LAB ASSISTANT – KWA

CHEMISTRY - MODULE 1
ELECTROCHEMISTRY, SURFACE CHEMISTRY

Electrochemistry- Electrochemical cell & Electrolytic Cell

 Electrochemistry is the branch of chemistry concerned with the relation
between electrical energy and chemical energy.

Electrochemical cell
 devices that convert chemical energy of some redox reactions to
electrical energy.
The cells are of two types:
(a) Galvanic cells
(b) Electrolytic cells

Galvanic cell
 It converts chemical energy to electrical energy. Also called Voltaic cells.
Eg:-Daniel cell.
 It is constructed by dipping a Zn rod in ZnSO4 solution and a Cu rod in
CuSO4 solution.
 The two solutions are connected externally by a metallic wire through a
voltmeter and a switch and internally by a salt bridge.

 two half cell reactions:

(i) Cu2+ + 2 e- → Cu(s) (reduction half reaction)
(ii) Zn(s) → Zn2+ + 2 e- (oxidation half reaction)
  Overall Cell reaction - Zn(s) + Cu2+(aq) → Zn2+ (aq) + Cu(s)
 For Daniel cell, the cell representation
Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s)

 The reduction half reaction occurs on the copper electrode

 the oxidation half reaction occurs on the zinc electrode.
 These two portions of the cell are also called half-cells or redox couples.
 The copper electrode is called the reduction half cell and the zinc
electrode, the oxidation half-cell.
 Nernst Equation for Daniel Cell -

OR

Salt Bridge
 Its is a U-tube containing an inert electrolyte like NaNO3 or KNO3 in a
gelly like substance.
 The functions are
1. To complete the electrical circute.
2. To maintain the electrical neutrality in the two half cells.
Electrode Potential
 The tendency of a metal to lose or gain electron when it is in contact
with its own solution is called electrode potential.
 When the concentrations of all the species involved in a half-cell is unity
then the electrode potential is known as standard electrode potential.
 According to IUPAC convention, standard reduction potential is taken as
the standard electrode potential.
 In a galvanic cell, the half-cell in which oxidation takes place is called
anode and it has a negative potential. The other half-cell in which
reduction takes place is called cathode and it has a positive potential.
 In a cell, the electrons flow from negative electrode to positive electrode
and the current flows in the opposite direction.
  The potential difference between the two electrodes of a galvanic cell is
called the cell potential and is measured in volts.
 The cell electromotive force (emf) of the cell is the potential difference
between the two electrodes, when no current is flow through the cell.
 a galvanic cell, the anode is written on the left side and the cathode on
the right side. Metal and electrolyte solution are separated by putting a
vertical line and a salt bridge is denoted by putting a double vertical line.
Ecell = Eright – Eleft

Standard Hydrogen Electrode (SHE)

The potential of an individual half-cell cannot be measured. We can measure
only the difference between the two half-cell potentials that gives the emf of
the cell. For this purpose a half-cell called Standard Hydrogen Electrode (SHE)
or Normal Hydrogen Electrode (NHE) is used.
 Representation - Pt(s)|H2(g)|H+(aq)
 the electrode potential of SHE is zero
 Conditions - 1M HCl and hydrogen gas at 1atm pressure and
temperature maintained at 25℃
 It can act as anode half cell and cathode half cell as well.

 If we use a standard hydrogen electrode as reference to determine the

electrode potential of another electrode of half cell connected to SHE
then unknown potential will be equal to electromotive force of the cell.
Disadvantages of SHE
 It’s difficult to transport.
 It's difficult to construct and maintain.
 It's difficult to maintain the pressure of hydrogen gas and concentration
of the acid solution taken such as HCl.
  It's difficult to get pure hydrogen gas.
 It's difficult to make an ideal platinum electrode.
 Generally, impurities in hydrogen and HCl spoil ideal platinum electrodes
and reduce the life of standard hydrogen electrodes.
Electrochemical series
 It is a series in which various electrodes are arranged in the decreasing
order of their reduction potential. fluorine is at the top indicating that
fluorine gas (F2) has the maximum tendency to get reduced to fluoride
ions (F–). Therefore fluorine gas is the strongest oxidising agent and
fluoride ion is the weakest reducing agent.
 Lithium has the lowest electrode potential indicating that lithium ion is
the weakest oxidising agent while lithium metal is the most powerful
reducing agent in an aqueous solution.

