 What controls the rate of electrolysis?

What controls how

much product is formed?

 The amount of material in moles formed at the electrode in

electrolysis depends on three factors.

o The quantity of any product produced from electrolysis,

and its rate of production, depends on the number of
electrons that are transferred in the external circuit and
how fast the electrons flow in the circuit.

o The charge on the ion - the bigger the charge on the

ions, the more electrons must be transferred to give one
mole of the product compare the effect of one mole of
electrons in the table above and see examples 13.1.1 to
13.1.5 below in Part one)

o The current flow, current is the rate of flow of charge,

the higher the current flow (in amps), the more electrons
are transferred per unit time e.g. seconds (the current
flowing in amperes, A, see examples in Part two).
Therefore, the rate of product formation is proportional to
current.

o The time duration of the electrolysis, the longer the

electrolysis runs for, the more product is formed (time in
seconds, minutes or hours, see examples in Part two). 
Therefore, the amount of product formed is proportional
to time.

 If you know how much of a substance is made at one

electrode, you can theoretically calculate the amount of
substance formed at the other electrode.

 The basis of these calculations is the ratio of the electrons

involved in both electrode reactions (hence the introductory
table of electrode equations above).

 The electrode equations in the table above are referred to

in the examples below.

 In studying the examples below you must refer to the electrode

equations in the table above,
 o and remember 1 mole = formula mass in grams and 1
mol of gas = 24 dm3 at room temperature/pressure..

 Electrolysis calculation Example 13.1.1

o The electrolysis of brine, aqueous sodium chloride

solution, NaCl(aq) produces hydrogen gas, H2(g) at the -ve
electrode and chlorine gas, Cl2(g) at the positive electrode.
Atomic masses: H = 1, Cl = 35.5

o 2H+(aq) + 2e- ==> H2(g) and 2Cl-(l/aq) - 2e- ==> Cl2(g)

o 2 electrons are involved in both the formation of a

hydrogen molecule [Mr(H2) = 2] or a chlorine molecule
[Mr(Cl2) = 71].

o The ratio of the products for H2(g) : Cl2(g)  is 1 mol : 1

mol or 24dm3 : 24 dm3 or 2g : 71g

 If during the electrolysis of sodium chloride

solution, 25 cm3 of hydrogen were produced,
what volume of chlorine is theoretically
formed?

 Since the mole ratio is 1 : 1 for H2 : Cl2 for every 25

cm3 of hydrogen formed, 25 cm3 of chlorine will be
formed.

 Electrolysis calculation Example 13.1.2

o The electrolysis of molten aluminium oxide Al2O3 is a

more complicated affair. 

o Its best to think of the ratio effect of a current of 12 moles

of electrons passing through the electrolyte.

 4Al3+(l) + 12e- ==> 4Al(l) and 6O2-(l) - 12e- ==> 3O2(g)

 It takes 3 moles of electrons to form 1 mole of Al

from 1 mole of Al3+ ions.

 and 4 moles of electrons to form 1 mole of

O2 molecules from 2 moles of O2- ions.

 Atomic masses: Al = 27, O = 16

 o The ratio of the products from 12 moles of electrons is
therefore

   Al(l) : O2(g) is 4 mol : 3 mol or 108g : 96g or

72dm3.

o If 0.1 mol of molten aluminium oxide is completely

electrolysed (i) what mass of aluminium is formed
and (ii) what volume of oxygen is formed (at RTP)

 atomic mass Al = 27, molar volume of any gas at

RTP = 24 dm3

 (i) From 1 mole of Al2O3 you get 2 moles of Al

 therefore from 0.1 mol of Al2O3 you get 0.2

mol of Al

 mass Al = moles Al x atomic mass

 mass Al = 0.2 x 27 = 0.54 g Al

 (ii) From 1 mole of Al2O3 you get the equivalent of 3

moles of O atoms,

 BUT you must treat this as 1.5 mol

O2 molecules

 therefore from 1 mol Al2O3 you get 1.5 mol of

O2 molecules

 so from 0.1 mol Al2O3 you get 0.15 mol of

O2 gas

 volume of oxygen gas = moles of oxygen gas

x 24

 volume of oxygen = 0.15 x 24 = 3.6

dm3 (3600 cm3)

 Electrolysis calculation Example 13.1.3

o In the electrolysis of dilute sulphuric acid, 36 cm3 of

hydrogen, H2 was formed at the negative electrode
(cathode).
 o What volume of oxygen, O2 would be formed at the
positive electrode (anode)?

o 2H+(aq) + 2e- ==> H2(g) and 4OH-(aq) - 4e- ==> 2H2O(l) + O2(g)

 It takes an electron transfer of 2 electrons to form

each hydrogen molecule from 2 hydrogen, H+ ions
and the transfer of 4 electrons to make 1 molecule
of oxygen from 4 hydroxide, OH- ions.

