I. CONSTRUCTION OF ELECTROCHEMICAL CELLS

Electrochemical cells are devices that use chemical reactions to produce electrical power. These are sometimes known as Galvanic or Voltaic cells.

e.g. dry cells, car batteries.

It contains two half cells connected together by external circuits.

Half cell is an arrangement which consists of an electrode dipped into a solution containing its ions. When the two half cells are connected, the resulting component is called electrochemical power. A good example is Daniel cell. It is constructed from Zinc and copper electrode.

PROCEDURE FOR CONSTRUCTION OF ELECTROCHEMICAL CELL

  1. Identify between the electrodes, which electrode is supplying or gaining electrons by studying their electrode potential.
  2. An electrode with negative standard electrode potential is more reactive (supplies electrons) than the positive one.
  3. If both are negative the one which has more negative electrode potential is more reactive.

E.g. Sn = -0.16

Mg = -0.25 (more reactive)

If both electrodes are positive, the one which has less positive value is more reactive.

E.g. 0.07v (more reactive)

0.2v

The electrode which supplies electrons should be placed on the left and electrode which gains electrons should be on the right hand side.

E.g. construct a Daniel cell and shows the direction of flow of electrons and current given that

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Q1VXv5PI30oUi4vl0qnCLpD74TmGpmk4yrvZCO5dTmUA Kx2jBCKPapzYX0nubNL3GXdaB473n VFPTKw0Bt 77JmBzBJXFFraMNvbScMnAQV3bBm7fJubLc8FcrBITVaeaQxHU

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The electrode which supplies electrons oxidation takes place and the electrode is oxidized. This electrode is called ANODE. The electrode which receives electrons reduction takes place and the electrode is REDUCED. It is called CATHODE.

ecolebooks.com

Zn – anode

Cu – cathode

Overall reaction is obtained by adding the two half reactions and is called cell reaction.

Anodic reaction: X74musvZR8HXZiE7ELXYmWdrbYOYCu78ckz5W8CLjh0qz3Wm2weAL Mpmvkia2a52e7xN 7r4OG3cW0cIqOx 4B48h4iIB0XILyYdvD BtI0rAIqxp40My6FTV8LvhQNCgfKdUU

Cathodic reaction: QqXdq45U83YnoOKs4zu B57f9eYvXdZeuHGvsmh7sBRXoHQcpq OVc XMoI85ZGgTKh6Rhj MxkOzAYCUs1fVHbNhcz81801ZBsLPMJ0l9OSBvaBlF7 5O2asu1D ZPxicgidjs

Cell reaction: MGJ 4SCGYCsGvWqXk9 MOgROzecE3TQRWyCBy6KosKxVn1eRSPlw2MrxdViJ VOXTh1d UirWdpmPs3YTMn5qdQTCcwxhg1KTDeCPGAnauS06G NH3C1aOev3toE Xnc1LQK2m8

Electrochemical cell can also be represented in an abbreviation way known as cell notation.

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Anode cathode

I.e. for Daniel cell J8t48ZKUAu0iOdSilt4T7p5YCmgn BzLrWXUP1By9JFyajjtdpGZReNfQtVQE SHrBi5XPWpKHEuxIzAvmlBeT0UyYOTkEGTrvMAaboBlowjDpfHqBIojS1M RbYzUYpHiD StI

Questions

  1. Given the overall reactions, write their corresponding cell notations
    1. BNPNW6zXDaf5f O QwhIFKLQ4PWek8VCjjFhPLc4TcVAC5KPJsx5oX72 DKlCdKFDEdLMMk8 QnU7inGQLu7OSyBbWPOX2GwQ1ZSOaRs5w3cmVev4Zj8rsMi9RsODikDqtRb8Pw
    2. Z6IuQ7jKDlP K Nve2WCI AOFHdCZ6GdU8y88INW28jstzA HDFglh5RfKjqk51rOONlO3ADdYIWWiFKzRrKOA6kUgLuO ALnuItofQ VzTbpAKG0Fwc XE5 I6ocKGb9p5CrK4
  2. From the cell notation give the cell reactions
    1. T4E5BrxBoruIi34bvxZJj1e5 PgLzVdYwWwZAaVHRo62T6b3V7CS99BtH3EZjDfs03hNEOikYT0 DxQ5ay1M5il39HaBdvOf9Pgo2aKQpv JF1MVJ5q6nyJ5Fhg40koHyIVnQk8
    2. 8ukz4kdbpRXdKF23vPQWG6xoUX2VOmenAdsr5CNh NC5zkmEtjx2rASAXZN HD4ZYCGZPctf58Z7aTt7X6pExYEV4esFC Q8yNaX6t4LBQKk3rwZcAnqaUqjjdsrnmaGK CoM9w

Answers

  1. EnfC1JSb0XudOARcQ7AsbbooHeTpvLsYrjpTM6Z8IdQTPl5TRxeosa A3zL9T3ZVSy32bg6TY6snmLvWIMA93o1UBPAMrFrzqdbHkEj3L74eKAms Wo22B8bJiLDab Uj5DVOdM
    LJrp2ILtZ QAZAmE5SBfQ9aPyECxjJW BSCRToONUugWoUiRCbZvlSF1xRJYorlwScYyUFKptWueBtn1mtfERdfyNvS5dUXTcrEKcEpoeAM4jtbi2 RyPkyY8Pn8dSqUvmvZ3YY

Cu(aq) + 2Ag+(aq) → Cu2+(aq) + 2Ag(s)

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ELECTROMOTIVE (EMF) FORCE OF A CELL

The difference between electrode potential of the two electrodes constituting an electrochemical cell is known as electromotive (emf) or cell potential.

This acts as a driving force for a cell reaction and it is expressed in volts.

The emf of a cell is calculated by subtracting the standard electrode potential EU J J3V1zY0mS 4rfSzVg7orPXZoSEIY5wavCZ QoXIrSp4uj0UoKo5q9rkomkQGGJWrywjaujIfJnkQODvyUO0aBCTWYLVt07b4sR4SRiPnW1h1Qy1obROzzkC75gEvhkJ9b8 of the left electrode from that of the right electrode.

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For Daniel cell I3 RJYxkCe12eri Y6l9FMbBIwjKEcaPcBSw1i0 KvW3j3j KkTHLDqh7lDjQ MXBYQ 7RKQaSXxRIV2h7TTpHPFyD8P4fCnB7E1AC85X26HCTIcWMco4P3cQ5wHllVR1bRMvEQ

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K0e5VeEPUrw4r9MfHe7k1ExnL6nxejaG5 2Nd ToNmeFpt8JAwnWEfoU CJf2K9wjYCjpqFYcl5yX58I 6MnR4wtTnBFThiIqKBmkxhK6K3PVolLQQcjwS9tSlUiLGYNoiAjekA

HavRjO3uprzGLrA8bMShiRpIJ3QeUaQJC65AYfVFp DhpRG234xeJzPZGQKKsvTrqmeK168ARVNKRw0duvI XZ UJnjWnk5b 5MP8Ewasre 6Amp LF43sw6 OTZ9JDsVKiR6A8

3OXN32Ehz9IuZ3hQQPUwuk AX569DTQblKjPhu6jkGc1RqOEoEkN7DHD1s9Ph 62SBiRC6JE8CQcC2Dd67PsNRPqMlFvhRXBPvAg05SGeDnVLhae706FPdicCmVCH 43sPLah2g

= 0.34 – (-0.76)

Kv7lCEguPwvQCH8wEHzC0uvnrIzqZwRC8qD0GtQKDPHs4649ZGNmNp AB WIcPpq04xgLcsvRmDX8gGMU0cEBxfL32APZGhPG 34VOUH 2GXz GdK3OSHuDGGLMT2AFiK6NWaKM= 1.1v

Alternatively

Since standard electrode potentials are in reduced form, for oxidation half reaction the sign of electrode potential should be reversed.

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= 0.76 + 0.34

RJC9ZhqPbGx40uiQzdHWlyO4Nc2QSRKNW64ucizGpBgg46SqtHpQO2scttgDcT4YfgpJNIT6If0j5PcZs HX ZJHuVwIb24HirD N0iZOuIXdeFeHXKhNhvnMZfGhBY93lVfdq0= 1.1v

1. Prediction of the occurrence of chemical reaction.

If the emf of the cell calculated is negative the reaction is non spontaneous i.e. the reaction does not occur in the way it is written unless external forces apply but the reaction is spontaneous in the opposite direction.

