Experiment 3:

Conductance

- Conductance of solutions
 Conductance of Solutions

Electrical conduction is a property of ionic solutions.

From a macroscopic point of view, ionic conduction

of solutions is similar to electron or hole conduction
through solid objects.

Although water itself is a poor conductor of

electricity, the presence of ionic species in solution
increases the conductance considerably.

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 Conductance of Solutions

Conductivity is the ability of solution to pass an

electric current.
In solutions, cations and anions carry the current.
While for solids (i.e. metals), it is carried by
electrons.

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 Conductance of Solutions

Conductivity of a solution depends on:

Concentration
Mobility of ions
Valence of ions
Temperature

In aqueous solutions, the ionic strength varies from

the low conductivity of ultra pure water to the high
conductivity of concentrated chemical samples.

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 Measuring Conductivity

Conductivity of solutions is measured by how well

cations and anions migrate to the negative and
positive electrodes, respectively.

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 Conductive solution

Conductivity is typically measured in aqueous

solutions of electrolytes.
Electrolytes are substances containing ions. It could
be acids, bases, or salts and it can be either strong
or weak electrolytes.
Conductance behavior as a function of
concentration differs for strong and weak
electrolytes, respectively.

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 Electrolyte solutions

Electrolyte solutions obey Ohm’s law just as

metallic conductors do.
Conductance is the reciprocal of resistance (R). And
it is proportional to the cross-sectional area (A) and
inversely proportional to the length (l).

 1 𝜅∙𝐴
=
𝑅 𝑙

K is the specific conductance with units Ω-1m-1. The

reciprocal ohm (Ω) is equivalent to siemens (S).

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 Molar conductance

Cell constant defines the specific geometric

parameters, and should be calibrated to any
solution with specific conductance.
  𝑙𝑒𝑛𝑔𝑡h −1
𝑐 𝑒𝑙𝑙 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 = (𝑢𝑛𝑖𝑡 : 𝑚 )
𝑎𝑟𝑒𝑎
The specific conductance Κ (Greek letter kappa)
increases as the concentration increases.
A more fundamental unit of electrolytic
conductance is the equivalent conductance Λ.

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 Molar conductance

The equivalent conductance (Λ) has a unit of

cm2∙equiv-1∙Ω-1. And c is the concentration having a
unit of normality (equiv/L).
  𝜅 ∙1000
Λ=
𝑐

For simple 1-1 electrolytes A+B-, the equivalent

conductance is the same as molar conductance (Λm).

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 Strong electrolytes

A strong electrolyte is a solute that completely, or

almost completely, ionizes or dissociates in a
solution.
0.5
 Λ = Λ − 𝐴 𝑐
0

At concentrations below 0.1M, a plot of Λ against

c½ gives a straight line. The intercept of which
equals Λ0, or the equivalent conductance at infinite
dilution, and A is an empirical constant.

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 Strong electrolytes

At infinite dilution the ions act completely

independently, and it is then possible to express
Λ0 as the sum of the limiting conductance of the
separate ions. Hence for a 1-1 electrolyte A+B-:
−
+¿ +𝜆 0 ¿
 Λ =𝜆
0 0

 
The ionic equivalent conductance ( and ) are
equivalent to the ion mobility (U) multiplied by the
Faraday constant.
 𝜆
+¿ 𝐹¿
+¿ =𝑈 0 ¿  𝜆−
0 =𝑈 −
0 𝐹
0

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 Ion mobility

Ion mobility (U) is defined as the speed of the ion (v)

under the influence of an electric field strength (E).
±
 
± 𝑧 ∙𝜈
𝑈0=
𝐸

 
Note: represents the valences of positive and
negative ions.

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 Equivalent conductances

Table of conductivities of selected strong electrolytes:

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 Weak electrolytes

For a weakly ionized substance, Λ varies much more

markedly with concentration because the degree of
ionization, α, varies strongly with concentration.

 Λ ( 𝐻𝐴𝑐 )= Λ 0 ( 𝐻𝑋 ) + Λ0 ( 𝑀𝐴𝑐 ) − Λ0 ( 𝑀 𝑋 )
0

For sufficiently weak electrolytes, the ionic

concentration is small and the effect of ion
attraction on the mobilities is small.
  Λ
𝛼=
Λ0

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 Equilibrium constant

Knowing the concentration c of the weak

electrolyte, and its degree of ionization α at that
concentration, the concentrations of H+ and Ac- ions
and of undissociated HAc can be calculated.
The equilibrium constant in terms of concentrations
Kc can be calculated from:

𝐾 𝑐= ¿ ¿
 

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 Equilibrium constant

Once Kc is known, the concentration dependence of

the equivalent conductance can be predicted.

Ostwald’s Law of Dilution:

 1 1 Λ∙𝑐
= +
Λ Λ0 𝐾 𝑐 ∙ Λ20

If 1/Λ is plotted against Λ·c, the values of  Λ0 and

Kc can be obtained from the intercept and the
slope, respectively.
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