Electrolytic cell
 Device which converts electrical energy to chemical energy
 In comparison to the galvanic cell, the electrodes of an electrolytic cell
can be placed in a single compartment containing the molten or
aqueous electrolyte.
 since the external battery source is what drives the electrons through
the circuit, the electrodes will match the positive and negative terminal
of the battery.
 Anode: The negative electrode
 Cathode: The positive electrode
  Electrolyte: A salt solution
 The cathode undergoes oxidation, and the anode undergoes reduction.
 Both electrodes are dipped in the same electrolyte.
 When an external voltage is applied, the electrons start flowing from the
cathode to the anode.
 Used for the decomposition of compound
 Eg: Nickel iron cell, when CuSO4 solution is electrolysed by Cu
electrodes, Cu is deposited at the cathode and Cu2+ ions are liberated
from the anode.

How do electrolytic cells work?

When an external electric current flows into the cathode of the electrolytic
cell, the resulting negative charge attracts the dissociated positive ions present
in the electrolyte. This results in the deposition of the positively charged ions
onto the cathode. At the same time, the negatively charged ions flow towards
the anode, which is positively charged.
 Eg : two inert electrodes are dipped into molten sodium chloride (which
contains dissociated Na+ cations and Cl– anions). When an electric
current is passed into the circuit, the cathode becomes rich in electrons
and develops a negative charge. The positively charged sodium cations
are now attracted towards the negatively charged cathode. This results
in the formation of metallic sodium at the cathode.
 Simultaneously, the chlorine atoms are attracted to the positively
charged cathode. This results in the formation of chlorine gas (Cl2) at the
anode (which is accompanied by the liberation of 2 electrons, finishing
the circuit).

 Reaction at Cathode: [Na+ + e– → Na] x 2

 Reaction at Anode: 2Cl– → Cl2 + 2e–
 Cell Reaction: 2NaCl → 2Na + Cl2
  Thus, molten sodium chloride can be subjected to electrolysis in an
electrolytic cell to generate metallic sodium and chlorine gas as the
products.

Application of Electrolytic cell

 Used for the production of oxygen gas and hydrogen gas from water.
 They are also used for the extraction of aluminium from bauxite.
 Used in electroplating, which is the process of forming a thin protective
layer of a specific metal on the surface of another metal.
 The electrorefining of many non-ferrous metals is done with the help of
electrolytic cells.
 also used in electrowinning processes.
 In industrial production of high-purity copper, high-purity zinc, and high-
purity aluminium is almost always done through electrolytic cells.

Surface Chemistry – Colloids & Emulsions

 A colloid is intermediates of true solution and suspension with range of
diameters of particle between 1 and 1000 nm.
Classification of colloids
1. Based on Nature of attraction between Dispersed Phase and Dispersion
Medium

Lyophillic sols(solvent loving) Lyophobic sols(solvent hating)

1.There is much attraction existing
between Dispersed medium and
Dispersed phase. Eg;starch sol
2.Formed by simply mixing
Dispersed medium and Dispersed
phase
3.Reversible sols
4.Stable
There is less attraction existing
between Dispersed medium and
Dispersed phase. Eg; Gold sol
Requires special methods
Irreversible sols.
Unstable

