Experiment 3

GALVANIC CELLS AND CORROSION CELLS

Aim: 1. 2. To measure potentials of various galvanic cells. To examine various corrosion cells.

ELECTROCHEMICAL CELL THEORY. When a rod of metal M is placed in a solution containing ions, Mn+, of the metal M, a potential difference is set up between the metal and the solution. Such an arrangement constitutes a halfcell. An electrochemical cell consists of two halfcells each with its electrode immersed in an electrolyte solution. The electrolyte solution is an ionic conductor and forms a continuous path for ion diffusion (i.e. current) between electrodes. To complete the circuit, a conductor joins the electrodes. This is shown in Figure 1. Voltmeter

V
Metal Electrode M Salt Bridge Metal Electrode N

Solution with M ions of conc. y

+q

Solution with N ions of conc. x

+p

Half cell +q M (y) / M Figure 1.

Half cell +p N (x) / N

Referring to Figure 1, a cell can be written in the shorthand form :

+q +p M / M (y) / salt bridge / N (x)/N

or

M / M+q(y) // N+p(x) / N .

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If the half cell M+q/M (where [M+q] = 1 mol L1) is connected to the standard hydrogen halfcell, the voltage measured is the standard electrode potential E . M +q / M Standard potentials can be used to predict the direction of spontaneous reaction for a cell. When the concentration is equal to unity and the halfcell is the standard hydrogen half cell, the voltage recorded is the standard electrode potential E . M +q / M Question. What is the standard hydrogen halfcell?

When the electrodes of two halfcells are connected by a conducting wire and their solutions are connected by a salt bridge, an electrochemical cell has been established. A cell can be written for example, as follows:
2+ 1 Zn/Zn (x mol L )

//

2+ 1 Cu (y mol L )/Cu

electrode

solution salt bridge

solution

electrod

The anode is defined as the electrode at which oxidation occurs and the cathode as the electrode at which reduction takes place. In a cell electrons then flow from anode to cathode in the external circuit. By convention, when the anode is written on the left (and electrons flow from left to right in the external circuit), the cell potential is positive and is given by: Ecell = Ecathode Eanode where the halfcell E values are reduction potentials. (tabulated below) For the example above, if we have unit concentrations of the ions concerned, the cell potential is a standard potential and: Ecell = Ecathode Eanode = + 0.34 (0.76) = 1.1 V. This positive potential indicates that the cell has been written correctly. Corrosion Cells. A corrosion cell consists of two electrodes short circuited in a common environment. In today's experiment the common environment will be a salt solution. Thus the corrosion cells will have the form : M / NaCl(aq) / N . The electrochemical series is not a reliable guide in indicating which will be the anodic and which will be the cathodic member of a metal couple in such an environment. Moreover, it does not include alloys. Instead we draw up a "galvanic series" of metals and alloys for the environment concerned. (Ref: Callister, "Materials Science & Engineering", 4th ed, p. 558.) 22

EXPERIMENTAL
In the following, whenever electrodes are used make sure that they are clean. Emery paper is provided. DO NOT USE THE SAME SALT BRIDGE TWICE. DO NOT CONTAMINATE THE SOLUTIONS.

SIMPLE ELECTROCHEMICAL CELLS.

Connect the battery provided to the voltmeter so as to obtain a positive reading. Hence identify the lead which will connect to the anode of an electrochemical cell connected to give a positive reading. Set up the following simple cell: Zn/Zn++ (1 mol L1) // Cu++/Cu (1 mol L1)

Construct the cell in the following manner. Place 100 mL beakers containing 40 mL ZnSO4 and 40 mL CuSO4 side by side and connect them up by means of a salt bridge (a strip of filter paper soaked in saturated NH4NO3 solution). Place a copper electrode strip in the CuSO4 solution and a zinc electrode strip in the ZnSO4 solution. Connect the electrodes to the voltmeter so as to obtain a positive reading. Record the voltage. Retain the CuSO4 solution. Which halfcell is the anode? Explain how you experimentally decided this.

Question.

Write down the two separate half reactions occurring at each electrode in the direction that they occur. Write down the overall cell reaction. Look up the standard electrode potentials for the half reactions, and calculate the expected voltage. Does this agree with the experimental voltage?

Question.

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SIMPLE CORROSION CELLS NOTE: On no account should the tin plated iron or the galvanised iron be cleaned with emery paper. Set up the corrosion cell : M / NaCl(aq) / N by putting electrodes pairs M and N to be : a) b) c) d) e) f) g) h) i) j) k) l)

M and N into a beaker filled with salt solution. Choose the electrode Iron Iron Iron Iron Iron Iron Iron Iron Stainless Steel Stainless Steel Galvanised Iron Brass Aluminium Copper Nickel Tin plated iron Galvanised iron Stainless Steel Spring steel Brass Copper Aluminium Aluminium Stainless Steel

Measure and record the potentials. Prepare a table of your results showing the cell examined (e.g. Fe/NaCl(aq)/Al), which electrode is the anode, and which direction the electrons flow.

Question. Question Question.

