Electrochemistry: (Tuesday, 8 May 2017)
Electrochemistry: (Tuesday, 8 May 2017)
Electrochemistry: (Tuesday, 8 May 2017)
A. Objective
a) Learn some redox reactions
b) Learn what happened in the electrolysis of KI and CuSO4 solution
B. Introduction
Electrochemistry is the study of the relationships that exist between chemical reactions
and the flow of electricity. Included here are electrolysis reactions, in which nonspontaneous
changes are forced to occur by the passage of electricity through chemical system. Also
included are spontaneous oxidation-reduction reactions (redox reactions) that are able to supply
electricity. For convenience, we describe all these changes under the general heading of
electrochemical reactions.
Redox reaction is characterized by changes in oxidation state during reaction, for
example:
Cl-(aq) + MnO2(s) Cl2(g) + Mn2+(aq) (acidic)
In above reaction, reactant Cl- was changing in oxidation states to Cl2, whereas the
oxidation state of Mn4+ in MnO2 fell into Mn2+. In order to fulfill the law of conservation of
mass and conservation of change, the above equation is equated as follows:
2Cl-(aq) + MnO2(s) + 4H+(aq) Cl2(g) + Mn2+(aq) + 2H2O
The impact of electrochemical reactions on modern society is found nearly everywhere.
Critically important industrial chemicals such as aluminium, chlorine, and sodium hydroxide,
without which modern society couldn’t function, are manufactured exclusively by electrolysis
reactions. And all of the tiny (and not so tiny) portable sources of electricity that we commonly
call “batteries” are able to function solely because electrochemical reactions within them are
able to provide electrical energy.
Redox Reaction
The term oxidation can be used to describe the process in which certain fruits turn brown
by reacting with oxygen. The original, historical definition of this term was “to combine with
oxygen.” Thus, oxidation occurred when iron rusted, and when magnesium was burned in
oxygen gas. The term reduction was used historically to describe the opposite of oxidation, that
is, the formation of a metal from its compounds. An ore is a naturally occurring solid
compound or mixture of compounds from which a metal can be extracted. Thus, the process of
obtaining a metal from an ore was known as a reduction. Copper ore was reduced to yield
copper, and iron ore was reduced to yield iron. The terms oxidation and reduction used to
describe changes to carbon-hydrogen and carbon-oxygen bonds within organic compounds.
These changes involve electron transfers.
The following chemical definitions describe these changes.
• Oxidation is the loss of electrons.
• Reduction is the gain of electrons.
Redox (reduction-oxidation) reactions include all chemical reactions in which atoms have
their oxidation state changed; in general, redox reactions involve the transfer of electrons
between species. The term "redox" comes from two concepts involved with electron transfer:
reduction and oxidation. It can be explained in simple terms:
Oxidation is the loss of electrons or an increase in oxidation state by a molecule, atom, or
ion. Reduction is the gain of electrons or a decrease in oxidation state by a molecule, atom, or
ion.
Electrolysis
The chemical reactions that take place at the electrodes during electrolytic conduction
constitute electrolysis, and an apparatus designed specifically to carry out such reactions is
called an electrolysis cell or an electrolytic cell. When a substance is subjected to electrolysis,
it is said to be electrolyzed.
An example of electrolysis occurs when molten (liquid) NaCl is electrolyzed. In this
system, Na+ ions migrate toward the negative electrode where they become oxidized to Cl
atoms. The Cl- ions migrate toward the positive electrode where they become oxidized to Cl
atoms, which combine to form Cl2 molecules. The reactions that take place at the electrodes
are,
Positive electrode 2Cl-(l) Cl2(g) + 2e- (oxidation)
+ -
Negative electrode Na (l) + e Na(l) (reduction)
For electrolysis, the negative electrode is the cathode and the positive electrode is the
anode. Therefore, in this electrolytic cell sodium is formed at the cathode and chlorine gas is
produced at the anode.