If the emf of the cell is positive the reaction is spontaneous.

Example: given the following reaction

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Predict the direction of the reaction given that reduction potential of nickel (Ni2+/Ni) Eo = -0.25v of mercury Hg+/Hg Eo = 0.14v

Solution

Cell notation

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Ru60A7fEUX1oilFmH5aMLwAyNloBQRmlYkWO7TnJE1RDPj8kPbpbvUwiPgqPSbxiCpAYm MADNQkpWJJnt7AutHG8wChVa ST HvXSnAyzYP4eFVAxTE8 DvASSe2bxWg02K8iI

EZ6BaDtm6s1wQsvu7Hoss2r5WRzxp2syQrrndnyYcZiyaDdCSDVsOehkNXhLRyqcK2ls5ITvmzwVJAojdUNg4K2mL1m0nzJkPb5Znct9sYv3QE8RAmN2oKaY QMgavNsGPmIHmc

The reaction is non spontaneous since emf is negative hence backward reaction is favored.

Example

For each of the following reactions at standard condition, decide if it occurs spontaneously in the direction written.

  1. R1agfCRoCR B ZwqYv BXKd4fo4ha0QJMbq 5bq Vv39M57leyZyGVCA8q9n QUzs5FfPVUsqQ Q56iB5dCcibhuJc7AXgAzUE3zJmB24wJoBrw F9FMNbse93V0Dz5Tyq RaVU
  2. NYPkq8UL5thr74 VjSKadiOmwWeWYgtYTJ4LlRkev3N02i99pR3C1cZC EKUtr 6VMAAVXOu4mK Wv55lnMqwq38sMvd3s13rlXPg1D30z96U9yq7ujoi0B3Z1tC77TcOQvAtM
  3. FcjV54E5UZ4rgc HaGHJrqFsXPYaAI EY ZZqrPU6llAEn8PIeyoN5698gXcE8hDfUQpK LC7c0IQff8cmoRbUmVT8fCflztNcGEQDZGEwUHXv9uUzvs2oQpSya OTvaRDQ3xXo

Given for My7nYw4awHDVquWbSnHDepiN1kKrYg 7QnRfaanxAmCxaQvbh4xIBR60eo2iSfoPnh Of8Faa GIjUwgwrs99jI Ia6p1qgB ImqT1Oycr3YB1lMBynvKK7n2ooEZjhWZasJKF4.

M553DIYvQNTLi HG1gA7gQ5T2NA2rlLB4qVvxO7HPcF3CjoPmFOOb6hYTpyaaljv O OHC LVbGnLY34l0N0CMViMTBwok4rgAIedo LRe2p9WF68kuHYw SsgLqjDPy DpOwHM

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L4kpgSj5jSN1tJf XDHPI1WbwIGlyg2aAN0hIMB49LK4mR2VZZUaGyNO9LviI 3cgf22V8upsjmcbLAlNfrGlat9LhwDpD8GD2Fm6wmhHysZGb9DUhfbs0R7CIFMYevppaBCytQ

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CAZzQkuRx0L3lSpQSbODj1VvgbIFKGu89EpNOpGD2Lsa4VIDi55moO3LkO DYsMy0kGce 9PwGXbnD1WcuXpkEZVKHseJuwogMJCMAsminq0bi7HLNgoBA 1UCC Cf6P OzMaaQ

ANSWERS

  1. 9VRjO12v U12xyeKYA50XWpZC3v9ynfwLzW8dW1h7s 4PYC77z1JLnEAqyJQyI30Tg7H93ysvWvfCn89mAsiaP7XDm4 OPyvq1BfxJvXqmEx99qAETESwI4uK6r6WcZySwuwNm8
    Q9m0oHPwcAGpeCdgpGALpX2LPvR BRR3KyCV3eErrewFP2riOnBwOwgD37dx RmrfI8MDg1vpEAW5Ge2HcRsj MlY7R6Wq6qNYBcjDLaJD6CiNTGpq RMz4vG2cHbTgMLG Cik

= -0.14 – (-0.76)

= 0.62V

  1. Cell notation:KkOBSHs3LI Q5ThYlk7zR7VCWfgu8KzLHVZ1Mhdkuf8d3CgODRCW2OlDpqY5AVzBzf7Pgny9RY5BDWvKVeh2A2smg86Gfr0ooqBxIBJPZz5Y3hUnzi7Ntchdp0O I SUFSyPTaM
    JbK MHuMVnG7 CGzNAxmmbj2saly8kscHldEdz9Sgn1vDhgdKj Ugp7T2fsGkLQ9bjeUlNnBezn 4cUfeby7CgyzhNUKTYbv1jVAgNhc Q DchPXVvcTZHwDWnFqsOtYLx2BEq4

=1.09 – (1.36)

= -0.27V

  1. Cell notation:  BVdWqwH8zxskjeUCAXxl8tcye2QKCHwwmenruoK LF RcUVluV ChIPG SIJSNkNlQnh3PK0nEdi LX7B KGxxIyQ6poVF3VrqDIuGdjks2oVS61DH5RgIwGKkDC5kJJ64W5mU
    JbK MHuMVnG7 CGzNAxmmbj2saly8kscHldEdz9Sgn1vDhgdKj Ugp7T2fsGkLQ9bjeUlNnBezn 4cUfeby7CgyzhNUKTYbv1jVAgNhc Q DchPXVvcTZHwDWnFqsOtYLx2BEq4

=-0.4 – 0.34

=-0.74V

Therefore reaction (1) is spontaneous while reaction (2) and (3) are non-spontaneous.

Example

Briefly explain what happens when

  1. Fe is dipped in CuSO4 solution
  2. Cu is dipped in FeSO4 solution

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Example

Given the following DOkLUQrzF5Nd8pznsSDV QPKgcIHBa2jWYHornqUOvZiOeuKJ7Mrwi20KkH4AjisqQ1hN8Zb7UdRCWjuTLIGaeL51BFFyd4OvsUqgfjeLvzEXdvEJ0SGzLxpdSaHfNyFJULLwgI values

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SL G4 Xe PxPN4uAf1kXw9oylL7rIWWnLMo 2PjFvIiaS5ejgGr0wkj9U9yOZ06AtCO1esKBSUhVaRBuWRihiR0hvNOkSIqO 2O2bvGRSG3 0jhWLuBeFRtqrcuNqkXmHcm44Q
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a) State which species are the strongest oxidant and which oxidant and weakest reductant.

b) State which species is the strongest oxidant and weakest reductant.

c) The lead rods are placed in a solution of each CuSO4, FeSO4, AgNO3 and ZnSO4. In which solution do you expect coating of another metal on lead rod? Explain.

ANSWERS

2. (i) Since Fe has a negative reduction potential then it has a positive oxidation potential and hence will displace copper metal from CuSO4 solution.

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(ii) Since Cu has positive reduction potential, then it has a negative oxidation potential and hence it will NOT displace Fe from FeSO4 solution therefore no reaction will be possible.

3. (a) strongest oxidant

Weakest reductant

Maximum and minimum emf of a cell

It is possible to decide which cell has to be constructed either of great or smallest emf for a given electrodes. A cell with greatest emf is obtained by choosing two electrodes of greatest cell reactivity difference. A cell with minimum emf, choose two electrodes with closest reactivity.

Example

Study the following electrodes.

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YNl JGLan5o1OjXUu0q7Rs8CsAmg0NmKy65JUSitvu4avk0yS27QCXsaCYA5TCYO2otobC4 Cv8wxC3ckuK3 WPasWbup99KuIbmsM3aBRlV9FGhybUOm ZrJiCJMT3mY5OQfU

4. Explain how you can construct a cell that will yield

  1. Maximum emf
  2. Minimum emf

ANSWER

For maximum emf, we choose two electrodes of greatest cell reactivity difference.

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GZgVJbasOvEVbiUF35Ey1G1OoSdx5ZOP5L3zCoovi1IMOLLOOs QkbuakKv3ZIWyF4uy5tq3ewFp1x FU9CmxW0 RUC0qXh 719nO3BUKbWLgZvgtT38keGSz6xruklmANht Q = 5.91v

For minimum emf, we choose two electrodes with closest reactivity

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GZgVJbasOvEVbiUF35Ey1G1OoSdx5ZOP5L3zCoovi1IMOLLOOs QkbuakKv3ZIWyF4uy5tq3ewFp1x FU9CmxW0 RUC0qXh 719nO3BUKbWLgZvgtT38keGSz6xruklmANht Q= -0.4 – (-0.44)

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EFFECTS OF CONCENTRATION AND TEMPERATURE ON CELL POTENTIALS

We have been considering electrode potential under standard conditions of molar solution, pressure of 1 atm and 298K. When the conditions are altered the values of electrode potential changes thus we have to define the potential of the cell under non-standard conditions.

