ELECTROLYTES

Introduction:
Anyone who is a fan of sports beverages has heard the word electrolytes before, but what does the
word really mean? This term refers to a substance that when dissolved in water will dissociate into
positively and negatively charged ions, which can conduct electricity in solution.

A substance that will not dissociate into ions when dissolved in water will not be able to conduct
electricity and therefore is called a non-electrolyte.

The greater the extent to which a substance dissociates, the stronger an electrolyte is, so as we look
at different types of electrolytes, we will be focusing on the efficiency of dissociation.

Strong electrolytes:
If a substance completely dissociates in solution, it is a strong electrolyte and will conduct electricity
very well. E.g., HCl, NaCl, KCl, etc.

Weak electrolytes:
If a substance only partially ionizes in solution meaning some particles dissociate and some do not
this will be called a weak electrolyte which will still conduct electricity but not as good as strong
electrolyte. E.g., CH3COOH, Zn (OH)2, carbonic acid, etc.

Non-electrolyte:
If a substance does not dissociate at all, it will be a non-electrolyte. E.g., sugar, urea, glucose, etc.

We can categories substances as being one of these three things by measuring the electrical
conductance of their corresponding aqueous solution. To conduct electricity, a substance must
contain freely mobile charged species such as in case of metallic wires, which allow for the free
movement of electrons. In a solution, these freely mobile charged species are the ions that result
when a substance dissociates. The more ions there are in a solution, the greater the conductivity and
the stronger the electrolyte. And we can measure the current flow or simply observe the brightness
of a light bulb included in the circuit to gather this kind of data.

Electrolytes can be further classified as ionic and covalent electrolytes.

Ionic electrolytes:
These are ionic compounds that will dissociate in aqueous solution to give individual cations and
anions. The dissolution occurs because the cations and anions will be able to make ion-dipole
interaction with the water molecule that comprise the solvent. And this energy storage, combined
with greater disorder of the solution over a crystallized ionic solid is what results in spontaneous
dissociation. The ions will therefore be dispersed throughout the solution to maximize solvation, that
is, to maximize ion-dipole interaction that are occurring for as many water molecules to interact with
each individual ion as possible.

This will be the case with most of the ionic solids, which is why ionic solids, whether comprised of
monoatomic or polyatomic ions, tend to be strong electrolytes.

Covalent electrolytes:
Acetic acid, being a weak acid, will only partially dissociate so it is a weak electrolyte. This is also an
example of covalent electrolyte because the molecule contains strictly covalent bonds and unlike
ionic solids that allow their interionic attractions to dissipate in favor of solvation, these covalent
species undergo an actual chemical reaction with the solvent molecules in solution to form charged
products.

These will typically be strong acids and bases that either donate a proton to a water molecule or
remove a proton from a water molecule. For example, hydrogen chloride is a covalent compound,
there are no formally charged particles in this substance, only neutral atoms. But when dissolved in
water it becomes hydrochloric acid, which is a strong acid and will completely transfer all its proton
to water molecules, resulting in a certain amount of hydronium ions and chloride ions. This means
there should be enough ions in solution for it to be considered a strong electrolyte, so that it will
conduct electricity. Of course, the identity of the solvent plays a big part in this, as for hydrochloric
acid to donate a proton, something must accept that proton, so if HCl were to be placed in an aprotic
solvents like ether or hexanes, this would not result in an electrolytic solution, as these solvents can’t
accept any proton the way a water molecule can. But for aqueous solutions, let’s keep in mind that
strong acids and bases will be strong electrolytes because they ionize completely in solution,
whereas weak acids and bases, like acetic acid, will only partially ionize, and will therefore be weak
electrolytes, as they will generate relatively small concentrations of ions in solution.

Lastly, something like ethanol won’t dissociate almost at all, so it won’t generate any current, making
a non-electrolyte. That’s because it doesn’t have appreciable acidity or basicity, so the reactions it
will make with water molecules in solution will be negligible. The same can be said for sugar, and any
other covalent compounds, or water insoluble ionic compounds.

Solid electrolytes
Solids with high ionic conductivity are conventionally known as solid electrolytes.

Solid electrolytes are intermediate between normal crystalline structures having fixed atoms or ions
arranged regularly and liquid electrolytes which do not have regular structures but do have mobile
ions.

Since solid electrolytes exhibit a high ionic conductivity comparable to that of liquid electrolytes,
these solids are also called Superionic solids / superionic conductors.

The first inorganic solid-state electrolytes were discovered in the 19th century by M.Faraday i.e.,
silver sulphide and lead fluoride.

Need of solid electrolytes:

Exploration of novel materials having the potential to be used in the electrochemical cell, such as
battery, fuel cell, electrochromic display or electrochemical sensor, requires a novel electrolyte that
can replace conventional liquid-based electrolytes. The conventional liquid-based batteries have
inherent disadvantages like spillage, time consuming, charging – discharging, limited lifetime,
restricted working, temperature range, etc.

In this regard, solid electrolytes not only eliminate the above limitations of liquid electrolytes but
also come with additional advantages including good electrode-electrolytes contact, non-corrosive.
Lesser weight makes them more portable freedom over shape, size, etc.
Ionic conductivity in solid electrolytes:
A solid compound in which ions migrate through vacancies or empty spaces within the crystal lattice,
which leads to ionic conductivity. In solid electrolytes, one of the welcoming features is that the
number of available sites relative to the number of charge carriers is large.