The electrolysis of aqueous solutions of electrolytes is somewhat more complex because
of the ability of water to be oxidized as well as reduced. The oxidation reaction for water is
2H2O(l) O2(g) + 4H+(aq) + 4e-
and the reduction reaction takes the forms
2H2O(l) + 2e- H2(g) + 2OH-(aq)
In acidic solutions another reaction that may take place is the reduction of H+, which is,
2H+(aq) + 2e- H2(g)
When electrolysis is carried out on an aqueous solution, there is the possible oxidation
and reduction of water as well as the possible oxidation and reduction of the solute. In other
words, at each electrode there are competing reactions. At the anoder there is the possible
oxidation of water of of the anion, and at the cathode there is the possible reduction of water or
the cation. What is actually observed in any particular electrolytic cell is determine, therefor,
by the relative tendencies of the competing reactions occur. This, in turn, is controlled both by
the thermodynamic ease of reaction and by the nature of the materials used to construct the
electrodes. As a result, it is not an easy matter to predict what will actually take place when
electrolysis is carried out without actually carrying out the experiment. As you wil see below,
however, what when learn from one experiment can often be used to predict outcome of others.
Galvanic Cells
In an electrolytic cell, a nonspontaneous chemical change is forced to occur by an
electrical voltage that is placed across a pair of electrodes that dip into the system. We now turn
to the opposite situation, in which a spontaneous redox reaction is used to provide a voltage
and an electron flow through some electrical circuit. Chemical system set up to function in this
way are called either galvanic cells or voltaic cell. For a galvanic cell, the positive electrode is
the cathode and the negative electrode is anode.
An example of a spontaneous redox reaction that you have seen before occurs when
metallic zinc is dipped into a solution of copper sulfate. Over a period of time, a dark brown,
spongy layer of metallic copper forms on the zinc. The blue color of the CuSO4 also fades and
if the solution is analyzed, it is found to contain Zn2+ formed by the dissolving zinc strip. The
reaction that has taken place here is
Cu2+(aq) + Zn(s) Cu(s) + Zn2+(aq)
For Daniel cell above, when both electrodes are connected, the electrons will flow from
Zn to Cu. These electrons generate from a spontaneous reaction on the electrode Zn|Zn2+:
Zn(s) Zn2+(aq) + 2e-
Electrons arriving at the electrode Cu|Cu2+ will interact with Cu2+ ions
Cu(s) + 2e- Cu2+(aq)
Thus the Cu ions are precipitated as the Cu atom. Overall cell reaction is obtained by
summing the above reaction:
Zn(s) + Cu2+(aq) Cu(s) + Zn2+(aq)
Cell diagrams
To give someone a complete description of a galvanic cell, the kinds of information we
would want to specify are (1) the nature of the electrode materials; (2) the nature of the
solutions in contact with the electrodes (including the concentrations of ions in solution); (3)
which of the half-cells is the anode and which is the cathode; and (4) the reactants and products
in each of the half cells. To provide this information in a compact way, electrochemists have
developed a standard notation called a cell diagram.
In constructing a cell diagram, we specify the anode half-cell first, followed by the
cathode half-cell. A pair of vertical bars is used to represent the salt bridge between them.
Within a given half-cell, the reactants are specified first, followed by the products. A single
vertical bar is used to represent a phase boundary, as between a solution and a solid electrode.
For substances in solution, molar concentration are indicated in parentheses after the formula.
The galvanic cell is made by joining these two half-cells by salt bridge (indicated by
double bars. ||), which gives
Zn(s)|Zn2+(1.00 M)||Cu2+ (1.00 M)|Cu(s)
C. Apparatus and Reagent
Test Tube Al, Cu, Fe, Mg, Pb, Zn metals
Graduated cylinder Solution of Pb(NO3)2 0.1 M
Burner Solution of Zn(NO3)2 0.1 M
Filter paper Solution of 0.1 M AgNO3
Beaker glass Solution of 0.1 M NaNO3
Dropping pipette Solution of 6 M HCl
Funnel Solution of 0.1 M KI and 0.25 M
Electrode Cu plate Solution of 0.1 M H2SO4
Salt bridge Solution of 0.1 M H2O2
Carbon electrodes Solution of starch
pH meter Solution of CuSO4
Tube with U type Solution of ZnSO4
6 V AC current source Solution of SnCl2 0.1 M
PP indicator CHCl3 / CCl4
D. Procedure
1) Redox reaction
2) Electrolysis of KI solution
Put electrodes and
Put 0.25M of KI into connect to the source of Write the changes in
an U type tube (up to 2 direct current 6 V for the catode and anode
cm from the orifice of chamber. Then, remove
the tube) 5 min, then the electrodes carefully
disconnect the current
Take 2 mL of each
Take each 2 mL solution
solution from the anode
from the catode chamber
into 2 test tubes. Add to
into 2 test tubes and add
the first tube 1 mL of
few drops of PP on the
CHCl3 layer. In another
first, and 2 mL of 0.1M
tube, add few drop of
FeCl3 to the second tube.