The Nernst equation shows the relationship between emf of the cell at standard conditions and emf under non-standard conditions.

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Where;

TDZhQwyKKUsWopkzm2 TBnEPoCDW8X1uavRst Z4TTk Hczg4f57ijV OA6ogb7x0b1EHnWSpxF6 AKtFM71EOL27abi6kI3dBnOD0021az5Q MniuqBGTs5p3Y0X4TPkLvifSU – emf of a cell at any conditions

Nlu VF9uHFFP3edWvJtBdySsST39HSsD0 EXJb4C1ZRWPlRhKAWpecHdrxAMsD7qidU2ty0tkvFWRkj6UPmVyzbamZaHINFbdLyVxj9sPS00 Ix3T8osMJYTznQ7IHncEQPJboQ – emf of a cell under standard conditions

R – Universal gas constant (8.314 Jmol-1K-1)

n – Number of moles electrons being transferred

F – Faraday’s constant (96500 C)

At standard temperature (298K)

4Zrlye5wiG OL5hIy6vCKzE EORq6uPf9o ELrfE1VilhL61rukr EohlJbXJ JSDrqzOmScsOroNr2wCthn6p4iGcvvQrAGBMZ8TOv P1Q Nkx7NJRDL ZTBqRjZGoL1A4kE1A

OR

McSM08ZDr6YU7RyUlkORjaO2v2Rz4nkxJmkuq YmwBVY X84kWttNnrtZNIdU SU3zW4hBhzb4zodwVXGvQgQ5djBDDDd4Lqeuw W3qDaESTGgNIIVqLfwtID O0wXI32 I8pVA

The above equation can be applied to half reactions and overall reactions.

NOTE

Always write a balanced cell reaction to obtain ‘n’ and position of ions, either reactants or products together with their stoichiometry.

Example

Calculate the emf of the given cell at standard temperature.

FBRuVK1A2QruAyBUuiZyZCHR9gmJvKScTgWWcDoMGxLeT5J6HZtLIJ9uJHWITdWofX0SqouJBNG8HQ6X3i8fd0KD4tEIKB HRgYXp7UjMpdEaKOxOlZkUhPqM463xaMHZKV1Sb4

Given

0cnX Gxg7m LsfA56xLgPVitHaExUz6TrQX6OAIFyK5LwSg4 DoH9O3ujd54uvgb22m0asms0OdbZt6F0semINSPeXmbE1 LXZdRwYvQ K80vZ0z9uuxUYAL2VwB6C6KJmfRRs

EgNs4092BWQrqcY1fQMYqwFlVKSMUoPrBEbkjrkJS6ZyWpAKCPZZDmrc LawRO5bZUysOXp42q4xsnKN5Vm5lH PvNrGQyAD7g2i1LAmeIJuqfXCitpyLuGZnm2qCymfN8U4oa8

Alternative Solution 1

JbK MHuMVnG7 CGzNAxmmbj2saly8kscHldEdz9Sgn1vDhgdKj Ugp7T2fsGkLQ9bjeUlNnBezn 4cUfeby7CgyzhNUKTYbv1jVAgNhc Q DchPXVvcTZHwDWnFqsOtYLx2BEq4

= -0.13 – (-2.56)

Kv7lCEguPwvQCH8wEHzC0uvnrIzqZwRC8qD0GtQKDPHs4649ZGNmNp AB WIcPpq04xgLcsvRmDX8gGMU0cEBxfL32APZGhPG 34VOUH 2GXz GdK3OSHuDGGLMT2AFiK6NWaKM= 2.43v

Alternative Solution 2

Z H9ObMcNYlsDVvFJm LxcRD7fV7wro9ucPAyILZq95gn1JCoyJ3D8qgpGBWgOZhmZ9FJSmVEVrgyHuB XGbCLYHZDf9LJLw7sjh4t8ZfXPc XH8eQezkrdNcL5b8gTQGRdZ1hg

Ok0bh1V9bDmAiJ0w Qg4HEBWYgKgPcUVCV1uK4e7fKjju UPr3Z075HUUl9beZVL6xNln53eimo CoKUz8z 4zefUohft4KkK6OWzdkUSJEcvYYmGosAvFwrvkxSc6H8SbbWBQU

n = 6

Now;

Gs5FY9qaQLF5EpETP3pOu6BBjev29 X76rzK1YMkP 6QT3qfWr1BCzvgj3MpyhlutKhTW7FXMGGX RTk89V21l9ypoGD3OjjgU0w18anhNgI37E13 WyiEFrmpDmVeSfLOJy0Ww

M1a162QXaYv RFiddBKhrBtsqgx0hUmvQxbNvBIKRhAarchsWFN76xQNnC7JTDHYNFIn RUGIfXzjjlwxP0pr D Q4DLju5fR9T1aVdSq1QVolKZug8zGqigpYyeW8ieFjX6vFg

Pmr 8jIwLJBggfQIXXiBtPUlmNZOLgpv1YI3QRu1CJ1hRrO6UERbFc9ElNBM4CG21qOGROP9tAz0XDotpONlMXADftQbYXIGYpMJYK1koaW9Wvd5Op9BJdun Jo6saNBln2TDik

Example 2

Calculate the emf of Daniel cell at TayaIbKAfsgRV84nb7N1w2JV9wuAyYKw5CtHMbu8RXOr9AcCQZiICgpIWUd9fZ6fhs31FV4xR0gymKUPbw5HkbR9n5 UmE2YfHCZgELKhkABHcIM1RgLjapft2lD2eb T8K7 YQ using 2M ZnSO4 solutions and 0.5M CuSO4 solution

DLhinv5uvuz4aNn80l U7X7047MOk28QRu5WgFQ73jUlLd PFRTP95k2zYfeULBMaSG45xVaoriL FMB3yeY1vAk9NB6BDTrSfdW XTNLVJnd7WW5BPLgOrfzQgjygPuIQVPCVg

Alternative Solution 1

JbK MHuMVnG7 CGzNAxmmbj2saly8kscHldEdz9Sgn1vDhgdKj Ugp7T2fsGkLQ9bjeUlNnBezn 4cUfeby7CgyzhNUKTYbv1jVAgNhc Q DchPXVvcTZHwDWnFqsOtYLx2BEq4

= 0.34 – (-0.76)

MWwQlAHhMvKTvwCEAv4 A 9zebq835YZqsNmOXn WkN7yBCzSerpA8IfgnBw7aP KHd8p2JUuyue CWW0XYGZgSQmp0Cc3DIBqtLoCW C9VTPKmxyzTbV4fiZOZ3Q2BgU2Ew9EM= 1.1v

Alternative Solution 2

Half reactions

BkdEXyVwy5JtY9mti6Nr2KqDzessnEJNAzxoEYj9dp0oaLoNzpG8cnXkGtMiNDkmNvZSdJD80uY139L9l4niWQBcF52mnmLvxDFfoDbUp5VLRnN4kYvIyVHlcpRJ8tibXkxh8Og (Oxidation)

QqXdq45U83YnoOKs4zu B57f9eYvXdZeuHGvsmh7sBRXoHQcpq OVc XMoI85ZGgTKh6Rhj MxkOzAYCUs1fVHbNhcz81801ZBsLPMJ0l9OSBvaBlF7 5O2asu1D ZPxicgidjs (Reduction)

73uInMTD8UY UEOGS2xS0NIjQloSzGx52fhp2XrkHlIvd7pZyK0j0t QTEeSZhtO0GbHXmMMBL QfZqePgISRwr6OZhdkHgYODbXZRmRHg BLHlZV53i6ebIzXSrfinsLLTWbDI

Here n = 2

Now using

SR4qr32r OPnqgxlmcQIj46NyQeuVe8do 6cTcOjjri0XMjCMl6XQX WGjk23705vqhsYzoOnrC3YGnzf5vKcaHEq5ha1XmzmwY9O U5p4o1uUpVTvJGtsEpBsf7cDKECdMsUao

