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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.
A. Generation of Electricity:
• A redox reaction occurs when the reducing
agent is in contact with the oxidizing agent.
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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
Electrochemical Cells
anode cathode
oxidation reduction
spontaneous
redox reaction
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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).
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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.
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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
Ecell
0 = E0
cathode - Eanode
0
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
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.
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.
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:
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
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.
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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.
B. Concentration Cells:
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