starch, and shake it
E. Observation Sheet
1) Redox titration
a) Reaction of metal and metal nitrat solution
Metal Pb(NO3)2 Zn(NO3)2 NaNO3 AgNO3
Al No reaction No reaction No reaction No reaction
Cu become
Cu No reaction No reaction No reaction black, have
bubble
Fe become
Fe No reaction No reaction No reaction rusty, there is
bubble
2) Electrolysis of KI solution
Observation Solution on anode Solution on cathode
Visual/ Yellow Colorless, bubbles
changes Color + starch solution: blue black + PP solution: pink color
+ CHCl3: CHCl3 form the + FeCl3 solution: yellowish
bottom layer brown
Smell Strong scent No smell
Reaction I2(g) + 2e- 2I-(aq) 2H2O(l) + 2e- H2(g) + 2OH-(aq)
3) Electrolysis of CuSO4
Observation Anode Cathode
Using C Any bubbles There is no bubble
electrode
Occurred change Odorless Odorless
Reaction 2H2O(l) 4H+ + O2(g) + 4e- Cu + 2e-
2+
Cu
F. Calculation
1) Redox reaction
a) Reaction of metal and metal nitrat solution
o Al (aluminium)
Aluminium metal and Pb(NO3)2 solution
2Al(s) + 3Pb(NO3)2(aq) 2Al(NO3)3(aq) + 3Pb(s)
Oxidation: Al(s) Al3+ + 3e- x 2 Eo = +1,662 V
Reduction: Pb2+ + 2e- Pb(s) x 3 Eo = -0,126 V
2Al(s) + 3Pb2+ 2Al3+ + 3Pb(s) Eocell = +1,536 V
(+) Spontaneous Reaction
o Cu (copper)
Cu metal and Pb(NO3)2 solution
Cu(s) + Pb(NO3)2(aq)
Oxidation: Cu(s) Cu2+ + 2e- x 1 Eo = -0,337 V
Reduction: Pb2+ + 2e- Pb(s) x 1 Eo = -0,126 V
Cu(s) + Pb2+ Cu2+ + Pb(s) Eocell = -0,463 V
( - ) Not spontaneous reaction
o Fe (iron)
Fe metal and Pb(NO3)2 solution
Fe(s) + Pb(NO3)2(aq) Fe(NO3)2(aq) + Pb(s)
Oxidation: Fe(s) Fe2+ + 2e- x 1 Eo = +0,440 V
Reduction: Pb2+ + 2e- Pb(s) x 1 Eo = -0,126 V
Fe(s) + Pb2+ Fe2+ + Pb(s) Eocell = +0,314 V
(+) Spontaneous Reaction
e) Zn + CuSO4
Zn(s) + CuSO4(aq) ZnSO4(aq) +Cu(s)
Ox: Zn(s) Zn2+(s) + 2e- x 1 Eo = +0,673 V
Red: Cu2+ + 2e- Cu(s) x 1 Eo = +0,337 V
Zn(s) + Cu2+ Zn2+ + Cu(s) Eocell = +1,010 V
Cu + ZnSO4
Cu(s) + ZnSO4(aq)
Ox: Cu(s) Cu2+ + 2e- x 1 Eo = -0,673 V
Red: Zn2+ + 2e- Zn(s) x 1 Eo = -0,337 V
Cu(s) + Zn2+ Cu2+ + Zn(s) Eocell = -1,010 V
b) Using Fe electrode
Ox: Fe(s) Fe2+ + 2e- x1
Red: Cu2+ + 2e- Cu(s) x1
Fe(s) + Cu2+ Fe2+ + Cu(s)
G. Discussion
Before doing this experiment, we must first know what is meant Electrochemistry?
Electrochemistry is the study of the relationships that exist between chemical reactions and the
flow of electricity. Included here are electrolysis reactions, in which nonspontaneous changes
are forced to occur by the passage of electricity through chemical system. Also included are
spontaneous oxidation-reduction reactions (redox reactions) that are able to supply electricity.
1) Redox Reaction
a) Reaction of metal and metal nitrat solution
The aims of this reaction is to look at the ability of a metal to reduce other metal
ions . This experiment was done by inserting each metal Al , Cu and Fe in the test tube
containing a solution of Pb(NO3)2, Zn(NO3)2, NaNO3 and AgNO3.
