UNIT 2
1. What do you mean by electrochemical series?
The arrangement of various metal electrodes in the order of increasing values of standard
reduction potential with respect to the standard hydrogen electrode is called the
electrochemical series.
2. What are reversible and irreversible cells?
1. Reversible cells
A cell that obeys the following three conditions of thermodynamic reversibility is
called a reversible cell.
1. If the Daniel cell is connected to an external source of emf equal to 1.1 volt, no
current flows, and also no chemical reaction takes place in the cell.
2. If the external emf is made slightly less than 1.1 volts, a small amount of current
flows from the cell and a small chemical reaction occurs.
3. If the external emf is made slightly greater than 1.1 volt, the current will flow in the
opposite direction.
Example: lead -acid battery
2. Irreversible cells
Cells which do not obey the conditions of thermodynamic reversibility are called
irreversible cells.
Examples
The zinc-silver cell is an example of an irreversible cell. It is represented as
Zn | H2SO4 (aq) | Ag
3. With valid points differentiate electrolytic cells from electrochemical cells.
(or)
How does electrolytic cell differ from electrochemical cells?
[Link]. Electrolytic Cell Electrochemical Cell
1. It is the cell which converts electrical It is the cell in which electrical energy is
energy into chemical energy, i.e., the generated by a spontaneous redox
supplied electrical energy is used to bring reaction.
about a chemical change.
The reaction is non-spontaneous and The reaction is spontaneous and produces
2.
requires an external electrical source. electrical energy.
Example: Galvanic or Voltaic cell
3. Example: Electrolysis of water.
(Daniel cell).
Salt bridge is used to connect the two
4. No salt bridge is used.
half-cells.
Used for electroplating, electrorefining, Used for converting chemical energy into
5.
and electrolysis. electrical energy.
4. How will you analyze the significance of the electrochemical series?
APPLICATION OF EMF SERIES (SIGNIFICANCE OF EMF SERIES)
1. Calculation of single electrode potential
The emf of a single electrode at a particular temperature can be calculated using the Nernst
equation.
[Link] of standard emf of a cell
The standard emf of a cell (E°) can be calculated using the following equation.
E°Cell = E°R.H.S – E°L.H.S
[Link] ease of oxidation and reduction
[Link] the value of E° in emf series, (metals those are above SHE), the metals have the
tendency to get oxidised and acts as anode.
[Link] the value of E° in emf series (metals those are below SHE) the metals have the
tendency to get reduced and acts as cathode.
For example in a galvanic cell zinc gets oxidized (anode) and copper gets reduced (cathode).
[Link] of one element by the other
Metals with low E° value can displace the metals with high E° value.
For example in emf series
E°Pb2+/Pb = – 0.13 V
E°Cu2+/Cu = + 0.34 V
So when lead is added to a solution of copper, copper is displaced easily by lead.
[Link] of equilibrium constant
Standard electrode potential can also be used to determine the equilibrium constant (K) for
the reaction. we know that from the value of E°, the equilibrium constant for the cell
reaction can be calculated.
6. Displacement of hydrogen from acids
Metals with negative reduction potential E° will displace the hydrogen from an acid
solution.
(i.e.) Metals above H2 in the emf series will displace H 2.
Example
Zinc displaces hydrogen from an acid (E°Zn = – 0.76 V)
The metal with positive reduction potential will not displace the hydrogen from an acidic
solution.
Ag + H2SO4 → No reaction (E°Ag = + 0.80 V)
5. What is potentiometric titration? Explain the redox titration between Fe 2+ and
Cr2O72- solutions.
(or)
Explain, how the measurement of EMF of the cell helps to identify the end point in
redox potentiometric titration?
Titrations in which both oxidation and reduction reactions take place
simultaneously are called oxidation-reduction (or) redox reactions.
Pt electrode is used as the indicator electrode. This may be coupled with a saturated calomel
electrode to form a complete cell.
Figure: Potentiometric Titration between Fe 2+ ions Vs K2Cr2O7
Example: Titration between ferrous sulphate and potassium dichromate in the presence of
dilute sulphuric acid. 50 ml of ferrous sulphate solution containing sulphuric acid is titrated
against potassium dichromate. Initially the solution contains Fe2+ ions only. When
potassium dichromate is added, Fe2+ ions will be oxidised to Fe3+
According to the Nernst equation
Hence, as the concentration of Fe3+ goes on increasing, the potential or emf of the cell will
also increase. The emf increases slowly at first and rapidly towards the end point. If a plot is
∆E
drawn between volume of potassium dichromate against emf and , the shown in Figure
∆V
graph will be obtained.
Advantages of potentiometric titrations
1. It requires cheap and easily available apparatus.
2. This method is applicable for coloured solutions and very dilute solutions.
6. Explain the estimation of hydrochloric acid by conductometric titration.
(or)
Discuss the experimental method of conductometric titration between a strong acid and
a strong base.
CONDUCTOMETRIC TITRATION
Acid-Base titration
Strong acid Vs strong Base (HCl vs NaOH)
A known amount of acid (HCl) is taken in a beaker containing the conductivity cell and the
alkali (NaOH) in the burette. Initially, the conductivity of the HCl is high; this is due to the
presence of fast-moving H+ ions. As t h e NaOH is a d d e d gradually, conductance
decreases due to the replacement of fast-moving H+ ions by slow-moving Na+ ions.
After neutralization addition of NaOH will introduce the fast-moving OH– ions.
Therefore, the conductance increases.
On plotting the conductance against the volume of alkali added, the two lines intersect at a
point “B” gives the end point. This corresponds to the volume of NaOH required for
neutralization.
Figure: Conductometric titration between strong acid and strong base
Advantages of conductometric titrations
1. It gives accurate end point.
2. Since the end point is obtained from graph, no keen observation was required.
3. It is used for the analysis of weak acids, dilute solutions and even coloured solution.