ELECTROCHEMISTRY
CHEMICAL SUBSTANCES
ELECTROLYTES
Substances that can conduct electricity when they are in molten state or aqueous and undergo chemical changes
Example: Ionic substances
NON-ELECTROLYTES
Substances that cannot conduct electricity either in molten state or aqueous
Example: Covalent substances (i) Naphthalene (ii) Sugar solution (iii) Latex (iv) Hydrogen chloride in organic solvents
(i) Dilute acid solution
(ii) Dilute alkaline solution (iii) Molten salts (iv) Aqueous salt solution
switch
switch
Carbon electrodes
Bulb Carbon electrodes . . . . . . .. .. . .
Bulb
. . . . . . . .
Heat
Heat
Solid lead (II) iodide
Molten lead (II) iodide
IN A SOLID STATE
Do not conduct electricity
Pb Pb
2+ 2+ -
Pb
2+
2+ -
2+
I
2+
Pb I
-
I
2+
Pb I
-
Pb
Pb
This is because the ions are held in a fixed crystal lattice.
They are held with the strong electrostatic forces of attraction Do not freely move
Solid lead (II) iodide
IN A MOLTEN STATE
Pb
2+
Pb I
-
2+
Can conduct electricity This is because the presence of moving ions. The ions are free to move in the molten or aqueous solution
Pb
2+
Molten lead (II) iodide
ELECTROLYTES AND NON ELECTROLYTES
Classify the following chemicals into electrolytes or nonelectrolytes
Potassium chloride, KCl solution Molten lead (II) bromide, PbBr2 Glucose solution Trichloromethane Molten zinc oxide, ZnO Sodium chloride, NaCl solution Ammonia in tetrachloromethane
ELECTROLYSIS
A process of breaking down the chemical compounds into their constituent elements using electric current Example: Electric current
Molten aluminium oxide (I) Copper (II) chloride (aq) aluminium (s) + oxygen (g) copper (s) + chlorine (g)
Electric current
ELECTROLYTIC CELL
ee+ (anode)
ee- (cathode)
Electrode . .. . .. .. .
Electrode
- .. + ...
Electrolyte
Anion
Cation
ELECTROLYTIC CELL
The set of apparatus needed to conduct electrolysis It consists of a battery, an electrolyte, and two electrodes (anode and cathode) Anode - the electrode which is connected to the positive terminal of an electric source in the electrolytic cell Cathode - the electrode which is connected to the negative terminal of an electric source in the electrolytic cell
During electrolysis:
CATHODE (NEGATIVE ELECTRODE)
ANODE (POSITIVE ELECTRODE)
Anions (negative ions) will be pulled towards the anode (positive electrode) At the anode, anions will be discharged by releasing the electrons to the anode
Cations (positive ions) will be pulled towards the cathode (negative electrode) At the cathode, cations will be discharged by receiving the electrons from the cathode
ELECTROLYSIS OF MOLTEN COMPOUNDS
QUESTIONS
(a) Molten zinc chloride (I) Electric current (b) Molten aluminium (III) bromide Electric current (c) Molten zinc (II) iodide Electric current (d) Molten lead (II) oxide Electric current
Example 1
ee+ (anode)
ee- (cathode)
Carbon electrode
. .. .
.. ..
.. .
Carbon electrode
...
Molten Potassium Iodide, KI
The ions that presents in electrolyte are: (i) Anion: (ii) Cation:
Example 2
ee+ (anode)
ee- (cathode)
Carbon electrode
. .. .
.. ..
.. .
Carbon electrode
...
Molten zinc oxide, ZnO
The ions that presents in electrolyte are: (i) Anion: (ii) Cation:
Example 3
ee+ (anode)
ee- (cathode)
Carbon electrode
. .. .
.. ..
.. .
Carbon electrode
...
Molten lead (II) bromide, PbBr2
The ions that presents in electrolyte are: (i) Anion: (ii) Cation:
Example 4
ee+ (anode)
ee- (cathode)
Carbon electrode
. .. .
