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17.7 Electrolysis

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By the end of this section, you will be able to:
  • Describe electrolytic cells and their relationship to galvanic cells
  • Perform various calculations related to electrolysis

In galvanic cells, chemical energy is converted into electrical energy. The opposite is true for electrolytic cells. In electrolytic cells , electrical energy causes nonspontaneous reactions to occur in a process known as electrolysis    . The charging electric car pictured in [link] at the beginning of this chapter shows one such process. Electrical energy is converted into the chemical energy in the battery as it is charged. Once charged, the battery can be used to power the automobile.

The same principles are involved in electrolytic cells as in galvanic cells. We will look at three electrolytic cells and the quantitative aspects of electrolysis.

The electrolysis of molten sodium chloride

In molten sodium chloride, the ions are free to migrate to the electrodes of an electrolytic cell. A simplified diagram of the cell commercially used to produce sodium metal and chlorine gas is shown in [link] . Sodium is a strong reducing agent and chlorine is used to purify water, and is used in antiseptics and in paper production. The reactions are

anode: 2 Cl − ( l ) ⟶ Cl 2 ( g ) + 2e − E Cl 2 / Cl − ° = +1.3 V cathode: Na + ( l ) + e − ⟶ Na ( l ) E Na + /Na ° = −2.7 V ¯ overall: 2 Na + ( l ) + 2Cl − ( l ) ⟶ 2Na ( l ) + Cl 2 ( g ) E cell ° = −4.0 V

The power supply (battery) must supply a minimum of 4 V, but, in practice, the applied voltages are typically higher because of inefficiencies in the process itself.

This diagram shows a tank containing a light blue liquid, labeled “Molten N a C l.” A vertical dark grey divider with small, evenly distributed dark dots, labeled “Porous screen” is located at the center of the tank dividing it into two halves. Dark grey bars are positioned at the center of each of the halves of the tank. The bar on the left, which is labeled “Anode” has green bubbles originating from it. The bar on the right which is labeled “Cathode” has light grey bubbles originating from it. An arrow points left from the center of the tank toward the anode, which is labeled “C l superscript negative.” An arrow points right from the center of the tank toward the cathode, which is labeled “N a superscript plus.” A line extends from the tops of the anode and cathode to a rectangle centrally placed above the tank which is labeled “Voltage source.” An arrow extends upward above the anode to the left of the line which is labeled “e superscript negative.” A plus symbol is located to the left of the voltage source and a negative sign it located to its right. An arrow points downward along the line segment leading to the cathode. This arrow is labeled “e superscript negative.” The left side of below the diagram is the label “2 C l superscript negative right pointing arrow C l subscript 2 ( g ) plus 2 e superscript negative.” At the right, below the diagram is the label “2 N a superscript plus plus 2 e superscript negative right pointing arrow 2 N a ( l ).”
Passing an electric current through molten sodium chloride decomposes the material into sodium metal and chlorine gas. Care must be taken to keep the products separated to prevent the spontaneous formation of sodium chloride.

The electrolysis of water

It is possible to split water into hydrogen and oxygen gas by electrolysis. Acids are typically added to increase the concentration of hydrogen ion in solution ( [link] ). The reactions are

anode: 2 H 2 O ( l ) ⟶ O 2 ( g ) + 4H + ( a q ) + 4e − E anode ° = +1.229 V cathode: 2 H + ( a q ) + 2e − ⟶ H 2 ( g ) E cathode ° = 0 V ¯ overall: 2 H 2 O ( l ) ⟶ 2H 2 ( g ) + O 2 ( g ) E cell ° = −1.229 V

Note that the sulfuric acid is not consumed and that the volume of hydrogen gas produced is twice the volume of oxygen gas produced. The minimum applied voltage is 1.229 V.

This figure shows an apparatus used for electrolysis. A central chamber with an open top has a vertical column extending below that is nearly full of a clear, colorless liquid, which is labeled “H subscript 2 O plus H subscript 2 S O subscript 4.” A horizontal tube in the apparatus connects the central region to vertical columns to the left and right, each of which has a valve or stopcock at the top and a stoppered bottom. On the left, the stopper at the bottom has a small brown square connected just above it in the liquid. The square is labeled “Anode plus.” A black wire extends from the stopper at the left to a rectangle which is labeled “Voltage source” on to the stopper at the right. The left side of the rectangle is labeled with a plus symbol and the right side is labeled with a negative sign. The stopper on the right also has a brown square connected to it which is in the liquid in the apparatus. This square is labeled “Cathode negative.” The level of the solution on the left arm or tube of the apparatus is significantly higher than the level of the right arm. Bubbles are present near the surface of the liquid on each side of the apparatus, with the bubbles labeled as “O subscript 2 ( g )” on the left and “H subscript 2 ( g )” on the right.
Water decomposes into oxygen and hydrogen gas during electrolysis. Sulfuric acid was added to increase the concentration of hydrogen ions and the total number of ions in solution, but does not take part in the reaction. The volume of hydrogen gas collected is twice the volume of oxygen gas collected, due to the stoichiometry of the reaction.

