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CHEMISTRY 205

ELECTROCHEMISTRY:
Voltaic Cell Measurements

I. Purpose:
• To get acquainted with the use of a
voltmeter.
• To measure the cell potentials of different
galvanic cells.
• To construct a concentration cell and
measure its potential.
• To compare the observed cell potentials
with the literature values and expected
ones from Nernst equation.

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II. Theory:
• Electrochemistry: the area of chemistry that
deals with the inter-conversion of electrical
energy and chemical energy.

• Electrochemical processes: redox reactions in


which the energy released by a spontaneous
reaction is converted to electricity.

• Electrochemical cell: the experimental


apparatus for generation of electricity through
the use of a redox reaction.

• A galvanic cell, also called a voltaic cell, is an


electrochemical cell in which electricity is
produced by means of a spontaneous reaction.

A. Generation of Electricity:
• A redox reaction occurs when the reducing
agent is in contact with the oxidizing agent.

• The electrons are transferred directly from the


reducing agent to the oxidizing agent in
solution.

• If these agents are physically separated from one


another, the transfer of electrons can take place
via an external conducting medium. As the
reaction progresses, it sets up a constant flow of
electrons and hence generates electricity.

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B. Example of a Galvanic Cell:
• Consider a zinc bar dipped into a ZnSO4
solution, and a copper bar dipped into a CuSO4
solution. The bars are called electrodes. By
definition:
anode: electrode at which oxidation occurs
cathode: electrode at which reduction occurs

• Zn electrode, anode: Zn (s) Zn2+(aq) + 2e-


• Cu electrode, cathode: Cu2+(aq) + 2e- Cu (s)
______________________________
Zn (s) + Cu2+(aq) Zn2+(aq) + Cu (s)

Electrochemical Cells

anode cathode
oxidation reduction

spontaneous
redox reaction

Ref. Chang Fig. 19.1

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• The two solutions must be separated from each
other; otherwise, the Cu2+ ions will react directly
with the zinc bar, and no useful electrical work will
be obtained.
• However, to complete the electric circuit, the
solutions must be connected by a conducting
medium, a salt bridge, an inverted U tube
containing an inert electrolyte such as KCl or
NH4NO3 in agar.
• During the reaction, electrons flow externally from
the anode (Zn electrode) through the wire and
voltmeter to the cathode (Cu electrode).

• In the solution, the cations (Zn2+, Cu2+ and K+)


move toward the cathode, while the anions (SO42-
and Cl-) move in the opposite direction, toward the
anode.
• By convention:
-The negative electrode in a galvanic cell is the
electrode from which electrons are emitted (i.e.
where oxidation occurs, anode). It is connected to
the minus pole of the voltmeter.

-The positive electrode is the electrode to which


the electrons are transferred (i.e. where reduction
occurs, cathode). It is connected to the plus pole
of the voltmeter.

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C. Electromotive Force:
• The fact that electrons flow from one electrode
to the other indicates that there is a voltage
difference between the two electrodes, called
the electromotive force, or emf (E), which can
be measured after connecting both electrodes
to a voltmeter.

• The emf of a galvanic cell, also referred to as


cell potential or cell voltage, is a direct
measure of the driving force or thermodynamic
tendency of the spontaneous redox reaction to
occur.

• The cell potential depends on:


-the nature of the electrodes and the ions,
-the concentrations of the ions,
-the temperature at which the cell is operated.
• The cell potential is the sum of the two electrode
potentials. It is not possible, therefore, to measure
individual absolute electrode potentials.
• However, a usual procedure is to assign a value of
0.00 Volts to the standard potential for the
electrode reaction,
2H+(aq)+ 2e- H2(g) EH+/,H2 = 0.000V @25°C
• Then, other electrode potentials can be given
definite values based on the assigned value.

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D. Standard Electrode Potentials:
Standard reduction potential (E0) is the
voltage associated with a reduction reaction
at an electrode when all solutes are 1 M and
all gases are at 1 atm.

Reduction Reaction
2e- + 2H+ (1 M) H2 (1 atm)

E0 = 0 V

Standard hydrogen electrode (SHE)


Ref. Chang, Fig. 19.3

Standard Electrode Potentials (continued):


Ecell
0 = 0.76 V

Standard emf (Ecell


0 )

Ecell
0 = E0
cathode - Eanode
0

Zn (s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt (s)


Ecell
0 = E 0+ - E 0 2+
H /H2 Zn /Zn

0.76 V = 0 - EZn 0 2+
/Zn
0
EZn 2+/Zn = -0.76 V
Zn2+ (1 M) + 2e- Zn E0 = -0.76 V
Ref. Chang, Fig. 19.4 (a)

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• E0 is for the reaction as
written
• The more positive E0 the
greater the tendency for the
substance to be reduced
• The half-cell reactions are
reversible
• The sign of E0 changes
when the reaction is
reversed
• Changing the stoichiometric
coefficients of a half-cell
reaction does not change
the value of E0
Ref. Chang, section 19.3