.. ..
.. .
Carbon electrode
...
Molten lead (II) oxide, PbO
The ions that presents in electrolyte are: (i) Anion: (ii) Cation:
Example 5
ee+ (anode)
ee- (cathode)
Carbon electrode
. .. .
.. ..
.. .
Carbon electrode
...
Molten zinc (II) chloride, ZnCl2
The ions that presents in electrolyte are: (i) Anion: (ii) Cation:
ELECTROLYSIS OF MOLTEN COMPOUND
ee+ (anode)
ee- (cathode)
Carbon electrode
..
.. .
Carbon electrode
.. .
..
...
Molten lead (II) bromide, PbBr2
The ions that presents in electrolyte are: (i) Anion: (ii) Cation:
ELECTROLYSIS OF MOLTEN COMPOUND
ee+ (anode)
e-
e- (cathode)
Carbon electrode
. Br .. .
-
Br
..
Pb2+ Pb2+
Carbon electrode
..
Pb2+
. Molten lead (II) bromide
Br-
Br..
2+
Pb
...
ANODE (POSITIVE ELECTRODE)
Br are attracted to anode Br discharge by releasing electrons to the anode Br Br + e
-
CATHODE (NEGATIVE ELECTRODE)
Pb
2+
are attracted to the cathode
Pb discharge by receiving electrons (provided by the battery) at the cathode to form neutral lead atoms
2+
Neutral atoms form and combine to form neutral bromine molecules
Br + Br
Br2 (g)
The half reaction at cathode can be represented by the half equation Pb (l) + 2e
2+ -
Pb (s)
The half reaction at anode can be represented by the half equation 2Br (l)
-
Br2 (g) + 2e
The Half Equation:
Pb2+(l) + 2eCathode:
Pb (s) Br2 (g) + 2e-
Anode:
2Br- (l)
Overall Equation: Pb2+(l) + 2Br- (l) Pb(s) + Br2 (g)
Write the half equation and the overall equation for the electrolysis of these molten compounds :
(A) Molten potassium iodide, KI (B) Molten zinc (II) chloride, ZnCl2 (C) Molten lead (II) oxide, PbO
ELECTROLYSIS OF AQUEOUS SOLUTION
Water molecules in an aqueous solution can slightly dissociate to produce H+ and OHH 2O Examples: Ions present H+ (aq) + OH-(aq) So, aqueous solution contains H+ and OH- and electrolyte ions
Aqueous Solution
NaCl solution CuSO4 solution HNO3 solution
Anion Cl- , OH-
Cation Na+ , H+
If they are more than one cations or anions attracted, the choice of ion to be discharged depends on :
Positions of the ions in the electrochemical series
Concentration of ions in the electrolyte Types of electrodes
Electrochemical Series (pg.101)
CATIONS ANIONS
K Na+ Ca2+ Mg2+ 3+ Al Zn2+ Fe2+ Sn2+ 2+ Pb H+ Cu2+ Ag+
FSO42NO3ClBrIOH
Tendency to discharge increases
Positions of the ions in the electrochemical series
ee+ (anode)
e-
e- (cathode)
Carbon electrode
Cl
-
Carbon electrode
OH
-
Cu2+ H+ Cu2+
OHClH+
Copper (II) chloride solution, CuCl2
Positions of the ions in the electrochemical series
Anode Ions that are attracted OH- , ClOH- are preferred to be discharged (OH- is below Cl- in the ES) Bubbles of gas, O2 is released
4OH (aq)
-
Cathode H+ , Cu2+ Cu2+are preferred to be discharged (Cu2+ is below H+ in the ES) Brown solid, Cu is formed
Observation and Product Half equation
2H2O (l) + O2 (g) +4e
-
Cu
2+
(aq) + 2e
Cu (s)
Concentration of ions in electrolyte solutions
Concentration of ions in electrolyte solution also can affects the choice of ions to be discharged An ion that is more concentrated is preferably discharged Anode the ions to be discharged is determined by the concentration of ions Cathode the ions to be discharged is determined by the position of the ion in the E.S
Concentration of ions in electrolyte solutions
ee+ (anode)
e-
e- (cathode)
Carbon electrode
Carbon electrode
OHClH+
Cu2+
Concentrated copper (II) chloride solution, CuCl2
Concentration of ions in electrolyte solutions
Anode Cathode
Ions that are attracted
