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La boratory 1 - Reference Electrodes

Objective

In this lab you will learn how a reference electrode is constructed by assembling a Cu/CuSO 4 reference electrode. You will then use this reference electrode and two others, a silver/silver chloride and saturated calomel, to measure the corrosion potential (E corr ) of several different alloys. Using number lines, you will then learn how to convert E corr for each material to other reference systems. When complete, you will have constructed a galvan ic series f or these materials and calculated the conversion factor between the three reference electrodes. The conversion factor for one of these electrodes will then be compared to the theoretical value you calculate using the Nernst equation.

Background - Thermod ynamics of Half Cell Reactions

The equilibrium reaction occurring at the surface of an electrode in equilibrium is called a half cell reaction. For the copper electrode in the Cu/CuSO 4 reference electrode the half cell reaction is equal to:

 ! ! + 2 ! ↔ (1) Notice this is written as a reduction reaction! This reaction is associated with a change in Gibb's energy , ΔG: ∆ = ∆ ! + 2. 303 (2)

where ΔG o is the standard Gibbs energy for the reaction and K is th e equilibrium constant and is equal to:

where a is activity.

= ! ( !"#\$%&'( )

! ( !"#\$%#&% )

(3)

It is possible to covert Eq. 2 to different energy systems, for example, since this is an

electrochemical reaction involving the p assage of current , it is more convenient to expression the change in energy in terms of electrical potential , E, using the relationships:

= and ! = !

(4)

where E o is the standard reduction potential for the reaction on t he normal hydrogen scale (NHE), n is equal to the number of electrons transferred in the reaction (2 for Cu ++ ) and F is Faraday's constant 96,500 C/equiv. Substituting the expressions in 3 and 4 into 2 we have:

= !

. !"! !" !"

!

(5)

Equation 5 is referred to as the Nernst equation and is used in the analysis of many electrochemical cells as well as the construction of Pourbaix diagrams. Here we will use this expression to evaluate the Cu/CuSO 4 electrode system.

Experimental Pr ocedures

Safety Be sure to follow all safety procedures outlined in the SOP for handling chemicals and wearing personal protective equipment .

Materials - Check that your station is set up with:

1. A Biologic potentiostat turned on and software.

2. Materials for constructing a Cu/CuSO 4 reference electrode.

3. Saturated calomel reference electrode (SCE)

4. Shared silver/silver chloride reference electrode

5. A drip tray containing a beaker/flask of 0.1M sodium sulfate solution (pH=9)

6. The following metal electrodes in solution :

- Aluminum (99.999%)

- Carbon steel 1018

- Copper

- Stainless steel 304L

Part I - What's Inside a reference Electrode? In the first part of this lab you will assemble a Cu/CuSO 4 reference electrode. The instructions for doin g this are below:

1. Make sure the copper rod is fully burnished. Remove any and all contaminants by using a new, unused, non- metallic scouring pad or sandpaper. Green scouring pads are recommended for the procedure. When green scouring pads are unavailab le, sandpaper can be used. Be sure to rinse the electrode after burnishing.

2. Once the copper rod assembly has been fully burnished, avoid any contamination, which may occur before the rod assembly is reattached to the tube for example, the pH from ungloved fingers, dirt, oil and any other foreign substance that may come in contact with before being reattached to the tube. may cause incorrect readings.

3. Reattach the rod assembly to the tube. Hand tighten only as not to damage the rubber o- ring by over torqueing. But, be sure to tighten well enough that the electrode does not leak.

that may have stuck to the threads of the tube. Copper sulfate is corrosive and poisonous please use care.

5. Screw the presaturated plug assembly onto the tube end, making sure again not to over torque the o - ring.

6. Shake the electrode until the CuSO 4 and H 2 O solution becomes dark blue in color and completely saturated with the CuSO 4 . There should always be CuSO 4 crystals at the bottom of the electrode to insure a saturated solution.

Part II - E corr Measurement Using 3 Different Reference Electrodes. The potential for an electrode in an environment is related to the kinetics of the oxidation and reduction reactions. When these re actions are at "steady state" (i.e . , not changing) we refer to the corresponding potential as the corrosion potential, E corr . W hile this may be similar to equilibrium it differs because the corrosion reactions are not reversible at this potential.

1. Place the Cu/CuSO 4 reference electrode in the flask containing the solution and

electrodes.

2. Connect the reference electrode to the corresponding alliga tor clip on the potentiostat.

Connect the C1018 electrode in the solution to the "working electrode" alligator clip. Monitor the potential for 10 minutes on the computer and record the steady state value in the table in the Results section.

3. Repeat procedure 2 for all of the metal electrodes placing the measured value in the

table.

