Thursday, 8 January 2015

6.3 Electrolysis of aqueous solutions

Cations and anions in aqueous solutions
■ Electrolysis of molten salt

►
Molten salt At anode (+) At cathode (-)
Movements of ion to electrode Anion of salt Cation of salt
■ Electrolysis of aqueous solution

► Water molecules in an aqueous solution dissociate partially to form H+ and OH- .
Aqueous solution At anode (+) At cathode (-)
Movements of ion to electrode Anion of salt and hydroxide ion, OH- Cation of salt and hydrogen ion, H+

► Factors affecting the selective discharge of ion:
○ Positions of ions in the electrochemical series
○ Concentration of ions in the solution
○ Types of electrodes
■ This video contains contains information about electrolysis of aqueous solutions.


Positions of ions in the electrochemical series
■ Positions of ions in the electrochemical series

► The lower the ion in electrochemical series, the easier to be discharged.

► The following mnemonic method can be used to memorize the sequence of electrochemical series.
○ For cation:
Potassium, sodium, calcium, magnesium, aluminium, zinc, iron, tin, lead, hydrogen, copper, argentum
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○ For anion:
Fluoride, sulphate, nitrate, chloride, bromide, iodide, hydroxide
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Laboratory Activity 6.3.1: Positions of ions in the electrochemical series
✍ Worked-example 6.3(a)
Predict the products of electrolysis of lead (II) nitrate solution at anode and cathode.

Solution  
Aqueous solution At anode (+) At cathode (-)
Movements of ion to electrode NO3-, OH- Pb2+, H+
Ion selected for discharged Ion OH- selected for discharged as it is lower position in electrochemical series. Ion H+ selected for discharged as it is lower position in electrochemical series.
Half-equation 4OH- → 2H2O + O2 + 4e-
Oxygen gas is collected
2H+ + 2e- → H2
Hydrogen gas is collected


Concentration of ions in electrolyte solution
■ Concentration of ions in electrolyte solution

► An ion will be selected for discharge, when the concentration of a particular type of ion is high.

► Usually, in the electrolysis of concentrated halide solution [Cl-, Br-, I-], the concentration of the halide ion is always higher than the hydroxide ion, OH-. Thus, halide ions will be discharged at the anode.

Laboratory Activity 6.3.2: Concentration of ions in electrolyte solution

✍ Worked-example 6.3(b)
Predict the products of electrolysis of concentrated sodium chloride solution at anode and cathode.

Solution  
Aqueous solution At anode (+) At cathode (-)
Movements of ion to electrode Cl-, OH- Na+, H+
Ion selected for discharged Ion Cl- selected for discharged as it has a higher concentration than hydroxide ion. Ion H+ selected for discharged as it is lower position in electrochemical series.
Half-equation 2Cl- → Cl2 + 2e-
Chlorine gas is collected
2H+ + 2e- → H2
Hydrogen gas is collected



Types of electrode
■ Types of electrod

► Commonly used electrode: Carbon and platinum [Inert to chemical reactions with the electrolyte or the products of electrolysis.]

► Others electrodes: Copper plates or mercury.

Laboratory Activity 6.3.3: Types of electrodes

✍ Worked-example 6.3(c)
Predict the products of electrolysis of concentrated sodium chloride solution with
(a) carbon electrodes
(b) mercury electrodes

Solution
(a) carbon electrodes
Aqueous solutionAt anode (+)At cathode (-)
Movements of ion to electrodeCl-, OH-Na+, H+
Ion selected for dischargedIon Cl- selected for discharged as it has a higher concentration than hydroxide ion.Ion H+ selected for discharged as it is lower position in electrochemical series.
Half-equation2Cl- → Cl2 + 2e-
Chlorine gas is collected
2H+ + 2e- → H2
Hydrogen gas is collected


(b) mercury electrodes
Aqueous solutionAt anode (+)At cathode (-)
Movements of ion to electrodeCl-, OH-Na+, H+
Ion selected for dischargedIon Cl- selected for discharged as it has a higher concentration than hydroxide ion.Ion Na+ is selected for discharged as mercury forms an amalgam with sodium..
Half-equation2Cl- → Cl2 + 2e-
Chlorine gas is collected
Na+ + e- → Na
Sodium is produced



Summary of problems solving involving electrolysis
■ Summary of problems solving involving electrolysis

► The animation below shows the summary of problem involving electrolysis.
■ Electrolysis of molten Ax By electrolyte

►
Molten salt At anode (+) At cathode (-)
Movements of ion to electrode Bx- Ay+
Half equation Bx- → B + xe- Ay+ + ye- → A
■ Summary of problems involving electrolysis of aqueus solution

►
Aqueous solution At anode (+) At cathode (-)
Movements of ion to electrode anion of salt and hydroxide ion,OH- cation of salt and hydrogen ion, H+
Ion selected for discharged
○ For dilute solution, use electrochemical series to judge which ion to be discharged.
○ For concentrated solution, the ions with high concentration will more likely to be discharged.
○ For active electrode, anode dissolves to form ions.
Use electrochemical series to judge which ion to be discharged.



⇲ For exercise(objective and subjective), download for free on Android OS.

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