UC202: Thermodynamics and Electrochemistry

Introduction to Electrolytes and

Debye-Hückel Theory

Reading: Chapter 2, D R Crow.

1
Objec9ves:
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.

2
What is an electrolyte? : A charge neutral substance which
dissociates into charged species when dissolved in a solvent
thereby making the solution electrically conductive.

Note: Dissolution is not Dissociation! Eg: Table salt (NaCl) is an

electrolyte, but sugar is not! Both dissolve in water but only
NaCl dissociates into its constituent ions upon dissolution

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

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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 Potential 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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Debye-Hückel Theory
How do interacFons between charged species change chemical
potenFals?
A quesFon that we would like to answer by the end of our discussion
on Debye-Hückel theory:

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

soluFons.

- For example, would the heat of dissoluFon be idenFcal for a dilute

soluFon of, let us say, 1 mM sugar in water and 1 mM NaCl in
water?
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Debye-Hückel Theory: Introduction
• Proposed by Peter Debye and Erich Hückel to explain deviations from ideality in
electrolyte solutions
• A reasonably good approximation to predict the activities (activity coefficients) of
ionic species in electrolyte solutions
• Based 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 solutions
• The local ion concentra7on near a central
Where, 𝜖 is the permittivity of the medium
∅ 𝑟 =
𝑧! 𝑒 (𝜖 = 𝜖" 𝜖# ), 𝜖" is the permittivity of vacuum ion will be different from the average
4𝜋𝜖𝑟 and 𝜖# is the relative permittivity 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 concentra;on of an ith ion in the vicinity of the central ion • The local ion concentration near a central
ion will be different from the average
01! 2∅
𝐶" = ./
𝐶" 𝑒 34 concentration
• Ions of like charge will be repelled and
−𝜌 opposite charge will be attracted to the
∇5∅ = (Poisson’s equa;on) --- 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 distribution.
= 9 𝑧$ 𝐶$ --- II
𝜖 𝜖 $
• The concentration in the vicinity of a
central ion can be approximated by a
Boltzmann distribution.
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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 rewriIen in spherical coordinates as:

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

Comparing LHS and RHS of the above equa;on, the term in the RHS
(excep;ng ∅) has the dimensions of L-2. We define this as 𝜆 the Debye
length – a characteris;c length scale over which the poten;al decays
by a factor of 1/e. (we will see this aTer the differen;al equa;on is
solved)
&%
𝜖𝑅𝑇 !
𝜆=
𝐹 ! ∑" 𝑧"! 𝐶"#$
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 The Debye length
With the defini;on of 𝜆 given in the previous slide, the
differen;al equa;on can be rewriIen as:

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

Integration 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 solution 𝑧E 𝑒 𝑒 I
∅=
to ∅ is:
4𝜋𝜖𝑟 1 + 𝑎=𝜆
Ionic distribution in the
vicinity of a central ion can 01! 2∅
./
be obtained. 𝐶" = 𝐶" 𝑒 34
Using the above equation
in conjunction 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) Electrolytic solutions have local charge distributions that are in

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

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Chemical Poten8al Changes Due to Electrosta8c
Interac8ons
• We are only interested in contributions to
How do we calculate contribu7ons to non-ideality from electrostatic
electrosta7c interac7ons alone?
interactions in a solution with
concentration Ci.
- • We discharge Ni ions in a reservoir,
reversibly, (corresponding to a

+
- concentration Ci), transfer them to the
Reservoir
Solvent solvent and recharge them to their
+ charge state.
• The net work done in this process should
be electrostatic component of the
chemical potential. 16
 Chemical Potential Changes Due to Electrostatic
Interactions
• The net work done for discharging (charging)
𝑧+ 𝑒 will be the electrostatic work for removing
∅ 𝑟=𝑎 ),-,)$.") = ---- I
4𝜋𝜖𝑎
(adding) a charge, at a distance r=a from (to)
For an ion in the reservoir, the ions are so far apart that their the ion center to (from) a distance infinitely
potential profile is that of an isolated ion in a background
dielectric. Here, 𝜖 is the permittivity of the medium (𝜖 = away from the ion center.
𝜖" 𝜖# ), 𝜖" is the permittivity of vacuum and 𝜖# is the relative
permittivity of dielectric constant of the medium. • In order to do this reversibly, we add or
remove an infinitesimally small amount of
𝑧+ 𝑒𝑥 1
∅ 𝑟=𝑎 = 5 ------ II charge, x.
-./$,01
4𝜋𝜖𝑎 1 + 𝑎>𝜆
• And since we are not interested in the
For an ion in the solvent system of interest, the poten;al is chemical contributions to non-ideality, we
affected by the ion cloud and we therefore use the electrosta;c
poten;al at r=a as calculated earlier. might as well assume that the transfer of
neutral species is ideal.
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Chemical Poten8al Changes Due to Electrosta8c
Interac8ons
Solving the integral gives:
The total work done for transferring all Ni ions, involves
charging all ions in solution 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):
123
𝜇$,./ = 𝑁0 ∫12" ∅45/,.67 − ∅#.4.#,5$# 𝑑𝑞 No;ng that we have assumed that the only contribu;on
to non-ideality is from electrosta;c interac;ons, this
contribu;on can be totally accounted for in the ac;vity
The frac;onal charge dq is the total charge on the
coefficient, i.e., :
ion ;mes the frac;onal change dx. Here e is the
𝜇",QR = 𝑅𝑇 ln 𝛾"
electronic charge
Therefore,
𝑑𝑞 = 𝑧$ O 𝑒 O 𝑑𝑥

The integral can be solved using the expressions for

−𝑧"5𝐹𝑒 1
ln 𝛾" =
∅’s given in equations I and II in the previous slide 8𝜋𝜖𝜆𝑅𝑇 1 + 𝑎=𝜆
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 Debye Length and Ionic Strength
Previously, we derived an expression for Debye Length: We can rewrite the expression for activity coefficient
&%

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 rela;ve strength of electrosta;c interac;ons: 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 concentra;on
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) 19
 − 𝑧; 𝑧% 𝛼 𝐼9
Special Cases 3) Hückel Law ln 𝛾± =
1 + 𝐵𝑎 𝐼9
+ 𝛽𝐼

Note that the activity coefficient decreases with increasing

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

The activity coefficient can then be written down as:

− 𝑧5𝑧( 𝛼 𝐼2
ln 𝛾± =
1 + 𝐵𝑎 𝐼2 20
Ac8vity Coefficient for a Solvent
Note that so far we have only calculated the activity coefficients for the solute
species. How about the changes in the activity of the solvent?

One could use the Gibbs-Duhem equation 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 differential equation can be solved to get the chemical potential for
the solvent.
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Limitations 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) Electrostatic interactions in electrolytic solutions are responsible

for large deviations from ideality.
2) At low dilutions, activity coefficients decrease with increasing
concentration of solute.
3) Debye-Hückel theory can be used to approximate activity
coefficients and associated thermodynamics properties,
especially in dilute solutions.
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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