VOLTAIC MINICELL LAB PURPOSE: Construct voltaic (galvanic) cells and develop an electrochemical series based on potential differences

between half-cells To understand the Nernst Equation.

BACKGROUND INFORMATION: Electrochemical Cells Any chemical reaction involving the transfer of electrons from one substance to another is an oxidation/reduction (redox) reaction. The substance losing electrons is oxidized and the substance gaining electrons is reduced. Let us consider the following redox reaction: Zn (s) + Pb+2 (aq) Zn+2 (aq) + Pb (s)

This redox reaction can be divided into an oxidation and a reduction half-reaction: Oxidation half-reaction: Zn (s) Zn+2 (aq) + 2 e-1

Reduction half-reaction:

Pb+2 + 2e-1 Pb (s)

A voltaic (galvanic) cell (Figure 1) is a device used to separate aredox reaction into its two component half-reactions insuch a way that the electrons are transferred through an external circuit rather than by direct contact of the oxidizing agent and the reducing agent. This transfer of electrons through an external circuit is electricity. Each side of the galvanic cell is known as a half-cell. For the redox reaction above, each half-cell consists of an electrode (the metal of the half-reaction) and a solution containing the corresponding cation of the half-reaction. The electrodes of the half-cells are connected by a wire along which the electrons flow. In the cell, oxidation takes place at the zinc electrode, liberating electrons to the external circuit. Reduction takes place at the lead electrode, consuming electrons coming from the external circuit. The electrode at which oxidation occurs is called anode. The electrode at which reduction occurs is called the cathode. Since oxidation releases electrons to the electrode, it is designated the negative electrode in the galvanic cell. Reduction removes the electrons from the cathode; it is the positive electrode. As zinc atoms are oxidized, the excess positive charge (Zn+2 ions) accumulates in solution around the zinc anode.

Likewise, excess negative charge (NO3-1) accumulates around the lead cathode as Pb+2 ions are removed from solution of Pb(NO3)2 by reduction to lead metal. These excess charges create an electric field that causes the ions to migrate: positive ions (cations) migrate toward the cathode and negative ions (anions) migrate toward the anode. In order to make this flow of ions between the two half-cells possible, the cells are connected by a porous barrier (or salt bridge) through which the ions flow. The barrier prevents free mixing of the two solutions but permits limited movement of ions so that the electrical neutrality is maintained in each half-cell. Different metals, such as zinc and lead, have different tendencies to oxidize; similarly their ions have different tendencies to undergo reduction. The cell potential of a galvanic cell is due to the difference in tendencies of the two metals to oxidize (lose electrons) or their ions to reduce (gain electrons). Commonly, a reduction potential, which is a tendency to gain electrons, is used to represent the relative tendency for a given metal ion to undergo reduction. The voltage measured in the cell is the result of the two half-reactions, and the magnitude of the potential depends on the concentrations of the ions, the temperature, and pressure of gases. When all the concentrations in the zinc/lead system are 1 molar and the temperature is 25 C, the cell voltage is 0.63 volts. It would be a monumental task to assemble a list of all possible cells and report their voltage. Instead we use the potential of the half-reactions. We cannot measure any half-cell potential directly, so we pick one half reaction, call it the standard, construct a cell, measure the cell voltage and report the potential relative to the standard. The standard that has been chosen by convention is: 2 H+1 + 2e-1 H2 (g) E0 = 0.00 Volts

Here the notation E0 is called the standard electrode potential and is the assigned potential of the standard hydrogen electrode when the concentration of H+1 is 1 M and the pressure of the hydrogen gas is one atmosphere. The measured cell voltage using the standard hydrogen electrode is therefore the potential of the other half reaction. Tables of standard half-reaction potentials have been computed. The reactions by convention are written as reductions and hence the tables are called tables of standard reduction potentials. A brief example follows below in an excerpt from a Standard Reduction Potentials table. The greater the tendency of the ion to gain electrons and undergo reduction, the less negative (or the more positive) the reduction potential of the ion. In the zinc/lead cell, the lead has a greater tendency to undergo reduction than the zinc. Some Standard Reduction Potentials at 250 C half-reaction Cu+2 + 2 e- Cu (s) 2 H+1 + 2 e- H (g) Pb2+ + 2 e- Pb (s) Zn2+ + 2 e- Zn (s) Mg2+ + 2 e- Mg (s) Li+ + e- Li (s) Potential (volts) +0.34 0.00 - 0.13 - 0.76 - 2.37 - 3.05

In the zinc/lead cell the measured potential of 0.63 volts can be deduced from the sum of the potentials of the two half-reactions: Zn Zn + 2 eEcell = +0.76 V Pb+2 + 2 e- Pb Ecell = -0.13 V __________________________________________________ Zn + Pb+2 Zn+2 + Pb Ecell = +0.63 V Note: The sign of the standard reduction potential for the zinc half reaction is reversed to give the potential of the oxidation half reaction. In Part I of this experiment, other metal/ion half-cell combinations will be tried. From the data, a table will be developed, listing various elements and ions in order of their tendency to gain or lose electrons. The Nernst Equation Theoretical predictions of tendency to gain electrons are used to predict the voltage difference between two electrodes. The voltage difference between electrodes, the cell voltage, is also called the electromotive force, or emf (or Ecell). Under standard conditions (25 C, 1 M solution concentration, 1 atm gas pressure), these theoretically predicted voltages are known as standard emfs ( or Ecell ). In reality, standard conditions are often difficult, if not impossible, to obtain. The Nernst Equation allows cell voltages to be predicted when the conditions are not standard. Walter Nernst developed the following equation in the late 1800's while studying the thermodynamics of electrolyte solutions: Ecell = Ecell

