TITLE: Electrochemistry

OBJECTIVES:
1. To explain the concept of electrons flow, anions and cations.
2. To determine the relative potential of reduction for the redox reaction.
3. To describe the effect of concentration to the cell potential.
4. To calculate the Avogadro’s number and Faraday constant by electrolysis process.
INTRODUCTION:
All electrochemical reactions involve in the transfer of electrons and are therefore "oxidation-
reduction" reactions. When, a piece of copper (Cu) is placed into an aqueous silver ion (Ag2+) solution,
the copper atoms will spontaneously released electrons (oxidation). Silver ions will move toward
copper and receive electrons (reduction), which are released by copper to form a layer of silver atom in
inter phase metal/solution copper. The formation of the copper ions will be moved out from the inter
phase to the solution. As result, the blue colour of the solution turns darker.

Overall reaction: Cu(s) + 2Ag+(aq)  2Ag(s) + Cu 2 + (a q )

Redox reaction above can be separated to half-reaction of oxidation and reduction. Every single half-
reaction is called redox pair.

Oxidation half-reaction equation: Cu ( s )  Cu2+(aq) + 2e-

Oxidation half-reaction equation: 2Ag+(aq) + 2e-  2Ag(s)

Oxidation reaction occurred at the anode and reduction reaction occurred at the cathode
Since electrons transfer occurs spontaneously, one set of galvanic cell can be designed by separations
of the redox pair. Electrons transfer does not occur in the inter phase anymore, but through an external
circuit. The two halves of the redox reaction are separated in two different containers (such as beaker)
and named half-cell. A common kind of half-cell consists of a piece of metal (the electrode) immersed
in a solution of its ions. The electrons are connected with a wire.
The circuit between the two solutions is completed with a salt bridge. A salt bridge allows
electrical contact between the two half-cells, internal circuit. It maintains the electrical neutrality
in each half-cell as ions flow into and out of the salt bridge. "Pored pot" also serves the same
function as the salt bridge.

Cell potential (Ecell) for a galvanic cell, is the potential difference (emf; electromotive force)
between reduction and oxidation half-cells. Potentiometer is used to measure cell potential
(E c ell ), values obtained represent the difference of probability between metal ions in each cell
through reduction.

Reduction potential for copper and silver redox pair can be written as E Cu2+/Cu and EAg+/Ag. So,
cell potential is,

Ecell = EAg+/Ag – ECu2+/Cu

Standard electrode potentials (E°) is the cell potentials measured when ion concentration is one
molar of salt solution at 25 °C.

Standard potential for Ag+(1 M)/Ag, E°Ag+/Ag is +0.80 V and for Cu2+(1 M)/Cu, E°Cu2+/Cu is +0.34
V. So,

E°cell = E°Ag+ / Ag - E°Cu2+/Cu

= +0.80 V - 0.34 V
= +0.64 V

* Please note that calculation might not be the same as theory, since activities occurred on the
surface of electrode or ions in the solution

The Nernst equation is used to calculate electrode potentials for concentrations and partial
pressures other than standard-state values, where:
 0.0592
Ecell = Eocell – log Q
n

n = number of moles of electrons transferred in the reaction of half-reaction

log Q = reaction quotient = ions concentrations while reaction

[Cu 2 ]
For Cu/Zn cell, Q =
[ Zn 2 ]

So, Nernst equation:

0.0592 [Cu 2 ]
Ecell = Eocell – log
2 [ Zn 2 ]

A straight line can be obtained, if one of the concentrations is being constant.

Voltmeter

Figure 2.1: Galvanic cell

OBSERVATION:
Section A
Electrochemical cell Cell potential/emf, Volt (v)
Mg – Cu reaction 0.28 V
Zn – Mg reaction 0.15 V
Mg – Fe reaction 1.06 V
Cu – Zn reaction 0.11 V
Fe – Cu reaction 0.14 V
Fe – Zn reaction 0.05 V

