Electrochemistry 2013
Lecture 3.
Ionion interactions in
electrolyte solutions.
1
Both cations and anions are charged up
using this protocol. This analysis is similar to that used in
We wish to isolate the Gibbs energy for deriving the Born equation.
ion/ion interactions due to one specific ion
which we label j.
rj dq
q z je
j , I N AWC N A
Hence we work in terms of chemical q 0
rj
z je
4 0 r rj
WC j , I
Hence the change in chemical
potential is given by the following
fundamental expression.
Initial state
rj
z j eN A
Final State j , I
2
Discharged reference ion j Charged reference ion j
of radius rj.
Ionic atmosphere
2
We draw from two disciplines to quantify the model.
The first is classical electrostatics, and the second
is statistical mechanics.
We also have a choice with respect to ion dimensions.
(i) Point charge model: most simple approach, valid
for very dilute solutions (slightly polluted
water!!), results in the formulation of the
DebyeHuckel (DH) Limiting Law.
(ii) Finite ion size model: more realistic, ion size is
quantified by a size parameter a.
(iii) The ion distribution about the central
reference ion is treated in terms of the Poisson
equation of classical electrostatics in terms of a
continuous charge density j(r). This is only an
approximation since in reality one has a discrete
distribution of counterions about the central
reference ion. Hence there is a local excess of
ions of opposite charge about a central
reference ion: this is the ionic atmosphere.
3
Mathematical development of DH Theory. Charge density
Central
reference
Reference ion j
 ion j

Surrounding ions
+ yield excess
Charge density
  +
medium j j (r)
Medium of
Solvent dielectric j r
Electrolyte molecules Constant r
Solution
j (r)
2 j ( r ) We now note that the excess charge
density is defined as the charge per unit
volume and we can readily define it in the
1 2 following manner.
2 r
r 2 r r
j r zi eni ( r )
1 2 j r j r i
r
r r
2
r
In this latter expression ni (r)
represents the number density
We note that the charge distribution about the central
(concentration) of ion labelled i
reference ion is spherically symmetric and so the
in the ionic atmosphere distant
potential is also spherically symmetric.
r from the central ion j.
4
Now is where Statistical (Sadistical??) Mechanics
rears its head and enters stage left.
We can relate the number density of ion i in the ionic
atmosphere to the bulk concentration of the ion i which we
label ni∞ via the well known Boltzmann Equation.
U (r)
ni ( r ) ni exp ij
In the latter expression the quantity Uij (r ) k BT
represents the Potential of mean force. Now if the
central reference ion j is a cation, we can state
that we have a local deficit of cations and a local
excess of anions in the ionic atmosphere.
Mathematically this can be stated by:
n ( r ) n n r n
The opposite pertains if the reference ion is an anion.
We also assume that the potential of mean force is given by
The following simple expression:
U ij ( r ) zi e j r
This assumption is termed the central approximation. Now Uij relates to the time
Average forces between the ions. If ion/ion interactions are absent then Uij= 0.
Hence nj (r ) = nj∞. If the interaction force is attractive then Uij < 0 and nj (r ) > nj∞,
And there is a local accumulation of ions in excess of bulk values. In contrast, if the
interaction force is repulsive with Uij > 0 then nj (r ) < nj∞, and there is a local depletion
of ions.
If the central ion has a finite size a then we can write the following.
U ij r a
zi z j e 2
U ij ra
4 r
This condition implies that electroneutrality pertains the bulk solution and that
the excess charge density is defined only on a local scale.
Now comes the important bit. We substitute the Boltzmann equation from Statistical
Thermodynamics into the Poisson Equation from claiiical electrostatics, and obtain
The famous (or infamous depending on your viewpoint) PoissonBoltzmann (PB) Equation.
