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INTRODUCTION By the end of this lesson, students will be able to: 1.

Explain the electrode potential of a metal in a solution of its ions 2. Explain how the Helmholtz double layer arises 3. describe and label the Standard Hydrogen Electrode (SHE)
General reading: pages 405 - 408

1. Drag Zn electrode and dipped into solution containing Zn2+ ions. 2. An electrode potential is produced when a metal is dipped into a solution of its own ions

3. Click on Process 1. At the Zn metal surface, Zn atoms lose electrons to become Zn2+ ions leaving behind a layer of negatively charged electrons on the metal surface: Zn(s) Zn2+(aq) + 2e- (oxidation)

4. At the same time Zn2+ ions in solution comes to the metal surface and accepts 2e- to become Zn atoms. Zn2+(aq) + 2e Zn(s) reduction Click process 2. 5. A dynamic equilibrium is achieved between the 2 processes

6. Charge on metal surface depends on which of the 2 processes takes place more readily. 7. For Zn metal, the forward reaction or the oxidation reaction occurs more readily; the Zn electrode is negatively charged and the solution positively charged 8. The double electric layer between the metal surface and the metal ions is called the Helmhotz double layer 9. A potential difference develops between the negatively charged zinc electrode and the positively charged solution. This potential difference is called the electrode potential. The system is called a Zn half-cell 10. If the metal used is Cu, then it is found that the reduction process takes place more readily. Then the Cu metal electrode becomes positively charged and the solution is negatively charged

A potential difference develops between the negatively charged zinc electrode and the positively charged solution. This potential difference is called the electrode potential. The system is called a Zn half-cell

H2 is a gas. Pt is used as inert electrode At equilibrium : 2H+(aq) +2eH2(g)

There is a potential difference between the H2 gas at the Pt surface and H+ ions in solution. Under std conditions is called std electrode potential, E0 of H2. The value is 0.00V.

A non-metal / ion half-cell ; example a chlorine half-cell Cl2 is a non-metal so Pt is used as an inert electrode -ve electrode process is oxidation from left to right. Click 4 +ve electrode process is reduction from left to right. Click 5

An ion/ ion half-cell Pt electrode is inert electrode. Electrode is ve (oxidation ) from left to right
Calomel half-cell: Hg2Cl2(s) + 2e 2Hg(l) + 2Cl-(aq) E0=+0.244V (pg412)

Summary: 1. The standard Hydrogen electrode consists of a Pt rod / wire immersed in an acidic solution containing 1 mol dm-3 of H+ ions at a temperature of 298 K. H2 gas at a pressure of 1 atm is bubbled over the surface of Pt. 2. The electrode potential of Hydrogen under standard conditions is called the standard electrode potential of Hydrogen, E0 of H2. It is assigned a value of 0.00 V. 3. There are 3 types of half-cells: a) a metal / ion half-cell eg Zn(s) / Zn2+ (aq) b) a non-metal (gas) / ion half-cell eg H2(g) , H+(aq) /Pt(s) c) an ion / ion half cell eg Pt(s) / Fe2+(aq) , Fe3+(aq)

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At the end of this lesson, students are able to: 1. Explain the use of the standard hydrogen electrode (SHE) as a reference electrode in the determination of the electrode potential of other half-cells 2. Use the standard electrode potential series to compare the strengths of oxidising and reducing agents 3. Use the electrochemical series (ECS) to compare the reactivity of metals

1. Above diagram is for a Zn half-cell. As an isolated half-cell, its electrode potential cannot be measured. However can measure the potential difference between 2 half-cells. 2. Click SHE. Click E0H+/H2. Click connect. Click voltmeter. Click Zn electrode. Click IUPAC, half reactions, click overall reaction, cell-diagram.

measure the E0 of a half-cell like Zn half-cell must connect it to the SHE half-cell. Click SHE
4. To

5. SHE is the reference electrode. Its potential difference is given a value of 0.00V 6. Click E0 H+/H2 . Click connect 7. The E0 of Zn half-cell is recorded by a high resistance voltmeter. It is called the electromotive force or e.m.f. 8. Click voltmeter. Click Zn electrode. 9. The standard electrode or redox potential E0 of Zn electrode is -0.76V. 10. Click IUPAC 11. ve sign shows Zn is ve electrode. Reaction here is oxidation 12. Click half-reactions, overall reaction and cell-diagram

Above shows measurement of SEP (standard electrode potential) of Cl2 elec Summary: The standard electrode potential of an element is the potential difference between the standard H half-cell and the half-cell of the element under standard conditions The SEP, E , of an element M is defined as the potential difference measured between an electrode of metal, M in contact with 1.0M Mn+ ions in solution at 298K relative to SHE.

