A deeper look 1   The Debye–Hückel theory

The strategy for the development of the Debye–Hückel 1

theory of electrolyte solutions is to establish the rela-
tion between the work needed to charge an ion and its 0.8

Potential, ϕ/(Z/rD)
chemical potential. Then that work is related to the ion’s
interaction with the atmosphere of counter ions that has 0.6
assembled around it as a result of the competition of the
attraction between oppositely charged ions, the repulsion 0.4
∞
of like-charged ions, and the distributing effect of thermal
3
motion. 0.2 1
0.3
Step 1  Calculate the work of charging an ion 0
0 0.5 1
Imagine a solution in which all the ions have their actual Distance, r/rD
positions, but in which their Coulombic interactions have
been turned off and so are behaving ‘ideally’. The differ- Figure 1  The variation of the shielded Coulomb potential
ence in molar Gibbs energy between the ideal and real with distance for different values of the Debye length, rD/a.
solutions is equal to we, the electrical work of charging the The smaller the Debye length, the more sharply the potential
system in this arrangement. For a salt MpX q, decays to zero. In each case, a is an arbitrary unit of length.

 Gm, charged
  
ideal
Gm , uncharged Coulomb potential by the shielded Coulomb potential, an
w e = ( pµ+ + qµ− )− ( pµ+ideal + qµ−ideal ) expression of the form
Zi − r /r
= p( µ+ − µ+ideal )+ q( µ− − µ−ideal ) (1) φi = e  D
Shielded Coulomb potential   (3b)
r

From eqn 5F.26 (µi = µiideal + RT ln γ±) the terms in paren- where rD is called the Debye length. When rD is large, the
theses are written as shielded potential is virtually the same as the unshielded poten-
tial. When rD is small, the shielded potential is much smaller
µ+ − µ+ideal = µ− − µ−ideal = RT ln γ± than the unshielded potential, even for short distances (Fig. 1).
To calculate r D, it is necessary to know how the charge
so it follows that
density, ρi, of the ionic atmosphere, the charge in a small
region divided by the volume of the region, varies with
µ − µ ideal µ − µ ideal

+  
+

−  
−
distance from the ion. This step draws on another standard
w e = p RT ln γ ± + q RT ln γ ± = ( p + q )RT lnγ ± result of electrostatics, in which charge density and poten-
tial are related by Poisson’s equation:
and therefore
ρ
w ∇ 2φ = −  Poisson’s equation   (4a)
ln γ ± = e s = p + q (2) ε
sRT
where ∇ 2 = ∂ 2/∂x 2 + ∂ 2/∂y 2 + ∂ 2/∂z 2. Because the ionic
This equation implies that the final distribution of the ions atmosphere is spherically symmetric the charge density
and then the work of charging them in that distribution varies only with distance from the central ion and eqn 4a
must be found. becomes
1 d  2 dφi  ρ
Step 2 Calculate the Coulomb potential experienced by  r  =− i  (4b)
r 2
dr  dr  ε
an ion
The Coulomb potential at a distance r from an isolated ion Substitution of the expression for the shielded potential
of charge zie in a medium of permittivity ε is (eqn 3b) results in
Zi zi e εφi
φi = Zi =  (3a) rD2 = −
r 4 πε ρi  (5)

However, the ionic atmosphere causes the potential to Step 3  Calculate the Debye length
decay with distance more sharply than this expression To solve eqn 5 for r D, ρi must be related to ϕi. For this step,
implies. Such shielding is a familiar problem in electro- note that the energy of an ion depends on its closeness to
statics, and its effect is taken into account by replacing the the central ion, and then use the Boltzmann distribution
2 A deeper look 1  The Debye–Hückel theory

to evaluate the probability that an ion will be found at
each distance.
The energy of an ion j of charge zje at a distance where
it experiences the potential ϕi of the central ion i relative
to its energy when it is far away in the bulk solution is its
charge zje times the potential ϕi. Therefore, according to
the Boltzmann distribution, the ratio of the molar concen-
tration, cj, of ions at a distance r where their electrostatic
energy is z j eφi and the molar concentration in the bulk, c °,
j  e − r /r 1 
Step 4  Calculate the work of charging the ion in the pres-
ence of the ionic atmosphere
To calculate the work of charging the central ion it is
necessary to know the potential at the ion due to its
atmosphere, ϕatmos. This potential is the difference between
the total potential, given by eqn 3b, and the potential due
to the central ion itself:
D

where their electrostatic energy is zero, is φatmosphere = φ − φcentral ion = Zi  −  (11a)