Section B
Electrolyte concentration, [ ], M Emf, volt (v) Observation

0.0001 M CuSO4(aq) 0.00V No solution No change

added to 0.0001
M CuSO4

When added No change

NH4OH(aq)
0.04V

1.02V When added The electrodes

Na2S(aq) corrode. The
solution change
from colourless
to brown colour
DATA AND CALCULATION:
Section A
Preparation of stock solution:
For CuSO4·5H20
𝑛 = 𝑚𝑣(𝐿)
𝑛 = (0.1𝑀)(0.25𝐿) = 0.025𝑚𝑜𝑙
Molar mass: 249.6850 𝑔/𝑚𝑜𝑙
𝑚𝑎𝑠𝑠(𝑔)
𝑛= 𝑔
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 ( )
𝑚𝑜𝑙
𝑚𝑎𝑠𝑠(𝑔)
0.025 𝑚𝑜𝑙 = 𝑔 = 6.242 𝑔
249.6850 ( )
𝑚𝑜𝑙
For ZnSO4·7H2O
𝑛 = 𝑚𝑣(𝐿)
𝑛 = (0.1𝑀)(0.25𝐿) = 0.025𝑚𝑜𝑙
Molar mass: 287.58 𝑔/𝑚𝑜𝑙
𝑚𝑎𝑠𝑠(𝑔)
0.025 𝑚𝑜𝑙 = 𝑔 = 7.19 𝑔
287.58( )
𝑚𝑜𝑙
For MgSO4·7H2O
𝑛 = 𝑚𝑣(𝐿)
𝑛 = (0.1𝑀)(0.25𝐿) = 0.025𝑚𝑜𝑙
Molar mass: 246.52𝑔/𝑚𝑜𝑙
𝑚𝑎𝑠𝑠(𝑔)
0.025 𝑚𝑜𝑙 = 𝑔 = 6.163 𝑔
246.52( )
𝑚𝑜𝑙
For FeSO4·7H2O
𝑛 = 𝑚𝑣(𝐿)
𝑛 = (0.1𝑀)(0.25𝐿) = 0.025𝑚𝑜𝑙
 Molar mass: 278.01𝑔/𝑚𝑜𝑙
𝑚𝑎𝑠𝑠(𝑔)
0.025 𝑚𝑜𝑙 = 𝑔 = 6.95 𝑔
278.01( )
𝑚𝑜𝑙

Section B,
Preparation for stock solution of 0.001 M CuSO4 solution
M1V1=M2V2
(0.1M) (V1) = (0.001M) (250mL)
V1= 2.5mL

DISCUSSIONS:

From the experiment that we had conducted, for section A the experiment is about
galvanic cell. Galvanic cell is an electrochemical cell that involve in redox reaction which give
the electrical energy for the electron transfer through the wire between two different types of
solutions and electrodes. This type of cell converts chemical energy to electrical energy. Salt
bridge used to allow the flow of ions from one solution to the other solution without mixing the
two solutions. We need to prepare different types of stock solutions of CuSO4 solution, ZnSO4
solution, MgSO4 solution and FeSO4 solution by performing dilution step.

For the electrochemical cell of magnesium and copper reaction which we used
magnesium electrode dip in MgSO4 solution and copper electrode dip in CuSO4 solution, the cell
potential is 0.28V. Oxidation takes place at magnesium which act as anode that transfer electron
while the reduction is copper which act as cathode that receive the electron. For zinc and
magnesium reaction, the cell potential is 0.15V . The zinc electrode is dip in ZnSO4 solution and
the magnesium electrode is dip in MgSO4 solution. The zinc is the cathode which receive the
electron while the magnesium is the anode that transfer the electron.

The magnesium and iron reaction , the cell potential is 1.06 V they are dip in its solution.
The high value of potential difference because of these two metals are located further from each
other in table of reduction potential. The further the distance between metals in table of reduction
potential, the higher the cell potential. For copper and zinc reaction, the cell potential is 0.11V
the zinc is the anode that transfer electron where oxidation occur and the copper is the cathode
that receive electron where reduction takes place.

Next, iron and copper reaction the cell potential is 0.14 V the copper is the cathode that
receive electron where reduction takes place while the iron is the anode where oxidation take
place. For the next reaction which is iron and zinc, the potential difference is 0.05V the small
value of potential difference because the metals are located nearer to each other in table of
reduction potential.

In section B, the experiment is about cell potential. In this experiment, we used different
concentration of CuSO4 solutions of 0.1 M and 0.001 M the result of cell potential is 0.00V.
The cell potential is zero because there is no transfer of electrons between the cells as the
voltmeter reading depicted that the electrons are moving between the cells through the wire.

Next, for the effect of complex formation, solution of NH4OH is being added to the 0.001
M and the cell potential is 0.04 V there is no changes in the solution which remain colorless.
Next, for the effect of precipitation, 5mL of Na2S solution is being added to the 0.001 M of
CuSO4 solution which before 5mL of NH4OH is added. The solution change from colorless to
brown solution and the voltmeter reading is 1.02 V. The high voltmeter reading depicted that
there are electrons are moving through the circuit.