1. The SEP of all other half-cells can be measured in the same way. 2. Table above shows the E of half-cells arranged in order of increasing values from the most ve to the most +ve.

3. Such a series is called the standard electrode potential series or the redox series. 4. All the half-reactions are written as reduction processes 5. The standard electrode potentials (SEPs) are also called standard reduction potentials (SRPs) 6. All species on the LEFT are oxidising agents 7. All species on the RIGHT are reducing agents 8.The more negative the value of E ; the stronger the species on the RIGHT as a reducing agent 9. Which is stronger as a reducing agent: Zn or Cu? 10. The more positive the value of E , the stronger is the species on the LEFT as an oxidising agent. 11. Which is a stronger oxidising agent: Br2 or MnO4-?

The part of the standard electrode potential series that includes only metals is called the electrochemical series. (ECS). The higher the metal in the ECS the more ve the value of E , the stronger it is as a reducing agent and the more reactive it is

The table above shows the E0 values for halogens nonmetals The more +ve the value of E0,, the stronger are the halogens as oxidising agents and the more reactive is the halogen.

Summary: 1. The SEP series shows half-cells arranged in order of increasing standard electrode potentials (SEPS) from the most ve to most +ve 2. All half-cell reactions are written as reduction processes from left to right. 3. All species on the LEFT are oxidising agents; all species on the RIGHT are reducing agents 4. The more ve the value of E , the stronger is the species on the RIGHT as a reducing agent 5. The more +ve the value of E , the stronger is the species on the LEFT as an oxidising agent. 6. The part of the series that includes only metals is the ECS 7. The higher the metal in the ECS, the more ve the value of E , the more reactive is the metal

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Objectives in this lesson: students are able to 1. Calculate the e.m.f of an electrochemical cell from E values 2. Determine the direction of electron flow in an electrochemical cell 3. Predict the stability of aqueous ions and the feasibility of a redox reaction from E values

An electrochemical cell is formed when 2 half-cells in the redox series are combined An electrochemical cell converts chemical energy to electrical energy The above cell is called the Daniell cell

1. The half-cell with the smaller or more ve electrode potential is the negative electrode 2. At the ve electrode oxidation takes place 3. The negative electrode is also called the anode 4. The half-cell with the bigger or less negative electrode potential is the positive electrode. 5. The positive electrode is also called the cathode because reduction take place here 6. Electrons flow from the negative electrode (anode) to the positive electrode( cathode) 7. The salt bridge allows movement of ions from one solution to another so as to maintain electrical neutrality

Diagram above shows the cell - diagram or the cell-notation for the Daniell cell. (read also pg 408)

The potential difference between the two half-cells is called the electromotive force (e.m.f) or the standard electrode potential of the cell, E cell E
cell =

E+ - E- . Another formula is E = Eox + Ered

For Daniell cell E = Eox + Ered = Ezn/zn2+ + Ecu2+/ cu = (+0.76V) + (+0.34V) = +1.10V

Click on electrode where oxidation occurs; electrode where reduction occurs. Click on overall reaction. Click on cell-diagram. Label anode and cathode. Click on ve electrode Show how to calculate E E
cell cell

= E+ - E-..

= Eox + Ered = EMg/Mg2+ + ESn2+/ Sn.. E

= (+2.38V) + (-0.14V) =+2.24V

Homework: 1. Try questions 1.1 and 1.2 under topic electrochemical cells on pages 3 and 4 of handout Electrochemistry 1 2. Answer problems Q1 and Q2 in handout Questions for practice. 3. Solve all problems under Quick Check 13.4

Summary: 1. An electrochemical cell converts chemical energy to electrical energy. 2. The anode is the electrode where oxidation takes place. Anode is the ve electrode 3. The cathode is the electrode where reduction takes place. Cathode is the +ve electrode 4. Electrons flow from the negative electrode to the positive electrode 5. The e.m.f of a cell, E0cell = Ecathode Eanode = E+ - E= Eox + Ered Homework: Read example 13.3 and answer all questions under Quick Check 13.4

Redox reactions that occur spontaneously are said to be energetically feasible If E0cell is +ve, redox reaction is energetically feasible If E0cell is ve, the redox reaction is enegetically not feasible

E0 for the reaction between H2(g) and Cu2+(aq) is +ve. It is energetically feasible but there is still no reaction. This is because the rate of reaction is close to zero. The reaction is kinetically not feasible For the 2nd reaction, E0 is ve. It is therefore energetically not feasible under standard conditions. However when concentrated HCl is added and the mixture heated, chlorine gas is liberated. This means that when the conditions are changed not 1.0M and 1 atm pressure and 298K ( not standard conditions) the reaction now becomes energetically feasible.

