रसो वै सः ॥

Master of Science (Chemistry)

Compulsory Course (CC) -2 Physical Chemistry

Unit 2
Electrochemistry: Debye Huckel Theory

Sonu Ram Shankar

Assistant Professor
University Department of Chemistry
Lalit Narayan Mithila University, Darbhanga

1
 Ionic Strength

Summation of the charge and concentration of each ion in the solution

1
𝐼𝑜𝑛𝑖𝑐 𝑠𝑡𝑟𝑒𝑛𝑔𝑡ℎ, 𝜇 = 𝑐𝑧
2

𝑐 is the molar concentration of each ion 𝑧 is the charge of each ion

for 0.10 M NaCl, ignoring [H3O+]and [OH–] ≈1.0×10−7 ≪ [Na+] and [Cl–] 𝐾 = 1.0 × 10

1 1 1 1
𝜇 . = 𝑁𝑎 × 1 + 𝐶𝑙 × −1 = 0.1 × 1 + 0.1 × 1 = 0.1 + 0.1 = 0.2 = 0.10
2 2 2 2

for 0.10 M Na2SO4 ignoring [H3O+], [OH–] and [HSO4–] 𝐾 = 1.0 × 10

1 1 1 1
𝜇 . = 𝑁𝑎 × 1 + 𝑆𝑂 × −2 = 0.2 × 1 + 0.1 × 4 = 0.2 + 0.4 = 0.6 = 0.3
2 2 2 2
2
 Activity of Ion

FeCl3 and KSCN solutions are colorless.

Mixing them produce Fe(SCN)2+ reddish–orange color solution

Fe3+(aq) + SCN− (aq) ⇌ Fe(SCN)2+ (aq)

𝑆𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝑓𝑟𝑒𝑒 𝑒𝑛𝑒𝑟𝑔𝑦, ∆𝐺 = 𝑅𝑇 ln 𝐾

𝐹𝑒 𝑆𝐶𝑁
𝐹𝑜𝑟𝑚𝑎𝑡𝑖𝑜𝑛 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝐾 =
𝐹𝑒 𝑆𝐶𝑁

Adding KNO3 to the solution makes the solution’s lighter color

shifts reaction to the left,

decreasing the effective concentration of Fe(SCN)2+ and increasing the concentrations of Fe3+ and SCN–.
3
 Activity Coeffiecient

The true thermodynamic equilibrium constant using activities.

𝐴𝑐𝑡𝑖𝑣𝑖𝑡𝑦 𝑜𝑓 𝑆𝑝𝑒𝑐𝑖𝑒𝑠 𝐴 = 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝑠𝑝𝑒𝑐𝑖𝑒𝑠 𝐴 × 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑑𝑒𝑝𝑒𝑛𝑑𝑒𝑛𝑡 𝑎𝑐𝑡𝑖𝑣𝑖𝑡𝑦 𝑐𝑜𝑒𝑓𝑓𝑖𝑒𝑐𝑖𝑒𝑛𝑡

𝑎 = 𝐴𝛾

𝑎 𝛾
𝐹𝑜𝑟𝑚𝑎𝑡𝑖𝑜𝑛 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝐾 =
𝑎 𝛾 𝑎 𝛾

Finding relation between activity coefficient and ionic strength

It is due to the ion-ion interaction

4
 Ion-ion interaction
Model:

1. There is an ion with 𝑧 charge

2. There is a charge distribution around that ion +

3. the ion is interacting with charge distribution

4. All the ions interacting with each other

Assumptions

1. The solution a dielectric continuum of dielectric constant (relative permittivity) 𝜀. +

2. The ions are hard spheres.

3. The concentration is relatively low.

5
 Debye- Huckel Limiting Law
𝑛 number of ion per unit volume,

an ion with charge 𝑧 𝑒

At distance 𝑟, the potential 𝜓, ,

Potential energy of the ion with charge, 𝜓𝑒

According to Boltzmann distribution

The probability of a positive ion in region of potential; 𝑛 = 𝑛𝑒𝑥𝑝

The probability of a negative ion in region of potential 𝜓; 𝑛 = 𝑛𝑒𝑥𝑝

Net Charge density: 𝜌 = 𝑛 − 𝑛 𝑒 = 𝑛𝑒 𝑒𝑥𝑝 − 𝑒𝑥𝑝

6
 Debye- Huckel Limiting Law
The Poisson equation

𝜌
∇ 𝜓 𝑟 = −4𝜋
𝜀

the Laplacian operator, ∇ ,

in Cartesian coordinates: ∇ = + + is.

