Chlorine

Tonion Smith
Celetia Corral
Kimberly Fagan

Electrolysis of brine using the

diaphragm cell
Electrolysis of brine (sodium chloride) solution
can be used to make three useful substances
chlorine
sodium hydroxide
hydrogen

Three types of cells are used in the

electrolysis of brine:
Mercury Cells
Diaphragm Cells
Membrane Cells

Electrolysis of brine using the

diaphragm cell
Brine is a concentrated solution of
sodium chloride ranging from about
3.5% to 26%
Brine consists of high concentrations of
Na+ and Cl- ions
Water is present in lower
concentrations
H+ and OH- ions are produced from the
equilibrium of water with its ions:

The Diaphragm Cell

http://www.greener-industry.org.uk/pages/chlorine/7chlorine_PM2.htm

Electrolysis using the Diaphragm

Cell
At the Anode:
The anode is the positively charged
electrode
The anode is in the diaphragm cell is titanium
Negative ions, Cl- and OH-, are attracted
towards the positive anode
It is easier to liberate OH- ions (to give oxygen)
than Cl- ions (to give chlorine), however, Clions are higher in concentration than OHions in brine
Cl- ions are selectively oxidised at the anode

At the Anode
Major reaction at Anode:
Chlorine is produced according to the
equation:

Chloride ions lose electrons at the

anode (oxidation), and the atoms
produced combine to give chlorine
gas

At the Anode
Chlorine is contaminated with small
amounts of oxygen due to oxidation
of OH- ions (from water)

Chlorine is purified by liquefying

under pressure to remove oxygen (O2
stays as a gas when compressed)

At the Cathode
The cathode is the negatively,
charged electrode
The cathode in the diaphragm cell is
steel
Na+ and H+ ions (from the water) are
attracted to the negative cathode
It is much easier for a H+ ion to pick
up an electron (to form H2) than for a
Na+ ion (to form Na metal)

At the Cathode
Major reaction at Cathode:
Hydrogen gas is produce according to
the following equation:

2H+(aq) + 2e H2(g)
Hydrogen ions are reduced
As the hydrogen ions are removed and
converted into H2 gas, the water
equilibrium shifts to the right to replace
them (Le Chateliers principle)

Net effect:
there is a build up of sodium ions and newlyproduced hydroxide ions around the cathode
Na+ and OH- ions combine to form dilute
solution of sodium hydroxide at the cathode

The Diaphragm Cell (contd)

The sodium hydroxide solution leaving
the cell:
is highly contaminated with unchanged NaCl
solution
is concentrated by evaporation during
which, NaCl crystallizes out as solid
The crystallized salt can be separated,
dissolved in water, and passed through the
cell again
Even after concentration, the sodium
hydroxide solution will still contain a small
percentage of sodium chloride

Function of the Diaphragm

The diaphragm:
separates the anode and cathode, but allows
ions to pass in both directions
is a porous mixture of asbestos and polymers

There is a higher level of liquid on the anode

side:
to make sure that the flow of liquid is always from
left to right (from anode to cathode)
to prevent the NaOH solution that is formed from
finding its way back to where chlorine is being
produced

The need to keep all the products

separated
If chlorine gas comes into contact with
hydrogen gas, it will produce a mixture
(hydrogen chloride gas) which will
explode violently on exposure to sunlight
or heat
If chlorine gas comes in contact with
sodium hydroxide solution a mixture of
sodium chloride and sodium hypochlorite
(the main ingredient in bleach) is formed

The need to keep all the products

separated
Therefore, if you are trying to
manufacture chlorine and sodium
hydroxide rather than bleach, you
have to keep the chlorine and
sodium hydroxide apart as well
The diaphragm and membrane cells
are designed so that all the products
are kept separate

The Membrane Cell

Anode and cathode are
separated by a polymer
membrane that only
allows positivelycharged cations to
flow through it
Membrane can only be
permeated by sodium
cations (Na+)
Membrane restricts the
flow of chloride (Cl-) and
hydroxide (OH-) anions,
as well as water
molecules

Electrolysis using membrane cell

Electrolysis using membrane cell

At the Anode:
Chlorine anions are reduced at the
titanium anode:
2Cl-(aq) Cl2(g) + 2eJust like in the diaphragm cell, the chlorine
gas is contaminated with oxygen gas, so it
is liquefied under pressure to separate it
from the oxygen (which remains in
gaseous state under liquefaction)

Electrolysis using membrane

cell
At the cathode:
Hydrogen gas is produced just as in the diaphragm
cell
A sodium hydroxide solution of approximately 33%
purity is produced as well:
Na+(aq) + e- Na(l)
Na(l) + H2O(l) NaOH(aq)
The membrane cell has a major advantage of the
polymer membrane not allowing the propagation of
OH- ions and Cl- anions from the cathode to the anode
thus producing a purer sodium hydroxide solution

The Mercury Cell

Electrolysis using Mercury

Cell

Anode:

The anodes may be graphite or titanium

Chloride is oxidized as shown:
Cl-(aq) Cl2(g) + 2ePassing a current through the brine solution
causes chloride anions to flow to the anodes
Cl- ions are oxidized into chlorine gas, which
escapes the cell and is collected externally