 Therefore, from the same amount of electrons

(current), the ratio of hydrogen : oxygen formed is
2:1

 so the volume of oxygen formed is 18 cm3. (36 : 18

have the ratio 2 : 1)

 Electrolysis calculation Example 13.1.4

o In the electrolysis of copper sulphate solution using

carbon electrodes, what mass and volume of oxygen
would be formed at the positive electrode if 254g of
copper was deposited on the negative electrode? Atomic
masses: Cu = 63.5, O = 16.

o Cu2+(aq) + 2e- ==> Cu(s) and 4OH-(aq) - 4e- ==> 2H2O(l) +

O2(g)

 It takes a transfer of 2 moles of electrons to form 1

mole of solid copper (63.5g) from 1 mole of
copper(II) ions, Cu2+

 and a transfer of 4 moles of electrons to form 1

mole of oxygen from 4 moles of hydroxide,
OH- ions.

 Therefore the expected mole ratio of Cu(s) :

O2(g) from the electrolysis is 2 : 1

 The moles of Cu deposited = 254/63.5 = 4 moles

 so moles oxygen formed = 2 moles, since Mr(O2) =

2 x 16 = 32
 o mass of oxygen formed = 2 x 32 = 64g, volume of
oxygen = 2 x 24 = 48 dm3 

 Electrolysis calculation Example 13.1.5

o In the industrial manufacture of aluminium by electrolysis

of the molten oxide (plus cryolite) 250kg of aluminium are
formed.

o What volume of oxygen would be theoretically

formed at room temperature and pressure?

o [ Ar(Al) = 27 and 1 mole of gas at RTP = 24 dm3 (litres) ]

 Aluminium oxide is Al2O3, so on splitting in

electrolysis the atomic ratio for Al : O is 2 : 3,

 and a mole ratio of Al : O2 or 4 : 3

 4Al3+(l) + 12e- ==> 4Al(l) and 6O2-(l) - 12e- ==> 3O2(g)

 Note: It takes 12 electrons added to four Al3+ ions

to make four atoms of Al, and 12 electrons
removed from six oxide ions, O2-, to form six
oxygen atoms, which combine to form three
O2 molecules (see next line).

 BUT, oxygen exists as O2 molecules, so the mole

ratio of Al atoms : O2 molecules is 4 : 3

 250kg Al = 250000g, Al = 250000/27 moles =

9259.26 moles Al metal.

 Therefore scaling for moles O2 = 9259.6 x 3/ 24 =

6944.44 moles O2 molecules.

 Since volume of 1 mole of gas at RTP = 24

dm3 (litres)

 Volume of oxygen formed = 6944.44 x 24

= 166667 dm3 

 Electrolysis calculation Example 13.1.6 of ATOM

ECONOMY
 o % atom economy = 100 x theoretical mass of useful
product / total theoretical mass of reactants

 These calculations assume a pure compound

molten electrolyte and a 100% yield and are based
on the law of conservation of mass.

 The calculations are more complicated when

dealing with a solution like aqueous sodium
chloride (brine).

o Aluminium oxide Al2O3 (atomic masses: Al =27, O = 16)

 Formula mass = (2 x 27) + (3 x 16) = 54 + 48 = 102

 For aluminium: % atom economy = 100 x 54 / 102

= 52.9%

 The oxygen is a waste product in this case. In fact

its a nuisance because it gradually burns away the
carbon electrodes in the electrolytic extraction of
aluminium.

o Sodium chloride NaCl (atomic masses: Na = 23, Cl =

35.5)

 Formula mass = 23 + 35.5 = 58.5

 For sodium: % atom economy = 100 x 23 / 58.5

= 39.3%

 For chlorine: % atom economy = 100 x 35.5 / 58.5

= 60.7%

 In this case the total atom economy is 100%

because both products are useful.

