Physical Chemistry 2

Chapter 7: Solutions of Electrolytes

Dr Mohammed Alomari
In this chapter
• 7.1 Faraday’s law of electrolysis,
• 7.2 Molar conductivity,
• 7.3 Weak electrolytes: Arrhenius theory. Ostwald’s dilution law,
• 7.4 Strong Electrolytes, Debye-Hückel theory,
• 7.5 Independent Migration of ions,
• 7.6 Transport numbers,
• 7.7 Ion conductivities,
• 7.8 Thermodynamics of Ions
• 7.10 Activity coefficients,
• 7.11 Ionic equilibria.
7.1 Faraday's Laws of Electrolysis
• Faraday's first law: The mass of an
element produced at an electrode is
proportional to the quantity of
electricity Q passed through the liquid;
the SI unit of Q is the coulomb (C).
The quantity of electricity is defined as
equal to the current I {SI unit=
ampere, A) multiplied by the time t
{SI unit = second, s):

𝑄 = 𝐼𝑡
• Faraday’s second law: The mass of
an element liberated at an electrode is
proportional to the equivalent weight
of the element.
• The modern practice is to speak
atomic mass instead of equivalent Na+ + e- → Na(s)
weight
7.1 Faraday's Laws of Electrolysis
• Charge of 1 e- = 1.602 x 10-19 C
• Charge of one mole of electrons= 𝟔. 𝟎𝟐𝟑 × 𝟏𝟎𝟐𝟑 𝑚𝑜𝑙 −1 × 𝟏. 𝟔𝟎𝟐 × 𝟏𝟎−𝟏𝟗 C = 𝟗𝟔𝟒𝟖𝟓 C𝑚𝑜𝑙 −1 =
𝟏. 𝟎 𝑭 (𝑭𝒂𝒓𝒂𝒅)
• Suppose, for example, that we pass 1 A of electricity for 1 h through a solution of silver nitrate, AgNO3 the
masses liberated at the cathode is 4.025 g Ag (atomic mass = 107.9 g/mol)
Ag+ + e- → Ag(s)
4.025
𝑚𝑜𝑙 𝐴𝑔 = = 3.73 × 10−2 𝑚𝑜𝑙
107.9
This is the same amount of charge
𝐼𝑡 1(𝐴) × 3600(𝑠)
𝑚𝑜𝑙 𝑒− = = = 3.73 × 10−2 𝑚𝑜𝑙
𝐹 96485
• However copper (II) sulfate, CuSO4. The mass liberated at the respective cathode is 1.186 g of Cu
Cu2+ + 2e- → Cu(s)
1.186
𝑚𝑜𝑙 𝐶𝑢 = = 1.865 × 10−2 𝑚𝑜𝑙
63.6
𝐼𝑡 1(𝐴) × 3600(𝑠)
𝑚𝑜𝑙 = = = 1.865 × 10−2 𝑚𝑜𝑙
𝒛𝐹 2 × 96485
𝑸
• Where z is the charge of ion 𝒎𝒐𝒍 = 𝒛𝑭
Example 7.1
An aqueous of gold (III) nitrate Au(NO3)3 was electrolyzed with a current of 0.025 A until 1.200 grams of Au (atomic mass
197 g/mol) has been deposited at cathode. Calculate
A) Quantity of electricity passed?
B) The duration of the experiment?
C) The volume of O2 (at NSTP) liberated at the anode? (NSTP New standard temperature and pressure: 25.0 °C and 1 bar)
𝑨𝒖𝟑+ −
(𝒂𝒒) + 𝟑𝒆 → 𝑨𝒖(𝒔)
𝒎𝒂𝒔𝒔 𝟏.𝟐
a) 𝒎𝒐𝒍𝒆 𝒐𝒇 𝑨𝒖 = = 𝟏𝟗𝟕 = 𝟔. 𝟎𝟗 × 𝟏𝟎−𝟑 𝒎𝒐𝒍
𝒂𝒕𝒐𝒎𝒊𝒄 𝒎𝒂𝒔𝒔
𝑸 = 𝒛𝑭 × 𝒎𝒐𝒍 = 𝟑 × 𝟗𝟔𝟒𝟖𝟓 × 𝒎𝒐𝒍𝒆 𝒐𝒇 𝑨𝒖 = 1763 C
𝑄 1763
b) 𝑡 = 𝐼
= 0.025 = 70511 𝑠 = 19.6 ℎ
c) At anode : 𝟐𝑯𝟐 𝑶 → 𝑶𝟐 +𝟒𝑯+ + 𝟒𝒆−
𝟏 ′
𝟏 𝟏𝟕𝟔𝟑
𝒎𝒐𝒍 𝑶𝟐 = 𝒎𝒐𝒍 𝒆 𝒔 = × = 𝟒. 𝟓𝟕 × 𝟏𝟎−𝟑 𝒎𝒐𝒍
𝟒 𝟒 𝟗𝟔𝟒𝟖𝟓
𝑷𝑽 = 𝒏𝑹𝑻
𝒏𝑹𝑻 𝟒. 𝟓𝟕 × 𝟏𝟎−𝟑 × 𝟖. 𝟑𝟏𝟒𝟓 × 𝟐𝟗𝟖. 𝟏𝟓
𝑽= = 𝟓
= 𝟏. 𝟏𝟑 × 𝟏𝟎−𝟒 𝒎𝟑 = 𝟎. 𝟏𝟏𝟑 𝑳
𝑷 𝟏 × 𝟏𝟎
7.2 Molar Conductivity
• A solution of sodium chloride or acetic acid, on
the other hand, forms ions in solution and has a
much higher conductivity. These substances are
known as electrolytes.
• Strong electrolytes: occur almost entirely as
ions when they are in aqueous solution. Such as
NaCl(s) H2O Na+(aq) +Cl-(aq)
• Weak electrolytes: are present only partially as
ions (e.g., acetic acid in solution
CH3COOH (aq) ⇄ CH3COO-(aq) + H+(aq)
7.2 Molar Conductivity
• According to Ohm’s Law: 𝑽=𝑹 ×𝑰
𝑽 𝑽
𝑹= = 𝒖𝒏𝒊𝒕 𝑶𝒉𝒎 𝜴
𝑰 𝑨
• The electrical conductance (G)
𝟏 𝟏
𝑮= 𝒖𝒏𝒊𝒕 = = 𝛀−𝟏
𝑹 𝜴
= 𝑺 𝑺𝒊𝒆𝒎𝒆𝒏𝒔 𝒐𝒓 𝒎𝑺, 𝝁𝑺
• The electrical conductance of material of length l
and cross-sectional area A is proportional to A
and inversely proportional to l:
𝑨
𝑮=𝜿
𝒍
The proportionality constant k, which is the conductance of
a unit cube is known as the conductivity (formerly as the
specific conductivity);
 7.2 Molar Conductivity
• specific conductivity of a solution of an
electrolyte, it is known as the electrolytic
conductivity. Its SI unit is 𝛺−1 𝑚−1 (≡ S m-1),
but the unit more commonly used is
𝛺−1 𝑐𝑚−1 (≡ S cm-1).
• Molar conductivity: is defined as the
electrolytic conductivity k divided by
concentration c, 𝜅
𝚲=
𝒄
𝑺 𝑺
𝜿 𝒄𝒎 𝒄𝒎 𝑺 × 𝟏𝟎𝟎𝟎 𝒄𝒎𝟑 𝟏𝟎𝟎𝟎 𝑺. 𝒄𝒎𝟐
𝚲= = = = =
𝑪 𝒎𝒐𝒍 𝒎𝒐𝒍 𝒄𝒎 × 𝒎𝒐𝒍 𝒎𝒐𝒍
𝑳 𝟏𝟎𝟎𝟎 𝒄𝒎𝟑