QUESTIONS AND ANSWERS:

Section A: Galvanic Cell

1. Identify anode and cathode electrodes for each rection.
For Mg – Cu reaction,
Anode : Magnesium
Cathode : Copper
For Zn-Cu reaction,
Anode : Zinc
Cathode : Copper
 For Zn-Mg reaction,
Anode : Zinc
Cathode : Magnesium
For Fe-Cu reaction,
Anode : Iron
Cathode : Copper
For Fe-Zn reaction,
Anode : Iron
Cathode : Zinc
For Mg-Fe reaction,
Anode : Magnesium
Cathode : Iron

2. Write half-cell equation for each reaction.

For Mg – Cu reaction,
Oxidation at anode: Mg(s) → Mg2+(aq) + 2e-
Reduction at cathode: Cu2+(aq) +2e- → Cu(s)
For Zn-Cu reaction,
Oxidation anode: Zn(s) → Zn2+(aq) + 2e-
Reduction at cathode: Cu2+(aq) +2e- → Cu(s)
For Zn-Mg reaction,
Oxidation at anode: Zn(s) → Zn2+(aq) + 2e-
Reduction at cathode: Mg2+ (aq) + 2e- → Mg (s)
For reaction Fe-Cu,
Oxidation at anode: Fe (s) → Fe2+(aq) +2e-
Reduction at cathode: Cu2+(aq) +2e- → Cu(s)
For reaction Fe-Zn,
Oxidation at anode: Fe (s) → Fe2+(aq) +2e-
Reduction at cathode: Zn2+ (aq) +2e- → Zn(s)
For reaction Mg-Fe,
 Oxidation at anode: Mg(s) → Mg2+(aq) + 2e-
Reduction at cathode: Fe2+(aq) + 2e- → Fe(s)

3. Write overall reaction equation for each reaction.

For reaction Zn – Mg,
Zn(s) + Mg2+(aq) → Zn2+(aq) + Mg (s)
For reaction Fe – Zn,
Fe(s) + Zn2+(aq) → Fe2+(aq) + Zn(s)
For reaction Zn – Cu,
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)
For reaction Fe – Cu,
Fe(s) + Cu2+ (aq) → Fe2+(aq) + Cu(s)
For reaction Mg – Fe,
Mg(s) + Fe2+(aq) → Mg2+(aq) + Fe(s)
4. Give two reasons why reduction potential readings ae difference from theory.
The reduction potential readings are difference from theory because the molarity of the
electrolyte does not accurate. Next, the electrode had touched the salt bridge during
taking the reading.

Section B: Cell Potential

1. Identify anode and cathode electrode in step 1.

Anode: Copper in 0.1 M CuSO4
Cathode: Copper in 0.001 M CuSO4
2. Write half-equation.
Anode: Cu(s) → Cu2+ (aq) + 2e-
Cathode: Cu2+(aq) + 2e- → Cu(s)

3. Write overall reaction equation.

Overall equation: Cu2+(aq) + 2e- → Cu(s)
 4. Explain why there is potential in step 2 ?
Bcause the cross of ions through the salt bridge. So, there will be a potential reduction.

5. Explain why potential changed with the addition of NH3 (aq) ?

Because the concentration of the ions in the electrolyte increasing due to the addition of
the NH3 and N2S. So, the potential of the was slightly changed. The cations and anions
will cross through the salt bridge to the anode and cathode. The redox reaction will occur
at the electrode.

CONCLUSIONS:

From this experiment, we can explain about the electrons flow, anions and cations. Substances
that produce ions in solution are electrolytes. Ions with a positive charge are called cations and
ions with a negative charge are called anions. Ions in solution will move from an area of high
energy toward an area of low energy producing, a current. This movement of ions in solution is
known as electrolytic conduction. If the electrodes of a battery are placed in an ionic solution, a
current flows between the electrodes just as the movement of electrons in a metal results in a
current. This produces a redox reaction at each electrode by a process known as electrolysis.
Next, we can describe the effect of concentration to the cell potential. We can determine the
0.0592
electrode potentials for concentration using Nerst equation Ecell = Eocell – n log Q . The
equation above indicates that the electrical potential of a cell depends upon the reaction
quotient Q of the reaction. As the redox reaction proceeds, reactants are consumed, and thus
concentration of reactants decreases. Conversely, the products concentration increases due to the
increased in products formation.

REFERENCES:
1. Chemistry The Central Science. 13TH edition. Theodore L. Brown.
2. Laboratory Manual SKU3033 (Chemistry II).
3. Title : The electrochemical series
Date retrieve : 22/3/2016
http://www.chemguide.co.uk/physical/redoxeqia/ecs.html