Electrochemistry

CHM 3010_Electrochemistry

CHM 3010_Electrochemistry

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CHM 3010_Electrochemistry

Electrolysis: Learning Outcomes

Electrolyte 1. Use Faradays law to calculate amounts of conductivity, Faradays products formed, amounts of current passed, time elapsed and oxidation state law,
2. Describe the differences between electrolytic cell and galvanic cell 3. Recognize oxidation and reduction half reactions 4. Write half reactions and overall cell reactions 5. Use standard reduction potential to calculate the standard cell potential, to identify the cathode and anode, to predict the spontaneity of a redox reaction
4

Electrochemical cell, standard electrode potential and redox reaction

CHM 3010_Electrochemistry

Electrolysis: Learning Outcomes

6. Use Nernst equation to relate electrode potentials and cell potentials to different concentrations and partial pressures

Nernst equation

Application of electrochemistry in determination of equilibrium constant and Gibbs free energy

7. Relate standard cell potential to the standard Gibbs free energy change and the equilibrium constant

CHM 3010_Electrochemistry

Introduction
Discusses the relation between chemical processes and electrical energy.

Battery or Voltaic cell Chemical processes

Electrical energy

Electrolysis

CHM 3010_Electrochemistry

References
Whitten: Chapter 21 Brady: Chapter 21

CHM 3010_Electrochemistry

Electrochemistry
Electrochemistry deals with the chemical changes produced by electric current & with the production of electricity by chemical reactions All electrochemical reactions involve the transfer of electrons oxidation-reduction reactions (redox reactions) In most applications the reacting system contained in a cell, and an electric current enters or exits by electrodes

CHM 3010_Electrochemistry

Electrochemistry
The two parts of the reaction are physically separated. The oxidation reaction occurs in one cell. The reduction reaction occurs in the other cell. There are two types of electrochemical cells: 1.Electrolytic cells are those in which electrical energy from an external source causes nonspontaneous chemical reactions to occur 2.Voltaic or galvanic cells are those in which spontaneous chemical reactions produces electricity & supply it to an external circuit
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Figure 21.3 General characteristics of voltaic and electrolytic cells

VOLTAIC CELL System does work on its Energy is released from spontaneous redox reaction surroundings

ELECTROLYTIC CELL Surroundings(power supply) Energy is absorbed to drive a nonspontaneous redox reaction do work on system(cell)

Oxidation half-reaction X X+ + e-

Oxidation half-reaction AA + e-

Reduction half-reaction Y++ e- Y

Overall (cell) reaction X + Y+ X+ + Y; DG < 0

Reduction half-reaction B++ eB

Overall (cell) reaction A- + B+ A + B; DG > 0
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CHM 3010_Electrochemistry

Electrical Conduction
Electric current represents transfer of charge Charge can be conducted through metals & through pure liquid electrolytes (i.e. molten salts) or solutions containing electrolytes Metals conduct electric currents well in a process called metallic conduction. Involves the electron flow with no atomic motion & no obvious changes in the metal
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Electrodes
Electrodes are surfaces on which oxidation or reduction half-reactions occur They may or may not participate in the reactions

Electrodes that do not react with the liquids or products of the electrochemical reactions are called inert electrodes
Two examples of common inert electrodes are graphite and platinum.
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Electrodes
The following identification for electrodes is correct for either electrolytic or voltaic cells:

The cathode is the electrode at which reduction occurs as electrons are gained by some species (CR)
The cathode is negative in electrolytic cells and positive in voltaic cells.