1000 𝜅
𝚲= 𝒖𝒏𝒊𝒕 𝑺. 𝒄𝒎𝟐 𝒎𝒐𝒍−𝟏
𝒎𝒐𝒍
𝑪[ ]
𝑳
 −4 𝑆
Example: Acetic acid solution was found to have 𝜅 = 5.3 × 10
𝑐𝑚
at a concentration of 0.1 M, calculate 𝚲
𝟏𝟎𝟎𝟎 × 5.3 × 10−4
𝚲= = 𝟓. 𝟑 𝑺. 𝒄𝒎𝟐 𝒎𝒐𝒍−𝟏
𝟎. 𝟏
 Behavior of molar conductivity L with concentration
• The importance of the molar conductivity L is
that it gives information about the conductivity
of the ions produced in solution by 1 mol of a
substance.
• In all cases the molar conductivity diminishes as
the concentration is raised, and two patterns of
behavior can be distinguished.
• For strong electrolytes the molar conductivity falls
only slightly as the concentration is raised.
• For weak electrolytes produce fewer ions and
exhibit a much more pronounced fall of A with
increasing concentration, as shown by the lower
curve in the figure.
 Behavior of molar conductivity L with concentration
• We can extrapolate the curves back to zero
concentration and obtain a quantity known as Lo,
the molar conductivity at infinite dilution, or
zero concentration.
• With weak electrolytes this extrapolation is
unreliable, and an indirect method will be
explained later.
7.3 Weak Electrolytes: The Arrhenius Theory
• For weak electrolytes such that
𝐀𝐁 ⇌ 𝐀+ + 𝐁−
• At very low concentrations this equilibrium lies over to the right, and
the molar conductivity is close to Lo.
• As the concentration is increased, this equilibrium shifts to the left and
the molar conductivity decreases from Lo to a lower value L.
• The degree of dissociation, that is, the fraction of AB in the form (A+
,B-) which is denoted by the symbol a is given by:
𝚲
α= 𝒐
𝚲
Where L is the molar conductivity and Lo is the molar conductivity at
infinite dilution.
Colligative Properties:
• Van 't Hoff had found that the osmotic pressures of solutions of
electrolytes were always considerably higher than predicted by the
osmotic pressure equation for nonelectrolytes.
Π = 𝒊𝑀𝑅𝑇
where i is known as the van ' t Hoff factor.
• For strong electrolytes, such as
𝐍𝐚𝐂𝐥 → 𝐍𝐚+ + 𝑪𝒍− , i =2
𝐌𝐠𝐂𝐥𝟐 → 𝐌𝐠 𝟐+ + 𝟐𝑪𝒍− , i =3
𝐀𝐥𝐂𝐥𝟑 → 𝐀𝐥𝟑+ + 𝟑𝑪𝒍− , i =4