OnjEHFRiASO4GGFUvbw E 3bkXcz1oFesBDIXi2XQ49yiO3EfoRvy JI89f5cYETplu9KpylM2auQkDvLdKVl6 H7nMqLbozQTE2wHS9IXfhyHSBEPcawX0FGQ FNqTkgARTcik

Ecell = 1.08v

Example 3

Calculate the emf for the following voltaic cells

  1. 3nQ7i2syWYXSPc1DZdKYS2nN HnZke4VPkPgs18OwEtDd92Xfi0LOrI L7 NYU PLDFM5 YQTnY6bCgdS64BgOFf308NGuAq05F H YWGN4bRepxP4d5ppFoZBmedjSWkEpviIY
  2. Zn/Zn2+ (10-3 M)//Ag+ (10-3 M)/Ag
  3. RvHc LYp9RluStqNJpdAeBaDjn2VXpolvRD8CUHTCkmjkA1z CXcLj5ZWL3tW EYP8IlSS9o2ZRyzaF2ukH44R MXwOh5 UuLth1 SOGqrTKtCCKDhtQbsNbWSdDJ2 JcNGYRjE

Given

SnIwc41uVpmRvP8AZdR2xVjqH SRq5hEG8Vu1J9o F0vJlL5jsFLju5JeUqILN5JUJ57Dd7FrikNlDGOb A0JgTAJXqsvoA269p1XAzCjKVdnHVcFk1eNv55UUZAoEjusExG94

PVz9 AIAXlBMSKlH64LPpghIGH3 N2sTY0zZLlq0pI5SWdJa3C22uECXGdLi6VHvhtN5gNJeBQoskE26jpVq En7zVObRsoVWZLbOSDbDwMTGBqfYBT575 UC0aF8f2nEHetUS8

GWnMBuxNTOoFcUFPb6Q FLF2FUYOjgw8RsqpC3HyBkpkGnsR5GOV4R7xK74R1D1tjnihFZG8fF1aDKqWg95JdpAXAjP46WMAYaW76 2stbjfj5bqfjjrkfVeSNH0qEPic0 SPs

Dav2GL3wmdYoCLU1q9R2Kwat4VPdGq1IbeaHLrpfXldyell2i2yODoypXIoqZeG 2fd00IMV59nS GIL7FM HoBTTwgCREM49VkHF4MWXTjOhZxvkiQ0m8uoIz21jG4BW806FIo

Alternative Solution 1

WPb64YJ5OeS6pMQM4UC9gqj0XhYElGcnq4icPhqN 2WX NYC7j2EzNhzRFG1thdWrS9HYlxpnODXs EKKZL352 WpRpWVCrT6cRmKQW3VXsvlg9CpsFvB2TSr5PFli1BqA2u3Fo

EWHahL GZbFI8PzW2fKfXncADSViQJq22e8WaGr47uSP2DZOyVyNMNgjxgdPc3DMGFBxgFp79GNCFdgk4gVmBpFlXQkSallI2zqS6f7bvrEWAGmRDm9gPdI3FGT8lo93 Omkyk

n = 2

Now;

S ItELOJ26UGyJNhtpr Y BgAr DUYgv6YJY9LqBRM97FJ7Om Chmi ZRGJ6EV CQt69Dm6lJjtojCS3tklOJGtLBCietvlpOb2tEgjJw3UX989ZdhKz8BYYKTZzQkCuwLlHc

= 0.8 – (-0.76)

Kv7lCEguPwvQCH8wEHzC0uvnrIzqZwRC8qD0GtQKDPHs4649ZGNmNp AB WIcPpq04xgLcsvRmDX8gGMU0cEBxfL32APZGhPG 34VOUH 2GXz GdK3OSHuDGGLMT2AFiK6NWaKM= 1.56v

Alternative Solution 2

From NcACA35wuEBvDPb6Or0E87apgwCI5YsmDabO TH7VRDyJX5iXjUcDcHJlitGPoRvq2vc 7W03aFeo3WuMA2o3KeQOg7sdnBxrs2lONYNWw7USWXY5 2uYxURJReCPvnf QMb2zY

BX8a1qsDNC1131ZIyVI Qz 9HzosZvdPCUDYhosNdLL90 LW73OlKMti5oin7aHsdk 484UwmM7Mk5Sp XuN9jgpXxOrdfGlsnbnIK 17QvQE1FN3APjyqqCd6RcDKRwZe8MwI

VMtHMTn8yIVlUgEcqFq3GqVVP5zKDI RxRzVqdQUuGXnxpUpKTUkCj8fBPiKC1HxcvXA4yWcrHHwTKLy2jjVbZ HsIxEHrfx5h6xFfKr7clBP8XBy3hM7Hg5wfmRdJfQosquwDk= 1.47v

8urWlZMMdE QWzhwFeqDbIfC2edgyVqdK3 ZNH2 CV0ZzZlO2YKbXS9hXxhrw RTjdDq4vVlSMLpz6vYdnYDTzRfeObvBBnrnxW2MHQ33KuAdvLj2DxwbvdIO2XP4nKTVyE

= 1.47v

d) Solution

Alternative Solution 1

A61WP5Vw4LihMZ15JteAHFvgKueIh8olnv2Xhg6b YNMsHBypwoZk7KOkRW8xXHw7McOYKGYlu7O66FVxfSFNGJ3Jw 2dXdNCOHptff6vb7EgeYVBLymG7txVFqgkKBcfkJUPbg

= 0.8 – (0.77)

Tz2Rsg4KtNf0rJ9C2hA4SrM6Z5 MNZhP2Hz 4QZHl48DnR0L9kKOK6haCwA335 VBNhCS HsHa71HkmkWz4tZBU92fvVFL6 5y QxwXq QKxashcdtWKXDlpd 30kliSJvfFYTo= 0.03v

Alternative Solution 2

Half reactions

NXRWbraUV5I8s4LY6G9TlSe59vMrZE4 QT7wQfstU0xaXVb7EWKxBHOEW X4wS5Uj 7KZZCJkyT1t6eCx5d8xM4qnPCwPg3968vQbVoGBrQocc IXP9Yv0QxhJ8b84RUScFC Gg

F29SfYYH A2uGnDtROhUWQiZTwjUYh5lv57jJmKjepP4KORijm8bbCGFpVWswiu8zeXJD CqIKfrrHwBCq0jDSoy7eWTB SYb26duvkntMq64X46sAJtcdK4Sm2LIIt1K56AGU

PE J6KY6F Wuj1XdAgp4qxTA3TwKz2ggJUQZcx8k 9DEfSZNFyS0See85mLCrjFXdlUbF3FckdCPEmm9sAJMXl1KuyEqnqKwm7UrENxFV3RRD2PZBKg0LxrdQVCt9boDShH60n8

n = 1

Now using

 KgViha0EEij3Rw5Cl7ixSSyY60B0gDf3GWxONI9acDx7jARrTZKmHfY0tJHBayOpXKVkeTqPe5IBuH0pTMQ5PfDoGU1s5ARO1xdzqXSngBrZ 6LaFF0WKEHBQxmnzK3ns8M51k

SRD0Wd7jWN0BMJCDtdUHofiNlmZzmoEQjHq7Oq5n H7bH2Ft 8zpMZ JqKvKTSuduJ 88QOQVpR0LskRk06hK4dVQEM 50s Cok6D6DR4tlOJE5cjLyYvimZlQCAV4UfHVvFzlE

Ecell = 0.0122v

c) Solution

S ItELOJ26UGyJNhtpr Y BgAr DUYgv6YJY9LqBRM97FJ7Om Chmi ZRGJ6EV CQt69Dm6lJjtojCS3tklOJGtLBCietvlpOb2tEgjJw3UX989ZdhKz8BYYKTZzQkCuwLlHc

= -0.14 – (-2.56)

RnqrIz7jgwxWM4JoWWdMZKTX5pze8IxF LBnTr7SmNxhNS4yEB96qykRNjhtE1UIK4IWLCZNyLNy2ZukxcZSJDqQKhxqCJPtqOZRLNqPlwqok LyZdLo0F6mSotey8rmmpvaYVE= 2.42v

Half reactions

TyHlwex6wE5WScAKmOeUfOsRQfeeF0oQnQqoARGtODqVdevv3UOUVDLZ7gytAgfnlUB2q4aHZXPhG4weZ3YGhlHeDRBLSH4IWY N6Td4uqToywdKOjYEChYXxhkrWJRyXmyI0jQ