OH- , ClCl- are preferred to be discharged (Cl- is more concentrated)
H+ , Cu2+
Cu2+are preferred to be discharged (Cu2+ is below H+ in the ES) Brown solid, Cu is formed
Observation and Product Half equation
Yellow bubbles gas, Cl2 is released
2Cl (aq)
-
Cl2 (g) + 2 e
Cu
2+
(aq) + 2e
Cu (s)
Types of Electrodes
ee+ (anode)
e-
e- (cathode)
Silver plate
Carbon electrode
Ag+
Ag+
Ag
Silver nitrate, AgNO3 solution
Types of Electrodes
Anode Ions Ag atom releases one electron to form Ag+ Observation and Product Half equation Ag+ receives one electron to form metal atoms Cathode
The silver plate corrodes
Ag (s) Ag (aq) + e
+ -
Grey silver solid, Ag is formed
Ag (aq) + e
+ -
Ag (s)
Exercises
Electrolysis of copper (II) sulphate, CuSO4, solution using carbon electrodes Anode Ions that are attracted Ion that are prefer to be discharged Cathode
Observation
Product
Half equation
Exercises
Electrolysis of concentrated potassium chloride, KCl, solution using carbon electrodes Anode Ions that are attracted Ion that are prefer to be discharged Observation Product Half equation Cathode
Exercises
Electrolysis of nickel (II) sulphate, NiSO4, solution using nickel plate as anode and cathode Anode Half equation Observation Cathode
Product
Factors that influence electrolysis of aqueous solutions
POSITION OF IONS IN THE ELECTROCHEMICAL SERIES
CONCENTRATION OF IONS
IN THE ELECTROLYTE SOLUTION
TYPES OF ELECTRODES
EXTRACTION OF METALS
USES OF ELECTROLYSIS IN INDUSTRIES
Reacts with a carbonate metal to form carbon OF PURIFICATION dioxide gas (CO2),water METALS (H2O) and salt
ELECTROPLATING OF METALS
Extraction of Metals
Electrolysis can be used to extract metals from their ores Reactive metals that are more reactive than C such as (K, Na, Ca, Mg, Al) cannot be extracted through heating of their metal oxides with C They need to be extracted from their molten ores using the electrolysis process In this process:
Electrolyte Anode
Cathode
The molten ore
Carbon electrode
Carbon electrode
Example:
Extraction of aluminium from electrolysis of molten aluminium oxide, Al2O3
Purification of Metals
Metals that have been extracted from their ores are normally not pure. They contains impurities which need to be removed These metals can be purified by electrolysis process In the purification process
Electrolyte Anode Cathode The solution that contains the metal ions The impure metal plate The pure metal plate
Example:
Purification of copper
Electroplating of Metals
Many types of metals can be plated with other metals through electrolysis. The aim of metal plating through electrolysis includes: (i) making the metal more resistant to corrosion (ii) making the metal appear more attractive In the electroplating process
Electrolyte
Anode Cathode
The solution which contains ions of plating metal Plating metal
Metal to be plated
Example:
Electroplating of a iron spoon with copper metal
ELECTROLYTIC CELL
ee Carbon electrode
-
ee-
- (cathode)
+ (anode)
Carbon electrode
Copper (II) sulphate solution
VOLTAIC CELL
ee-
V
e- (anode)
e+ (cathode)
Zn Cu Copper (II) sulphate
Zn (s) Zn
2+
(aq) + 2e
Cu
2+
(aq) + 2e
Cu (s)
VOLTAIC CELL
Also known as galvanic cell Has two different metals which are immersed into an electrolyte and connected by wire Produces electrical energy from the chemical reactions occurring inside the cell
Chemical energy electrical energy
Example : Daniell cell
DANIELL CELL
ee-
V
Zn (-) (Anode) eeCu (+) (Cathode)
Dilute H2SO4
(Salt bridge) ZnSO4 solution
Zn (s) Zn
2+
