SS209: Electrochemical Systems

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Lecture 21:
Introduction to Electrolytes and Debye- Hückel Theory
Objec&ves:
1) Understand what an electrolyte implies and the categoriza7on of electrolytes
2) Develop a background understanding for calcula7ng ac7vi7es (ac7vity
coefficients) of ions in electrolyte solu7ons.
3) Develop analy7c equa7ons to calculate the contribu7ons to non- ideality
arising out of electrosta7c interac7ons.
4) Develop an understanding of the solute and solvent proper7es that
contribute to non-ideality
5) Discuss limita7ons of Debye-Hückel Theory.
Reading: Chapter 2, D R Crow.
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What is an electrolyte? : A charge neutral substance which
dissociates into charged species when dissolved in a solvent
thereby making the solu9on electrically conduc9ve.

Note: Dissolu9on is not Dissocia9on! Eg: Table salt (NaCl) is an

electrolyte but sugar is not! Both dissolve in water but only
NaCl dissociates into its cons9tuent ions upon dissolu9on

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 Types of Electrolytes
• Strong Electrolytes: Dissociate
completely when dissolved in a
solvent. Degree of dissocia7on is 1.
• Non-electrolytes: Do not dissociate
when dissolved in a solvent. Degree
of dissocia7on is 0.
• Weak electrolytes: Dissociate
par7ally when dissolved in a solvent.
Degree of dissocia7on is between 0
and 1.
• Dissociation is solvent dependent. NaCl is
a strong electrolyte when water is the
solvent, however it is a non-electrolyte for
a non-polar solvent such as tetraglyme.
• Dissociation is also concentration
dependent. While NaCl is a strong
electrolyte at low concentrations in water,
ion association decreases degree of
dissociation at high concentrations – no
longer a strong electrolyte.
• The definition of weak electrolytes tends
to be rather arbitrary.
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What is the need for understanding dissocia4on: Degree of
dissocia9on dictates the ac9vi9es of electrolyte species in
solu9on. Hence, knowing degree of dissocia9on is necessary to
define the ac9vity of a compound in solu9on.

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Chemical Poten5al of Electrolyte Solu5ons

• The chemical poten7al of an electrolyte A that fully dissociates in a

solvent is given:

𝜇! = # 𝜈"! 𝜇"
"
where 𝜈" ‘s are the moles of each 𝑖 th component of A with a charge z" . Note
that Chemical poten7al is defined for 1 mole of A.
Charge neutrality of A dictates that ∑" 𝜈"! 𝑧" = 0 ( This is called Guggenheim
Condi7on)

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Electrochemical Poten5al Hypothetical Electrodes that probe potentials
𝜇," = 𝜇" + 𝑧" 𝐹∅ (absolute potentials are not measurable. Only
potential differences can be measured.
Work done for transferring a mole of ions
from phase 𝛼 to the phase 𝛽 is simply the
electrochemical potential differences
𝜙$ 𝜙#
between the two phases (see Figure) salt bridge
# #
𝜇," − 𝜇,"$ = 𝜇" − 𝜇"$ + 𝑧" 𝐹(∅# − ∅$ )

The total electrochemical work is an

algebraic sum of the work done for
transpor7ng neutral species and the 𝛼 𝛽
electrosta7c work done
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Key Learnings

1) Electrolyte defini9on is solvent dependent – degree of

dissocia9on differen9ates strong, weak and non-electrolytes.
2) An addi9onal contribu9on to the chemical poten9al from
electrosta9c interac9ons needs to be considered for electroly9c
solu9ons.
3) How do interac9ons between charged species change chemical
poten9als? Debye-Hückel Theory!

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A ques9on that we would like to answer by the end of our discussion
on Debye-Hückel theory:

- What sort of correc9ons to ideality do we expect for electrolyte

solu9ons.

- For example, would the heat of dissolu9on be iden9cal for a dilute

solu9on of, let us say, 1 mM sugar in water and 1 mM NaCl in
water?

