Electrochemistry
Electrochemistry
Electrochemistry
Types of Electrolytes
G=1/R
It is expressed in the unit called reciprocal ohm (ohm-1 or Ω-1)
In SI system, the unit of conductance is Siemen, S
Specific Conductance
The resistance of any conductor varies directly as its length (l) and inversely as its
cross-sectional area (a), i.e R l/a
or
R = (l/a)
• Where is a constant depending upon the nature of the material and is called
specific resistance of the material If, l =1cm and a =1cm2, then = R
• Specific resistance is defined as the resistance in ohms of a specimen 1cm in
length and 1cm2 cross-section (1cm3 of the material).
• The reciprocal of specific resistance, i.e., 1/ is called specific conductance (ĸ).
Therefore, the number of ions per unit volume (per cc) actually decreases.
Hence, the specific conductance decreases although molar conductance and
equivalant increases on progressive dilution.
Questions:
1. Define conductance, molar conductance and specific conductance. Give their units.
3. The specific conductance of 0.01 M solution of acetic acid was found to be 0.0163 S
m‒1 at 25 °C. Calculate the degree of dissociation of the acid. Molar conductance of
acetic acid at infinite dilution is 390.7 × 10‒4 S m2 mol‒1 at 25 °C.
5. What is the effect of dilution on (a) the specific conductance of CH3COOH (b) the
equivalent conductance of CH3COOH and on (c) the equivalent conductance of NaOH
6. Molar conductivity of a solution is 1.26 x 102 Ohm‒1 cm2 mol‒1. Its molarity is 0.01.
What will be its specific conductivity?
12
Ionic Mobility
H H O H
O H
+O
H H O H
H
13
• Ionic Mobility
• The high mobility in hydroxylic solvents such as water can be
explained by Grotthus type mechanism in which the proton moves
rapidly from H3O+ to a hydrogen bonded water molecule and is
transferred further along a series of hydrogen bonded water
molecules by a rearrangement of hydrogen bonds.
• This accounts to high mobility of hydrogen ions in water.
H
O
Grotthus-type
H H
Mechanism for H + H
O O H
High mobility of
H
+O
H O H
H+ ions H
H H
O
H 14
• Ionic Mobility
• Grotthus model also explains as to why H+ ions move about 50
times more rapidly through ice than through liquid water
• Ice has tetrahedral structure with each oxygen atom surrounded
by four hydrogen atoms
H H
O 1
H
15
Each hydrogen atom lies on the H H
O 1
center of line joining of the oxygen
atoms. H
structure H
coefficients being very nearly the same for all the ions in a given
solvent.
vicinity of 25 °C
17
18
Conductometric Titrations
Principle:
• On plotting conductance
against volume of alkali
Conductance
• On plotting conductance
X against volume of alkali
Equivalence point
added, the point of
intersection X of these two
lines gives the volume of alkali
Volume of alkali added required for the neutralization
• Conductometric titrations: Mixture of HCl+CH3COOH against
NaOH: When a mixture of a strong and a weak acid is to be
titrated against a strong alkali a combination of earlier curves
is obtained.
B C
Volume of NaOH added
• Conductometric titrations:
X
Equivalence point
• Since the mobility of K ion in nearly the same as that of silver ion
which it replaces, the conductance will remain more or less
constant and will begin to increase only after the end point.
Conductance
Equivalence point
X
3. Why the mobility of Li+ ion is less than that of Na+ ion?
4. Explain with the help of plots, how does conductance varies when (a)
CH3COOH acid is titrated against NaOH and (b) AgNO3 is titrated against
KCl.
BATTERIES
Battery is a device that converts chemical energy contained
within its active materials directly into electric energy by
means of an electrochemical oxidation-reduction (redox)
reaction. This type of reaction involves the transfer of
electrons from one material to another via an electric circuit.
DEFINITION AND CLASSIFICATION
Types of batteries
1. Primary Batteries
2. Secondary Batteries
3. Flow Batteries and Fuel Cells
Secondary cells are different from primary cells due to the fact that they can be
recharged. When a secondary cell is discharging, it is acting as a galvanic cell.
When a secondary cell is recharging, it is acting as an electrolytic cell.
Important Units
Difference between Primary and
Secondary Battery
Primary Battery Secondary Battery
At Anode:
Pb(s) + HSO4−(aq) → PbSO4(s) + H+(aq) + 2e−
H+(aq) and e− move to the cathode
At cathode:
PbO2(s) + HSO 4 − (aq) + 3H+(aq) + 2e− → PbSO4(s) + 2H2O(l)
Overall Chemical Reaction:
Pb(s) + PbO2(s) + 2H2SO4(aq) → 2PbSO4(s) + 2H2O(l)
E0cell = 2.05 V
Discharging Process
Each Electrode pair gives rise to an EMF of 2.05 V
When it falls below a certain limit, the battery can not produce enough
current
At Anode:
• PbSO4(s) + H+(aq) + 2e−→ Pb(s) + HSO4−(aq)
At cathode:
• PbSO4(s) + 2H2O(l) → PbO2(s) + HSO4 − (aq) + 3H+(aq) + 2e−
Overall Chemical Reaction:
• 2PbSO4(s) + 2H2O(l) →Pb(s) + PbO2(s) + 2H2SO4(aq)
Charging Process
The concentration of H2SO4 increases during charging process
Q1. Define conductance, molar conductance and specific conductance. Give their units.