2. Based on Type of Particles of the Dispersed Phase

(i) Multimolecular (ii) Macromolecular (iii)Associated colloids

colloids: colloids: (Micelles):
These are formed by These type colloidal There are some
the association of systems contain substances which at
atoms or smaller macromolecules with low concentrations
molecules of diameter particle size in colloidal behave as normal
< 1nm to form species range. Examples are strong electrolytes, but
having size in the starch, cellulose etc at higher
colloidal range. For concentrations they
example, a gold sol. exhibit colloidal
behavior. Eg: Soap
solution
Preparation of Colloids
• Electrical disintegration or Bredig’s Arc method - Colloidal sols of metals
such as gold, silver, platinum, etc., can be prepared by this method. In this
method, electric arc is struck between electrodes of the metal immersed in
the dispersion medium
• Peptization - Peptization may be defined as the process of converting a
precipitate into colloidal sol by shaking it with dispersion medium in the
presence of a small amount of electrolyte.
Properties of colloids
• Tyndall effect: When a strong beam of light is passed through colloid, the
path of the path of the beam can be observed,termed as Tyndall effect. The
Tyndall effect is due to the scattering of light by colloidal particles.
Zsigmondy used Tyndall effect to set up an apparatus known as
ultramicroscope.
• Brownian movement: Zig-zag motion of colloidal particles in the
dispersion medium
• Charge on colloidal particles: Colloidal particles always carry an electric
charge.
• Electrophoresis: The movement of colloidal particles towards anode or
cathode under an applied electric potential
• Coagulation : The process of settling of colloidal particles is called
coagulation of the sol. When excess of an electrolyte is added to colloidal
solution, negative ion causes the precipitation of positively charged sol and
vice versa.
Hardy-Schulze rule
 the greater the charge of the coagulating ion added, the greater is its
power to cause coagulation.This is known as Hardy-Schulze rule.
 In the coagulation of a negative sol, the flocculating power is in the
order: Al3+>Ba2+>Na+ Similarly, in the coagulation of a positive sol, the
flocculating power is in the order: [Fe(CN) 6]4– > PO4 3– > SO4 2– > Cl-
Emulsions
 Colloids where both the Dispersion phase and Dispersion medium are
liquids.
 Emulsions are biphasic liquid systems consisting of two immiscible liquid
phases. These phases are present in such as way that one phase is
dispersed in the other continuous phase.
 Examples - mayonnaise, milk, lotions, etc.
 There are two types of emulsions.
Oil dispersed in water (O/W type) Water dispersed in oil (W/O type).

The oil phase is dispersed in a The aqueous phase is the dispersed

continuous aqueous phase
Eg;Milk and vanishing cream
Emulsifying agents :
Proteins,gums
phase and the oil phase is the
continuous phase,
Eg: butter ,cold cream,code liver
oil
Emulsifying agents : Long chain
alcohols, lampblack

Properties of Emulsions

 Emulsion form dynamic inhomogeneous structures on small length

scale.
 Emulsions are highly unstable systems and require an emulsifying
agent or emulsifier ( These are usually surface active agents also
known as “surfactants”)
 Emulsions are prepared by continuous mixing or agitation of the two
phases
 When kept for longer periods of time or in case of absence of an
emulsifying agent, the phases in the emulsion tend to separate,
resulting in “cracking of emulsion” or ” phase inversion”.
Emulsifying Agents

 These are surface active agents that are added to the emulsions to
stabilize the two phases. It acts on the interface and increases the kinetic
stability of an emulsion so that the size of the droplets does not change
significantly with time, thus stabilizing the emulsion.

 According to the Bancroft rule, Emulsifiers and emulsifying particles tend

to promote dispersion of the phase in which they do not dissolve very
well. For example, proteins dissolve better in water than in oil, and so tend
to form oil-in-water emulsions (that is, they promote the dispersion of oil
droplets throughout a continuous phase of water)

 Emulsifiers that are more soluble in water generally form oil-in-water

emulsions, while emulsifiers that are more soluble in oil will form water-in-
oil emulsions. Examples include egg yolk, sodium phosphates, sodium
stearoyl lactylate, etc

Mechanisms of Emulsification

A number of different chemical and physical processes and mechanisms can be

involved in the process of emulsification.