r r
cj − z e φ /kT The potential at the central ion (at r = 0) is obtained by tak-
=e j i
 (6)
c °j ing the limit of this expression as r → 0 and is
The charge density, ρi, at a distance r from the ion i is
1− r / rD +  1  Z
the molar concentration of each type of ion multiplied φatmosphere (0) = Zi lim  −  =− i (11b)
r →0  r r rD
by the charge per mole of ions, zieNA = ziF (F is Faraday’s
constant, F = eNA). It follows that This expression shows that the potential due to the ionic
atmosphere is equivalent to the potential arising from
ρi = c+ z + F + c− z − F = c+° z + Fe − z eφ /kT + c−°z − Fe − z eφ /kT 
+ i − i
(7) a single charge of equal magnitude but opposite sign to
that of the central ion and located at a distance r D from
Because the average electrostatic interaction energy is small the ion. Therefore, if the charge of the central ion were
compared with kT it is permissible to use e x = 1 + x +  Q and not zie, then the potential due to its atmosphere
and to write the charge density as would be

ρi = c+° z + F 1− ( z + eφi
kT ) (z eφ
+  + c−° z − F 1− − i + 
kT ) φatmosphere ( 0 ) = −
Q
4 πε rD  (11c)

  0
  The work of adding a charge dQ to a region where the elec-
Feφi trical potential is ϕatmosphere(0) (from dw = ϕdQ), is
= (c+° z + + c−° z − ) F − (c+° z +2 + c−° z −2 ) +
kT

The term in blue is zero because it is the charge density in dwe = ϕatmosphere(0)dQ (12)
the bulk, uniform solution, and the solution is electrically
It follows that the total molar work of fully charging the
neutral. The replacement of e by F/NA and NAk by R results
ion i in the presence of its atmosphere is
in the following expression:
F 2φi
zi e NA zi e

ρi = −(c+° z +2 + c−°z −2 ) we,i = N A ∫ φatmosphere (0)dQ = − ∫ Q dQ

RT  (8) 0 4π ε rD 0

N A zi2e 2 zi2 F 2
=− =−
The higher-order unwritten terms are assumed to be too 8π ε rD 8πN Aε rD  (13)
small to be significant. This equation can be expressed in
terms of the ionic strength by noting that in the dilute Step 5  Evaluate the activity coefficient
aqueous solutions being considered c ≈ bρ, where ρ is the
The total work of charging p cations and q anions in the
mass density of the solvent. Therefore
presence of their atmospheres is we = pwe,+ + qwe,−, and
⦵
2 Ib therefore the mean activity coefficient of the ions is
  
c+° z + + c−° z − ≈ (b+° z + + b−° z −2 ) ρ = 2 Ib ρ
2 2 2 −−
○

pw e,+ + qwe,− ( pz +2 + qz −2 )F 2
ln γ ± = =−  (14a)
sRT 8πNA sRTε rD
With these approximations, eqn 8 becomes
However, for neutrality pz+ + qz− = 0; therefore
2 Ib ρ F 2φi
−−
○

ρi = −  (9)
RT
− qz−
− pz+ s −|z+ z−|
   
2 2
When this expression is substituted into r = −εφi /ρi , the ϕi2
D
pz + qz = pz + z + + qz − z − = − ( p + q ) z + z − = s | z + z − |
+ −
cancel and the result is
1/2
It then follows that
 ε RT 
rD =   Debye length   (10)
 2 ρ F 2 Ib  | z+ z− | F 2
−−
○

ln γ ± = −  (14b)
8πN A RT ε rD
3 A deeper look 1  The Debye–Hückel theory

The replacement of r D with the expression in eqn 10 (log γ± = −|z +z−|AI1/2). Indeed, conversion to common loga-
gives rithms (by using ln x = ln 10 × log x) gives

1/2 A
| z + z − | F 2  2 ρ F 2 Ib 
−−
○
   
ln γ ± = −  1/2
 1/2
8πN A RT ε  ε RT  F 3
 ρb
−−
○

log γ ± = − | z + z − |  I  (16a)
4 πN A ln10  2ε R T  
 3 3 3
 
 F 3  ρb   1/2
−−
○ 1/2

= −| z+ z− | I  (15)
4 πN A  2ε 3 R 3T 3   which is the Debye–Hückel limiting law (eqn 5F.27) with
 
1/2
F3  ρb−−○ 
A=  (16b)
where terms have been grouped to show that this expres- 4 πN A ln10  2ε 3 R 3T 3 
sion is beginning to take the form of the limiting law