Ans.: Conductance (G) is defined as the reciprocal of the resistance of given electrolytic solution in
electrochemistry. The units of conductance are ohm-1 or mho or Siemen(S).
Molar conductance is defined as the magnitude of conductance produced from all the ions
when one mole of electrolyte is dissolved in the solution. The units of molar conductance are
S m2 mol-1.
Specific conductance is the magnitude of conductance from ions present in the 1cm3 of the
solution. The units of specific conductance are S m-1.
Q2. Solutions of two electrolytes A & B each having concentration of 0.2M have conductivities
2×10 ‒2 and 4 × 10‒4 S cm‒1. Which will offer greater resistance to the flow of current and
-
why?
Ans.: The solution with conductivity 4 × 10-4 S cm-1 will offer more resistance. As the specific
conductance of solutions are provided. We know that :
R = (l/a)ρ
Or R = (l/a ĸ) as 1/ ĸ = ρ
Here R is inversely proportional to ĸ.
So a solution with lower value of ĸ, will have more resistance which is solution B.
Q3. The specific conductance of 0.01 M solution of acetic acid was found to be 0.0163 S
m‒1 at 25 °C. Calculate the degree of dissociation of the acid. Molar conductance of acetic
acid at infinite dilution is 390.7 × 10‒4 S m2 mol‒1 at 25 °C.
Ans.: ĸ = 0.0163 S m-1 C = 0.01 M = 10 mol m-3
Q4. Specific conductance of a decimolar solution of KCl at 18°C is 1.12 Sm‒1. The resistance
of a conductivity cell containing the solution at 18°C was found to 55 Ω. Calculate the
cell constant.
Ans.: R = 55 Ω, G = 1/55 S ĸ = 1.12 Sm-1
Q7. What is ionic mobility? A potential of 12.0 volts was applied to two electrodes placed 20
cm apart. A dilute solution of NH4Cl was placed between the electrodes when NH4+ ion
was found to cover a distance of 1.60 cm in one hour. What is the mobility of NH4+ ion?
Ans.: Ionic mobility = distance travelled by ion per second under a potential gradient of 1 volt per
meter.
So from the data given
distance travelled by NH4+ ion = 1.6 × 10-2 m
H H
+ H H
O O +
H O H O
H
H
O
Q9. Why the mobility of Li+ ion is less than that of Na+ ion?
Ans.: The ionic radii of Na+ is greater than that of Li+ ion. Hence, the charge density for Li+ ion is
higher. Therefore, Li+ attracts a large number of water molecules around it than Na+ ion owing
ion-dipole interaction. In other words, Li+ ions is hydrated to a greater extent than Na+. Hence,
while moving Li+ has to drag a larger shell of water with it. Therefore its ionic mobility is less
as compared to Na+.
Q10. What is meant by conductometric titration? Explain with the help of plots, how does
conductance varies when (a) CH3COOH acid is titrated against NaOH and (b) AgNO3 is
titrated against KCl.
Ans.: (a) When acetic acid it titrated against NaOH, the conductance first increase slowly, till
equivalence point, due to formation of sodium acetate which is stronger electrolyte. Once all
the acetic acid is neutralized, thereafter conductance increases sharply since the faster
moving Na+ and ⁻OH ions are added.
CH3COOH (aq) + [Na+ (aq) + OH- (aq)] à Na+ (aq) + CH3COO- (aq) + H2O (l)
Graphically:
(b) Ionic equation: Ag+ (aq) + NO3- (aq) + K+ + Cl- K+ (aq) + NO3-(aq) + AgCl(s)
Effectively, the Ag+ ions are being replaced by K+ ions which have little higher ionic mobility.
Therefore conductance increases till the equivalence point little slowly but after equivalence
point, the conductance increases more sharply due to addition of K+ and Cl- ions which have
high mobility.
Graphically:
Q11. In conductometric titrations, more concentrated solution is added from the burette,
why?
Ans.: To minimize the change in conductance from dilution effects, more concentrated solution is
taken in the burette.
Q12. What are the advantages of conductometric titrations over volumetric titrations?
Ans.: I. Coloured solutions which cannot be titrated by ordinary volumetric methods with help of
indicators, can be successfully titrated conductometrically
II. The method can also employed in the case of very dilute solutions and also for weak acids
and bases.
III. No special care is necessary near the end point as it is determined graphically.
*****END*****