4. Remove the Cu/CuSO 4 reference electrode from the flask containing the solution and

electrodes and replace it with the Ag/AgCl reference electrode. Connect the reference electrode to the corresponding alligator clip on the potentiostat. Record E corr for each

electrode as before.

5. Repeat procedure 4 for the saturated calomel reference electrode placing the measured

steady state value of E corr in the table below .

Results

Table 1. Steady state values of E corr in 0.1M sodium sulfate.

 E CuSO4 E AgCl E SCE V V V Copper C1018 SS 304L Al

Assignment

Part I - Converting Potential Measurements B etween Scales It is common for investigators to use different reference electrodes (scales) for different electrochemical systems or applications. For example, a scientist may want to maintain a chloride free environment for a precise study of pitting potential or a field engineer may need a robust "problem free" electrode to withstand the rigors of pipe- to- soil measurements. Even within one application more than one type of reference electrode can be used and it is typical to convert electrode potentials back and forth between scales. Potentials from the various types of reference electrodes are typically converted to the norma l hydrogen electrode (NHE) for comparison on a common scale. Converting between reference electrodes is similar to converting between Celsius and Kelvin temperature scales. I n this section you will learn how to convert between scales a nd the NHE using number lines.

1. The conversion factor between SCE and the NHE is 0.271 V. To convert from SCE to NHE you must add 0.271V. To convert from NHE t o SCE you must subtract 0.271V. That is, if you measure the potential of an SCE relative to NHE, the SCE would be 0.271 V more positive than the NHE electrode. To visualize this, first write the values for E corr you recorded using the SCE on the number line below, placing tick marks and the corresponding E corr value for each alloy above the l ine . On the NHE scale below the number line convert each of the E corr potentials measured with the SCE to NHE. Copy these values in to Table 2 order ing them from highest (most noble) to lowest (most active). The table you have created is a galvanic serie s. Note that it is specific to sodium sulfate solution. Table 2. Galvanic series for 0.1M sodium sulfate solution.

material     E corr , V vs. NHE     3. As you found in problem 2, the potential of a given electrode is not changing when yo u

change reference electrodes, just the frame of reference is changing. In addition, if you measure the potential between an electrode and two reference electrodes in the same solution it is possible to calculate the conversion factor between the two references. To apply this knowledge to a new system, in the diagram below, write in the E corr values you

measured for the C018 electrode using the SCE and the Cu/CuSO 4 reference electrodes.

C1018%

E corr (SCE)=%  Δ%

0.0%V%CuSO 4%      0.0%V%SCE%

E corr (CuSO 4 )=%

Now calculate the conversion factor, Δ, to convert from Cu/CuSO 4 to SCE . BE CAREFUL OF THE SIGN (+/ - ):

Δ =

4. Using the conversion factor to convert from Cu/CuSO 4 to SCE you calculated in Problem

3, and the conversion factor we provided in Problem 2, calculate the conversion factor

from CuSO 4 to NHE (be careful of the sign) :

Conversion to NHE =

5. Using a similar procedure as in Problem 4 except this time using the E corr you measured

for C1018 using the Ag/AgCl reference electrode, calcu late the conversion factor, Δ, to convert from AgCl to SCE. BE CAREFUL OF THE SIGN (+/ - ):

Δ =

6. Now, calculate the conversion factor from Ag/ Ag Cl to NHE (be careful of the sign) :

Conversion to NHE =

Part II - Theoretical Electrode Potentials

In Part I, P roblem 4 you calculate d an empirical potential for the Cu/CuSO 4 electrode vs. NHE (a conversion factor). It is also possible to use the Nernst equation, Eq 5 , to calculate the theor etical electrode potential for the Cu/CuSO 4 electrode relative to NHE.

To do this, for the Cu/CuSO 4 reference electrode:

=

( )

( ! ! ) =

1

( ! ! ) ; ! = 0. 342;

and a Cu++ = mγ +/ where γ +/ is the activity coefficient and m is CuSO 4 concentration in molal (g solute/g solvent). The saturation concentration for CuSO 4 at 20 o C is 32g / 100g H 2 O and the activity coefficient (γ ) can be calculated by interpolating the concentration data (x) in the following table from Ajayi and Wigwe (1978) :

 m Cu/CuSO4 γ +/ − g/gH 2 O 0. 09 0. 100 0. 1 0. 144 0. 2 0. 103 0. 3 0. 083 0.4 0.070

and the relationship :

! ! ! ! = ! ! ! !

!

! ! ! !

!

! ! ! !

Now, using these values, calculate the theoretical potential for the Cu/CuSO 4 electrode vs. NHE and compare this value to the conversion factor you calculated in Part I - Problem 4 above.

 Empirical: Cu/CuSO4 is V vs. NHE Theoretical: Cu/CuSO4 is V vs. NHE