The electrolysis of aqueous sodium chloride

The electrolysis of aqueous sodium chloride is the more common example of electrolysis because more than one species can be oxidized and reduced. Considering the anode first, the possible reactions are

( i ) 2 Cl − ( a q ) ⟶ Cl 2 ( g ) + 2 e − E anode ° = +1.35827 V ( ii ) 2 H 2 O ( l ) ⟶ O 2 ( g ) + 4 H + ( a q ) + 4 e − E anode ° = +1.229 V

These values suggest that water should be oxidized at the anode because a smaller potential would be needed—using reaction (ii) for the oxidation would give a less-negative cell potential. When the experiment is run, it turns out chlorine, not oxygen, is produced at the anode. The unexpected process is so common in electrochemistry that it has been given the name overpotential. The overpotential    is the difference between the theoretical cell voltage and the actual voltage that is necessary to cause electrolysis. It turns out that the overpotential for oxygen is rather high and effectively makes the reduction potential more positive. As a result, under normal conditions, chlorine gas is what actually forms at the anode.

Questions & Answers

Three charges q_{1}=+3\mu C, q_{2}=+6\mu C and q_{3}=+8\mu C are located at (2,0)m (0,0)m and (0,3) coordinates respectively. Find the magnitude and direction acted upon q_{2} by the two other charges.Draw the correct graphical illustration of the problem above showing the direction of all forces.
Kate Reply
To solve this problem, we need to first find the net force acting on charge q_{2}. The magnitude of the force exerted by q_{1} on q_{2} is given by F=\frac{kq_{1}q_{2}}{r^{2}} where k is the Coulomb constant, q_{1} and q_{2} are the charges of the particles, and r is the distance between them.
Muhammed
What is the direction and net electric force on q_{1}= 5µC located at (0,4)r due to charges q_{2}=7mu located at (0,0)m and q_{3}=3\mu C located at (4,0)m?
Kate Reply
what is the change in momentum of a body?
Eunice Reply
what is a capacitor?
Raymond Reply
Capacitor is a separation of opposite charges using an insulator of very small dimension between them. Capacitor is used for allowing an AC (alternating current) to pass while a DC (direct current) is blocked.
Gautam
A motor travelling at 72km/m on sighting a stop sign applying the breaks such that under constant deaccelerate in the meters of 50 metres what is the magnitude of the accelerate
Maria Reply
please solve
Sharon
8m/s²
Aishat
What is Thermodynamics
Muordit
velocity can be 72 km/h in question. 72 km/h=20 m/s, v^2=2.a.x , 20^2=2.a.50, a=4 m/s^2.
Mehmet
A boat travels due east at a speed of 40meter per seconds across a river flowing due south at 30meter per seconds. what is the resultant speed of the boat
Saheed Reply
50 m/s due south east
Someone
which has a higher temperature, 1cup of boiling water or 1teapot of boiling water which can transfer more heat 1cup of boiling water or 1 teapot of boiling water explain your . answer
Ramon Reply
I believe temperature being an intensive property does not change for any amount of boiling water whereas heat being an extensive property changes with amount/size of the system.
Someone
Scratch that
Someone
temperature for any amount of water to boil at ntp is 100⁰C (it is a state function and and intensive property) and it depends both will give same amount of heat because the surface available for heat transfer is greater in case of the kettle as well as the heat stored in it but if you talk.....
Someone
about the amount of heat stored in the system then in that case since the mass of water in the kettle is greater so more energy is required to raise the temperature b/c more molecules of water are present in the kettle
Someone
definitely of physics
Haryormhidey Reply
how many start and codon
Esrael Reply
what is field
Felix Reply
physics, biology and chemistry this is my Field
ALIYU
field is a region of space under the influence of some physical properties
Collete
what is ogarnic chemistry
WISDOM Reply
determine the slope giving that 3y+ 2x-14=0
WISDOM
Another formula for Acceleration
Belty Reply
a=v/t. a=f/m a
IHUMA
innocent
Adah
pratica A on solution of hydro chloric acid,B is a solution containing 0.5000 mole ofsodium chlorid per dm³,put A in the burret and titrate 20.00 or 25.00cm³ portion of B using melting orange as the indicator. record the deside of your burret tabulate the burret reading and calculate the average volume of acid used?
Nassze Reply
how do lnternal energy measures
Esrael
Two bodies attract each other electrically. Do they both have to be charged? Answer the same question if the bodies repel one another.
JALLAH Reply
No. According to Isac Newtons law. this two bodies maybe you and the wall beside you. Attracting depends on the mass och each body and distance between them.
Dlovan
Are you really asking if two bodies have to be charged to be influenced by Coulombs Law?
Robert
like charges repel while unlike charges atttact
Raymond
What is specific heat capacity
Destiny Reply
Specific heat capacity is a measure of the amount of energy required to raise the temperature of a substance by one degree Celsius (or Kelvin). It is measured in Joules per kilogram per degree Celsius (J/kg°C).
AI-Robot
specific heat capacity is the amount of energy needed to raise the temperature of a substance by one degree Celsius or kelvin
ROKEEB
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Source:  OpenStax, Chemistry. OpenStax CNX. May 20, 2015 Download for free at http://legacy.cnx.org/content/col11760/1.9
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