Materials with high ionic conductivity either anion or cation (move) but not both. They have
negligible electronic conductivity but high ionic conductivity.

A vacancy is a missing particle and when it is moving through the lattice, the vacancy follows a
random path through the solid causing a particle to be displaced over a lattice distance. An
interstitial is an additional or foreign particle present in an ideal crystal. The motion of an interstitial
ion to another interstitial site directly without displacing the other atoms in the lattice is called
DIRECT INTERSTITIAL MECHANISM.

An Interstitial ion can also move by pushing a regular neighbor aside and the latter becoming
Interstitial. When the trajectory of interstitial passes through the lattice, it simultaneously hits the
atomic site, and an atom is displaced effectively over a lattice distance. This mechanism is called
INDIRECT INTERSTITIAL MECHANISM.

Classification:
Solid electrolytes

Based on structure Based on mobile species

1. Framework crystalline materials 1. Anionic electrolytes 2. High disordered materials 2. Cationic

electrolytes Based on structure 1. Framework crystalline material Consist of an almost rigid
crystalline skeleton and mobile ions. These rigid materials have planes or channels through which
ions can move, are called framework electrolyte. (a) Soft framework crystals: The mobile ions are
generally polarizable and heavy The binding is largely ionic The Debye temperature is low Example:
Cul, Agl, etc. (b) Hard framework crystals: They are usually oxides and are characterized byCovalent
bond Passes high frequencies for local vibrations High Debye temperature Low polarizability of the
mobile ions. Example: beta-alumina Type compound. 2. Highly disordered materials are
characterised by their loss of long range order and exhibit large structural complications. (a) Glassy
electrolytes: these materials are either amorphous or crystalline, depending on temperature and
composition; the amorphous material may show a glass transition. Conductivity is rather high at
modest temperatures, especially for amorphous materials. (b) Polymeric solid electrolytes: they offer
technological advantages because the crosslinking of the polymer results in higher mechanical
properties. Based on mobile species 1. Solid cationic electrolytes: They often have a low temperature
form in which the cations are ordered on a subset of sites in the structure; at high temperatures, the
cations become disordered over the sites, and ionic conductivity increases. Example: lithium-ion
conductors, silver-ion conductors, etc. 2. Solid anionic electrolytes: anion mobility can occur at high
temperatures due to the presence of anion vacancies. lon transport in these solids occur by an
interstitial mechanism. Hence, the solid structures that have huge conductivities as they offer a
pathway for the movement of ions. Examples: Fluorides ion conductors, oxides ion conductors, etc.
Applications of solid electrolytes 1. Solid state electrolytes Serve as heat resistive separators as well
as conductors. Highly beneficial because they are free from leakage. Most of these are passive
devices that do not require power sources. 2. Fuel cell Convert chemical energy into electrical
energy. Generates electricity with minimum or no pollution. They are not heated engines and their
for not subjected to carnot cycle. 3. Sensors Measure physical or chemical changes on the system
under investigation. The essential part of sensor is the transducers which converts any physical
quantity to be measured in terms of an electrical signal

Electrolysis

Electrolysis is electrical current flow through a liquid which causes chemical changes. Now all liquids
cannot conduct, the liquid should be a molten ionic compound or an aqueous solution. In either
case, it must be able to carry current. For example, Table salt, if we heat sodium chloride to over 801
degrees Celsius it will melt. The liquid will contain free flowing positive sodium ions and negative
chloride ions. This simply means that sodium and chloride ions are free to move within the liquid
sodium chloride. Now consider putting two electrical conductors into the liquid. Copper would be
good as it has a higher melting point. Nothing happens to the ions at this point. But if we connect the
two bits of copper to an electrical cell or a power supply then things start to get interesting. We do
need to sidestep for a moment to look at electrical current in a metal. We know that electrons in a
metal aren’t bound to a particular atom. They form a sea of electrons that can move easily if a
potential difference or a voltage is applied across it. This could be from an electrical cell or a battery.
The electrons will begin to drift towards the positive terminal of the battery. Current is the
movement of charge. In this case, electrons. Now, let’s go back to our “molten sodium chloride”.
We’ve added our copper wires, let’s call them electrodes, and now we’ll connect these to an
electrical cell. The electrons will start to flow in the wires, and this will cause one electrode to
become positively charged, and the other negatively charged. This has an immediate knock-on effect
in the molten sodium chloride, which you’ll remember, is a mixture of sodium cations and chloride
anions. Anything positively charged in a liquid, in this case the sodium ions, is going to be attracted to
the negative electrode. And anything negatively charged, in this case the chloride ions, is going to be
attracted to the positive electrode. When the ions meet the electrodes electron exchange happens,
and this triggers a chemical reaction. Solids can form, gases can be given off, and new solutions can
be left behind. It all depends on the liquid and what material the electrodes are made from. There
are special names for the electrodes which are usually metal plates with a larger surface area than a
piece of wire. The positive electrode is called the anode, it attracts anions, and the negative
electrode is called the cathode, it attracts cations. The liquid is effectively conducting the electrical
current. The only difference is that the charge carries in the liquid. In other words, the charge
particles that are moving are ions. If a liquid has free moving ions and can conduct like this, it is
called an electrolyte. Remember that electrolysis can also take place in ionic solutions as well as
molten compounds. The more concentrated that solution, the greater the ion flow rate. Ion flow rate
can also be increased by increasing the potential difference or voltage across the cell.