S6vbVFgQ7T21K1bXAcbKdgBmcPfKzeCm4aO9kxOtsQfPl5UkA P4kRZutBpsUI3LcdP7pvKC8uYy8 US3AVMMcM O16rQ7K1TmvPHNhn5heBy83NptY8TMnop7UeFXOO3T6kOqA

2Al + 3Sn2+ → 2Al3+ + 3Sn

n = 6

Now;

F5BqWYtlmc6EDyWBN KbvS0CjaQQyk XZ1rvuAdKM48ngIi8YqqyisFvOx48vpp3U03l YuhSSTyTMj4O W4gGX7aSSA8 UWtthlLmbK3xDWGaX9BtLsTc16qcJ52yzhZK3Ksws

JW8FgHmCW0Ux3XFyxfxpWWoAxcLrwakcm7NtFEPfPIG9NxGaY96TiOt11dxXB8324dY0x3RgvB62OcptaGpZNUR5rjEVoWaXucN LaWU7O5pjbe2YTDf4qvUoAGekY4Wq1k5Zak

Ecell = 2.418v

EQUILIBRIUM CONSTANT OF GALVANIC CELL

Consider what happens to a Daniel’s cell if we use it to do some electrical work i.e. it can be connected to a small electric motor. After some time the motor will stop. The cell will run down. When this happens LKpH2 G VvZaCcN BzQW6TN GBTBUtdf7GYSufCovKyYCqogL2Q FOYQTvkH IAiK4gPilFQGLMGiWeF Epnc6veoepp1ivOb QtF2H IdfFvjL9EtE7TumlHiIKyzOpZQwskZM and there is no overall transfer of electricity from one half cell to the other. When there is no overall change taking place in a chemical reaction the equilibrium has been established. At equilibrium, electron density of both electrodes is equal and there is no transfer of electricity between the two half cells.

Applying the Nernst equation to a Daniel’s cell

3DQd2o YOpRAJC6VJmV QStJWmLl6i41t18Da6H7fnXXEV0oRSfmRbmemtuS IdNMUcN9xt9XEyhBA1ky76QmS9 FEs456iU 3zj4C3porN9uU SVtIDrw8XVfFEkAPMKQlInKc

63ob DNIUFEly2URLY9TOrwUt8 Zhcp2vgk6uN MTmWPmv 9ruMtbPGLB5bmWY DNrpjqSBtvI SzLYSO YGtADJrmmwEnFbiAYnPo7jfCJS31HpHCrrwtDhc912QZ12JfZG8ZQ

Since the reaction is at equilibrium, the ratio Cv7sifdsD5dgTTAQn4p82ENlsi37Gz KHGnhUymydJzTmog XyhlpTtJM3dLm9N Eb5J0UrPelQFk2FABW ZP0lQnw4KmDhEpCJoWm VvAjUtTVgI7EQy2OUdx8eAZBeFu1AHos NuUz3Eo8N 7iZTosO PkE8A Uv1vkFJRXdjY VDMGMP9oQf Mu X8MXKx4kjzpWPn0PufyGsMq37 RuNqEI3Jwxx1AdgTY7B YepQiBgA Jhnk4TtWcEarkgBGCChxTcUsHl8f0

Brbp9835yybIOekbRhJlNByiKW1 Ac YxeSdRLw5cXz AkyTKnI6Cioro6WnjjKnxIdLYxsrc1GwSczwq8YJoZCyK0AI MtJvdRH J0dcHnqyE0Jn89awgiamOce4hak0JwYyps 0CImrY4VpyMjl7u42jXMwtdW64IGT9WHub8 F7k5PmrUO 4nVWkjNHSZimQFOq9d6CIny7lzS7fD42m5Mjd8xnOX6bAd6o Qxw7BXvxHq5PQKmaxqhkf2AyzbARFErX5v8PW3V0

 GfETMkkLl5QB9i4vtVAbaZvs 8DkmTiuapEX5C0GW4hFQQZS31x6F Rinyi5PXRjGHG4PHqYgKFgG PshjJDOGHfrITy5 NA9oSYRxrj8 R8T7vStJMIi0DXcCIbHW9ecrNq W HCr HbNu4LuYG79Fyuc9QGjiNGXE0OLRtLrAT6fzje2 O6gnacV7x8Yko8GqJSg3jObMdq08T Gq64CwHYpxfIaaB3 RUWeGiJ9h Si2HRw7Q1QGcwEYWsRiP2WaPhrfN5Z5eA

KC = 1.67 x 1037

The large value tells us that, the equilibrium lies almost entirely in favour of copper metal and zinc ions.

Generally, the cell at equilibrium at standard temperature is given by the following expression;

Yrfh5nbb H4ZZQJFqDFQc7nZHbNMQ2 2 ZruikOFdD6CLEJQSVfzVxX5VYktArTbTjsL QAhAo4GE9jK7tRnkXT3zVyiOL75pbD4DlpnzN2iOwKgKZ7HWvjnpWwTDhAhTNzdiHA

Example

Calculate KC for the following voltaic cell

PwRAK MwjML7ObfZ64IuGRjOSiu ZzKV4Vdb4UViFZH6m8bOyH12y94bXcG1cj6zJXrIYKr0A0dImBWklQ1gsUPXAj3dSMy7TC2WDsV 001n8ogpgmUvB3mXZ5K 4qRRVOcmAqs

Given

DQTAwpoNx9O BEtHZSV9pAXDEcVzZTZDfmsS A0OmICegSE3DJaXauN R7pZnjR33dFBltSAa 65wBknzN2eiKln DQuK1tem0FhQRFVrGLXU1hgf4ot1nUMnByYUfQ CFUyC0

Gnfvuew854nLEmcLkCLiLl2N3fM7Ogw0PikF0yjesJRSqoqCwYSJi0IREOQJtds4lnCWFY5c G8sexHh2pCKKNzQCyIxcoiisT5tNiYNdoQ0r65GdhV2Pytmg57lfUMytMObAtA

Cell reaction

ED3VRGRUUSX1p9rr3Ac8j 8K Vv MDBKPdBv0G4DF0s98hBB6vgD9Ts6tX7QaxyzPFsyEYVlV2OKiIqGRAJG KLEm188NBU Jnc4yU39G02vBxTs46 HE5KL2IXNdomvPC8lVc4

XBohOApNUpVBdO MtsBR6Kbt0xMbgIBDhStaDCdOovTwkDu0lxuTsOdjdBxb3WcROJhPHDCzyiUznVLSI HyctcMe3wSXdtHXrGChbQ4 XrAqbgmueTNYs5 BMngIA5xF97GNGo

IJMOFgxbOWlNdefxdTgz8DdGwGc9cHCSBZBzEcYHQqYavr3BEawoFBbpZJvQxaw0nbaP J35IbJHnvD1Xr0qpX7 Cc10z0hno8pKN QswgFrvyaQkKbhKnaHFha5LoPxofjoW58

From

S ItELOJ26UGyJNhtpr Y BgAr DUYgv6YJY9LqBRM97FJ7Om Chmi ZRGJ6EV CQt69Dm6lJjtojCS3tklOJGtLBCietvlpOb2tEgjJw3UX989ZdhKz8BYYKTZzQkCuwLlHc

= -0.12 – (-0.46)

= 0.34v

Now, Pmdi3xgIWA1E1rORMwFereQA7H28l9b7DYRh2Mo1I9NknZDzOHYlXIZ2pNBXlmIfqgM9G0GOjPuqUrqN3nsvvvoJhjwEcszUU5p9syg RM4PdK9lTPRCqGCFzvIr1r2B SXlSiA

LfZH51d8mUPAlh8kiq6D50dLIHdEHf BH5maHCJb9MGkec3Irl75vbVF AeIh44wUoO 0DMF7klzsAGWwjm2jgG YKlZ6lVDMhEXd4yofeIq7ikm6DQ1YAVpYOlzoY2OX6rFZs0

