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Notes

MYP 5
Chemistry
A. Electrolysis of acidified water (dilute sulphuric acid)

Electrolysis (of acidified water) is a way of splitting up


(decomposition) of the compound (water) using electrical energy. The
electrical energy comes from a d.c. (direct current) battery or power
pack supply. A conducting liquid, containing ions, called the
electrolyte (dilute sulphuric acid), must contain the compound (water)
that is being broken down. The electricity must flow through
electrodes dipped into the electrolyte to complete the electrical circuit
with the battery. Electrolysis can only happen when the circuit is
complete, and an electrical current (electricity) is flowing, then the
products of electrolysing dil. sulphuric acid are released on the
electrode surfaces where they can be collected. Electrolysis always
involves a flow of electrons in the external wires and electrodes and a
flow of ions in the electrolyte and there is always a reduction at the
negative cathode electrode (which attracts positive ions, cations) and
an oxidation at the positive anode electrode (which attracts negative
ions, anions) and it is the ions which are discharged to give the
products.
The products of electrolysing water acidified with sulfuric acid
are hydrogen gas and oxygen gas
The electrolyte is dilute sulphuric acid (= acidified water) which,
during electrolysis is split into hydrogen and oxygen gases.
Theoretically into a 2: 1 ratio by gas volume.
Water only ionises to a tiny extent giving minute concentrations of
hydrogen ions and hydroxide ions, so the presence of high
concentrations of hydrogen ions (H+ or H3O+) and sulphate
ions (SO42) from the acid, makes water a much better electrical
conductor (a much better electrolyte solution). These small extra ion
concentrations of hydrogen ions (H+) and hydroxide ions (OH) are
from the self-ionisation of water itself.

The electrode reactions and products of the electrolysis of acidified


water are illustrated by the theory diagram above
The half-equations for the electrolysis of water (electrolyte of acidified with
dilute sulphuric acid).

(a) The negative cathode electrode reaction for the electrolysis of water
The negative cathode electrode reaction is a reduction (electron gain).
The hydrogen ions (H+) are attracted to the negative cathode and are
discharged as hydrogen gas.
The hydrogen ion or water molecules are reduced to hydrogen gas
molecules by electron gain at the negative electrode
2H+(aq) + 2e ==> H2(g) (hydrogen gas, bubbles seen on the negative
electrode)
positive ion reduction by electron gain

or 2H3O+(aq) + 2e ==> H2(g) + 2H2O(l)


All three equations amount to the same overall change i.e. the formation of
hydrogen gas molecules and the electrolysis of many salts (of reactive
metals) or acid solutions produce hydrogen at the negative cathode
electrode. All acids give hydrogen at the cathode.
(b) The positive anode electrode reaction for the electrolysis of water
The positive anode reaction is an oxidation electrode reaction (electron
loss).
The negative sulphate ions (SO42-) or the traces of hydroxide ions (OH) are
attracted to the positive electrode. But the sulfate ion is too stable and
nothing happens. Instead either hydroxide ions or water molecules are
discharged and oxidised to form oxygen.
The hydroxide ions or water molecules are oxidised to oxygen gas
molecules by electron loss at the positive electrode
(i) (+) 2H2O(l) 4e ==> 4H+(aq) + O2(g) (oxygen gas)
or 2H2O(l) ==> 4H+(aq) + O2(g) + 4e
molecule oxidation by electron loss
(ii) 4OH(aq) 4e ==> 2H2O(l) + O2(g) (oxygen gas)
negative ion oxidation by electron loss
or 4OH(aq) ==> 2H2O(l) + O2(g) + 4e
Overall equation for the electrolysis of water: 2H2O(l) ==> 2H2(g) + O2(g)

Overall equation for the electrolysis of water: 2H2O(l) ==> 2H2(g) + O2(g)

B.The electrolysis will only take place when electricity is passed


through the sodium chloride solution.

he electrolyte sodium chloride solution (brine), provides a high


concentration of sodium ions Na+ and chloride ions Cl to carry the current
during the electrolysis process. Initially there are only traces of hydrogen
ions H+ and hydroxide ions OH from the self-ionisation of water.
Brine is moderately concentrated sodium chloride solution (brine) with
carbon (graphite) gives equal volumes of hydrogen gas (hydrogen
ions H+ discharged at the ve cathode) and green chlorine gas (chloride
ions Cl discharged at the +ve anode) withsodium hydroxide left in
solution. The electrolysis will only take place when electricity is passed
through the sodium chloride solution.
The electrode equations and the theory of what happens in the
electrolysis of aqueous sodium chloride
The half-equations for the electrolysis of sodium chloride solution (the
electrolyte brine).