CuSO4 solution
(aq) + 2e
-
Cu
2+
(aq) + 2e
Cu (s)
SALT BRIDGE
Can be made from any electrolyte that does not react with the electrodes in Daniell Cell Function : (i) to allow the flow of the ions so the electric current is completed Example: (i) diluted H2SO4 (ii) sodium nitrate, NaNO3 solution (iii) Potassium chloride solution, KCl
DANIELL CELL
ee-
V
Zn (-) (Anode) eeCu (+) (Cathode)
CuSO4 solution Porous pot contains ZnSO4
Reactivity Series
METALS
K Na Ca Mg Al Zn Fe Sn Pb H Cu Ag
MORE ELECTROPOSITIVE (negative terminal)
MORE ELECTRONEGATIVE
(positive terminal)
Anode and Cathode
Anode the electrode where the process of donation of electrons takes place Cathode the electrode where the process of receiving of electrons takes place
VOLTAIC CELL
ELECTROLYTIC CELL Negative terminal Cathode Positive terminal - Anode
Negative terminal Anode Positive terminal - Cathode
ELECTROCHEMICAL SERIES
Electrochemical Series (pg.101)
CATIONS ANIONS
K Na+ Ca2+ Mg2+ 3+ Al Zn2+ Fe2+ Sn2+ 2+ Pb H+ Cu2+ Ag+
FSO42NO3ClBrIOH
Tendency to discharge increases
ELECTROCHEMICAL SERIES
An arrangement of metals, based on the tendency of each metal atom to donate electrons
ELECTROCHEMICAL SERIES
The higher the position of a metal in the electrochemical series:
More electropositive
The greater the tendency of the metal atoms to donate electrons
PRINCIPLES DURING CONSTRUCTING THE ELECTROCHEMICAL SERIES
Potential differences between two metals in the voltaic cell
Ability of a metal to displace another metal from its salt solution
Potential differences between two metals in the voltaic cell
When two different metals are immersed in an electrolyte solution, a potential difference is generated The value of the potential difference of a simple voltaic cell is affected by the position of the metals in the electrochemical series The further the two metals in the electrochemical series
The larger the value of the cell voltage is produced
Potential differences between two metals in the voltaic cell
The metal that is more electropositive
Located higher in the electrochemical series
Act as the negative terminal
The metal that is less electropositive
Located lower in the electrochemical series
Act as the positive terminal
Potential differences between two metals in the voltaic cell
Mg Zn Pb 3.0 V 1.1 V 0.4 V 0.5 V
Cu
Ag
Predict the negative terminal, positive terminal and cell voltage of the following voltaic cell
(a) Magnesium and silver (b) Magnesium and zinc (c) zinc and lead (d) zinc and silver
Metal Displacement
A metal that is more electropositive can displace another metal which is less electropositive from its salt solution
A metal that is located higher in the electrochemical series can displace another metal which is located lower in the electrochemical series from its salt solution
This reaction displacement reaction
Metal Displacement
Example: Zinc, Zn can displace copper, Cu, from copper (II) nitrate, Cu(NO3)2 solution Zn (s) + Cu(NO3)2 (aq) Zn(NO3)2 (aq) + Cu (s)
Metal displaced
Zn is more electropositive than copper
Zn can displace Cu from copper (II) nitrate, Cu(NO3)2 solution The zinc, Zn, will dissolve and brown copper solid, Cu, will form
It can determined the terminals of voltaic cells
IMPORTANCE OF THE ELECTROCHEMICAL SERIES
Reacts with a carbonate It can determined the metal voltage carbon cell to form for a pair of dioxide gasmetals (CO2),water (H2O) and salt
It can predicted the potential of a metal to displace another metal from its solution