1 d 2 d j ( r ) 1 zi e j ( r )
2 j r zi eni exp
r
2
r dr dr i k BT
5
The PB equation is found in a great We now substitute this approximation into
many physical situations pertinent to the PB equation to obtain the following.
electrochemical systems, most notably
when one is discussing the interface
1 d 2 d j r 1 zi e j r
between a planar electrode and an r zi eni 1
electrolyte solution and when one r 2
dr
dr
i k BT
considers the interface between a 1 1 zi e ni j r 1
2 2
zi2 e2 ni j r
colloidal particle and its surrounding zi eni 2 j r
i i k BT i k BT
environment. In these important
situations one will often have to
attempt to solve the full non linear In the latter we have introduced the electroneutrlity
equation which can be quite challenging. Condition which states that
However under the present
circumstances we do not need to do this i
zi eni 0
and we can simplify matters
We also have introduced the DH parameter such that
considerably by making the important
assumption
e2 1
that the solution is so dilute that the
ions will rarely be close together.
2
z 2 n
k BT i i i L2D
Under such circumstances, the
interionic potential energy will be much
We will show that the inverse kappa 1 = LD is an
less than the average thermal energy. effective measure of the ionic atmosphere.
This assumption means that we can We see that depends on the number density of
state the following. ions in the atmosphere and also note the following
zi e j quantitative relationship: N c
1 ni A 3 i N A o mi
k BT 10
Where ci denotes the molar
Now we can make the following zi e j r zi e j r concentration of ion i and 0
assumption. When x is small we can exp 1 denotes the density of the
assume that exp[x] ≈ 1x . k B T k BT
solvent.
1 1
We recall the definition of ionic strength I as 2 ci zi 2 mi zi
2 2
i i
2 N Ae 2 0
Hence the DH parameter k is related to the ionic strength I as follows 2 I
k BT
We now introduce the Debye Length LD as 1/ and write that
1 k BT 12
LD I
2 0 N Ae 2
Hence the Debye Length is a measure of the thickness of the ionic atmosphere
And we note that it decreases with increasing ionic strength I.
For an aqueous medium we note that 0 = 0.997 x 103 kgm3, r = 78.5, and assuming
That T = 298 K, kB = 1.38 x 1023 JK1, e = 1.60 x 1019C, NA = 6.023 x 1023 mol1 and
0 = 8.854 x 1012 C2N1m2 we can calculate that the Debye Length can we written in the
following useful format.
Hence as m 0, the ionic atmosphere spreads out and becomes more diffuse.
6
We can calculate the total excess charge contained in the ionic atmosphere
which surrounds the central ion as follows.
Shell volume d
j r z je
2 j r 2 exp r
4 r
z je
j r 2 exp r r
4 r
The last integral may be solved via integration by parts to obtain the final significant result.
Hence we have shown that the total charge on the surrounding ion cloud
qcloud z j e qion is equal and opposite to that on the central reference ion.
Electroneutrality is therefore satisfied.
r ion
j j r ion (r ) cloud (r )
cloud (r ) j r ion (r )
r j
z je
ion (r )
Atmosphere absent
j 4 r
ze
j (r ) j exp r
4 r
Ion absent
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We now wish to evaluate the total potential at the surface of the reference ion (assumed to be a point
charge).
z je 1 1
j (r )
4 r LD
zr
j (r 0) j ,0 j
4 LD
Now we finally recall that the change in chemical potential due to ion/ion interactions is given by
The following expression.
N A z je
2
NA z je (1)
j , I j ,0
2 8 LD
This is the fundamental theoretical result which we require. We now relate this result to the
Thermodynamics of electrolyte solutions.
For an ideal solution containing noninteracting solute we can write the following expression for the
Chemical potential.
j (ideal ) 0j RT ln m j
In contrast for a real solution containing interacting solute particles we introduce activities rather
than molalities where we note that aj = jmj.
j (real ) 0j RT ln a j 0j RT ln j m j
log j
N A z je z e
2 2
ln j LD1 LD1
j
(3)
8 0 r RT 8 0 r k BT S DHLL Az 2j
We now recall that the inverse Debye Length is related
To the Ionic strength I of the solution according to the following relationship.
2 0 N Ae 2 1/2
LD1 I (4)
0 r k B T
From eqn.3 and eqn.4 we derive the relationship between the ionic activity
coefficient abd the square root of the Ionic Strength which is the fundamental
result of the DebyeHuckel Theory valid for very dilute electrolyte solutions, and is termed the DH Limiting Law.
The DH limiting law expressed in eqn.5 will be valid only for very dilute solutions
where m < 103 mol kg1.
One rapidly observes marked deviations from this law as the solution becomes
more complicated.