KC = 3.20 x 1013

Example

What concentration of Fji2lxeW6b0x4U0T LYCayyUXLlRL7w G2cikOob Eq0qK2 5U1OlE1WsTmF2gJAqd8UGkwiNpY9yFolJQ5w35WKwn5n3KUu5SvNUy5JG6QRTUfhNNGG4D9 Y7d EBrUFQ6P5wU will emf of the cell be zero at BLaE7YbY3NV XsVrNst1Eqp QdBcz9DVIxb1BLnUX37wM7vuPUzk SZ8AVB99TnuSNh6nlqmqK0zVe3D 9hlqbPn3QTgoj8krZNCu0cW93cfsNxBia2p L16NjRZS2z LW7MoDNs if concentration of  Ojsq45c5xPvAkyJZNvz1i QcfpkqEamXVBBGzZtowVdCbH6 PpECPaMvFBzcSLsvKoh0Yy5 DaNG UfdRhzybc8q 28ibEW7LXJ34VIjg0CJqho4p0S5kLo0ZFXaYTnzit 1Y is Lu E0JTOsYDyds60PTvXOTd7MKkCgA6p75Gjoyo INGtfu9PYCsrkhlIUxXCl3gALyxsTcnRqDjTuSwJU8MDAUMZiuAZ9A6RE1boDy7YcZhIWHRJg4hs6bZ4E3t0q MJ7qjVhh4

SwLFOp 5o7dTxqRHoFftuMLkzrvmsGBEObbOtSjfJr L7MSkCQEvEs Q0MbTklL2RGeRSOmm6inJ6U8G3sFg7LH8AiAbu8H1jrUSzYeK3UIzpx Wo3eLcI1x0tM RHGBnxmDnWQ

3. MEASUREMENT OF pH OF A SOLUTION USING STANDARD ELECTRODE POTENTIAL

pH is the degree of alkalinity, or acidity of a substance. It is obtained by using the hydrogen ion concentration pH = –U2mCV6yR0 WOXmCdX68XO8gxGe1wKikXAHpnLAV3e1qYvdgXgnCABbnVPna9S LfB2QfWOJUDwIAR3RpnZiwxCBehay7DBO6wcFZInvXOT6YGTK06KgZ S9n6oxd692YuNdYkE

The pH of a solution is determined by using any electrode provided its standard electrode potential is known and the concentration of ions in that electrode should be 1M. This will be one of the half cells another half cell is made up hydrogen electrode dipped into the solution whose pH is to be determined.

J2zYm9rADp91z3c30zTpIBFKbxaN Nr6PJFbD52LWj4q 2VDARqYcys47G2foPtOibt1Xst9UpIS0YduQxfFr585QNf7SF8JCgHa7n1GkVIVl01xmKwZRKZW0Hm8G KS RVbMPE

Reaction:

H2(g) + 2H+(aq) + 2e E0 = 0.00v

2Ag+(aq) + 2e → Ag(s) E = 0.8v

H2(g) + 2Ag+(aq) → 2H+(aq) + Ag(s) E0 = 0.8V

Applying Nernst equation at standard temperature

Ecell = Ecell0 – (RT/nF) ln Q

= 0.8 – HYOsZrN8LCr6aH G9euRb1xbdHK FxjowLxveLWxatlAHdTI9S4bIBqA8HMZH5GrHvswEYZQFtaB35cIWdn4sK0YHAHEDBdBuZBTTnqd EHZm 3K6mgsSixYBGSzunBVNRswkSI

Question: Calculate the 8Huyr TNGfydbu1IhgWCRO7T4fCHes736SNWz44hhhE8U3AeXldugHRuXudwhqIk7HpfC VU7eOHGxHauFv2iRRvtAsGOv BQYxgnJDEvwKjVMTSUeSjI7rHqg 1 9bAYYN9o of the following cell and hydrogen ion concentration.

Zn/Zn2+//H+/H2, pt

Zn2+/Zn = -0.76v

Ecell = 0.115v

Solution

Ed4SU4YHI PDXX72Gv2zla0lKpWcO3JZVXKS8kPDox04w3c52IeUS9XY 1CVoB3ilhW3dHmOR1D9r9BQruN5tDk ZkDiX3fky Ku5vo3JAxk2h20lmc0zhvmWcCZ4v1uNc2f2f4= 0 – (-0.760)

Ed4SU4YHI PDXX72Gv2zla0lKpWcO3JZVXKS8kPDox04w3c52IeUS9XY 1CVoB3ilhW3dHmOR1D9r9BQruN5tDk ZkDiX3fky Ku5vo3JAxk2h20lmc0zhvmWcCZ4v1uNc2f2f4= 0.76v

DcrtjNmFOTFnN61 HcDltsOiCmGovFjyeEt 5TwC0syyJqMU8m NVT7nf1jMuhp31NJUQUYBYyJacwR2fLJpw4TpTHncgpmKMme Y YqMNRBr1WUfA7l2DxwbvdIO2XP4nKTVyE = IMpJCny Fk6kws8oC7YY4PlqaEfAZwN9T MeIafCtKgrZQ80foDFWXr4 XF3xL535VR2LvsYj3pBqQdQAA7ImwMg4payGYri3E5zA3yU0XEMjD3MNpP2cdq4qLhkMlmb6cEanosQl8XL1rBsN7Gc YWrzUwSqYakOH4P XnGQ6MQ5eX3FdTXsP3qf4TPRdZlcE VIqnwLgzQZMgzOvk1XitF9C6Sodv YBURvw1wZoPrfsgDH1lZCZ4SNe0jPUjnGaI W PFDxaiGo

Zn(s) → Zn2+(aq) + 2e

4bULcVm8F0rs0RhBsXwUbPL K RaF2ifcgvcnWmzov1VkbmfNe9OSEJ Lp0PgXOzYLgk9jLu J1h1Wti8RQgjZo6CxzMj1NIOkt 5xxdTV0TkXRRkMkeOLJzsW2A3muAI5nsjrI = IMpJCny Fk6kws8oC7YY4PlqaEfAZwN9T MeIafCtKgrZQ80foDFWXr4 XF3xL535VR2LvsYj3pBqQdQAA7ImwMg4payGYri3E5zA3yU0XEMjD3MNpP2cdq4qLhkMlmb6cEanos + CCTORosAepDsPUwb52mINerSEVPsIELIWhwjkxpotQGMMb8do0Xkyn BVrFrDM0E6oyhwe7rwaOGr3Pt9F4amAb5In7A5TRCmdEDA6SLgWLfwcWqKeBATnKlD2s ZS5j6gUowXM x 2 Jz82nPEuClJBsSHaaHOlUzsL93cWOeHwt9fV4xSIO6sjDMuWzyxxq4RPra0XQWb6hs8saP0 Er0pQVtZdXh PUvEHVkhrmUPrfpymacKw1JtvIG1sc6Irk5Pjvvh KYO4lJlit0

0.115 = 0.76 + 0.0591log [H+]-2

Ecell = 0.8 + 0.0591 x 2(-log[H+])

pH= -log[H+]

Question 1

Calculate 72wbQV5CWbmQzFZU8ZSnMkv6QbqGB5fxblJmMKhc1m1hQJHySsAMDFi6 BgSDA CSRx 4ZUQYByqlSB7dfq2W3p6k8Gjwne0ieb4HlpcT79wRvq MKxgK5uZtk1DV CwX2Bev1I of the following cell-

Zn/Zn2+//H+/H2, pt

Zn2+/Zn = -0.76v

Ecell = 0.115v

Question 2

If E for Zn /Zn2+//Cn2+/Cn is 1.1v

  1. Calculate the Ecell when concentration of Zn2+ is 2M and Cu2+ is 0.5M
  2. What is Ecell when concentration of Zn is 0.1M, Cu2+ is 0.1M

Question 3

Write down the expression for the cell emf for the following reaction;

4JL9G KL5obDFa87QDxEkXuxegsmku C3FsrBIWuBfnBuZ 0AE7Usni BYLII7Xf7RDYReEpCbVLADyTJnCk 7lU4LNfjbk419OSp4ZaaGcorOtxsylcl3Mj5HP8EysoM VFbnk

Briefly explain why the oxidizing power of permanganate (VII) ion is quite sensitive to the concentration of H+ in the solution.

ELECTROCHEMICAL SERIES

Is the series of standard electrode potential with respect to their elements from more negative standard electrode potential to the more positive standard electrode potential.

Is the arrangement of electrodes of elements in order of reducing power.

Uses

It is a good guide for predicting reaction that takes place in solution especially displacement reaction.

Displacement reaction

Is a type of reaction in which an atom or element displaces another element or atom in a compound.

Example

What will happen when magnesium ribbon is added to a solution of AgNO3?