• For nonelectrolytes, such as

𝐔𝐫𝐞𝐚(𝒔) ⇌ 𝐔𝐫𝐞𝐚(𝒂𝒒) , i =1
Colligative Properties:
• For weak electrolytes the van 't Hoff factor i involves the degree of
dissociation.
For the reaction:
𝑨𝒏 𝑩𝒎 ⇌ 𝒏𝑨 + 𝒎𝑩 if we start with x mol of AnBm
1–a na ma
So i = 1 – a + (n+m) a if n+m = n
→ i=1–a+na
𝒊−𝟏
Finally 𝜶=
𝝊−𝟏
Colligative Properties:
• All other colligative properties can be treated as in osmotic pressure
∆𝑇𝑏 = 𝑖𝐾𝑏 𝑚 boiling point elevation
∆𝑇𝑓 = 𝑖𝐾𝑓 𝑚 Freezing point depression
Ostwald's Dilution Law
• For the equilibrium:
[𝐀+ ][𝐁− ]
AB ⇄ A+ + B- 𝑲𝒄 =
[𝐀𝐁]
• If n mole of AB is present in a volume V
AB ⇄ A+ + B-
amount present at equilibrium: n(1 – a) na na
𝒏(𝟏−𝜶) 𝒏𝜶 𝒏𝜶
Concentrations at equilibrium:
𝑽 𝑽 𝑽
𝒏𝜶Τ𝑽 𝟐 𝒏𝜶𝟐
𝒄𝜶𝟐
𝑲𝒄 = = =
𝒏(𝟏 − 𝜶) Τ𝑽 (𝟏 − 𝜶)𝑽 𝟏−𝜶
𝚲
But α=
𝚲𝒐
𝐜(𝚲Τ𝚲𝐨 )𝟐
𝐊𝐜 =
𝟏 − (𝚲Τ𝚲𝐨 )
 7.4. The following are the conductivities k of chloroacetic acid in aqueous solution at 25 °C and at various
concentrations c:

c/10-4 M 625 312.5 156.3 78.1 39.1 19.6 9.8

k/ mS cm-1 3.3188 2.26 1.51 1.00 0.64 0.4 0.24
1000 𝜅
𝚲= L/𝑺. 𝒄𝒎𝟐 𝒎𝒐𝒍−𝟏 53.1 72.4 96.8 127.7 164.0 205.8 249.2
𝑪

Plot Λ against c. If Λ° = 362 S cm2 mol–1, are these values in

accord with the Ostwald Dilution Law? What is the value of the
dissociation constant? (See also Problem 7.11.)
 c/10-4 M 625 312.5 156.3 78.1 39.1 19.6 9.8
k/ mS cm-1 3.3188 2.26 1.51 1.00 0.64 0.4 0.24
L/𝑺. 𝒄𝒎𝟐 𝒎𝒐𝒍−𝟏 53.1 72.4 96.8 127.7 164.0 205.8 249.2

𝐜(𝚲Τ𝚲𝐨 )𝟐
𝐊𝐜 =
𝟏 − (𝚲Τ𝚲𝐨 ) Kc 0.001575951 0.001563 0.001526 0.001502 0.001467 0.001468 0.00149

Kaverage = 0.001513045 = 1.5 x 10-3

 𝐜(𝚲Τ𝚲𝐨 )𝟐
Linearize 𝐊 𝐜 =
𝟏−(𝚲Τ𝚲𝐨 )
𝐊 𝐜 𝟏 − (𝚲Τ𝚲𝐨 ) = 𝐜(𝚲Τ𝚲𝐨 )𝟐
𝐊 𝐜 𝟏 − (𝚲Τ𝚲𝐨 )
𝐜=
(𝚲Τ𝚲𝐨 )𝟐
𝐊 𝐜 − 𝐊 𝐜 (𝚲Τ𝚲𝐨 ) 𝚲𝟐𝒐
𝐜=
𝚲𝟐
𝐊 𝐜 𝚲𝟐𝒐 − 𝐊 𝐜 𝚲𝚲𝐨
𝐜=
𝚲𝟐
𝐊 𝐜 𝚲𝟐𝒐
𝐜𝚲 = − 𝐊 𝐜 𝚲𝐨
𝚲
Plot of cL against 1/L gives slope = 𝐊 𝐜 𝚲𝟐𝒐 and intercept = 𝐊 𝐜 𝚲𝐨
7.4. The following are the conductivities k of chloroacetic acid in aqueous solution at 25 °C and at various
concentrations c: calculate Lo and Kc

