L2 -BTC225

Electrochemistry Part
By

Dr. Safaa El-Taweel

Associate Professor of Physical Chemistry
 Variable
Unknown resistance R3 or
resistance resistance box

Known
Known resistance
resistance R2
R1
To measure the resistance of electrolytic
solution put it in wheatstone bridge.
Change the variable resistance till obtain
potential difference between point B and D
equals zero using the voltammeter G.
 Λ𝑚
Λ𝑐 = 𝑛

n is total number of charge of cation or anion

Strong electrolytes are completely ionized at all
concentrations (or dilutions). The increase in equivalent conductance is
not due to the increase in the number of current carrying species. This is,
in fact, due to the decrease in forces of attraction between the ions of
opposite charges with the decrease in concentration (or increase in
dilution). At higher concentration, the forces of attraction between the
opposite ions increase (F ∝ q1 q2 / r ). Consequently, it affects the speed
of the ions with which they move towards oppositely charged electrodes.
This phenomenon is called ionic interference. As the solution becomes
more and more dilute, the equivalent conductance increases, till it
reaches a limitary value. This value is known as equivalent
conductance at infinite dilution (zero concentration) and is denoted by
L.
Weak electrolytes have low ionic concentrations and
hence interionic forces are negligible.
Ionic speeds are not affected with a decrease in
concentration (or increase in dilution). The increase in
equivalent conductance with increasing dilution is due to
the increase in the number of current carrier species. Thus
increase in equivalent conductance (Λ) in case of a weak
electrolyte is due to the increase in the number of ions.
C = 0.05 M = 0.05 N R= 400 ohm cell constant = 0.15 Cm-1

 = cell constant / R = 0.15 cm-1 /400ohm =3.75𝑥 10−4

1000 𝜅 1000 𝑥 3.75𝑥 10−4
Λ= 𝑁 = 0.05
= 7.5 𝑆𝑐𝑚 2 𝑒𝑞 −1

Λ∞ = 𝜆+ ∞ + 𝜆− = 40.9+ 349.8 = 390.7 𝑐𝑚2 𝑒𝑞 −1

∞
By comparing Λ with Λ ∞ , as dilution increases , the conductivity of
weak electrolyte increases
𝛼 = ΛΛ∞𝑐 = 390.7
7.5
= 0.0191
 = 1.073x 10-3 S cm-1
1000 𝜅 1000 𝑥 1.073𝑥 10−3
Λ= 𝑁 = 0.01
= 107.3 𝑆𝑐𝑚 2 𝑒𝑞 −1

Λ∞ = 𝜆+ 𝑁𝐻4∞ + 𝜆 −
𝑂𝐻∞ =Λ (𝑁𝐻4 𝐶𝐿)∞ + Λ ∞ ( 𝑁𝑎𝑂𝐻) − Λ ∞(𝑁𝑎 𝐶𝑙) =
149.74+229.71-126.45= 253 𝑐𝑚2 𝑒𝑞 −1
By comparing Λ with Λ ∞ , as dilution increases , the conductivity of
weak electrolyte increases
𝛼 = ΛΛ∞𝑐 = 107.3
253
= 0.424