To find out whether the above reactions can take place, we find E0cell .If E0cell is +ve then it can take place; if E0cell is ve then the redox reaction cannot take that is not feasible energetically. Homework: Read example 13.2 and do all questions in Quick Check 13.3

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E0Zn/Zn2+ is a more powerful reducing agent than all above species on the right except V(s). Hence VO2+ (yellow) will be reduced until V2+(aq) is obtained colur is violet.

Stability of aqueous ions in solution System

Ti2+/ Ti -1.63 Ti3+ / Ti2+ -0.37 V2+ / V Cr2+ / Mn2+ / Fe2+ / Co2+ / Co Cr Mn Fe -1.18 -0.44 -0.28 Co3+/ Co2+ Ni2+ / Ni -0.25 Cu2+ / Cu +0.34 -

Eo / V System Eo / V

-1.20 -0.91 V3+ / V2+

Cr3+ / Mn3+ / Fe3+/ Cr2+ Mn2+ Fe2+ +1.49

-0.26 -0.41

+0.77 +1.82

1. Note that Eo for the system M2+/M is ve except for Cu2+/Cu Thus all the above metals M are very reactive. When these metals are added to acids (containing H+ ions), the metals react to produce H2 gas. All the metals will dissolve in the acid to form M2+ ions. The exception is Cu. 2. The E cell for reaction M + 2H+ systems except Cu2+ / Cu. M2+ + H2 is +ve for all

3. For half-cells M3+ / M2+; note that there are 3 values where E M3+ / M2+ are ve and 3 values that are positive. 4. Eg. Ti3+ + e Mn3+ + e Ti2+ E = -0.37V Mn2+ E = + 1.49 V

It is clear from above E0 values that Mn2+ is more stable than than Mn3+ while Ti2+ is more stable than Ti3+ under aqueous conditions based on E0 values 5. Note also that O2 + 4H+ + 2e 2H2O E = +1.23V

The stability of the ions M2+ and M3+ depends on the presence of O2. Thus when O2 is present, Ti2+, V2+, Cr2+ and Fe2+ will be oxidised by O2 present to M3+ ion 6. On the other hand Co3+ and Mn3+ are such powerful oxidising agents that they are also unstable and will oxidise water present to O2 gas. They are reduced to Co2+ and Mn2+

For rx 1, E cell is +ve. The redox reaction is spontaneous. Hence the product Cr3+ is more stable than the reactant Cr2+ For rx 2, E cell is +ve. The redox reaction is spontaneous. The product Co2+ ion is more stable than the Co3+ ion in aqueous solution For rx 3, E cell is ve, redox reaction is not energetically feasible. Here Co3+ is more stable than the Co2+ when complexed with NH3 . Also refer notes

Stability of ions in aqueous solutions complex formation 1. Besides the presence of O2, the formation of complexes can also affect the stability of an ion 2. Transition elements can exist in variable oxidation states and can form a large number of complex ions 3. In forming a complex the oxidising and reducing power of an ion will be affected hence Eo will change 4. Co3+(aq) + e O2(g) + 4H+(aq) + 4e [Co(NH3)6]3+ + e Co2+(aq) 2H2O [Co(NH3)6]2+ E = +1.82V E = +1.23V E = +0.10V

Note Co3+(aq) is such a strong oxidising agent that is oxidises water to give out O2 gas. It is therefore extremely unstable. However when it is complexed with NH3, its oxidising power reduced tremendously. It will not be able to oxidise water. It is now very stable

5. Fe3+(aq) + e [Fe(CN)6]3- + e

Fe2+(aq) [Fe(CN)6]4-

E = +0.77V E = +0.36V

6. Note in above, aqueous Fe3+(aq) is a more powerful oxidising agent compared with [Fe(CN)6]3-. This is because the Eo for Fe3+(aq) is more +ve. Note also that the oxidation state of Fe in both ions is 3+. Understand that the stronger a species is as an oxidising agent, the more unstable it is. Hence by complexing with CN-, Fe3+ is stabilised. 7. I2 + 2e 2IE = + 0.54V. Note that if Fe3+(aq) is added to a solution containing I- ions, a reaction will take place; if however [Fe(CN)6]3- is added to I- ions, then no reaction will occur. This is the answer to Q7(c)

Summary: 1. The positive value of E cell indicates that the reaction is energetically feasible 2. The negative value of E cell indicates that the reaction is energetically not feasible. 3. A reaction may be energetically feasible but may be kinetically non-spontaneous 4. The E

value is independent of the rate of reaction.

5. The formation of complexes generally stablises the oxidation state of the ion 6. Refer to role of O2 in notes 7. Refer to fuel cells in notes

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