School of Chemistry and Biochemistry, TIET, Patiala

Applied Chemistry (UCB008)

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?

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
Λm = ĸ/c = 0.0163/10 = 1.63 × 10-3 S m2 mol-1
α = Λm/ Λ°m = 1.63 × 10-3/390.7 × 10-4 = 0.0472

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
Kcell = ĸ/G = 1.12 × 55 = 61.6 m-1
Q5. 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
Ans.: (a) With dilution, specific conductance of CH3COOH decreases as the number of ions in 1cm3
of the solution decrease with dilution.
(b) Equivalent conductance of CH3COOH increases with dilution since with dilution degree
of dissociation increases for CH3COOH. In other words, increase in number of ions as an
effect of dilution increases the magnitude of conductance (equivalent).
(c) Equivalent conductance of NaOH also increases with dilution. Here dissociation is
already 100% since NaOH is a strong electrolyte but still with dilution equivalent
conductance increases which is due to the fact that now ions have more volume to roam
freely and inter-ionic interference to their mobility decreases. Hence, effectively
conductance increases.
Q6. 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?
Ans.: Λm = ĸ/c
So ĸ = Λm × c
= 1.26 × 102 Ohm-1 cm2 mol-1 × 10-5 mol cm-3
= 1.26 × 10-3 Ohm-1 cm-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
distance travelled by NH4+ ion per second = (1.6 × 10-2)/3600
Potential gradient = 12/20 V cm-1 = 60 V m-1
Mobility of NH4+ ion = (1.6 × 10-2)/(3600 × 60) = 7.41 × 10-8 m2 V-1 s-1
Q8. Draw diagram of Hittorf’s theoretical device and explain that number of ions
discharged at respective electrodes are same though mobilities are different.
Ans.: The number of ions discharged at respective electrodes are same though their mobilities
are different. It can be shown using Hittorf’s theoretical device:
Case-I: When neither cation moves nor anion moves in the given time:

Case-II. When in the given time: 2 cations move and 3 anions move

Similarly, other cases can be discussed, mobility of cation is more or both ions move with
same mobility.
Q9. What do you mean by transport number? How the transport number is related to the
mobility of cation and anion?
Ans.: The fraction of the total current carried by an ion is known its the transport number.
Since current is proportional to the ionic mobility, therefore
• Thus, if u+ is the mobility of cation and u- that of the anion then
Transport number of the cation, t+ = current carried by the cation/ total current
= u+ / [ u+ + u- ]
Transport number of the anion, t- = u- / [ u+ + u- ]
Further t+ + t- = 1
Q10. Why do hydrogen ions (H+) have a very large ionic mobility (molar conductance)
when compared to all other common ions?
Ans.: The H+ ions or more precisely hydronium (H3O+) ions exist as H3O+·3H2O in the solution. The
structure of the same is given below: The H+ ions can rearrange themselves from one water
molecule to another water molecule via rearrangement of hydrogen bond which happens
very quickly in hydroxylic solvents. This mechanism is known as Grotthus-type mechanism
which provided exceptionally high mobility to H+ ion is such solvents.
H
O

H H
H + H
O O H
H
+O
H O H
H
H H
O

Q11. 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+.
Q12. 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)]  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:
Q13. 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.
Q14. 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.

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