- RT ln Q
nF

In this equation, R is the gas constant (8.314 J/mole K), T is the temperature (Kelvin), F is Faraday's constant (96,485 coulombs/mole), n is the number or electrons transferred in the balanced oxidation/reduction reaction, and Q is the reaction quotient, or ([products]/ [reactants]). Note that in this equation, that if the reaction quotient is equal to 1, then Ecell = Ecell. In Part II of this experiment, voltages will be measured at various solution concentrations for the copper/zinc galvanic cell and compared with voltages calculated using the Nernst Equation. PRE LAB QUESTIONS: 1. Calculate the standard electrode potential for a nickel-aluminum cell. 2. According to the Nernst equation, what is the potential of a Ni-Al cell with [Ni2+] = 5.0 M and [Al3+] = 0.010 M? 3. By definition, oxidation always occurs at which electrode? 4. Calculate the theoretical cell potentials for each pair you will measure in the procedure below.

MATERIALS: 24 well plate Metal electrodes PROCEDURE: 1. Fill four cells with .1M solutions of Fe(NO3)3, Pb(NO3)2, Mg(NO3)2 , and Cu(NO3)2 as shown in Figure 1. Have the center well filled with the KNO3 solution. Each well should be a little over half-full. In the second half of the spot plate, fill three cells with .1M solutions of Zn(NO3)2, Al(NO3)2, and Cu(NO3)2, with the center well filled With the KNO3 solution. 2. Obtain mini metal electrodes corresponding to each Of your well solutions. Make sure your electrodes are fairly clean. If not, shine them with sandpaper or steel wool. 3. Fold the filter paper salt bridges into a U shape (crease it to get it to stay) and place about 3 drops of KNO3 solution on the paper. Fill the center well half-full with KNO3 solution. Position the filter paper salt bridges as demonstrated in Figure 1. 4. Place the electrodes in their respective cells (Al in Al+3, Cu in Cu2+, Zn in Zn2+, etc.) away from the salt bridge. Do not attach the multimeter until you are completely ready to read voltage. Record the cell potentials listed in Table I by attaching the multimeter leads (Figure 2). Because this is a spontaneous reaction, the potential of the cell is always positive. If you have a negative reading, it is because you have switched the leads. This is not really a problem because switching the leads only changes the sign of the voltage, so you can change the sign if needed. If you see black on any of your electrodes, you have made a mistake and will need to clean the electrode. 5. Clean the 24 well plate. Set up a similar arrangement as shown above, but use the substances listed in Table II and III below. Record the cell potentials for Tables II and III. Figure 2 multimeter ion solutions filter paper strips forceps Figure 1

I. Voltaic Cell

Standard Cells Experimental Potential (Volts) Theoretical Value (Volts)

Pb (s) | Pb2+(.10 M) | | Cu+2 (.10 M) | Cu (s) Fe (s) | Fe+2 (.10 M) | | Cu+2 (.10 M) | Cu (s) Mg (s) | Mg+2 (.10 M) | | Cu+2(.10 M) | Cu (s) Al (s) | Al+3 (.10 M) | | Cu+2 (.10 M) | Cu (s) Zn (s) | Zn+2 (.10 M) | | Cu+2 (.10 M) | Cu (s) II. Voltaic Cell Al(s) | Al+3 (0.010 M) | | Cu+2 (.10 M) | Cu(s) Zn(s) | Zn+2 (0.010 M) | | Cu+2 (.10 M) Cu(s) III. Voltaic Cell Cu(s) | Cu+2 (.10 M) | | Cu+2 (0.010 M) | Cu(s) Concentration Cell Experimental Literature Potential (Volts) Value (Volts) Nonstandard Cells Experimental Potential (Volts) Literature Value (Volts)

Conclusions: 1. Why woul you e!"e#$ no "o$en$i%l $o be gener%$e be$ween $wo h%l&-#ells in $his e!"eri'en$ un$il $he ()*3 solu$ion 'igr%$es $o % "oin$ where i$ o+erl%"s bo$h o& $he h%l&-#ell solu$ions, 2. -is#uss so'e "ossible sour#es o& error $h%$ #oul %##oun$ &or $he i&&eren#es in $he e!"eri'en$%l +%lues o& $he #ell "o$en$i%ls you ob$%ine %n $he li$er%$ure +%lues. 3. Explain why there is voltage flow between the two copper wells in Table III, if they contain identical metals. Include a reference to LeChateliers principle. 4. Using your data, develop a series of reduction half-reactions in either ascending or descending order for the metals used in Table I. 5. How could you determine an activity series for metals using only the exact chemicals and equipment in this lab, but without using the voltmeter? Why did we not conduct the experiment like this?

6. We could have used large pieces of metal and large beakers filled with solution to perform this experiment. How would the measured potentials have differed? Explain.