The anode is the electrode at which oxidation occurs as electrons are lost by some species (AO)
The anode is positive in electrolytic cells and negative in voltaic cells.
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Electrochemical process
When a metal is immersed in a solution containing its ion an equilibrium exists. M(s) M+(aq) + e Oxidation and reduction occur on the electrode surface where electron is transferred to or from the electrode. Electrical neutrality of every component of the cell must be maintained, therefore:
i.
+ + +

ii. When oxidation occurs on one electrode, reduction must occur on the other

Anode electrode where oxidation occurs Cathode electrode where reduction occurs
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Voltaic or galvanic cell

A cell where electrical current is generated from spontaneous chemical reaction on the electrode surface in the solution.
Zn
1 hour CuSO4

Spontaneous chemical reaction occurs Cu2+ + Zn Cu + Zn2+ Energy is produced in form of heat (wasted) and cannot be benefited or used.
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Figure 21.4

The spontaneous reaction between zinc and copper(II) ion

Zn(s) + Cu2+(aq)
CHM 3010_Electrochemistry

Zn2+(aq) + Cu(s)
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Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

Electrochemical cell
An electrochemical cell consists of at least two electrodes connected by a wire and an electrolyte.
Galvano/voltmeter electrodes

Connection wire

electrolyte

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Voltaic or Galvanic Cells

Voltaic or galvanic cells are electrochemical cells in which a spontaneous (product-favored) chemical redox reactions produce electrical energy. The two halves of the redox reaction are separated, requiring electron transfer to occur through an external circuit useful electrical energy is obtained
electrons (from redox reaction) are forced to travel through wires and creating a potential difference

Examples of voltaic cells include:

Automobile batteries Flashlights batteries Computer & calculator batteries
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A Galvanic Cell: The Copper Silver Cell

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Zn-Cu cell
Daniel cell 2 part of the cell are separated and are connected by wire.
Zn ZnSO4 Cu Zn ZnSO4 Salt bridge

Cu
CuSO4

CuSO4

Porous pot

Zn metal is oxidised to Zn2+ while Cu2+ in the solution is reduced to Cu. Zn electrode Zn Zn2+ + 2e [O] anode Cu electrode Cu2+ + 2e Cu [R] cathode Electron is continuously taken from Cu thus become +ve electrode and given to Zn thus become ve electrode. Electron flows from Zn (-ve) to Cu (+ve) giving electric current (energy).
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The Construction of Simple Voltaic Cells

Salt bridge allows the movement of ions to keep the solutions neutral A tube filled with a solution composed of a salt of ions not involved in the cell reaction saturated salt/5% agar solution (sets to the consistency of firm gelatin) Common salt solutions: KNO3 or KCl Porous plugs are fitted at each end prevents the salt solution from pouring out but at the same time allows ion exchanges with the solutions in half-cells

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The Construction of Simple Voltaic Cells

Salt bridge serves 3 functions: Allows electrical contact between the two solutions Prevents mixing of the electrode solutions Maintains the electrical neutrality in each halfcell as ions flow into & out of the salt bridge A cell in which all reactants & products are in their thermodynamic standard states (1 M for dissolved species & 1 atm partial pressure for gases) is called a standard cell
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Figure 21.5 A voltaic cell based on the zinc-copper reaction

Oxidation half-reaction Zn(s) Zn2+(aq) + 2e-

Reduction half-reaction Cu2+(aq) + 2eCu(s)

Overall (cell) reaction Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

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Figure 21.6

A voltaic cell using inactive electrodes

Reduction half-reaction MnO4-(aq) + 8H+(aq) + 5eMn2+(aq) + 4H2O(l)

Oxidation half-reaction 2I-(aq) I2(s) + 2e-

Another example

Overall (cell) reaction 2MnO4-(aq) + 16H+(aq) + 10I-(aq) 2Mn2+(aq) + 5I2(s) + 8H2O(l)

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

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Sample Problem 21.2:

Diagramming Voltaic Cells

PROBLEM: Diagram, show balanced equations, and write the notation for a voltaic cell that consists of one half-cell with a Cr bar in a Cr(NO3)3 solution, another half-cell with an Ag bar in an AgNO3 solution, and a KNO3 salt bridge. Measurement indicates that the Cr electrode is negative relative to the Ag electrode. PLAN: Identify the oxidation and reduction reactions and write each halfreaction. Associate the (-)(Cr) pole with the anode (oxidation) and the (+) pole with the cathode (reduction).
eCr
Voltmeter salt bridge