c/10-4 M 625 312.5 156.3 78.1 39.1 19.6 9.8

k/ mS cm-1 3.3188 2.26 1.51 1.00 0.64 0.4 0.24
L/𝑺. 𝒄𝒎𝟐 𝒎𝒐𝒍−𝟏 53.1 72.4 96.8 127.7 164.0 205.8 249.2

cL 3.31875 2.2625 1.512984 0.997337 0.64124 0.403368 0.244216

1/L 0.018832392 0.013812 0.010331 0.007831 0.006098 0.004859 0.004013

𝐊 𝚲𝟐
𝐜𝚲 = 𝐜𝚲 𝒐 − 𝐊 𝐜 𝚲𝐨
𝐊 𝐜 𝚲𝟐𝒐 = 208.3256761
−𝐊 𝐜 𝚲𝐨 = − 0.6174748
𝚲𝐨 = 𝟑𝟑𝟕. 𝟒 𝑺. 𝒄𝒎𝟐 𝒎𝒐𝒍−𝟏
𝐊 𝐜 = 𝟏. 𝟖𝟑 × 𝟏𝟎−𝟑
7.4 Strong Electrolytes
• Ostwald Dilution Law is not applied for strong electrolyte.
Λ
• Degree of ionization ∝= from conductivity measurements were
Λ𝑜
𝒊−𝟏
different from those calculated from van’t Hoff factor ∝=
𝝊−𝟏
• Examining the absorption spectra of solutions of a number of strong
electrolytes (such as HNO3, HCl and H2SO4) and found no evidence
for the existence of undissociated molecules.
• The fall in L with increasing concentration must therefore, for strong
electrolytes, be attributed to some cause other than a decrease in the
degree of dissociation.
Debye-Hückel Theory
• The decrease in the molar conductivity of a strong electrolyte was
attributed to the mutual interference of the ions, which becomes more
pronounced as the concentration increases.
• Because of the strong attractive forces between ions of opposite signs,
the arrangement of ions in solution is not completely random.
• In the immediate neighborhood of any positive ion, there tend to be
more negative than positive ions, whereas for a negative ion there are
more positive than negative ions.
Debye-Hückel Theory
The distribution of chloride ions around a sodium ion

in the crystal lattice in a solution of sodium chloride

In the solution the interionic distances are greater, and the distribution is not so regular; but
near to the sodium ion there are more chloride ions than sodium ions.
 Debye-Hückel Theory
1. Relaxation Effect:
• The ionic atmosphere around a moving
ion is not symmetrical; in the ionic
atmosphere, ions behind it are relaxing A stationary central positive ion with a spherically
symmetrical ion atmosphere.
while that in the front are building up.
• The relaxation force is given by:
𝒆𝟐 𝒁𝒊 𝜿
𝒇𝒓 = 𝒘𝑽′
𝟐𝟒𝝅𝜺𝑶 𝜺𝒌𝑩 𝑻
where V' is the applied potential gradient and
w is a number whose magnitude depends on
the type of electrolyte; for a uni-univalent
electrolyte, w is 2 - 2 = 0.586.
A positive ion moving to the right. The ion atmosphere
behind it is relaxing, while that in front is building up. The
distribution of negative ions around the positive ion is now
asymmetric
Debye-Hückel Theory
2. Electrophoretic Effect:
• Ionic atmosphere is attracted to
solvent molecules mainly by ion-
dipole interaction, therefore when
they move they drag solvent along
with them,
the electrophoretic force is given by:
𝒆𝒁𝒊 𝜿
𝒇𝒆 = 𝑲𝒄 𝑽′
𝟔𝝅𝜼
where Kc is the coefficient of frictional
resistance of the central ion with
reference to the solvent and h is the
viscosity of the medium..
Thickness of the Ionic Atmosphere
• The thickness of the ionic
atmosphere (1/k) is given by:
𝟏/𝟐
𝟏 𝜺𝑶 𝜺𝒌𝑩 𝑻
= 𝟐
𝜿 𝒆 σ𝒊 𝑪𝒊 𝒁𝟐𝒊 𝑳
Where:
−𝟏𝟐 𝑪𝟐
T= 25 oC (298.15 K), 𝜺 = 𝟕𝟖, 𝜺𝑶 = 𝟖. 𝟖𝟓𝟒 × 𝟏𝟎 𝑵.𝒎𝟐
𝑱
𝒌𝑩 = 𝟏. 𝟑𝟖 × 𝟏𝟎−𝟐𝟑 𝑲 , 𝒆 = 𝟏. 𝟔𝟎𝟐 × 𝟏𝟎−𝟏𝟗 𝑪
𝑳 = 𝟔. 𝟎𝟐𝟑 × 𝟏𝟎𝟐𝟑 𝒎𝒐𝒍−𝟏