In spherical coordinates ∇ = 𝑟 + sin 𝜃 +

There is spherically symmetrical distribution of charge. There is no effect of 𝜃 and 𝜑

1 𝑑 𝑑𝜓 𝑟 𝜌
∇ 𝜓 𝑟 = 𝑟 = −4𝜋
𝑟 𝑑𝑟 𝑑𝑟 𝜀
7
 Debye- Huckel Limiting Law
Substituting for charge density

4𝜋𝑛𝑒
∇ 𝜓 𝑟 =− 𝑒𝑥𝑝 − 𝑒𝑥𝑝
𝜀

When 𝜓 is small: 𝑒𝑥𝑝 =1+ + ⋯ and 𝑒𝑥𝑝 =1− +⋯

Substituting these

4𝜋𝑛𝑒 𝑒𝜓 𝑟 𝑒𝜓 𝑟 4𝜋𝑛𝑒 𝑒𝜓 𝑟 𝑒𝜓 𝑟 4𝜋𝑛𝑒 2𝑒𝜓 𝑟 8𝜋𝑛𝑒

∇ 𝜓 𝑟 =− 1− − 1+ =− 1− −1− =− − = 𝜓 𝑟
𝜀 𝑘𝑇 𝑘𝑇 𝜀 𝑘𝑇 𝑘𝑇 𝜀 𝑘𝑇 𝜀𝑘𝑇

If 𝜅 = ; 𝑟 =𝜅 𝜓 𝑟

8
 Debye- Huckel Limiting Law
If ; 𝜓 𝑟 =
Then

𝑑𝜓 𝑟 𝑑 𝜇 𝑑 1 𝑑 1 1𝑑 1 1 𝑑𝜇 𝜇 1 𝑑𝜇
= = 𝜇. =𝜇 + 𝜇 =𝜇 − + = − +
𝑑𝑟 𝑑𝑟 𝑟 𝑑𝑟 𝑟 𝑑𝑟 𝑟 𝑟 𝑑𝑟 𝑟 𝑟 𝑑𝑟 𝑟 𝑟 𝑑𝑟

Substituting =− +

1 𝑑 𝑑𝜓 𝑟 1 𝑑 𝜇 1 𝑑𝜇 1 𝑑 𝑑𝜇
𝑟 = 𝑟 − + = −𝜇 + 𝑟
𝑟 𝑑𝑟 𝑑𝑟 𝑟 𝑑𝑟 𝑟 𝑟 𝑑𝑟 𝑟 𝑑𝑟 𝑑𝑟

1 𝑑 𝑑 𝑑 𝑑𝜇 1 𝑑𝜇 𝑑 𝑑𝜇 𝑑𝜇 𝑑
= −𝜇 + 𝑟 = − +𝑟 + 𝑟
𝑟 𝑑𝑟 𝑑𝑟 𝑑𝑟 𝑑𝑟 𝑟 𝑑𝑟 𝑑𝑟 𝑑𝑟 𝑑𝑟 𝑑𝑟

1 𝑑𝜇 𝑑 𝜇 𝑑𝜇 1 𝑑 𝜇 1𝑑 𝜇
= − +𝑟 + = 𝑟 =
𝑟 𝑑𝑟 𝑑𝑟 𝑑𝑟 𝑟 𝑑𝑟 𝑟 𝑑𝑟

9
 Debye- Huckel Limiting Law

Substituting 𝜓 𝑟 = in 𝑟 =𝜅 𝜓 𝑟

1 𝑑 𝑑𝜓 𝑟 𝜇
𝑟 =𝜅
𝑟 𝑑𝑟 𝑑𝑟 𝑟

Since 𝑟 =𝜅 and 𝑟 =

1𝑑 𝜇 𝜇
=𝜅
𝑟 𝑑𝑟 𝑟

𝑑 𝜇
=𝜅 𝜇
𝑑𝑟 10
 Debye- Huckel Limiting Law

Solving the differential

The differentiation of an exponential function is the product of the constant and the exponent function.