SOLUTION:

Oxidation half-reaction Cr(s) Cr3+(aq) + 3eReduction half-reaction Ag+(aq) + eAg(s) Overall (cell) reaction Cr(s) + Ag+(aq) Cr3+(aq) + Ag(s)

K+ NO3Cr3+ Ag

Ag

Cr(s) | Cr3+(aq) || Ag+(aq) | Ag(s)

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CHM 3010_Electrochemistry

Cell notation
Represent a cell in written form. The Zn-Cu cell can be represented as: Zn(s)/Zn2+(aq)//Cu2+(aq)/Cu(s) or Zn(s)/ZnSO4(aq)//CuSO4(aq)/Cu(s) Anode left, cathode right. Metals (or conducting materials) for electrical terminals at both ends. Phase separation - /. Salt bridge - //. If electrolyte contain > 1 participating in the reaction they are separated by a coma (,). Examples: Cd(s)/Cd2+(aq)//H+(aq)/H2(g)/Pt Ag/AgCl/Cl-(aq)//Fe3+(aq),Fe2+(ak)/Pt

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Notation for a Voltaic Cell

components of anode compartment (oxidation half-cell) phase of lower phase of higher oxidation state oxidation state components of cathode compartment (reduction half-cell) phase of higher oxidation state phase of lower oxidation state

phase boundary between half-cells Examples: Zn(s) Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu (s) Zn2+(aq) + 2eCu2+(aq) + 2eCu(s)

graphite | I-(aq) | I2(s) || H+(aq), MnO4-(aq) | Mn2+(aq) | graphite

inert electrode
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Why Does a Voltaic Cell Work?

The spontaneous reaction occurs as a result of the different abilities of materials (such as metals) to give up their electrons and the ability of the electrons to flow through the circuit. Ecell > 0 for a spontaneous reaction 1 Volt (V) = 1 Joule (J)/ Coulomb (C)

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Table 21.1 Voltages of Some Voltaic Cells

Voltaic Cell

Voltage (V)

Common alkaline battery Lead-acid car battery (6 cells = 12V) Calculator battery (mercury)

1.5
2.0 1.3 0.15 0.070

Electric eel (~5000 cells in 6-ft eel = 750V)

Nerve of giant squid (across cell membrane)

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Electromotive force (emf)

A force is needed to move a charge. Total force to move electron(s) from a ve electrode to a +ve electrode in an electrochemical cell is termed emf (in volts or V). Emf of a cell is often called cell potential or Ecell. emf depends on 3 factors:
Tendency of two half reactions to occur spontaneously. Electrolyte concentration and gas pressure. Temperature.

Standard emf - Ecello measured at 25 oC, 1 atm of gas pressure and 1.0 electrolyte concentration

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Electrode and cell potentials

Each ion has tendency to take up electron and undergoes reduction. However the ability to be reduced is different and ion with higher ability will succeed while the other undergoing oxidation. Example Zn-Cu cell, Zn2+ vs Cu2+. Cu2+ has higher ability to gain electron thus reduced and Zn2+ oxidised. This tendency is termed electrode (half cell) potential and the different (+ve value) between two electrode potentials is the cell potential. Thus Ecell = Ecathode Eanode Ecell > 0 so Ecathode > Eanode Based on cell notation Ecell = Eright - Eleft

Only cell potential can be measured experimentally. The electrode potential is calculated from the cell potential if the potential for the other half cell is known. Ecathode = Ecell + Eanode or Eanode = Ecathode - Ecell
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Standard hydrogen electrode and standard electrode potential

An electrode potential is calculated from a cell potential where the potential of one electrode is known. It is conventionally agreed that the potential of hydrogen electrode at 25 oC, [H+] = 1 M and PH2 = 1 atm is 0.0000 V. Example to determine the potential for Cu/Cu2+. Pt/H2(g)/H+(aq)//Cu2+/Cu The cell potential (from meter) is 0.34 V Ecello = ECuo EH2o = 0.34 V or ECuo = 0.34 V By this way a list of electrode (half cell) potentials are obtained. They are also referred to as standard reduction potentials. See the list in reference books.
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The standard hydrogen electrode. Hydrogen gas at 1 atm is passed over finely divided platinum. The solution contains 1.00 M hydrogen ion. The reduction potential is exactly 0 V at 298 K (25oC).