Ci : the concentration of ions

Zi : the ionic valencies
Example 7.3
Estimate the thickness of the ionic atmosphere for a solution of: (a) 0.01 M NaCl; (b) 0.001 M ZnCl2
(a) 0.01 M NaCl
𝐍𝐚𝐂𝐥 → 𝐍𝐚+ + 𝑪𝒍−
𝟎. 𝟎𝟏 𝐌 𝟎. 𝟎𝟏 𝐌 𝟎. 𝟎𝟏 𝑴,
σ𝒊 𝑪𝒊 𝒁𝟐𝒊 = 𝟎. 𝟎𝟏 +𝟏 𝟐
+ 𝟎. 𝟎𝟏 −𝟏 𝟐
= 𝟎. 𝟎𝟐 𝐦𝐨𝐥Τ𝐝𝐦𝟑
𝟏/𝟐
𝟏 𝜺𝑶 𝜺𝒌𝑩 𝑻
=
𝜿 𝒆𝟐 σ𝒊 𝑪𝒊 𝒁𝟐𝒊 𝑳

𝟏 𝟖. 𝟖𝟓𝟒 × 𝟏𝟎−𝟏𝟐 × 𝟕𝟖 × 𝟏. 𝟑𝟖 × 𝟏𝟎−𝟐𝟑 × 𝟐𝟗𝟖. 𝟏𝟓

=( 𝟑 )𝟏/𝟐 = 𝟑. 𝟎𝟑 × 𝟏𝟎−𝟗 𝒎 = 𝟑. 𝟎𝟑 𝒏𝒎
𝜿 𝒎𝒐𝒍 𝟏𝟎𝟎𝟎 𝒅𝒎
(𝟏. 𝟔𝟎𝟐 × 𝟏𝟎−𝟏𝟗 )𝟐 𝟎. 𝟎𝟐 𝟑 × 𝟑 × 𝟔. 𝟎𝟐𝟑 × 𝟏𝟎𝟐𝟑
𝒅𝒎 𝟏𝒎
(b) 0.001 M ZnCl2
𝐙𝐧𝐂𝐥𝟐 ⇌ 𝐙𝐧𝟐+ + 𝟐𝑪𝒍−
𝟎. 𝟎𝟎𝟏 𝐌 𝟎. 𝟎𝟎𝟏 𝐌 𝟎. 𝟎𝟎𝟐𝑴