Self-assessment Quizzes on electrolysis calculations [based on part

1 only]

Part Two: The relationship between current and the quantity of

electrode product
 More mathematics to do with electrolysis

 As described and explained at the start the amount of

product formed is proportional to time and current.
 This is expressed by the following formula ...
o Quantity of charge transferred (Coulombs, C) = current
flow (amperes, A) x time (seconds, s)
o Q=Ixt
o The amount of product formed is proportional to Q,
the charge transferred to oxidise or reduce ions in the
electrolyte.
o So you can logically deduce the following sort of
proportionality from the Q = It equation ..
 Doubling the current with double the rate of
production etc., halving the current halves the
rate ... etc.
 Doubling the time will double the amount of
electrode products formed etc., halving the time will
halve the amount of product formed ... etc.
 Substituting numbers into the equation enables you
to predict how charge flows, then by a subsequent
calculation, you can predict by calculation how
much product will be formed e.g.
 e.g. if you run a current of 1.50 A for 2
minutes, how charge has flowed?
 Q = I x t = 1.50 x (2 x 60) = 180 C
 The 180 Coulombs can be converted into
moles of electrons, and then, adjusting for
the charge on the ion, converted into moles
of ion discharged at the electrode, and finally
moles of product.
 The following examples show you how to do
all these calculations in a logical manner.
 You may also need to rearrange the equation
to determine current needed or time taken.
 Q = I x t,   I = Q / t  and  t = Q / I   (do we
need a triangle guys?)
 How long would it take to pass 5000
Coulombs, with a current of 4A?
 t = Q / I = 5000 / 4 = 1250 s (or 20.83
minutes, 20 mins & 50 seconds)
 What current do you need to pass 96500
Coulombs in 2 hours?
 I = Q / t  = 96500 / (20 x 60 x 60) = 1.34A
 1 Faraday (F) = 96 500 Coulombs (C) = 1 mole of electrons.
o This can be expressed as the Faraday Constant =
96500 Cmol-1
o A current of 1A = 1C/s
o 1 mole of any gas = 24 dm3 or 24000cm3 at 25oC/1
atmosphere.
 Quantity of electricity in coulombs = current in amps x time
in seconds
o Q (C) = I (A) x t (s)
 Example 13.2.1: A current was passed through an electrolysis
circuit of silver nitrate solution and O.54g of silver was formed.
o Ar(Ag)= 108 and the electrode equation is Ag+ (aq) +
e- ==> Ag(s) 
o Ar(Ag)= 64 and the electrode equation is Cu2+ (aq) +
2e- ==> Cu(s) 
o If in the same circuit a copper(II) sulphate and copper
electrodes cell was connected, how much copper is
deposited at the negative (-) cathode?
o 0.54g Ag = 0.54 / 108 = 0.005 mol Ag
o now 1 mole electrons deposits 1 mol of silver, but only
0.5 mol of copper for the same electrons.
o so mol copper deposited = 0.005 / 2 = 0.0025 mol
Cu, mass Cu = 0.0025 x 64 = 0.16g Cu
o -
 Example 13.2.2: How much copper is deposited if a current of
0.2 Amps is passed for 2 hours through a copper(II) sulphate
solution ?
o Electrode equation: (-) cathode Cu2+(aq) +
2e- ==> Cu(s) and Ar(Cu) = 64
o the quantity of electricity passed in Coulombs
 = current in A x time in secs (Q = I x t)
 = 0.2 x 2 x 60 x 60 = 1440 Coulombs, and 1 mole
electrons = 96500 Coulombs
 therefore moles of electrons passed through circuit
= 1440 / 96500 = 0.01492
 it takes two moles of electrons to form one mole of
copper
 therefore moles copper = 0.01492 / 2 = 0.00746
 mass of copper = moles of copper x atomic mass
of copper
 = 0.00746 x 64 = 0.4775g of copper deposited.
 -
 Example 13.2.3: In the electrolysis of molten sodium chloride
60 cm3 of chlorine was produced.
o Electrode equations:
 (-) cathode Na+ + e- ==> Na or 2Na+ +
2e- ==> 2Na for electron 'molar' comparison
 (+) anode 2Cl- -2e- ==> Cl2 
o Calculate ...
