which one
atom, molecule or ion (as the case may be) is transferred from the interior of a
standard phase to the interior of the phase of interest.
If
is the minimum net work that must be expanded to achieve this transfer than the
activity of species in the destination phase is defined as:
If the transfer of 1 mole of i in the direction of the arrow increases the total Gibbs
energy (or free energy) of the system (both reservoirs) by
18
The reservoirs in the previous diagram are imagined as huge enough - so large
that the transfer does not significantly alter the composition of the two phases,
or any other of their intensive properties. The last restriction causes a problem
when i is an ion.
Whereas it may be possible to imagine the transfer of such a small number of
ions into such a large reservoir that no significant change in the electrical
potential occurs, experiments with this objective are not feasible.
One practical effect of this difficulty is to prevent the measurement of
individual ionic activities.
A quantity that can be measured is the mean ionic activity
and an anion defined by
of a cathion
z+ and z- are the charge numbers of the cation and the anion.
19
Example:
the mean ionic activity of
and
ions is
The inability to measure the individual ionic activity causes less difficulty that
might be supposed.
It turns out that mean ionic activities are what one often needs.
Activity coefficients of a single ions are also immeasurable.
We can measure only a mean ionic activity coefficient, given by:
20
22
strength of the solution, but not directly on the concentration of the ion. The
activity coefficient decreases with the increase of .. For the mean ionic activity
coefficient of a cation-anion pair in aqueous solutions at 250 C
23
24
25
26
One and the same thermodynamic principles apply to all these equilibria.
An eqilibrium constant K can be established for each of them
27
Where
is the change in the standard Gibbs energy that accompanies the left-toright reaction of the equilibrium. In the general case of an equilibrium
Extensive tabulations of
values are available for compounds and ions in aqueous
solutions.
Elements and H+(aq) ion have standard Gibbs energies of zero, by definition.
28
29
Example:
For the process
= -13.92 Kilojoules per mole (kJ/mole) - according to the data in the table
- 237.13 + 164.67 - (-58.54) - 0 = -13.92
30
31
pH
Holds for
the activities of hydrogen and hydroxide ions are not independent variable
in aqueous solutions instead of reporting either aH+(aq) or aOH-(aq), it is more
usual to cite the pH of an aqueous solution which is related to the activities of
the two ions by the relation
33
If we apply its forth and fifth entries (in the table) to the self-ionization of H2O
(equilibrium 2:7:7) occurring in pure or almost pure water - equilibrium constant
given by 2:7:17
will be obtained
so that
Example:
Its equilibrium constant at 25 0C is K8 = 3.24 x 107 (equation 2:7:10).
Applying the Table of activity replacement we obtain:
Whether or not
can be replaced by the use of Debye-Hueckel theory depends on
the ionic strength of the solution and the accuracy we would like to obtain.
By the use of 2:7:22 we can calculate the equilibrium pressure of hydrogen gas in a
30mM HCl solution in contact with silver and silver chloride.
It can be theoretically estimated
An undetectably small pressure is obtained. This explains the experimental fact that
silver does not dissolve in HCl.
35
closely related to
36
~
a
For uncharged species the electrical activity is invariably unity, so that i and
are identical.
~
a
For electrons the chemical activity equals unity, so that
contains only an
e
electrical term.
~
It is only for ions that we need to be concerned with both contributions to a
.
i
37
38
a~iI
and
a~iII
According to
39
Example:
Thin membranes of certain glasses are permeable to hydrogen ions, but
not to other ions.
Aqueous solutions of HCl are separated by
thin glass diaphragm. The concentrations
in phase I and phase II are unequal.
If:
40
Example:
Signal transmission by nerve impulses in animals - makes use of transfer equilibria.
Cell walls have limited permeability to ions and differences between intracellular and
intercellular ionic concentration are maintained by both active (metabolically-fuelled
pump) and passive transport (difference in electrochemical activity).
The wall of the resting nerves have greater permeability for K+ than to other ions and K+
is primarily responsible for the resting potential difference that exists between the
inside and outside of the cell.
41
results to
the resting
2.10 Summary
Extremely dilute solutions of electrolytes behave not different thermodynamically than
0
do non-ionic solutions. The activity of solute i being ci/c (demands imposed by the
electroneutrality principle should be fulfilled).
The interionic forces present at higher concentrations affect the activity of a solute ion
by a factor, the activity coefficient i, that depends on the solutions ionic strength.