Does iron act as the same electrode in all cases? Write the equation for the corrosion (oxidation) reaction in cell (a). Write the equation for the reduction reaction in cell (a).

Question. If cell (b) was connected to cell (i) through the copper electrodes, what would be the voltage? (Predict this from your table.)

Test your prediction Does it agree?

Question.

Compare the reading on cell (f) in your table with your prediction, and with the above cell. Explain the agreement (or adjustment). Find another triple of cells which obeys this addition rule.

Question. Since iron and steel are mainly composed of Fe atoms, why is there a potential difference between these electrodes? 24

SOME REDUCTION POTENTIALS

Oxidising Agents F2 + 2e O3 + 2H + 2e S2O8 + 2e Ag
2+ 2 +

Reducing Agents = 2F = = = = = = = = = = = = = = = = = = = = = = = H2O + O2 2SO4 Ag

+ 2+ 2

E(V) 2.85 2.07 2.05 1.98 1.84 1.79 1.77 1.68 1.67 1.63 1.60 1.60 1.52 1.52 1.51 1.46 1.42 1.33 1.36 1.23 1.23 1.20 1.09 0.99 0.96 0.95 0.94 0.91 0.87 0.86 0.85 0.82 0.81 0.80 0.80 0.77

+e

Co + e 2 + PbO2 + SO4 + 4H + 2e H2O2 + 2H + 2e

+ +

3+

Co 2H2O + PbSO4 2H2O Au 2H2O + MnO2 H2O + 1/2 Cl2 2H2O + BiO
3+ +

Au + e + MnO4 + 4H + 3e HClO + H + e
+ 4+ +

BiO3 + 4H + 2e

Ce + e + MnO4 + 8H + 5e BrO3 + 6H + 5e
3+ +

Ce 2+ 4H2O + Mn 3H2O + 1/2 Br2 Mn 2+ 2H2O + Pb Au 3+ 7H2O + 2Cr 2Cl

2+ 2+

Mn + e + PbO2 + 4H + 2e Au + 3e 2 + Cr2O7 + 14H + 6e Cl2 + 2e

+ 3+

MnO2 + 4H + 2e O2 + 4H + 4e
+ +

2H2O + Mn 2H2O

IO3 + 6H + 5e Br2(aq) + 2e
+ +

3H2O + 1/2 I2 2Br

HNO2 + H + e
+

H2O + NO 2H2O + NO 2H2O + Mn Hg2 CuI Hg 2H2O 2H2O + 2NO2 Ag 2Hg Fe

2+ 2+ 3+

NO3 + 4H + 3e MnO2 + 4H + e
+

= = = = = = = = = = = =

NO3 + 3H + 2e 2Hg
2+

H2O + HNO2 3OH

+ 2e

HO2 +H2O + 2e Cu
2+ 2+

+I +e

Hg + 2e + 7 1 O2 + 4H (10 mol L ) + 4e 2NO3 + 4H + 2e Ag + e 2+ Hg2 + 2e Fe + e

3+ + +

25

Oxidising Agents + O2 + 2H + 2e S2O6 + 4H + 2e MnO4 + e I2 + 2e

+ 2 +

= = = = = =

Reducing Agents H2O2 2H2SO3 MnO4 2I

2

E(V) 0.68 0.57 0.54 0.53 0.52 0.48 0.45 0.40 0.34 0.27 0.22 0.20

Cu + e 3 Fe(CN)6 + e H2SO3 + 4H + 4e O2 + 2H2O + 4e Cu + 2e Hg2Cl2 + 2e AgCl + e 2 + SO4 + 4H +2e Co(OH)3 + e Cu

2+ 2+ +

Cu 4 Fe(CN)6 3H2O + S 4OH

= = = = = = = =

Cu 2Hg + 2Cl Ag + Cl H2O + H2SO3 Co(OH)2 + OH Cu

+

0.17 0.17 0.15 0.10

+e

Sn + 2e 3+ Co(NH3)6 + e NO3 + H2O + 2e

+ 1 3+

4+

= = = = = = = = = = = = =

Sn 2+ Co(NH3 )6 2OH + NO2 H2 Fe Cr(OH)3 + 5OH Pb Sn 4 Mn(CN)6 N2H 5 Co H2 Cr

2+ +

2+

0.00 0.00 0.04 0.13 0.13 0.14 0.22 0.23 0.28 0.41 0.41 0.44 0.49 0.51 0.60 0.76 1.18 1.67 2.34 2.71 2.87 2.92

2H (1 mol L ) + 2e

Fe + 3e 2 CrO4 + 4H2O + 3e Pb
2+ 2+

+ 2e

Sn + 2e 3 Mn(CN)6 + e N2 + 5H + 4e
2+ +

Co + e + 7 1 2H (10 mol L ) + 2e Cr
3+ 2+

+e

Fe + 2e 2CO2 + 2e S + 2e Au(CN)2 + e Zn Al
2+

= = = = = = = = = = =

Fe 2 C2O4 S Au + 2CN Zn Mn Al Mg Na Ca K
2

+ 2e + 3e

Mn Mg

2+

+ 2e + 2e

3+

2+

Na + e
2+

Ca + 2e K +e
+

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