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 Using a hydrogen half-cell, other reduction potentials can be measured

A galvanic cell comprised of copper and hydrogen halfcells. The reaction is Cu2+(aq)+H2(g) Cu(s)+2H+(aq) Cell notation: Pt(s), H2(g)|H+(aq)||Cu2+(aq)|Cu(s)
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Redox reactions
The reduction potentials table can also be used to determine whether a redox reaction can occur spontaneously. The strength of a reduction or oxidation agent depend on the potential value. A substance or an ion with high reduction potential will be easily reduced thus is a strong oxidation agent and vice versa. MnO4-, O3, F2 strong oxidants Li, K, Na strong reductants Example: Will the following mixture react spontaneously at standard state? Zn2+(aq) + Fe2+(aq) ??? (a) Zn2+(aq) + 2e Zn Eo = -0.76 V (b) Fe3+(aq) + e Fe2+ Eo = 0.77 V (a)-2(b); Zn2+(aq) + 2Fe2+(aq) Zn(s) + 2Fe3+(aq)
o Ereaction 0.76 (0.77 ) 1.53

The forward reaction is not spontaneous.

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Free energy and Ecell

DG is the maximum work that can be obtained or extracted from a system or process. DG = -wmax In electrochemical cell Work (w) = - charge (Q) x emf = - nF x emf = - nFEcell Therefore DG = - nFEcell For standard state DGo = - nFEcello Example: Zn + Cu2+ Zn2+ + Cu Eo = 1.10 V DGo = - 2 x 96500 x 1.10 = - 212300 J = - 212.3 kJ

Spontaneous reaction Nonspontaneou s reaction

DG = -ve DG = +ve

E = +ve E = -ve

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Nernsts equation
For a general reaction aA + bB eE + fF The corresponding relation for Gibbs free energy is: Therefore Or At 25 oC

[ E ]e [ F ] f DG DG RT ln [ A]a [ B ]b
o

[ E ]e [ F ] f nFE nFE RT ln [ A]a [ B ]b

o

[ E ]e [ F ] f E E RT ln [ A]a [ B ]b
o

Nernsts equation

0.0592 [ E ]e [ F ] f EE log n [ A]a [ B ]b

o

If all species are at unit concentration log Q = 0 and Ecell = Ecello

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The Nernst Equation

D = D - (0.059/n)log10(Q)
D, in analogy with DG, indicates the direction
of spontaneous change:

D > 0 reaction goes left to right D = 0 no net reaction (equilibrium) D < 0 reaction goes right to left
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Walther Hermann Nernst

Born: Briesen near Thorn (Torun) (Germany), 1864 Died: Ober-Zibelle near Bautzen (Germany), 1941 In 1883 Nernst became assistant of Wilhelm Ostwald in Leipzig, 1891 professor in Gttingen, 1905 in Berlin. He succeeded in explaining the phenomena connected with galvanic elements (Nernsts equations 1889) and calculated the mobility of ions and the coefficient of diffusion. He received the Nobel Prize in 1920.
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A Standard Half Reaction

Note that the Nernst equation combines the tendency of both the oxidation reaction to proceed and the reduction reaction to proceed as a pair of coupled reactions. To establish a scale of reactivity we measure half reactions against a standard half reaction:
H2 2H+ + 2e
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The Hydrogen Electrode

The hydrogen electrode is the standard reference electrode for aqueous half-cell potentials. The half-cell reaction is the reduction 2 H+(aq) + 2e H2 (g)

The standard potential of this half-cell is set equal to zero. Potentials measured for a cell containing the standard hydrogen electrode will be equal to the half-cell potential of the other electrode. A table of standard half-cell potentials may be obtained from any of the references.
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Conventions for (Half-cell Potentials)

1. Assign standard hydrogen electrode a potential of 0.0 V. 2. When half reactions are written as reductions, reactions that proceed as reductions more readily than H+/H2 are assigned positive voltages, those that proceed less readily are assigned negative voltages. 3. If the direction of the half reaction is reversed, the sign of the standard half cell potential is reversed. If the reaction is multiplied by some factor, the standard half cell potential remains unchanged.