෍ 𝑪𝒊 𝒁𝟐𝒊 = 𝟎. 𝟎𝟎𝟏 +𝟐 𝟐 + 𝟎. 𝟎𝟎𝟐 −𝟏 𝟐 = 𝟎. 𝟎𝟎𝟔 𝐦𝐨𝐥Τ𝐝𝐦𝟑

𝒊
𝟏
= 𝟓. 𝟓𝟑 𝒏𝒎
𝜿
 Debye-Hückel -Onsager Equation
𝜦 = Λ𝑜 − 𝑷 + 𝑸Λ𝑜 𝒄
based on the assumption of complete
dissociation (Strong Electrolyte); such
as NaCl and AgNO3.
P and Q are constant
• For aqueous solutions of uni-univalent
electrolytes, the theoretical equation is
found to be obeyed very satisfactorily
up to a concentration of about 2 x 10-3
mol dm-3; at higher concentrations,
deviations are found.
7.5 Independent Migration of ions
• Kohlraush’s law of independent migration of ions:
𝚲𝒐 = 𝝀𝒐+ + 𝝀𝒐−
where 𝝀𝒐+ and 𝝀𝒐− are the ion conductivities of cation and anion, respectively, at infinite dilution.
𝚲𝒐 𝑲𝑪𝒍 = 𝝀𝒐𝒌+ + 𝝀𝒐𝑪𝒍− = 𝟏𝟒𝟗. 𝟗 𝑺. 𝒄𝒎𝟐 𝒎𝒐𝒍−𝟏
𝚲𝒐 𝑵𝒂𝑪𝒍 = 𝝀𝒐𝑵𝒂+ + 𝝀𝒐𝑪𝒍− = 𝟏𝟐𝟔. 𝟓 𝑺. 𝒄𝒎𝟐 𝒎𝒐𝒍−𝟏
The difference, 23.4 S cm2 mol-1, is thus the difference between the 𝝀𝒐+ values for K+ and Na+ :
𝝀𝒐𝒌+ − 𝝀𝒐𝑵𝒂+ = 𝟐𝟑. 𝟒 𝑺. 𝒄𝒎𝟐 𝒎𝒐𝒍−𝟏
and this will be the same whatever the nature of the anion.
 Ionic Mobilities
• Mobility of an ion (u+) is defined as the speed
with which the ion moves under a unit potential
gradient (in an electrical field). 𝒎
𝑺𝒑𝒆𝒆𝒅
𝑼𝒏𝒊𝒕 𝒐𝒇 𝒎𝒐𝒃𝒊𝒍𝒊𝒕𝒚 = = 𝒔 = 𝒎𝟐 𝑽−𝟏 𝒔−𝟏
𝑷𝒐𝒕𝒆𝒏𝒕𝒊𝒂𝒍 𝑮𝒓𝒂𝒅𝒊𝒂𝒏𝒕 𝑽
𝒎
More common 𝒄𝒎𝟐 𝑽−𝟏 𝒔−𝟏
• The electric conductivity due to positive ion (𝜿+ )
𝑪𝒖𝒓𝒓𝒆𝒏𝒕 𝒛+ 𝑭𝒖+ 𝑽𝒄+
𝜿+ = =
𝑷𝒐𝒕𝒆𝒏𝒕𝒊𝒂𝒍 𝒅𝒓𝒐𝒑 𝑽
𝜿+ = 𝒛+ 𝑭𝒖+ 𝒄+
• But
𝜿+ 𝒛+ 𝑭𝒖+ 𝒄+
𝝀𝒐+ = = = 𝒛+ 𝑭𝐮+
𝒄+ 𝒄+
Example:
The mobility of sodium ion 𝐮𝑵𝒂+ = 𝟓. 𝟏𝟗 × 𝟏𝟎−𝟒 𝒄𝒎𝟐 𝑽−𝟏 𝒔−𝟏 at 25 oC,
calculate the molar conductivity:
V=I R, (V=A.𝛀 )
𝑨.𝒔 𝒄𝒎 𝟐 𝑨.𝒄𝒎𝟐
𝝀𝒐+ = 𝒛+ 𝑭𝐮+ = 𝟗𝟔𝟒𝟖𝟓 × 𝟓. 𝟏𝟗 × 𝟏𝟎 −𝟒 = 𝟓𝟎. 𝟏 =
𝒎𝒐𝒍 𝑽.𝒔 𝑽.𝒎𝒐𝒍
𝒄𝒎𝟐
𝟓𝟎. 𝟏 = 𝟓𝟎. 𝟏 𝑺. 𝒄𝒎𝟐 𝒎𝒐𝒍−𝟏
𝛀.𝒎𝒐𝒍
7.6 Transport number (migration number)
• The fraction of the current carried by each ion present in solution.
Consider an electrolyte of formula 𝑨𝒂 𝑩𝒃 , which ionizes as follows:
𝑨𝒂 𝑩𝒃 𝒂𝑨𝒁+ + 𝒃𝑩𝒁−
𝒂𝑭𝒛+ 𝒖+ 𝑭(𝒂𝒛+ 𝒖+ ) 𝒂𝒛+ 𝒖+
𝒕+ = = =
𝒂𝑭𝒛+ 𝒖+ +𝒃𝑭𝒛− 𝒖− 𝑭(𝒂𝒛+ 𝒖+ +𝒃𝒛− 𝒖− ) 𝒂𝒛+ 𝒖+ +𝒃𝒛− 𝒖−
• Similarly, the transport number of the negative ions is
𝒃𝒛− 𝒖−
𝒕− =
𝒂𝒛+ 𝒖+ + 𝒃𝒛− 𝒖−
In order to have electrical neutrality 𝒂𝒁+ = 𝒃 𝒁−
𝐮+
𝒕+ =
𝐮+ + 𝐮−
𝐮−
𝒕− =
𝐮+ + 𝐮−
Also for electrolyte of formula 𝑨𝒂 𝑩𝒃 , which ionizes as
follows:
𝑨𝒂 𝑩𝒃 𝒂𝑨𝒁+ + 𝒃𝑩𝒁−
𝒂𝝀+
𝒕+ =
𝚲𝑨𝒂 𝑩𝒃
𝒃𝝀−
𝒕− =
𝚲𝑨𝒂 𝑩𝒃

Exercise: Use the table in slide 30 to calculate the transport

numbers of the Li+ and Cl- ions in LiCl solution.
7.7 Ion Conductivities
𝚲𝒐 = 𝝀𝒐+ + 𝝀𝒐−
• For acetic acid from the values in Table 7.3 the value of 𝚲𝒐 = 349.8 + 40.9 = 390.7
S cm-2 mol-1.
• alternative procedure avoids the necessity of splitting the 𝚲𝒐 values into the
individual ionic contributions. The molar conductivity 𝚲𝒐 of any electrolyte MA
can be expressed, for example, as
𝚲𝒐 (𝑴𝑨) = 𝚲𝒐 (𝑴𝑪𝒍) + 𝚲𝒐 (𝑵𝒂𝑨) −𝚲𝒐 (𝑵𝒂𝑪𝒍)
Example:
𝚲𝒐 𝑪𝑯𝟑 𝑪𝑶𝑶𝑯 = 𝚲𝒐 𝑯𝑪𝒍 + 𝚲𝒐 𝑪𝑯𝟑 𝑪𝑶𝑶𝑵𝒂 −𝚲𝒐 𝑵𝒂𝑪𝒍
= 𝟒𝟐𝟔. 𝟐 + 𝟗𝟏. 𝟎 − 𝟏𝟐𝟔. 𝟓 = 𝟑𝟗𝟎. 𝟕 𝑺. 𝒄𝒎𝟐 𝒎𝒐𝒍−𝟏
• This procedure is also useful for a highly insoluble salt, for which direct
determinations of 𝚲𝒐 values might be impractical.
7.8 Thermodynamics of Ions
• We cannot, carry out experiments on ions of one kind.
• The conventional procedure is to set the ΔH°f, ΔH°hyd, ΔG°f, ΔG°hyd,
ΔS°f and ΔS°hyd values for H+ to zero.
Where:
ΔH°f : Standard molar enthalpy of formation.
ΔH°hyd : Standard molar enthalpy of hydration.
ΔG°f : Standard molar Gibbs energy of formation.
ΔG°hyd : Standard molar Gibbs energy of hydration.
ΔS°f : Standard molar entropy of formation.
ΔS°hyd : Standard molar entropy of hydration.
Absolute Procedure
• Absolute thermodynamic values can’t be measured directly
but can be estimated on the basis of theory.
For H+ ion:
ΔH°hyd (absolute ) = - 1090.8 KJ/mol
ΔS°hyd (absolute ) = - 131.8 J/mol.K
ΔG°hyd (absolute) = - 1051.4 KJ/mol