Electrolysis using Mercury

Cell
Cathode:
A thin layer of flowing mercury used as the
cathode
Sodium cations are reduced to sodium metal:
Na+(aq) + e- Na(l)
The sodium metal that is formed dissolves in
the mercury to form an amalgam:
Na(l) + Hg(l) Na-Hg (Na amalgam)
An amalgam is any substance formed by the
reaction of mercury with another metal

Electrolysis using Mercury

Cell

See diagram on slide 19:

Brine floats on top of the amalgam, allowing
the metals to be tapped off of the bottom of
the vessel
From there, they flow to a second vessel that
has been partly filled with water
The amalgam reacts with the water as shown:
2Na(l) (+Hg(l)) + 2H2O 2NaOH(aq) + H2(g) (+Hg(l))
H2 gas is released
NaOH solution is left in a pure, aqueous form
After Na metal is removed, the remaining mercury is
recycled back into the electrolytic cell

Summary of three methods

Anode
(+ve)

Diaphragm
Membran
Cell
Mercury Cell e
Graphite or
Titanium

Titanium

Cathode (ve)
Steel

Mercury

Nickel

Product at
Cl2
Anode

Cl2

Cl2

Product at
H2, NaOH
Cathode

Na Amalgam,
NaOH, H2
H2, NaOH

Titanium

Comparison of three
methods
Diaphragm Cell:
cell is relatively cheap to produce
keeps the chlorine gas and sodium
hydroxide products separated at the end
of the electrolysis process
does not produce a pure NaOH solution,
even after concentration it will still be
slightly tainted with a small percentage
of NaCl

Comparison of three
methods
Membrane Cell:
more expensive than a diaphragm cell but
cheaper than a mercury cell
preferred over the diaphragm cell or mercury
cell method because it uses the least amount
of electric energy
has a major advantage since the cationexchange membrane does not allow the
passage of OH- and Cl- anions from the
cathode to the anode (thus producing a
purer sodium hydroxide solution)

Comparison of three
methods
Mercury Cell:
are the most expensive cells to build
reaction needs a higher voltage than the
diaphragm cell
Sodium formed at the cathode forms an
amalgam with mercury from the cathode
Mercury can be recycled
potential damage to the environment due
to mercury deposits (toxic effects of Hg)

Industrial importance of chlor-alkali

products
Chlorine:
Used to make solvents for dry cleaning,
metal work and the electronics industry
Used in the manufacture of products such
as :
Dyes
Antiseptic
Insecticides
Paints

Industrial importance of chlor-alkali

products
Chlorine (contd):
Used as a disinfectant in water treatment
- kills bacteria and other microbes in drinking
water and swimming pools
- It is used to make household bleach

Largest use of chlorine is the production of

organic compounds such as poly vinyl
chloride (PVC) and chlorofluorocarbons
(CFCs)
Used along with other compounds to bleach
wood pulp in paper production

Industrial importance of chlor-alkali

products
Sodium Hydroxide:
Sodium hydroxide is strongly alkaline
and is used in the production of:
Soaps
Ceramics
Oven cleaner

Industrial importance of the chlorine

and its compounds

Poly vinyl chloride (PVC)

PVC is predominant in the construction industry due to its
low production cost, ease to mold and lightweight
It is used as a replacement for metal in many applications
where corrosion can compromise functionality and
escalate maintenance costs
Used in industrial and municipal applications to make pipe
fitting and pipe conduits
Used in the health care industry it is used to make feeding
tubes, blood bags, intravenous (IV) bags, parts of dialysis
devices etc.
Common consumer products such as raincoats, plastic
bags, toys, credit cards, hoses, doors and window frames
etc.

Industrial importance of the the

chlorine and its compounds
Chlorofluorocarbons (CFCs)
CFCs are generally unreactive and stable,
non-toxic and non-flammable
Used in refrigeration systems and air
conditioners
Used as solvents to clean electronic
components
Used as blowing agents in the production
of plastic foams
Used as propellants in air conditioners

Impact of the chlor-alkaline Industry

on the environment
Mercury
The pollutant of most concern from the chloralkali industry is mercury, which is specific to
the mercury cell.
Between 1930 and 1960, several tonnes of
mercury waste were dumped in Minamata Bay in
Japan.
Thousands of people living around the bay
developed methyl mercury poisoning through the
consumption fish.
The victims suffered from severe neurological
damage, which later became known as Minamata
Disease

Impact of the chlor-alkaline Industry

on the environment (contd)
Mercury (contd)
Japan was the first country to install the
membrane cells on a massive scale in the mid1980s.
In other countries, the replacement of the
existing mercury and diaphragm cell with
membrane cells is taking place at a slower rate
because of the high capital costs of
replacement and the fact that most existing
chlorine plants were installed with a plant life of
40-60 years

Impact of the chlor-alkaline Industry

on the environment

Asbestos
The main problem with the diaphragm cell is
asbestos.
Dry asbestos fibres can cause serious health
problems if the not properly used and handled
in the diaphragm process.
Asbestos fibres are toxic, thin , sharp crystals,
which are considered to be carcinogenic.
They can enter the human body by either
inhalation or ingestion causing lung cancer,
asbestosis, and or mesothelioma.

Impact of the chlor-alkaline Industry

on the environment
Chlorine and chlorinated products

Other concerns of the chlor-alkali industry

are associated with the chemical processes
that use chlorine
Chlorine bleaching of wood pulp releases
dioxins in the environment.
The production of chlorofluorocarbons
(CFCs) contributes to the depletion of the
ozone layer.
PVC is not biodegradable