Based on voltaic array the position of Al is on the left metals Zn, Pb and Ag and
Al metal is on the right Na. So, Al can react with Ag, Zn, and Pb and cannot react with
Na. But based on our experiment results, Al does not react with all metals nitat solution.
The reaction is supposed to occur are as follows :
2Al(s) + 3Pb(NO3)2(aq) 2Al(NO3)3(aq) + 3Pb(s)
2Al(s) + 3Zn(NO3)2(aq) 2Al(NO3)3(aq) + 3Zn(s)
Al(s) + 3Ag(NO3)2(aq) Al(NO3)3(aq) + 3Ag(s)
While for Cu metals only react with AgNO3 solution. It is characterized by the
changes of Cu becomes black and veiled by the bubbles that look like crystals. Based
on the series voltaic, E˚ Cu is smaller than E˚ Ag and greater than E˚ Pb , E˚ Zn and E˚
Na ( Na < Zn < Pb < Cu < Ag ) so Cu can reduce ion Ag+ to Ag which forms a
precipitate with the following reaction :
Cu(s) + 2Ag(NO3)2(aq) Cu(NO3)2(aq) + 2Ag(s)
As for Fe metals only react with AgNO3 this is marked by the metal become rusty,
and there are gas bubble. As for the other solution, Fe does not react because there is no
change when both are mixed . The reaction is as follows :
Fe(s) + 2 Ag (NO3)2(aq) Fe (NO3)2(aq) + 2 Ag(s)
Based on voltaic array, Fe metal is located to the right of Na and Zn as well as
being on the left of Pb and Ag. Supposedly Fe also can react with Pb, but based on the
results of experiment Fe does not react with Pb. The reaction is supposed to occur are as
follows :
Fe(s) + Pb (NO3)2(aq) Fe (NO3)2(aq) + Pb(s)
2) Electrolysis of KI solution
The ionization of KI solution is, 2KI(aq) 2K+ + I2-. From the ionization, we can get
that K+ as cathode and I2- as anode. After being electrified for 5 minutes, then the occured
reaction is characterized by the changes at the top of the tube U. At the anode, the solution
was colored yellow and scent smelled (the characteristic of halogen elements). While the
cathode contained gas bubbles and haven’t smell. The gas bubbles formed because in
cathode reaction produce H2 gas.
The solution in the anode is tested with starch solution and CHCl3. The solution add
starch solution had turned from yellow to dark blue color and a precipitate is formed. And
if solution at the anode add with CHCl3, is formed two layers. CHCl3 will formed the
bottom layer.
While the solution at the cathode was tested with the PP indicator and FeCl3 solution.
The results if tested with PP indicator is the colour was become pink. This is because at the
cathode containing OH- ion. Then the solution of the cathode was tested with FeCl3 and the
color become yellowish brown.
The electrolysis equation is :
An: 2I- I2(g) + 2e- x1
Cat: 2H2O(l) + 2e- H2(g) + 2OH- x1
2H2O(l) + 2I- 2OH- + H2(g) + I2(g)
2KI + 2H2O(l) 2KOH + H2(g) + I2(g)
3) Electrolysis of CuSO4
The ionization of CuSO4 is, CuSO4 Cu2+ + SO42-. So, Cu2+ as cathode and
SO42- as anode. In this experiment, we using two kind of electrode, that is C electrode and
Fe electrode.
Using C electrode
After being electrified for 5 minutes, we can observe the occured changes that occur at
the top of the U tube. At the anode the solution is colorless and have any bubbles. The gas
bubbles formed because at anode reaction produce O2 gas. While, in cathode there are
haven’t gas bubbles and odorless color.
The electrolysis equation;
An: 2H2O(l) 4H+ + O2(g) + 4e- x1
Cat: Cu2+ + 2e- Cu(s) x2
2H2O(l) + 2Cu2+ 4H+ + O2(g) + 2Cu(s)
Using Fe electrode
The electrode Fe in anode and cathode are corroding. But, in anode, Fe corroding more
than in cathode. The occurred change in anode, CuSO4 solution become more muddy color.
While, in cathode, CuSO4 solution become more clear.
The electrolysis equation;
An: Fe(s) Fe2+ + 2e- x1
Cat: Cu2+ + 2e- Cu(s) x1
Fe(s) + Cu2+ Fe2+ + Cu(s)
We can see that the reaction in anode using C electrode and using Fe electrode is
difference. On electrolysis using C electrode, in anode which electrolyzed was water. But,
on electrolysis using Fe electrode, in anode which electrolyzed was Fe. It is because, C
include electrode inert and Fe not electrode inert.