Absolute values for the other ions can be calculated

using their conventional values.
 Example
• Calculate the absolute enthalpy of hydration of Li+, I- and
Ca2+ on the basis of a value of -1090.8 KJ/mol for the proton
(H +), using the values listed in Table 7.4.
• Answer: Since we are given the absolute enthalpy of
hydration of H+ we need to form an ionic compound with I-
➔ HI
H+ I- Total
Conventional 0 -1397 -1397
Absolute -1090.8 X -1090.8 + X

-1397 = -1090.8 + X ➔ X=-306.2 KJ/mol

= ΔH°hyd (absolute) for I-
• For Li+: Since now we’ve calculated the absolute enthalpy
of hydration of I- we can form an ionic compound with Li+
➔ LiI

Li+ I- Total
Conventional 576.1 -1397 -820.9
Absolute X -306.2 -306.2 + X

-820.9 = -306.2 + X ➔ X=-514.7 KJ/mol

= ΔH°hyd (absolute) for Li+
• For Ca2+: Since now we’ve calculated the absolute enthalpy
of hydration of I- we can form an ionic compound with Ca2+
➔ CaI2
Ca2+ 2I- Total
Conventional 589.1 2(-1397)=-2794 -2204.9
Absolute X 2(-306.2)=-612.4 -612.4 + X

-2204.9 = -612.4 + X ➔ X=-1592.5 KJ/mol

= ΔH°hyd (abs.) for Ca2+
7.10 Activity coefficients
• Coulomb interaction between ions causes the
non-ideal behavior of ionic solutions. Opposite charges attract each
other. Thus it is more likely that anions are found closely to cations
and vice versa.
• An ideal solution is a solution whose colligative properties are
proportional to the concentration of the solute. Real solutions show
departures from this kind of ideality.
• The concept of activity: the properties are proportional to the
activities of the ions. Activity is proportional to concentration, The
proportionality constant is known as an activity coefficient (γ) ➔
(activity, a) = (concentration, c) (activity coefficient γ)
𝒂𝒊 = [𝒄𝒊 ]𝜸𝒊
Where 𝜸𝒊 is the activity coefficient
Debye-Hückel Limiting Law (DHLL)
• Therefore:
AgCl ⇌ Ag+ + Cl –
Solubility product Ksp = [Ag+][Cl –]
If we assume DHLL to apply then:
Ksp = [Ag+] γ+ [Cl –] γ- = [Ag+] [Cl –] γ±2
Where
γ+ : the activity coefficient of Ag+
γ- : the activity coefficient of Cl –
γ± : the mean activity coefficient (note: γ±2 = γ+ γ- )
Debye-Hückel Limiting Law (DHLL)
Experimentally, we cannot determine γi of a single ion.
𝐥𝐨𝐠𝛄± = −𝟎. 𝟓𝟏 𝒁− 𝒁+ 𝑰
This is called DHLL
where:
γ± : mean activity coefficient
Z+: charge on cation
Z-: charge on anion
I : ionic strength of solution

➔ We can calculate γ± from ionic strength I

Ionic Strength of a Solution (I)
• Ionic strength of a solution (I) is a measure of the electrical
intensity of a solution containing ions
(a measure of the total ion concentration in solution)
𝟏
𝑰= σ𝒊 𝑪𝒊 𝒁𝟐𝒊
𝟐
Examples:
What is ionic strength of 0.01 M NaCl solution?
1
I = (0.01 M Na+ . (1)2 + 0.01 M Cl- . (-1)2) = 0.01 M
2

What is ionic strength of 0.01 M Na2SO4 solution?