 Surface tension theory – According to this theory, emulsification

takes place by the reduction of interfacial tension between two
phases
 Repulsion theory – The theory proposes that the emulsifying agent
creates a film over one phase that forms globules, which repel each
other. This repulsive force causes them to remain suspended in the
dispersion medium
 Viscosity modification – Certain emulgents such as acacia,
tragacanth, carboxymethylcellulose, polyethylene glycol, etc increase
the viscosity of the medium, which helps create and maintain the
suspension of globules of the dispersed phase
Instabilities in Emulsions

The ability of an emulsion to retain its properties over time is known as the
stability of an emulsion..
  Flocculation – When the particles or droplets of the dispersed phase
aggregate together on account of attractive forces, the phenomenon
is known as flocculation and results in an unstable system.
Flocculation is mainly observed in case of oil in water type of
emulsions.
 Coalescence – When the droplets of discontinuous phase bump into
each other to form a larger droplet thus increasing the average
particle size over time, it is known as coalescence which is a form of
instability.
 Creaming – When the droplets in an emulsion rise to the top of the
emulsion under the influence of buoyancy or centripetal force, it
results in the creaming of emulsion
 Ostwald Ripening – It describes the change of an inhomogeneous
structure over time, i.e., small crystals or sol particles dissolve and
redeposit onto larger crystals or sol particles. Ostwald ripening is
generally found in water-in-oil emulsions.

Uses of Emulsion

 As Food: Oil-in-water emulsions are common in food products.

Examples include butter, margarine, homogenized milk, mayonnaise,
etc
 In Healthcare Many cosmetic and pharmaceutical dosage forms are
in the form of emulsions. Cosmetics such as lotions, creams, biphasic
makeup removers are in fact emulsions. Many oral, as well as topical
dosage forms, are emulsions. Microemulsions are used to deliver
vaccines and kill microbes. Cod liver oil, cortisol, polysporin are some
examples of emulsion formulations.
 In Chemical Synthesis Emulsions are used in the manufacturing of
polymer dispersions. These include primary components of glues and
paints.
Colloids around us
 The sky’s color is blue: The sky looks blue because dust particles and
water floating in the air scatter blue light reaching our eyes.

 Blood: Albumin protein contains respiratory pigments that are water-

soluble. The pigmented system utilizes albumin as that of the phase
separation and uses water as a dispersion medium.

 Soils: Humus acts as a protective colloid infertile soil, colloid in nature.

Because of its colloidal nature, soil collects moisture and nutritious
ingredients.

 The delta’s formation: A colloidal clay solution can be found in river

water. Seawater contains a wide range of electrolytes. The electrolytes
from seawater cause the colloidal solution of clay to solidify, producing
its deposition and creating the delta whenever river water joins
seawater.

 liquid aerosol

 The aerosol sprays that we either use as personal perfumatory products

usually contain aerosol
 The various types of insecticide spray or repellents we use against
mosquitoes and other insects
 Smog or the smoke and fog combination which creates a thick slowly
moving colloidal material. Naturally occurring fog and clouds
 Solid aerosol

 The naturally occurring smoke or man-made fire smoke carries

suspended particles in the air
 Dust storm or simply dust in the atmosphere
 Foam

 The shaving cream lather used for shaving purpose

 The whipped cream we get to see in cream batter
 Emulsion

 Various types of cosmetic lotions we use on a daily basis

 Mayonnaise we use as bread spread
 Naturally occurring milk
 Gels

 The butter that we usually use as bread spread

 Jelly products that we use as various spreads
 Sols

 Man-made paints
 Ink and other products which are basically combination made at a high
temperature
 Solid sols

 Various products made from Styrofoam, insulation and other cushion

materials
 Apart from these, there are many bio colloids which we get to see on a
daily basis like medicines and injectables