H. Conclusion
Based on this experiment, we can conclude that;
1) Redox reaction occur when E0 cell is positive (spontaneous reaction) and also can be
determined by volta’s series. Element in the left at volta’s series can reduce elements in the
right side.
2) In electrolysis, reduction reaction occurs at the cathode (positive pole) and the oxidation
reaction occurs in anode (negative pole). Electrolysis of KI produce I2 in the anode and OH-
and H2 gas in the cathode. Meanwhile electrolysis of CuSO4 with C electrode will produce
Cu in the cathode and O2 gas in the anode. And electrolysis of CuSO4 with Fe electrode will
produce Fe2+ in the anode and Cu in the cathode.
I. Reference
Brady, James E.1990.General Chemistry: Principles and Structure. Canada: John Wiley &
Sons, Inc.
Lecturer Team.2015.Handout Basic Chemistry Labwork.UNNES; Laboratorium Kimia
Dasar FMIPA.
Supardi, Kasmadi I. and Luhbandjono, Gatot.2014.Kimia Dasar 2.UNNES: Fakultas
Matematika dan Ilmu Pengetahuan Alam.
Appendix
Problem
a) Redox titration
1) Write down all of the occurred reaction in this experiment
o 2Al(s) + 3Pb(NO3)2(aq) 2Al(NO3)3(aq) + 3Pb(s)
o 2Al(s) + 3Zn(NO3)2(aq) 2Al(NO3)3(aq) + 3Zn(s)
o Al(s) + 3AgNO3(aq) Al(NO3)3(aq) + 3Ag(s)
o Cu(s) + 2AgNO3(aq) Cu(NO3)2(aq) + 2Pb(s)
o Fe(s) + Pb(NO3)2(aq) Fe(NO3)2(aq) + Pb(s)
o Fe(s) + 2AgNO3(aq) Fe(NO3)2(aq) + 2Ag(s)
o Fe(s) + 2HCl(aq) FeCl2(aq) + H2(g)
o Mg(s) + 2HCl(aq) MgCl2(aq) + H2(g)
o Zn(s) + 2HCl(aq) ZnCl2(aq) + H2(g)
o Pb(s) + 2HCl(aq) PbCl2(aq) + H2(g)
o H2O2(aq) + H2SO4(aq) + 2KI(aq) I2(g) + K2SO4(aq)
o FeCl3 (aq) + H2SO4(aq) + 2 KI(aq) I2(g) + K2SO4(aq)
o Zn(s) + CuSO4(aq) ZnSO4(aq) +Cu(s)
2) Sort of seven metals (Al, Pb, Zn, Ag, Na, Cu, Fe) by diminishing the power reduction
and give explanation
Answer
Na > Al > Zn > Fe > Pb > Cu > Ag
Further to the left the position of a metal in the voltaic series the characteristic of
reductant is stronger and its reduction potential gets smaller.
3) Where is the position of Hydrogen in the series above
Answe
The posisition of H is between Pb and Cu
Na > Al > Zn > Fe > Pb > H > Cu > Ag
b) Electrolysis of KI solution
1) What is the function of the salt bridge?
Answer
The fuction of salt bridge is to neutralize the excess ions on the cathode and anode so
the difference of its content isn’t too large. The excess of ions (+) from the oxidation
half reaction will be neutralized by negative ions in the salt bridge. The excess ions (-)
from the reduction reaction will be neutralized by ions (+) in the salt bridge.
2) Explain why the reaction can take place spontaneously in terms of free energy?
Answer
A reaction can take place spontaneously if the value of free-energy is less than zero
(negative). This is due to a spontaneous reaction can take place if the value of E˚ cells is
positive. According to the formula:
5) In the electrolysis using Fe electrode, what happens at each electrode? Write the
equation
Answer
In the anode, Fe corroding more than in cathode
In cathode, Fe corroding but a bit
Ox: Fe(s) Fe2+ + 2e- x1
Red: Cu2+ + 2e- Cu(s) x1
Fe(s) + Cu2+ Fe2+ + Cu(s)
Documentation
Figure 1. Cu metal and metal nitrat solution Figure 2. Al metal and metal nitrat solution
Figure 3. Fe metal and metal nitrat solution Figure 4. Reaction of metal and HCl solution