4. The value of the half cell potential is a measure of the tendency of the reaction to proceed from left to right as written.
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Usage of Ecell
Determination of Equilibrium Constant
aA + bB

eE + fF

[ E ]e [ F ] f DG DG o RT ln [ A]a [ B ]b

DG 0
o

and

[ E ]e [ F ] f K eq [ A]a [ B ]b

RT E ln K eq nF

The eq const can be calculated from E o cell or vice versa

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Figure 21.9 The interrelationship of DG0, E0, and K DG0

DG0

E0cell

Reaction at standard-state conditions

spontaneous

<0 0 >0 DG0 = -nFEocell DG0 = -RT lnK

>1

>0

1
<1

0
<0

at equilibrium
nonspontaneous

By substituting standard state values into E0cell, we get E0cell E0cell = -RT lnK nF
Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

E0cell = (0.0592V/n) log K (at 250C)

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Electrolysis

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 Electricity can be used to make nonspontaneous redox reactions to occur The process is called electrolysis Electrolysis occurs in an electrolysis or electrolytic cell These cells require a source of direct current, possibly one of the batteries just discussed, to provide electrical energy
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Electrolytic Cell

Galvanic Cell

Cathode is negative Cathode is positive (reduction) (reduction) Anode is positive (oxidation) Anode is negative (oxidation)

In both types of cells oxidation occurs at the anode and reduction occurs at the cathode Electrolysis in aqueous solutions often involves water molecules This is often unintended and called a competing reaction
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Electrolytic cell
+
Battery

Cathode

Example: Electrolysis of fused NaCl

Anode

Cl2 released

ClNa+

Na deposit

Na+ is attracted to ve electrode and reduced while Cl- attracted fo +ve electrode and oxidised. Na+(l) + e Na(s) anode Cl-(l) 1/2Cl2(g) + e cathode In term of electrode charge electrolytic cell is different from voltaic cell Cell Electrolytic Voltaic
CHM 3010_Electrochemistry

Anode +ve -ve

Cathode -ve +ve

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Electrolysis from aqueous solution

Consider electrolysis of aqueous NaCl. The process become complex in the presence of water as the water itself can be oxidised or reduced. Cathode H2 is released Anode O2 is released for dilute NaCl Cl2 is released for conc. NaCl Cathode : 2 competing reactions 2H2O + 2e H2 + 2OHEo=-0.83 V Na+ + e Na Eo=-2.71 V H2O with higher red. potential is reduced. Anode : 2 competing reactions 2H2O O2 + 4H+ + 4e Eo = -1.23 V Cl- Cl2 + 2e Eo = -1.36 V The oxidation pot. for H20 is a little higher and since the conc of Cl- is low H2O is oxidised. However for high conc. NaCl, due to the concentration effect Cl- is oxidised.

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Faradays Law
Faraday relates the amount of substance obtained at the electrode with the amount of charge transferred during electrolysis. Na+ + e Na(s) Cl- 1/2Cl2 + e I mole of e is required to deposit 1 mole of Na and release half mole of Cl2 Charge of 1 e = 1.602 X 10-19 C Charge of 1 mole of e = 6.022 X 1023 X 1.602X 10-19 96500 C This is well known as Faradays number, 1 F = 96500 C
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Electrolysis of molten sodium chloride. The passage of an electric current through molten sodium chloride decomposes the material into molten sodium and chlorine gas. The products must be kept separated because they react on contact to re-form NaCl.