(a) The negative cathode electrode reaction for the electrolysis of brine
(sodium chloride solution)
The negative () cathode attracts the Na+ (from sodium chloride)
and H+ ions (from water). Only the hydrogen ions are discharged at the
cathode. The more reactive a metal, the less readily its ion is reduced on
the electrode surface.
The hydrogen ions are reduced by electron (e) gain to form hydrogen
molecules at the negative electrode which attracts positive ions.
2H+(aq) + 2e ==> H2(g)
positive ion reduction by electron gain
other equations
2H2O(l) + 2e ==> H2(g) + 2OH-(aq)
or 2H3O+(aq) + 2e ==> H2(g) + 2H2O(l)
Nothing happens to the sodium ion, but it is still important (see after the
anode reaction has been described).

Test for the cathode gas - colourless gas gives a squeaky pop with a lit
splint hydrogen

(b) The positive anode electrode reaction for the electrolysis of brine
(sodium chloride solution)
The positive anode attracts the negative hydroxide OH ions (from water)
and chloride Cl ions (from sodium chloride). Only the chloride ion is
discharged in appreciable quantities i.e. it is preferentially oxidised to
chlorine.
The chloride ions are oxidised by electron loss to give chlorine molecules at
the positive electrode which attracts negative ions.

an oxidation electrode reaction


2Cl(aq) 2e ==> Cl2(g)
or 2Cl ==> Cl2(g) + 2e
negative ion oxidation by electron loss

Test for the anode gas - pale green gas turns damp blue litmus red and
then bleaches it white chlorine (test 2 gas 2)

Usually nothing happens to the hydroxide ion BUT it is important, because,


the hydroxide ion, with the unchanged sodium ion, the residual solution
contains sodium hydroxide. In fact this is how sodium hydroxide is
manufactured in the chemical industry.
Na+ + OH = NaOH, a familiar formula! The presence of the alkali sodium
hydroxide, can be shown by adding universal indicator to the brine solution
(aqueous sodium chloride). The indicator will turn from green to purple.

Note that, if most of the chloride ions have been discharged as chlorine
molecules, you can then get some oxygen gas formed at the anode i.e. like
in the electrolysis of water, and chloride ions are being replaced by
hydroxide ions which can be oxidised to oxygen at the anode.
2H2O(l) 4e ==> 4H+(aq) + O2(g)
or
4OH(aq) 4e ==> 2H2O(l) + O2(g) (oxygen gas)

C. Electrolysis of molten sodium chloride gives silvery sodium metal


and pale green chlorine gas.
This is a simpler electrolysis situation where the ionic compound sodium
chloride on melting provides a highly concentrated mixture of positive
sodium ions and negative chloride ions. It also illustrates the difference
sometimes, between electrolysing the pure molten salt and its aqueous
solution in water. Here there is no possibility of hydrogen being formed.

(i) molten sodium formed at the negative cathode electrode which attracts
the positive sodium ions

Na+(l) + e ==> Na(l) a reduction electrode reaction (electron gain)


positive ion reduction by electron gain
sodium ion reduced to sodium metal atoms: typical of electrolysis of
molten chloride salts to make chlorine and the metal

(ii) chlorine gas formed at the positive anode electrode which attracts the
negative chloride ions
2Cl(l) 2e ==> Cl2(g)
or 2Cl(l) ==> Cl2(g) + 2e an oxidation electrode reaction (electron loss)
negative oxidation by electron loss.
SUMMARY OF PRODUCTS FROM THE ELECTROLYSIS OF SODIUM
CHLORIDE solution or melt
with inert electrodes like carbon (graphite) or platinum

Electrolyte

molten
sodium
chloride
NaCl(l)
aqueous
sodium
chloride
solution
(brine)
NaCl(aq)

negati
ve
catho
de
produ
ct
molte
n
sodiu
m

negative electrode
cathode half-equation

Na+(l) + e ==> Na(l)

positi
positive electrode
ve
anod
e
anode half-equation
prod
uct
chlor
ine
gas

2Cl(l) 2e ==> Cl2(g)


or 2Cl(l) ==> Cl2(g) +
2e

2H+(aq) + 2e ==> H2(g)


hydro
gen

2Cl(aq) 2e ==> Cl2(g)


or 2H3O+(aq) + 2e ==> H2(g) + chlor
2H2O(l)
ine
or 2Cl(aq) ==> Cl2(g) +
gas
2e
or 2H2O(l) + 2e ==> H2(g) +
2OH(aq)

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