𝑒± = ±𝜅𝑒 ± and 𝑒± = ±𝜅 𝑒 ±

the differential equation in 𝜇 must have had an exponential in 𝜅𝑟

Two possible exponential functions, one of them would have a positive exponent and the other a negative one

The general solution of the linearized equation can therefore be written as

𝜇 = 𝐴𝑒 + 𝐵𝑒

where A and B are constants to be evaluated.

11
 Debye- Huckel Limiting Law
The Constant B

Since 𝜓 𝑟 =

𝑒 𝑒
𝜓 𝑟 =𝐴 +𝐵
𝑟 𝑟
the Coulombic forces,
𝜓 𝑟 → 0 as 𝑟 → ∞.
if B had a finite value
At infinity, 𝑟 → ∞, 𝜓 𝑟 → ∞
the electrostatic potential would shoot up to infinity, a physically unreasonable proposition.
This condition would be satisfied only if 𝐵 = 0.

So equation reduces to 𝜓 𝑟 = 𝐴

12
 Debye- Huckel Limiting Law
The constant 𝑨,
From Coulomb’s law
the potential is due to an isolated point charge of value 𝑧 𝑒.
𝑧𝑒
𝜓 𝑟 =
𝜖𝑟
At infinity, the concentration tends to zero, 𝑛 → 0

Since, 𝜅 = ∑𝑛 𝑧 then 𝜅 → 0

When 𝜅 → 0 then 𝑒 → 1 then 𝜓 𝑟 =

Substituting 𝜓 𝑟 = in 𝜓 𝑟 =

𝐴 𝑧𝑒
=
𝑟 𝜖𝑟
Or
𝑧𝑒
𝐴=
𝜖 13
 Debye- Huckel Limiting Law

Substituting 𝐴 = in 𝜓 𝑟 = 𝐴

𝑧 𝑒𝑒
𝜓 𝑟 =
𝜖 𝑟
the electrostatic potential varies with distance r from reference ion
𝑒 can be expanded using a Taylor series as

𝜅𝑟 𝜅𝑟
𝑒 = 1 − 𝜅𝑟 + − +⋯
2! 3!
For small values of 𝜅𝑟 (where 𝜅𝑟 ≪ 1), higher-order terms 𝜅𝑟 , 𝜅𝑟 ,… become negligible.
𝑒 ≈ 1 − 𝜅𝑟
Expanding the solution and retaining the first two terms
𝑧𝑒 𝑧𝑒𝜅
𝜓(𝑟) = −
𝜀𝑟 𝜀
14
 Debye- Huckel Limiting Law

𝑧𝑒 𝑧𝑒𝜅
𝜓(𝑟) = −
𝜀𝑟 𝜀

The term represents the Coulomb potential, gives the charge on the electrolytic solution as a whole.
This is zero because the solution as a whole must be electrically neutral.
𝑧𝑒
=0
𝜀𝑟
− is the potential due to the charge, 𝑧𝑒, at a distance, ,
The screening effect introduced by the exponential decay term.
𝑧𝑒𝜅
𝜓(𝑟) = −
𝜀

15
 Debye- Huckel Limiting Law

The Poisson equation 𝑟 = −4𝜋

Linearized equation 𝑟 =𝜅 𝜓 𝑟

The linear relation between excess charge density and potential

𝜀
𝜌=− 𝜅 𝜓 𝑟
4𝜋
Substituting 𝜓 𝑟 =

𝜀 𝑧 𝑒𝑒 𝑧𝑒 𝑒
𝜌=− 𝜅 =− 𝜅
4𝜋 𝜖 𝑟 4𝜋 𝑟
This ionic cloud;
𝑒 : The excess charge density decays with distance r in an exponential way.
-ve sign: The excess charge residing on the ion cloud is opposite in sign to that of the central ion.
a positively charged reference ion has a negatively charged ion atmosphere, and vice versa.