E. Determination of Cell Potential:

• E°cell= E°red + E°ox

With E°M/M2+ = -E°M2+ /M

• E°cell= E°Cu2+/Cu + E°Zn/Zn2+


• E°cell= E°Cu2+/Cu - E°Zn2+/Zn
+0.34 –(- 0.76) = + 1.10V

Ecell
0 = E0
cathode - Eanode
0

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F. Cell Diagram:
• Cell diagram is the conventional notation for
representing galvanic cells. For example:
Zn(s)|ZnSO4(aq,1.00M)|KCl(sat’d)|CuSO4(aq,1.00M)|Cu(s)
where:
-the vertical lines represent phase boundaries;
-the Zn bar is a solid and the ZnSO4 is a solution, thus
a line is drawn in between to show the phase
boundary.
-the concentration of the species in solution is given,
-the salt bridge is included in between two vertical
lines.
• The anode is written first at the left (always by
convention) and the other components appear in the
order in which they are encountered in moving from
anode to cathode.

G. The Nernst Equation:


As mentioned earlier, the emf of a cell depends on
the concentrations of reactants and products. For a
redox reaction of the type aA+ bB cC + dD
the relationship between emf and concentrations of
the species is given by

E = E0 - RT ln Q (1)
Where: nF
Eºcell is the standard emf of the cell,
R is the universal gas constant,
T is the absolute temperature,
n is the number of moles of electrons
transferred during the course of the reaction,
F is faraday’s constant,
Q is the reaction quotient, given by:

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Q =
[C ]c [D ]d (2)
[A ]a [B ]b
• Equation (1) is known as the Nernst equation.

• At 298 K (25ºC), the Nernst equation can be


written as

E = E - 0.0257 V ln Q
0
(3)
n

E = E0 - 0.0592
n
V log Q

H. Concentration Cells:
• Same couple but different concentrations:

Anode M M2+(L) + 2e-


Cathode M2+(R) + 2e- M
__________________
M + M2+(R) M2+(L) + M

E=E − 0
ln
[
0.0257 M 2+ ( L) ]
2 [
M 2+ ( R)]

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I. Spontaneity of Redox Reactions:
• When E0 of a given cell is positive, the redox
reaction -taking place in the cell- is
spontaneous.
• E0 > 0 ⇔ spontaneous reaction

• To predict whether a reaction would proceed


spontaneously as written, one can find its
cell potential E and then if it is positive then
the reaction is spontaneous; Otherwise, if E
is negative then the reaction is not
spontaneous as written, the reverse reaction
is spontaneous.

Practice Exercises
1.Calculate E° and E (the cell emf) for the following cell
reactions:
a) Mg(s) + Sn2+(aq) Mg2+(aq) + Sn(s)
[Mg2+] = 0.045 M; [Sn2+] = 0.035 M.
b) 3Zn(s) + 2Cr3+(aq) 3Zn2+(aq) + 2 Cr(s)
[Cr3+] = 0.010 M; [Zn2+] = 0.0085 M.
Answer: (for E)
a) + 2.23 V b) = + 0.04 V
2. Which species in each pair is a better reducing agent
under standard-state conditions?
a) Fe2+ or Ag b) Br- or Co2+
Answer:
a) Fe2+ b) Br-

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III. Procedure:
A. Galvanic Cells:
1. Prepare the following Galvanic cell:
Zn(s)|ZnSO4(0.100 M)||CuSO4(0.100 M)|Cu(s)
- Use 50 mL beakers for the solutions
compartments, and Zn and Cu metal bars for the
electrodes.
- Obtain from the store room a KCl salt bridge
(polyethylene tube containing a 1.00 M KCl in agar
gel), and use it for the connection of the two
solutions.
- Measure the cell potential. Compare the predicted
cell potential from the literature values of the two
reduction potentials. Enter data in Table 1.

- Repeat the same experiment by changing the


concentrations of the two solutions as follows:
a- 0.100 M ZnSO4/0.00100 M CuSO4,
b- 0.00100 M ZnSO4/0.100 M CuSO4.

- Compare with the cell potentials calculated from


the Nernst equation. Enter values in Table 2.

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2. Prepare the following cell:
Zn(s)|ZnSO4(0.100M)||Pb(NO3)2(0.100M)|Pb(s)
-Repeat the procedure in (1) for this cell.

3. Prepare the following cell:


Zn(s)|Zn(NO3)2(0.100M)||AgNO3(0.100M)|Ag(s)
-Repeat the procedure in (1) for this cell.

4. Prepare the following cell:


Cu(s)|Cu(NO3)2(0.100M)||AgNO3(0.100M)|Ag(s)
-Repeat the procedure in (1) for this cell.

B. Concentration Cells:

- Select a metal M and construct the following


concentration cell:
M(s)|M2+(0.100M)||M2+(0.0010M)|M(s)

- Measure the cell potential. Compare with the cell


potential calculated from the Nernst equation.
Enter values in Table 3.

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