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A microscopic view of the changes at the anode in the electrolysis of molten NaCl. The positive charge of the electrode attracts Cl- ions. At the surface of the electrode electrons are pulled from the ions yielding neutral Cl atoms which combine to form Cl2 molecules that rise to the surface as a gas.
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 Sodium is a liquid at the melting point of sodium chloride (801 oC)

Reaction at the cathode: Na+(l) + e- Na(l) Reaction at the anode: 2Cl-(l) Cl2(g) + 2e Cell reaction: 2Na+(l) + 2Cl-(l) 2Na(l) + Cl2(g)

The electrode polarities are reversed in electrolytic cells relative to those in galvanic cells
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Electrolysis of an aqueous solution of potassium sulfate. The products of the electrolysis are H2 and O2 gas, not the expected products solid K and S2O82-. Why?

Look up the E0 values of all possible electrode reactions and work out how you may arrive at the statement given above. Refer Chemistry: Matter and Its Changes by brady and Senese (4th Edn) Chp 21.
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Example
Calculate the mass of Cu (atomic mass = 64) deposited at cathode in the electrolysis of CuSO4 if 2 A current was flowed for 1 hour. At cathode Cu2+ + 2e Cu 2 F is required to deposit 1 mole Cu Charge, Q = I X t = 2 C s-1 X 3600 s = 7200 C Mole of Cu deposited = 7200/(2 X 96500) = 0.0373 mole Mass of Cu = 0.0373 X 64 = 2.39 g

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Table 21.4 Comparison of Voltaic and Electrolytic Cells

Electrode Cell Type Voltaic Voltaic DG <0 <0 Ecell >0 >0 Name Anode Cathode Process Oxidation Reduction Sign +

Electrolytic Electrolytic

>0 >0

<0 <0

Anode Cathode

Oxidation Reduction

+ -

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Types of Cells
Look up uses

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Example
Calculate the mass of Cu (atomic mass = 64) deposited at cathode in the electrolysis of CuSO4 if 2 A current was flowed for 1 hour. At cathode Cu2+ + 2e Cu

2 F is required to deposit 1 mole Cu Charge, Q = I X t = 2 C s-1 X 3600 s = 7200 C Mole of Cu deposited = 7200/(2 X 96500) = 0.0373 mole Mass of Cu = 0.0373 X 64 = 2.39 g

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 A student added contains 50.00 mL solution of 0. 1216 M FeCl3 into an electrolytic cell. If a current of 0.310 A is passed through the cell for 40 minutes, how much (g) of Fe(s) would be deposited at the cathode? What is the concentration of Fe3+ (aq) in the cell at the end of the 40 minutes ? (One Faraday = 96500 Coulomb)

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Group Exercise 1: Take Home

Use this list of half-reactions to answer the following six questions.

MnO4-(aq) + 8H+(aq) + 5e- Mn2+(aq) + 4H2O(l) +1.51 V Cr2O72-(aq) + 6e- 2Cr3+(aq) + 7H2O(l) +1.33 V Pt2+(aq) + 2e- Pt(s) +1.20 V Cu2+(aq) + 2e- Cu(s) +0.34 V Pb2+(aq) + 2e- Pb(s) -0.13 V Al3+(aq) + 3e- Al(s) -1.66 V

Using the half-reactions in the above table, write down the cell notations for the four cells which can be constructed to give Eocell in excess of +1.90 V .
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Group Exercise 2: Take Home

The value of Ecell at 25oC for the cell shown below is +1.27 V. Show how you would determine the value of Eocell.
Cd(s) | Cd2+(aq), 2.0 M || Ag+(aq), 2.0 M | Ag(s)

Ans. 1.26 V
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Group Exercise 3: Take Home

Calculate the mass of cobalt that will be deposited when a current of 2.00 A is passed through a solution of CoSO4 for 10.0 hours. (Co=58.93)

ANSWER: 22.0 g
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