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Transport Number, T, Is The Fraction of The Total Current Carried by An

(1) Transport number (t) is the fraction of total current carried by an ion. For simple electrolytes, t+ + t- = 1. (2) Ion conductivity (λ) is related to transport number and molar conductivity (L). λ can be calculated from L and t values. (3) Experimentally, t+ and t- can be determined by measuring how an electrolyte solution partitions charge transport between cation and anion. This allows calculation of λ+ and λ-. (4) Conductivity varies between ions based on size, degree of solvation, and structure. Smaller, less solvated ions tend to conduct better, like Li

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107 views12 pages

Transport Number, T, Is The Fraction of The Total Current Carried by An

(1) Transport number (t) is the fraction of total current carried by an ion. For simple electrolytes, t+ + t- = 1. (2) Ion conductivity (λ) is related to transport number and molar conductivity (L). λ can be calculated from L and t values. (3) Experimentally, t+ and t- can be determined by measuring how an electrolyte solution partitions charge transport between cation and anion. This allows calculation of λ+ and λ-. (4) Conductivity varies between ions based on size, degree of solvation, and structure. Smaller, less solvated ions tend to conduct better, like Li

Uploaded by

Ernest Nana Yaw Aggrey
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PPTX, PDF, TXT or read online on Scribd
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Transport of ions

Transport number, t, is the fraction of the total current carried by an


ion.

For a simple electrolyte made up of a simple cation and anion then,


t+ + t- = 1.0

t is related to ionic conductivity

 
n  
t  where n+ = moles of cations

n  
t  where n- = moles of anions.

 
Thus, L+ and L- can be calculated directly if we measure L, the molar
conductivity of the solution and if we can measure the transport
numbers of the individual ions.

Experimentally, it is possible to partition the charge transport through


an electrolyte solution into contributions from anion and cation and
thus determine numerical values for t+ and t-.
A comparison of the conductivity of Ions
The Mobility and Conductivity of ions depend on the nature of the ion and
this in turn is affected by degree of solvation. Below is a comparison of the
conductivities of different ions.
Ion Li+ Na+ K+

Lo 38.69 50.11 73.22


r(Å) 0.69 0.92 1.33

Would expect the smallest Li+ ion to move fastest, but K+ does - this can be
explained by the fact that the ions are solvated and that the solvated ion
moves. The degree of solvation depends on the polarisability of the ion
and this is inversely related to the size of ion.

Li+ is hydrated to the greatest extent and thus the movement of the highly
hydrated Li+ is slower than the less hydrated K+ ion.
H+ has the highest mobility - hydrogen-bonding network in H2O
facilitates the transport of H+ . The proton exists in solution as the H3O+
species. The H+ species does not exist in aqueous solution, it
immediately attaches itself to a H2O molecule to form the hydronium
ion H3O+. The ‘splitting off’ of a proton from a H3O+ molecule can take
place provided there is a water molecule nearby that can act as a
receptor.
The receptor molecule must be in the correct orientation with respect
to the H3O+ ion before transfer of the proton takes place, but once the
orientation is favourable, the proton can be transferred rapidly by a
tunnelling process.

This is a quantum mechanical effect – the very low mass of the proton
facilitates the penetration of the energy barrier. Thus, it is evident that
the enhanced conductivity of the proton is intimately bound up to the
structure of the H3O+ ion and water molecule.

The proton is transported throughout the H2O hydrogen-bonded


network, without the physical movement of the hydronium ion. This is
a much faster process. In other solvents where this network does not
exist, H3O+ has a similar mobility to that of other cations of comparable
size.
Applications of Conductivity Measurements
(1) Measurement of dissociation constant
 
For dissociation equilibrium: AB → A+ + B-
 
where a = degree of dissociation and c concentration then:
AB → A+ + B-
c(1-a) ac ac

As an example, take 0.01 mol dm-3 CH3CO2H


CH3CO2H → H+ + CH3CO2 -
(1-a)(0.01) a(0.01) a(0.01)
 
a is related to conductivity of solution

For weak electrolytes  o

 

(c) 2  2c
Kdiss  
(1   )c (1   )

Kdiss is a constant but a varies with concentration


 

Substituting   o into the expression for a gives,

2
 
 o c 2 c
  =
Kdiss 

1 o 
o o   

Example 3: The molar conductivity of a 0.0025 mol dm-3 ethanoic acid
solution is 0.003165 W-1 m2 mol-1 at 298 K. The limiting molar
conductivity at infinite dilution is 0.03907 W-1 m2 mol-1.
(1) Determine at 298 K the dissociation constant and the pH of this
ethanoic acid solution.

(2) Determine the molar conductivity and pH of a 0.01 mol dm-3


ethanoic acid solution.
(1) Dissociation and equilibrium concentrations represented by:
(2) For the 0.01 mol dm-3 solution.

Kdiss remains constant  2 c = 1.78 x 10-5


Kdiss 
(1   )
 
Find a when c is equal to 0.01 mol dm-3. Since a is small compared to
unity then
 
Kdiss . x10 5
178
Kdiss = a c and
2
   0.0422
c 0.01

Since    , therefore L = a = 0.0422 x 0.03907


o
= 1.65 x 10-3 W-1 m2 mol‑1

[H+] = ac = 0.0422 x 0.01


and pH = -log[H+] = -log(0.0422 x 0.01) = 3.37
(2) Application - Solubility of a sparingly soluble salt
For a low solubility salt, the concentration of the dissolved salt is
negligible and the concentration, c, → 0


 but since c → 0 then   o
c
 

Make approximation that molar conductivity at saturation is equal to


molar conductivity at infinite dilution.

 
c o

 o  o
Example 4: Calculate the solubility product of AgCl if kAgCl = 2.28 x 10-4 W-1 m-1

o  . x103  1m2 mol 1


 6192
Ag
o   7.635x10 3  1m2 mol 1
Cl

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