o (a) how many moles of were chlorine produced?
 mol = vol / molar vol = 60 / 24000 = 0.0025 mol
Cl2 
 -
o (b) what mass of sodium would be formed?
 from the electrode equations 2 mol sodium will be
made for every mole of chlorine
 so 0.0025 x 2 = 0.005 mol sodium will be formed.
Ar(Na) = 23
 mass = mol x atomic or formula mass = 0.005 x 23
= 0.115g Na
 -
o (c) for how long would a current of 3 A in the electrolysis
circuit have to flow to produce the 60cm3 of chlorine?
 To produce 0.0025 mol of Cl2 you need 0.005 mol
of electrons
 0.005 mol electrons = 0.005 x 96500 coulombs =
482.5 C
 Q = I x t, so 482.5 = 2 x t, therefore t = 482.5 / 3
= 161 s (to nearest second)
 -
 Example 13.2.4: In an electrolysis of sodium chloride solution
experiment a current of 2 A was passed for 2 minutes.
o Electrode equations:
 (-) cathode 2H+ + 2e- ==> H2 and (+) anode 2Cl- -
2e- ==> Cl2 
o (a) Calculate the volume of chlorine gas produced.
 Q = I x t, so Q = 2 x 2 x 60 = 240 C
 240 C = 240 / 96500 = 0.002487 mol electrons
 this will produce 0.002487 / 2 = 0.001244 mol
Cl2 (two electrons/molecule)
 vol = mol x molar volume = 0.001244 x 24000
= 29.8 cm3 of Cl2 
 -
o (b) What volume of hydrogen would be formed?
 29.8 cm3 of H2 because two electrons transferred
per molecule, same as chlorine.
  -
o (c) In practice the measured volume of chlorine can be
less than the theoretical value. Why?
 chlorine is moderately soluble in water and also
reacts with the sodium hydroxide formed.
 -
 Example 13.2.5: In a copper(II) sulphate electrolysis
experiment ...
o Electrode equation: (-) cathode Cu2+(aq) +
2e- ==> Cu(s) and Ar(Cu) = 64
o (a) how much copper is deposited on the cathode by a
0.2A current flowing for 10 minutes?
 Q = I x t, Q = 0.2 x 10 x 60 = 120 C, mole electrons
= 120 / 96500 = 0.001244 mol e- 
 2 mole electrons deposits 1 mol of Cu, so mol Cu
deposited = 0.001244 / 2 = 0.000622
 mass = mol x atomic or formula mass = 0.000622 x
64 = 0.0398g Cu
 -
o (b) how long must a 0.1 A current be passed to deposit
1g of copper on the cathode?
 1g Cu = 1 / 64 = 0.015625 mol, needs 0.015625 x
2 mol electrons = 0.03125 mol e- 
 0.03125 mol e- = 0.03125 x 96500 = 3016 C
 Q = I x t, 3016 = 0.1 x t, t = 3016 / 0.1 = 30160s,
30160 / 3600 = 8.38 hours.
 -
 Example 13.2.6: What volume of oxygen is formed by passing
a current of 5A through acidified water for 25 minutes at a
temperature of 25oC and 101kPa (1 atmosphere pressure)
o Electrode equations:
 (-) cathode 2H+ + 2 e- ==> H2 or 4H+ +
4e- ==> 2H2 for molar electron comparison
 (+) anode 4OH- -2e- ==> 2H2O(l) + O2 
o Quantity of electricity in Coulombs = current in A x time in
seconds
o Q = I x t = 5 x 25 x 60 = 7500 C, now 1 mole of electrons
= 96500 C
o so moles of electrons = 7500 / 96500 = 0.07772 moles
o it takes 4 moles of electrons to form 1 mole of oxygen
gas
o therefore moles of oxygen formed = 0.07772 / 4 =
0.01943
 o 1 mole of gas = 24000 cm3, therefore volume of gas =
0.01943 x 24000 = 466.3 cm3 of O2
o -
 Example 13.2.7: How long will it take to produce 2 dm3 of
chlorine gas by passing a 6A current through concentrated
sodium chloride solution at 25C and 101kPa (1 atmosphere
pressure)
o (+) anode 2Cl- -2e- ==> Cl2 
o therefore chlorine to be produced = 2/24 = 0.08333
moles of chlorine
o 2 moles of electrons must be removed from 2 moles of
chloride ions to produce 1 mole of chlorine gas,
o therefore moles of electrons required = 0.08333 x 2 =
0.1666
o 1 mole of electrons = 96500 Coulombs, therefore
quantity of electricity required
o = 0.1666 x 96500 = 16077 Coulombs
o quantity of electricity in Coulombs = current in A x time in
seconds
o 16077 = 6 x time in seconds, so time in seconds = 16077
/ 6 = 2679.5 seconds
o or 2679.5 / 60 = 44.66 minutes to produce 2 dm3 of
chlorine gas.