Now we have derived an expression for the activity of a single ion j. Such a quantity cannot be measured
experimentally. Instead we can measure the mean ionic activity coefficient, and one can show that the following
holds.
log A z z I
1/2
V AF
8
The valence factor FV = z+ z can be evaluated as follows for different electrolyte types.
(1,3) LaCl3 z+ = 3, z = 1 3
(2,2) MgSO4 z+ = 2, z = 2 4
(2,3) Fe2(SO4)3 z+ = 3, z = 2 6
The DH limiting Law holds only for the most dilute solutions (slightly polluted water.
The model must be modified in a number of respects if agreement between theory
And experiment is to be obtained at higher concentrations.
Ion LD
a
Atmosphere
9
As previously noted the point charge picture is valid only for very
dilute solutions but becomes less so as concentration is increased. A
We therefore introduce the ion size parameter a the mean distance j r exp r
of closest approach.
r
We again may write the following expressions. A
In the latter A is a constant of integration
j r exp r
Which must be evaluated from the boundary conditions.
r
Again, the charge carried by an infinitesimally thin shell
of solution located at a distance r from the central ion is
given by the following expression.
dq 4 r 2 j r dr
Now for an ion of finite size, the ionic atmosphere begins at a distance a from the centre of the
reference ion j. Also the total charge carried by all the spherical shells between r = a and r = ∞
is obtained by summation over all spherical shells. This charge is balanced by the equal and opposite charge of the
central reference ion (the electroneutrality condition). Hence mathematically we can make the following
assertion.
r
This expression may be solved via integration by part to obtain the
4 j r r 2 dr z j e
r a following result.
1 a
4 2 A r exp r dr z j e z j e 4 2 A 2 exp a
a
z j e exp a
A
Hence the electrostatic potential at a distance r 4 1 a
From the reference ion j is given by the following expression.
z j e exp a
exp r
j (r )
4 1 a r
We again use the superposition principle to obtain an expression for cloud as follows.
cloud r j (r ) ion (r )
z je
ion (r )
4 r
z e exp a exp r
cloud (r ) j 1
4 r 1 a
Since no ions from the atmosphere can approach the central ion more closely than r = a,
then the potential that exists at the site of the central reference ion due to the ionic
atmosphere is obtained by setting r = a in th expression just derived above to obtain the
following result.
z je 1 z je 1 z je 1
j (r a) 1 1
4 a 1 a 4 a 4 1 1 a
Now for dilute dolutions a <<1 and the expression just derived decomposes to that altrady
Obtained for the point charge model as indeed it should.
10
We now consider the GuntelbergMuller
charging process. The reference ion is
introduced into the solution in an
uncharged state. One then increases the
charge gradually to its final value
given by zje. The work done in this
process is now evaluated.
The electrostatic work required per ion
Wc to increase the charge on ion j from
qj = 0 to qj = zje can be calculated via
the following procedure.
q j z je z je
1
WC
q j 0
j (r a )dq
4 1 a 0
q j dq j
This is the fundamental theoretical result for finite size ions. As before we can state the
following relationships.
j , I RT ln j
z 2j e 2 N A z 2j e 2
ln j
8 RT 1 a 8 k BT 1 a
Hence we may obtain the extended DH equation for finite size ions as follows.
Az 2j
log j
1 Ba
Where we have noted the following
2 N Ae 2 0
0 r k BT
2 0 N A e3 1 1.82 106
A 3/ 2
2.303 8 0 k B rT rT
3/2 3/ 2
2 N Ae 2 0 5.02 1011
B
0 r k BT rT
1/2
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Relationship between Ionic Strength I and molality m, I = km
Finally the extended DH equation may be written in terms of the mean ionic activity coefficient in
the following manner.
A z z AFV
log
1 Ba 1 Ba
A reasonable fit for the ion size parameter is 0.4 nm. The a factor is best
treated as an adjustable parameter used to obtain a best fit between
experimentally obtained and theoretically calculated activity coefficients.
Note that for high concentrations of some electrolytes the parameter a
attains negative values which of course are not physically reasonable for
concentrated ionic solutions.
The extended DH equation is generally valid up to I ≈ 0.05 mol kg1.
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