16
 Debye- Huckel Limiting Law

Interaction of ion with the cloud

Energy required to form the ionic atmosphere from 0 charge to 𝑧𝑒 charge

𝑧𝑒𝜅 𝜅 𝑧 𝑒 𝜅
𝑊 = − 𝑑 𝑧𝑒 = 𝑧𝑒 =
𝜀 2𝜀 2𝜀

For activity coefficient, of I ion 𝛾

𝑊 = 𝑘𝑇 ln 𝛾
Substituting

𝑧 𝑒 𝜅
ln 𝛾 =
2𝜀𝑘𝑇

17
 Debye- Huckel Limiting Law

If 𝜐 and 𝜐 are number of positive and negative ions

where
𝜐 =𝜐 +𝜐
mean activity coefficient
𝛾± = 𝛾 𝛾
𝜐 𝜐
ln 𝛾± = ln 𝛾 + ln 𝛾
𝜐 𝜐
For charge neutrality
𝜐 𝑧 =𝜐 𝑧

𝑒 𝜅
ln 𝛾± = − 𝑧 𝑧
2𝜀𝑘𝑇

18
 Debye- Huckel Limiting Law
For ionic strength

1
𝜇= 𝑐 𝑧
2

𝑐𝑁
𝑛 =
1000
𝑐 =𝑚𝜌
Where 𝜌 is density of the solvent

8𝜋𝑁 𝑒 𝜌 𝜇
𝜅 =
1000 𝜀𝑅𝑇

8𝜋𝑁 𝑒 𝜌 𝜇
𝜅=
1000 𝜀𝑅𝑇

19
 Debye- Huckel Limiting Law

for water 𝜌 = 1𝑔 𝑚𝑙

ln 𝛾± = −𝐴 𝑧 𝑧 𝜇

𝑁 𝑒 2𝜋
𝐴=
2.303𝜀𝑅𝑇 1000𝜀𝑅𝑇
Substituting the values of 𝑁 , 𝜋 and 𝜌
1.8246 × 10
𝐴=
𝜀𝑇

20
 Debye- Huckel Limiting Law

At 𝑇 = 25℃ and 𝜀 = 78.54 for water

𝐴 = 0.509

ln 𝛾± = −0.509 𝑧 𝑧 𝜇

21
 Debye- Huckel Limiting Law
Debye Huckell radius

Charge in a spherical shell of thickness

𝑞 = −𝑧 𝑒 𝜅 𝑟𝑒

At the maximum

𝑑𝑞 𝑑 𝑑
=0= −𝑧 𝑒 𝑒 𝜅 𝑟 = −𝑧 𝑒 𝜅 𝑒 𝑟 = −𝑧 𝑒 𝜅 𝑒 − 𝑟𝜅𝑒
𝑑𝑟 𝑑𝑟 𝑑𝑟

Since −𝑧 𝑒 𝜅 ≠ 0

𝑒 − 𝑟𝜅𝑒 =0

𝑒 = 𝑟𝜅𝑒

1 = 𝑟𝜅

1
𝑟=
𝜅 22
Debye- Huckel Limiting Law

23
 Debye- Huckel Limiting Law
Effective Diameters (α) for Selected Ions
ion effective diameter (nm)
H3O+ 0.9
Li+ 0.6
Na+, IO−3, HSO−3, HCO3−, H2PO−4 0.45
OH–, F–, SCN–, HS–, ClO3−, ClO4−, MnO4− 0.35
K+, Cl–, Br–, I–, CN , NO2−, NO3− 0.3
Cs+, Tl+, Ag+, NH4+ 0.25
Mg2+, Be2+ 0.8
Ca2+, Cu2+, Zn2+, Sn2+, Mn2+, Fe2+, Ni2+, Co2+ 0.6
Sr2+, Ba2+, Cd2+, Hg2+, S2– 0.5
Pb2+, SO42−, SO32− 0.45
Hg22+, SO42−, S2O32−, CrO42−, HPO42− 0.40
Al3+, Fe3+, Cr3+ 0.9
PO43−, Fe(CN)63− 0.4
Zr4+, Ce4+, Sn4+ 1.1
Fe(CN)64− 0.5
Source: Kielland, J. J. Am. Chem. Soc. 1937, 59, 1675–1678. 24