0lOOTQrLSwQi UDX3B4U86jcbQag2Cw2zRCWnkMzVIjO3FFcML1nQJDJDy2AUeK3rgKAtADbjFMaWtx3hO0MyI074zPiLNQk8cGwtoKf0wsSyx03RfKrqC3vS7IBhDmdQry1qvQ = -2.37v

1wUnw K9r0qsiL8aPVTixaxlcWrmQ6 CsGPNW54xDL9 UxUuK9aVsW DCesRW8h9NO9Exo9Fcz8MzpGhF 4FTi1VDg0u5Np3z3Jwrd01Jf83eK43ICp1LAbZji6q QZIVUiJmuE = 0.8v

The more negative the electrode potential the greater is the reducing power of that element i.e. the more likely it is to give out the electrons and acts as a reducing agent therefore Mg will reduce Ag+ ions to Ag(s).

Mg(s) + 2Ag+(aq) → Mg2+(aq) + 2Ag(s)

Mg(s)/Mg2+//Ag+(aq)/Ag(s)

= 0.8 – (-2.37)

= 3.17v

Thus, the element higher in electrochemical series will displace the one lower in the series.

2. Displacement of hydrogen from mineral acids

Metals which are higher in the electrochemical series than hydrogen react with acids and replace hydrogen but metals below hydrogen have no action with mineral acids.

Complete the following reaction:-

i. Zn(s) + 2HCl(aq) → ZnCl2(s) + H2(g)

ii. Cu(s) + HCl(aq) → No reaction

3. The knowledge of electrochemical series helps in choosing method for extraction of metals.

Higher most metal can’t be extracted from the oxides by chemical reduction process. This is because they are strong reducing agent hence they can be reduced easily from their oxide by electrolysis.

Questions

For electrolysis, fused or molten metal should be used and not aqueous solution. Why?

Answer:-

In aqueous solution, there are H+ ions. Hence metals prefer to react with element in lower electrochemical series than the metal itself, hence for electrolysis we use fused or molten metal and not aqueous solution.

CORROSION AND ITS PREVENTION

Corrosion is the deterioration of the metals due to the chemical reactions taking place on the surface. Usually, the process is due to the loss of metal to a solution in some forms by a redox reaction (unwanted redox reactions).

For corrosion to occur on the surface of a metal there must be anodic area where a metal can be oxidized to metal ions as electrons are produced.

Anode area:-

M(s) → Mn+ + ne

And cathode area where electrons are consumed by any of all of several half reactions.

Cathodic reaction:-

2H+(aq) + 2e → H2(g)

2H2O(l) + 2e → 2OH(aq) + H2(g)

4e + O2(g) + H2O(l) → 4OH(aq)

Anodic reactions occur at cracks or around the area with some impurities.

RUSTING OF IRON

The most common corrosion process is rusting of iron.

Rust is hydrated iron (III) Oxide (Fe2O3.XH2O) which appears as a reddish brown substance on the surface of the iron bar.

Both water and air (oxygen) are required for rusting to occur.

The presence of dissolved salts and acid in water increases its conductivity and speeds up the process of rusting.

If the iron object has free access to oxygen and H2O as in flowing water, a reddish brown ion (III) oxide will be formed which is rust.

UxZmVFhfUYD WF8ZRBdjaUe5OQoPhd36aDoLxZ ADRi8 0ys3nvZpS64aRhilbUuZuEjhIMO7wo0Sdk5XuWslCk2rZzVJp Ub JDqMt5I1Txm 4fghmfpzaoUiyqZ0WadXNRbPI

For iron:

Anode: Fe(s) → Fe2+(aq) + 2e

Cathode: O2(g) + 2H2O(l) + 4e → 4OH(aq)

2Fe(s) + O2(g) + 2H2O(l) → 2Fe2+(aq) + 4OH(aq) (rust)

4Fe(OH)2(s) + O2(g) + 2H2O(l) → Fe2O3.XH2O

If oxygen is not freely available: The further oxidation of iron (II) hydroxide is limited to formation of magnetic iron oxide.

6Fe(OH)2(s) + O2(g) → 2Fe3O4.H2O + 4H2O(l)

Fe3O4 Black magnetite

Prevention of rusting

Corrosion can’t be made non-spontaneous but it can be prevented by making the rate of the reaction negligible. This can be done by covering the metal surface with protective coating or by providing alternative redox pathways (oxidation-reduction pathways).

Protective coatings are usually of 3 types:

  1. Painting: – is the simplest and most common method where a metal surface is properly cleaned and then applied with several layers of rust-proofing paint.
  2. Corrosion inhibitors: – these interfere with flow of charges needed for corrosion to take place i.e. phosphate (II) coating on a surface of iron or steel. Using phosphoric acid serves that purpose.
  3. Galvanization: (sacrificial protection) a metal can also be protected by coating with a thin film of second metal where the second metal is oxidised instead of the 1st metal.

Often iron is coated with another metal like zinc, tin or chromium for protection on the surface.

Note: zinc is preferred to tin because zinc protects iron against rusting when its coating has broken down. This is because it has a more negative reduction potential than iron: it acts as a cathode hence it is not changed. This is called cathodic protection.

Tin protects iron only as long as coating is intact. Once the coating is broken down, tin actually promotes corrosion of iron as iron has more negative reduction potential than tin. Thus iron acts as anode and dissolves while tin acts as cathode and does not change.

Factors which affect corrosion:

  1. Position of metal in the electrochemical series (E.C.S). The reactivity of metal depends upon its position in the electrochemical series. More the reactivity, the more likely it is to be corroded.
  2. Presence of impurities in the metal. The impurities help to set up the voltaic cells which increase the speed of corrosion.
  3. Presence of electrolytes: Presence of electrolytes in water also increase the rate of corrosion. E.g. Corrosion of iron in sea water takes place to a larger extent than in distilled water.
  4. Presence of CO2 in water: water containing CO2 acts as an electrolyte and increases the flow of electrons from one place to another. (CO2 + H2O) form carbonic acid which dissolves into ions and hence acts as an electrolyte).

Examples

  1. Why do you think zinc on iron is sometimes called sacrificial anode?
  2. Explain why blocks of Mg can be attached to walls of ship or iron pipes with the aim of preventing rusting.
  3. Tin cans are made of Iron coated with thin film of tin. After a crack occurs in the film, a can corrodes much more rapidly than Zinc coated with Iron. Explain this behavior.
  4. Why is it that with enough time, corrosion will always defeat the protection applied to iron?

ANSWERS

Zinc or Iron is sometimes called sacrificial anode because after it wears off, the metal can get exposed and hence starts to undergo rust.

Conductivity in solutions

Electrolytes

These are substances which allow electricity to pass through them in their molten state or in form of their aqueous solution, and undergo chemical decomposition e.g., acids, bases and salts.

Classification of electrolytes

All electrolytes do not ionize by the same extent in the solution. According to this we have strong and weak electrolytes.

Strong electrolytes are those that ionize completely into ions in the solution e.g. Salts, mineral acids, some bases.

Weak electrolytes are those that ionize partially into ions in the solution e.g. organic acids, HCN, Na4OH.

Electrolytic conduction

When a voltage is applied to the electrodes dipped into an electrolytic solution, ions of the electrolyte move towards their respective electrodes and therefore electric current flows through the electrolytic cell. The process of the electrolyte to conduct electric current is termed as conductance or conductivity.

Like metallic conductors, electrolytic solution also obey Ohm’s law which states that “the strength of the current flowing through a conductor is directly proportional to the potential difference applied across the conductor and inversely proportional to the resistance of the conductor” i.e. V = RI.

Resistance of any conductor is directly proportional to the length L and inversely proportional to the area of cross-section.

R = ρ x (L/A)

ρ = Resistivity

Resistivity is the resistance of a conductor having unit length and unit area of cross-section. SI unit Ohm-meter (Ωm).

Conductance is the measure of the ease with which the current flows through a conductor (λ or Λ).

Conductance is the reciprocal of electric resistance. (G = 1/R)

From the above expression high resistance means low conductance and vice versa.

Conductivity is the reciprocal of resistivity and is also called specific conductance (κ).

R = ρ x (L/A) = (1/κ) x (L/A)

For an electrolytic cell, l is the distance apart between the two electrodes and A is the total area of cross-section of the two electrodes. Therefore, for a given cell, l and A are constant. If the dimensions of the cell are not altered, the ratio (l/A) is referred as cell constant (K).

R = ρ x K

Molar conductance (λm)

Is the conductivity of volume of a solution which contains 1 mole of the solute.

