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Maisari Utami
• Example:
3.2 The Hydrogen Electrode
• Unfortunately there is no way to measure the standard reduction
potential of an isolated half-cell. All we can measure is the difference
in potential produced when two half-cells are connected.
• Therefore, to assign numerical values for standard reduction
potentials, a reference electrode has been arbitrarily chosen and its
standard reduction potential has been defined as exactly zero volts.
• This reference electrode is called the standard hydrogen electrode
3.2 The Hydrogen Electrode
• This electrode is surrounded by a solution whose temperature is 25
°C and in which the hydrogen ion concentration is 1.00 M. The half-
cell reaction at the platinum surface, written as a reduction, is:
Standard Reduction Potentials at 25 °C
Exercise 2
• What spontaneous reaction occurs if Cl2 and Br2 are added to a
solution that contains both Cl- and Br-. Assume standard conditions.
Exercise 3
• A typical cell of a lead storage battery of the type used to start
automobiles is constructed using electrodes made of lead and
lead(IV) oxide (PbO2) and with sulfuric acid as the electrolyte. The
half-reactions and their standard reduction potentials in this system
are
• What is the cell reaction and what is the standard potential of this
cell?
Exercise 4
• A galvanic cell is constructed by placing 1.0 M aluminum nitrate in
one beaker with an aluminum electrode and a second beaker with 1.0
M copper nitrate and a copper electrode. When a salt bridge is
inserted to connect the two beakers, what cell potential do we expect
to measure between the copper and aluminum electrodes? Which
electrode is the anode and what is the spontaneous chemical
reaction?
Exercise 5
• Determine whether the following reactions, at standard state, are
spontaneous as written. If a reaction is not spontaneous, write the
equation for the reaction that is.
4. E°cell and G°
• The fact that cell potentials allow us to predict the spontaneity of
redox reactions is no coincidence.
• There is a relationship between the cell potential and the free energy
change for a reaction.
• Kc = equilibrium constant.
• Calculate the cell potential when [Ni2+] = 4.87 × 10-4] and [Cr3+] = 2.48
× 10-3 M.
Exercise 9
• The reaction of tin metal with acid can be written as
• Calculate the cell potential when (a) the system is at standard state,
(b) the pH is 2.00, and (c) the pH is 5.00. Assume that [Sn2+] = 1.0 M
and the partial pressure of H2 is 1.00 atm.
Exercise 10
• A laboratory was assigned the job of determining the copper(II) ion
concentration in thousands of water samples. To make these
measurements an electrochemical cell was assembled that consists of
a silver electrode, dipping into a 0.225 M solution of AgNO3,
connected by a salt bridge to a second half-cell containing a copper
electrode. The copper half-cell was then filled with one water sample
after another, with the cell potential measured for each sample. In
the analysis of one sample, the cell potential at 25 °C was measured o
be 0.62 V. The copper electrode was observed to carry a negative
charge, so it served as the anode. What was the concentration of
copper ion in this sample?
6. Electrolytic Cells
• In our preceding discussions, we’ve examined how spontaneous redox
reactions can be used to generate electrical energy.
• We now turn our attention to the opposite process, the use of electrical
energy to force nonspontaneous redox reactions to occur.
• When electricity is passed through a molten ionic compound or through a
solution of an electrolyte, a chemical reaction occurs that we call
electrolysis.
• This particular cell contains molten sodium chloride (a substance
undergoing electrolysis must be molten or in solution so its ions can move
freely and conduction can occur).
• Inert electrodes—electrodes that won’t react with the molten NaCl or the
electrolysis products—are dipped into the cell and then connected to a
source of direct current (DC) electricity.
6. Electrolytic Cells
• The DC source serves as an “electron pump,” pulling electrons away from
one electrode and pushing them through the external wiring onto the
other electrode.
• The electrode from which electrons are removed becomes positively
charged, while the other electrode becomes negatively charged.
• When electricity starts to flow, chemical changes begin to happen. At the
positive electrode, oxidation occurs as electrons are pulled away from
negatively charged ions. Because of the nature of the chemical change,
therefore, the positive electrode becomes the anode. The DC source
pumps the electrons through the external electrical circuit to the negative
electrode. Here reduction takes place as the electrons are forced onto
positively charged sodium ions, so the negative electrode is the cathode.
6. Electrolytic Cells
• The chemical changes that occur at the electrodes can be described
by chemical equations:
6.1 Comparing Electrolytic and Galvanic Cells
6.2 Electrolysis of Water in Aqueous Systems
• At the cathode, water is reduced.