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Debye-Hückel Theory: Introduc5on
• Proposed by Peter Debye and Erich Hückel to explain deviations from non-ideality
in electrolyte solutions
• A reasonably good approximation to predict the activities (activity coefficients) of
ionic species in electrolyte solutions
• Bases on the observation that strong electrostatic interactions between ions
could lead to a non-random distribution of ions.
• The non-random distribution of ions is due to the long range coulombic
interactions between ions in solution

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 The microscopic picture of ions in solu5ons
• The local ion concentra7on near a central
Where, 𝜖 is the permi,vity of the medium
∅ 𝑟 =
𝑧! 𝑒 (𝜖 = 𝜖" 𝜖# ), 𝜖" is the permi,vity of vacuum ion will be different from the average
4𝜋𝜖𝑟 and 𝜖# is the rela8ve permi,vity of dielectric
constant of the medium.
concentra7on
• Ions of like charge will be repelled and
opposite charge will be a_racted to the
central ion.

- - +
+
• At non-zero temperature, thermal energy

- + - +
-
will act to randomize this distribu7on.

- - + - +
• The concentra7on in the vicinity of a
central ion can be approximated by a
+ + Boltzmann distribu7on.
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Electrostatic potential around a central ion
The concentra8on of an ith in the vicinity of the central ion • The local ion concentra7on near a central
ion will be different from the average
01! 2∅
𝐶" = ./
𝐶" 𝑒 34 concentra7on
• Ions of like charge will be repelled and
−𝜌 opposite charge will be a_racted to the
∇5∅ = (Poisson’s equa8on) --- I
𝜖 central ion.
The total charge around the central ion is: • At non-zero temperature, thermal energy
−𝜌 𝐹 will act to randomize this distribu7on.
= 9 𝑧$ 𝐶$ --- II
𝜖 𝜖 $
• The concentra7on in the vicinity of a
central ion can be approximated by a
Boltzmann distribu7on.
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 The Debye length
%&! '∅
Using I and II and in the limit of )*
≪ 1, (note that it is useful to
realize that ∑$ 𝑧$ 𝐶$+, =0)
𝐹 !
∇! ∅ = ( 𝑧"! 𝐶"#$ ∅
𝜖𝑅𝑇 "

The expression can be rewriJen in spherical coordinates as:

1 𝜕 ! 𝜕∅ 𝐹! ! #$
𝑟 = ( 𝑧" 𝐶" ∅
𝑟 ! 𝜕𝑟 𝜕𝑥 𝜖𝑅𝑇 "

Comparing LHS and RHS of the above equa8on, the term in the RHS
(excep8ng ∅) has the dimensions of L-2. We define this as 𝜆 the Debye
length – a characteris8c length scale over which the poten8al decays
by a factor of 1/e. (we will see this aUer the differen8al equa8on is
solved)
&%
𝜖𝑅𝑇 !
𝜆=
𝐹 ! ∑" 𝑧"! 𝐶"#$
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 The Debye length
With the defini8on of 𝜆 given in the previous slide, the
differen8al equa8on can be rewriJen as:

1 𝜕 ! 𝜕∅ ∅
! 𝑟 = !
𝑟 𝜕𝑟 𝜕𝑥 𝜆
Solving this differen8al equa8on and realizing that
∅ → 0 𝑎𝑠 𝑟 → ∞, gives:
𝐴𝑒 ()⁄*
∅=
𝑟

The integra8on constant can be evaluated by using the

Gauss Theorem at the r=a boundary (a=rc+ri)

𝜌 𝑧+ 𝑒
3 𝐸 5 𝑑 𝑠⃗ = =
𝜖 𝜖

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 Potential Around the Central Ion a=rc+ri
(.0H)F
The final solu8on 𝑧E 𝑒 𝑒 I
∅=
to ∅ is:
4𝜋𝜖𝑟 1 + 𝑎=𝜆
Ionic distribu8on in the
vicinity of a central ion can 01! 2∅
./
be obtained. 𝐶" = 𝐶" 𝑒 34
Using the above equa8on
in conjunc8on with:

The parameter a for mul0component solu0ons is the

average value of the sum of the radii of pairs of
hydrated ions

For binary salt solu0on, it is usually the sum of the radii

of the anion and the ca0on

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Key Learnings

1) Electroly9c solu9ons have local charge distribu9ons that are in

general different from the average charge concentra9on.
2) Debye length is a characteris9c distance that defines the
perimeter around a central ion where the poten9al drops by 1/e.
3) What did we s9ll not answer: How does this poten9al around a
central ion lead to non-ideali9es?