Or

It is the conducting power of the ions produced by dissolving 1 mole of an electrolyte in a solution.

Molar conductance is given by λm = κ x V where V = volume containing 1 mole of a solute and is called dilution.

Concentration of an electrolyte depends on the volume i.e.

C = 1/V

Where C is the concentration in mol/dm3 and V is volume in dm3.

Example

1. What is the dilution of 0.2M NaOH solution?

Solution:

Given λ = 0.2 mol/dm3

V = 1/0.2 = 5 dm3/mol

2. 0.0055M silver nitrate has a molar conductivity of 2.98 x 10-3 S m2 Ω-1 mol-1. Calculate conductivity of that solution.

Solution:

κ = λ x c

= 2.98 x 10-3 x 0.0055

= 1.419 x 10-4 Ω-1 cm-1

ii) Calculate the molar conductivity of 0.3M KOH solution which has a conductivity of 391 Ω-1 m-1.

Solution:

λm = κ / c

= 391 / 0.3

= 1303 S m2 mol-1

VARIATION OF MOLAR CONDUCTIVITY WITH CONCENTRATION

The intensity of electricity that can pass through the solution depends on

  1. The number of concentration of free ions present in the solution.
  2. Speed with which ions move to their respective electrodes.

An increase in concentration gives an increase in total number of solute particles in a given volume of solution and this might well be expected to give an increased conductivity.

Conduction in strong electrolytes.

The molar conductivity is high since strong electrolytes ionize completely into free ions and the molar conductivity increases slightly in dilution. WHY?

In strong electrolytes, there are vast numbers of ions which are close to each other. These ions tend to interfere with each other as they move towards their respective electrodes. The positive ions are held back by the negative ions and vice versa which in turn interrupts their movement to the electrodes (reduce the speed with which they move).

Dilution ions get separated from each other and at an average distance they can move freely or easily.

NOTE:-

As the dilution increases, there comes a time when amount of interference becomes small so that further dilution has no effect.

At this point the molar conductivity remains constant and it is known as molar conductivity at zero concentration λ.

Conduction in weak electrolyte

The molar conductivity is less because there is less number of particles as the minority of particles are dissociated into ions. On dilution the molar conductivity increases as the molecules dissociate more into ions which increases the number of free ions. Therefore for weak electrolytes the molar conductivity depends on the degree of dissociation of molecules into ions.

BiIIoZ6zA 2P0zWyTsyPNh1QpGIGgzAqZXGlddTl6FAHh2XTEHI0KcK3QcTeDh8sjSMzz IMWWIChm0J44rwkniYOYE1wRw6 UBdRsY93QSGKKrpO2HhrFDN34iBMScVvPkn Yk

Question 1

At infinity dilution, will the molar conductivity of strong and weak electrolyte of same concentration be the same?

Answer

NO, the molar conductivity will be different because it also depends on the size of the ions which would either increase or decrease the speed of ions.

Question 2

Why at infinity dilution, the molar conductivity of weak electrolyte remains constant?

Answer

Because at infinity dilution the molecule must have to dissociate into free ions.

MOLAR CONDUCTIVITY AND DEGREE OF DISSOCIATION

The molar conductivity of weak electrolyte is proportional to the degree of dissociation.

i.e. λ = α λ

At infinity dilution, the weak electrolyte is completely ionized.

α = 1 or 100%

Taking ratio of equation (i) and (ii)

AWpz8gKWJsQrAGx Ls2O28ou7APw0NQAB 82C5LxIbhincnl8hRI 03nofg4I5mb4yQlhVkluhlqo3FIIaSAx D5WXvIAQhMA6pTkuebXT7SGWPgz1E 2XUtmq8bquWhmJGxLiQ

Ostwald’s dilution law

It states that “For a weak electrolyte the degree of dissociation is proportional to the square root of reciprocal of concentration”.

Consider a weak binary electrolyte AB (i.e. ethanoic acid) in solution with concentration C (mol/dm3).

AB ⇌ A+(aq) + B(aq)

1 mole 0 0 start

At equilibrium

Ka = C α2 / (1 – α)

For a weak electrolyte, degree of dissociation is very small thus the expression 1 – α ≈ 1

Ka = C α2

Example

1. At 25°C the solution of 0.1M of ethanoic acid has a conductivity of 5.0791 x 10-2 Sm2 mol-1. Calculate the pH of the solution and dissociation constant Ka (Answer Ka=1.69 x 10-2 M)

2. A 0.001 mol/dm3 solution of ethanoic acid was found to have molar conductivity of 14.35 Sm2 mol-1. Use this value together with molar conductivity at infinity dilution of ethanoic acid λ (C2H3COOH) is 390.7 Sm2 to calculate :

  1. Calculate degree of dissociation of acid
  2. Equilibrium constant

3. The resistivity of 1M KCl solution is 361Ω and conductivity cell containing such a solution was found to have a resistance of 550Ω

  1. Calculate the cell constant
  2. The same cell filled with 0.1M ZnSO4 solution had resistance of 72Ω. What is the conductivity of this solution?

KOHLRAUSCH’S LAW OF INDEPENDENT IONIC MOBILITY

Kohlrausch notes that the difference between molar conductivity at infinity dilution λ values for the two salts which were strong electrolytes and of the same cation and anion was always constant.

Using the λ values in D.. cm2 mol-1

HzwU HC8jPnJ8hoBAZv2GXhV856fW2iqk2rFTTu3hsuBfJPFQR PTxJSHqLgrekd C4orTKVQDEY6Z2SceRiQCCVN1N7XsnFo4C6mZ 0fO0uu3YNDa40ltRpmq9UqD5dLQ0Ffck

This observation shows that each type of ion (cation or anion) contribute a definite amount of molar conductivity of an electrolyte at infinity dilution independently from other ions present in the solution i.e. a fraction of current that an ion carries is always constant and it doesn’t depend on the compound in which it is contained.

Hence Kohlrausch’s law

States that: “The molar conductivity of an electrolyte at infinity dilution is equal to the sum of the molar conductivities of the cation and anion”.

OR State that the molar conductivity at infinity dilution of the solution equals the sum of molar conductivity at infinity dilution of its component ions.

i.e. λ(AB) = λ(A+) + λ(B)

E.g. Z3qw941qkT0 VFUeyhF8gTG6mG1nTi8RF9 UQWm3IFNdC2fB2w9KNAgfyWpZ8zEJpQda RwATnAmaSY8OsbD5UXDcrdaph GjL6M9VTDxmIdmYqsZ4tfNZNmpikgbIO6YsuojQ = λ(Al3+) + 3 λ(SO42-)

Application of Kohlrausch’s law

In direct determination of molar conductivity at infinity dilution for weak electrolytes. Thus by using strong electrolytes we can easily calculate the molar conductivities at infinity dilution for weak electrolytes.

E.g.: The λ of potassium ethanoate (CH3COOK), hydrochloric acid (HCl) and potassium chloride (KCl)

CH3COOH + KCl → CH3COOK + HCl

λ(CH3COOH) = λ(CH3COO) + λ(H+)

REVIEW QUESTIONS

  1. Calculate λ(NH4OH) given that λ of three strong electrolytes NaCl, NaOH and NH4Cl in Ω cm2 mol-1 are 126.4, 248.4, 149.8 respectively.
  2. The molar conductivity of 0.093 CH3COOH solution at 298K is 536 x 10-4 Sm2 mol-1. The molar conductivity at infinity dilution of H+ and CH3COO are 3.5 x 10-2 and 0.41 x 10-2 Sm2 mol-1. What is the dissociation constant of CH3COOH?
  3. A 0.05M HF solution has a conductivity of 91.81 mol-1 m-1 at 298K. At the same temperature λ of NaF, NaOH and H2O are 493, 360 and 162 Sm2 mol-1 respectively. Calculate dissociation constant.
  4. The λ of NaI, λ of CH3COONa and λ of CH3COO2Mg are 12.69, 9.10 and 18.78 Sm2 mol-1 respectively at 25°C. What is the molar conductivity of MgI2 at infinity dilution?



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2 Comments

  • 664725894f7bd28c214c8c6754e0c7bf

    Abyud Paskali, May 3, 2026 @ 10:00 pmReply

    TV

  • E323ba2c9b9a7f0dfc5d2aece4c7ccf6

    Flora Eshdavlatova, July 30, 2025 @ 1:17 pmReply

    Great!

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