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Chemical Poten.al Changes Due to Electrosta.c
Interac.ons
• We are only interested in contribu7ons to
How do we calculate contribu7ons to non-ideality from electrosta7c
electrosta7c interac7ons alone?
interac7ons in a solu7on with
concentra7on Ci.
- • We discharge Ni ions in a reservoir,
reversibly, (corresponding to a

+
- concentra7on Ci), transfer them to the
Reservoir
Solvent solvent and recharge them to their
+ charge state.
• The net work done in this process should
be electrosta7c component of the
chemical poten7al. 17
 Chemical Poten.al Changes Due to Electrosta.c
Interac.ons
• The net work done for discharging (charging)
𝑧+ 𝑒 will be the electrostatic work for removing
∅ 𝑟=𝑎 ),-,)$.") = ---- I
4𝜋𝜖𝑎
(adding) a charge, at a distance r=a from (to)
For an ion in the reservoir, the ions are so far apart that their the ion center to (from) a distance infinitely
poten8al profile is that of an isolated ion in a background
dielectric. Here, 𝜖 is the permi,vity of the medium (𝜖 = away from the ion center.
𝜖" 𝜖# ), 𝜖" is the permi,vity of vacuum and 𝜖# is the rela8ve
permi,vity of dielectric constant of the medium. • In order to do this reversibly, we only do this
by adding or removing an infinitesimally
𝑧+ 𝑒𝑥 1
∅ 𝑟=𝑎 = 5 ------ II small amount charge, x.
-./$,01
4𝜋𝜖𝑎 1 + 𝑎>𝜆
• And since we are not interested in the
For an ion in the solvent system of interest, the poten8al is chemical contributions to non-ideality, we
affected by the ion cloud and we therefore use the electrosta8c
poten8al at r=a as calculated in the previous lecture. might as well assume that the transfer of
neutral species is ideal.
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Chemical Poten.al Changes Due to Electrosta.c
Interac.ons
Solving the integral gives:
The total work done for transferring all Ni ions, involves
charging all ions in solu8on from x=0 to x=1

The chemical potential change for the ith ion is (remember

−𝑁! 𝑧"5𝑒 5 1
𝜇",QR =
that by using the chemical potential we are calculating this 8𝜋𝜖𝜆 1 + 𝑎=𝜆
for a mole, NA, of ions):
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𝜇$,./ = 𝑁0 ∫12" ∅45/,.67 − ∅#.4.#,5$# 𝑑𝑞 No8ng that we have assumed that the only contribu8on
to non-ideality, this contribu8on can be totally accounted
for in the ac8vity coefficient, i.e., :
The frac8onal charge dq is the total charge on the
ion 8mes the frac8onal change dx. Here is e is the
𝜇",QR = 𝑅𝑇 ln 𝛾"
electronic charge
Therefore,
𝑑𝑞 = 𝑧$ O 𝑒 O 𝑑𝑥
−𝑧"5𝐹𝑒 1
ln 𝛾" =
The integral can be solved using the expressions for 8𝜋𝜖𝜆𝑅𝑇 1 + 𝑎=𝜆
∅’s given in equa8ons I and II in the previous slide
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 Debye Length and Ionic Strength
In the previous lecture we derived an expression for We can rewrite the expression for ac8vity coefficient
Debye Length: &%

𝜆=
𝜖𝑅𝑇 !
−𝑧"5𝐹𝑒 1
ln 𝛾" =
𝐹 ! ∑" 𝑧"! 𝐶"#$ 8𝜋𝜖𝜆𝑅𝑇 1 + 𝑎=𝜆
All other parameters, except for ∑$ 𝑧$8 𝐶$+, are a constant for a
given solvent. In terms of the ionic strength:

Lewis and Randall introduced Ionic strength as a parameter to −𝑧"5𝛼 𝐼T

measure the rela8ve strength of electrosta8c interac8ons: ln 𝛾" =
The molal ionic strength is given by: 𝐼2 =
&
∑" 𝑧"! 𝑚" 1 + 𝐵𝑎 𝐼T
!
Where 𝑚$ is the molality of the ith ion. Where 𝛼 and B are solute concentra8on
independent constants given by:
A molar ionic strength can be equivalently given by:
&
𝐼3 = ∑" 𝑧"! 𝐶"#$ 2" Q V#$%&'() 2 V#$%&'()
!
𝛼= W 5X Y34 */"
𝑎𝑛𝑑 𝛽 =
Y34/5
It can be shown that 𝐼3 ≈ 𝐼2 𝜌-./$,01 (𝜌-./$,01 is the
density of the solvent) 20
 − 𝑧; 𝑧% 𝛼 𝐼9
Special Cases 3) Hückel Law ln 𝛾± =
1 + 𝐵𝑎 𝐼9
+ 𝛽𝐼

Note that the ac8vity coefficient decreases with increasing

1) In the dilute limit, i.e., in the limit of 𝐼9 → 0 concentra8on. However, this was experimentally found to
be obeyed at low concentra8ons.
ln 𝛾" = −𝑧"5𝛼 𝐼T At higher solute concentra8ons, ac8vity coefficient was
found to increase with increasing solute concentra8on.
This expression is commonly referred to as the Debye- Hückel proposed a modifica8on to the Debye-Hückel
expression based on this observa8on:
Hückel limi-ng law.
2) Activity coefficients for Binary Solutions
All ionic compounds dissociate into complementary ions and
therefore measuring individual ion ac8vi8es is nearly impossible
and also not useful. Therefore, define a geometric mean ac8vity
coefficient (𝜈’s are the stoichiometries of each of the ions)
^ _^ ^
𝛾±, - = 𝛾_ , 𝛾0^-

The ac;vity coefficient can then be wri=en down as:

− 𝑧5𝑧( 𝛼 𝐼2
ln 𝛾± =
1 + 𝐵𝑎 𝐼2 21
Ac.vity Coefficient for a Solvent
Note that so far we have only calculated the ac7vity coefficients for the solute
species. How about the changes in the ac7vity of the solvent?

One could use the Gibbs-Duhem equa7on at constant temperature and pressure
i.e.,:
# 𝑁" 𝑑𝜇" = 0 𝑜𝑟 # 𝐶" 𝑑𝜇" = 0
" "

0j
Therefore, 𝑑𝜇fgR/Qhi = k ∑"lfgR/Qhi 𝐶" 𝑑𝜇"
#$%&'()

The above differen7al equa7on can be solved to get the chemical poten7al for the
solvent.
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Limita5ons of Debye-Hückel Theory
1. Agreement with experiments only at high dilu7ons
2. Considers only long-range electrosta7c interac7ons: interac7ons such as ion-
pairing, ion-solvent interac7ons (solva7on shells) are ignored.
3. Local varia7ons in the dielectric constant of the solvent is ignored: A solu7on’s
dielectric constant need not necessarily be close to that of the solvent.
Especially so at high concentra7ons
4. A major assump7on is that the term 𝑧" 𝐹𝜙⁄𝑅𝑇 ≪ 1. This approxima7on fails in
the close vicinity of r=a since 𝜙 = 𝑧E 𝑒⁄4𝜋𝜖𝑎. Further, this approxima7on fails
in solvents with low dielectric constant
5. S7ll a good approxima7on, especially at large dilu7ons and at distances further
away from r=a.

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Key Learnings

1) Electrosta9c interac9ons in electroly9c solu9ons are responsible

for large devia9ons from ideality.
2) At low dilu9ons, ac9vity coefficients decrease with increasing
concentra9on of solute.
3) Debye-Hückel theory can be used to approximate ac9vity
coefficients and associated thermodynamics proper9es,
especially in dilute solu9ons.
Do you think that you can answer this ques9on? “Would the heat of dissolu9on be
iden9cal for a dilute solu9on of, let us say, 1 mM sugar in water and 1 mM NaCl in
water?”
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