1
I = (0.02 M Na+ . (1)2 + 0.01 M SO42- . (-2)2) = 0.03 M
2
 Debye-Hückel Limiting Law (DHLL)
PbCl2 ⇌ Pb2+ + 2Cl –
Solubility product Ksp = [Pb2+][Cl –]2

If we assume DHLL to apply then:

Ksp = [Pb2+] γ+ [Cl –]2 γ-2 = [Pb2+][Cl –]2 γ±3

Debye-Hückel Limiting Law (DHLL)
• In General: for an electrolyte MxAy
γ±(x+y) = (γ+x)(γ-y)

Examples:
NaCl, CaSO4, KNO3, etc… γ±2 = (γ+1)(γ-1)
ZnCl2, PbCl2, Mg(OH)2, etc… γ±3 = (γ+1)(γ-2)
Na2CO3, K2SO4, Li2S, etc… γ±3 = (γ+2)(γ-1)
Na3PO4, K3PO3, Li3N, etc… γ±4 = (γ+3)(γ-1)
7.11 Ionic Equilibria
• For weak electrolytes (e.g. acetic acid):
CH3COOH ⇌ CH3COO- + H+
initially c 0 0
change -x +x +x
Equilibrium c-x x x
c-cα cα cα

(Degree of dissociation α=x/c➔x=cα)

[𝐶𝐻3𝐶𝑂𝑂 − ]𝑒𝑞 [𝐻 + ]𝑒𝑞
𝐾𝑒𝑞 =
[𝐶𝐻3𝐶𝑂𝑂𝐻]𝑒𝑞
If we assume DHLL to apply then:

[𝐶𝐻3𝐶𝑂𝑂 − ]𝑒𝑞 𝛾− [𝐻 + ]𝑒𝑞 𝛾+

𝐾𝑒𝑞 =
[𝐶𝐻3𝐶𝑂𝑂𝐻]𝑒𝑞
[𝐶𝐻3𝐶𝑂𝑂 − ]𝑒𝑞 [𝐻 + ]𝑒𝑞 𝛾±2 𝑐𝛼 2 2
𝐾𝑒𝑞 = = 𝛾±
[𝐶𝐻3𝐶𝑂𝑂𝐻]𝑒𝑞 𝑐 − 𝑐𝛼
 𝑐𝛼 2 2 𝐾𝑒𝑞 𝑐𝛼 2
𝐾𝑒𝑞 = 𝛾± ⟹ 2 =
𝑐 − 𝑐𝛼 𝛾± 1−𝛼
Take log of both sides➔
𝑐𝛼 2
log = log 𝐾𝑒𝑞 − 2log𝛾±
1−𝛼
From DHLL 𝐥𝐨𝐠𝛄± = −𝟎. 𝟓𝟏 𝒁− 𝒁+ 𝑰
𝑐𝛼 2
log = log 𝐾𝑒𝑞 + 𝟏. 𝟎𝟐 𝒁− 𝒁+ 𝑰
1−𝛼
If solution contains only acetic acid
𝟏 1
𝑰= σ𝒊 𝑪𝒊 𝒁𝟐𝒊 = (ca. (1)2 + ca . (-1)2)
𝟐 2
I = ca
Example: The solubility product of BaSO4 is 9.2 x 10-11 mol2 dm-6 . (A) Calculate the
mean activity coefficient of the Ba2+ and SO42- ions in a solution that is 0.05 M in
KNO3 and 0.05 M in KCl, assuming the Debye-Hückel limiting law to apply. (B)
What is the solubility of BaSO4 in that solution, (C) and in pure water?
Answer: (A) We have 3 electrolytes: KNO3 and KCl are strong electrolytes and BaSO4
is a weak electrolyte. In this case, ionic strength can be calculated using only strong
electrolytes and ignore the weak electrolyte.
All these ions contribute to ionic strength

0.05 M in KNO3 ➔ 0.05 M K+ + 0.05 M NO3-

0.05 M in KCl ➔ 0.05 M K+ + 0.05 M Cl-

1
I = [ 0.05 (1)2 + 0.05(-1)2 + 0.05(1)2 + 0.05(-1) 2 ]
2
= 0.1 M
To Calculate the mean activity coefficient, use DHLL:
𝐥𝐨𝐠𝛄± = −𝟎. 𝟓𝟏 𝒁− 𝒁+ 𝑰
We need to apply this law to the Ba2+ and SO42- ions:
So Z+ = +2 and Z - = -2

𝐥𝐨𝐠𝛄± = −𝟎. 𝟓𝟏 𝟐 𝟐 𝑰
= -0.645
➔ 𝛄± = 0.226
(B) BaSO4(s) ⇌ Ba2+ + SO42
s s where s = solubility (mol/L)
Ksp = [Ba2+] γ+[SO42] γ- = [Ba2+] [SO42] γ±2
Ksp = s2 γ±2
9.2 x 10-11 = s2 (0.226)2
➔ s = 4.24x10-5 M
(C) In pure water:
Ksp = [Ba2+] [SO42] = s2 ➔ 9.2 x 10-11 = s2 ➔ s = 9.6x10-6 M
(no DHLL)

(with DHLL)
1
I = [ (9.6x10-6)(2)2 + (9.6x10-6) (-2)2 ] = 3.84x10-5 M
2

𝐥𝐨𝐠𝛄± = −𝟎. 𝟓𝟏 𝒁− 𝒁+ 𝑰 = -0.51 (2) (2) 3.84x10−5

➔ γ± = 0.97

Ksp = s2 γ±2

➔ 9.2 x 10-11 = s2 (0.97) 2

➔ s = 9.87x10-6 M
Exercises
Example: Calculate the ionic strength of 0.1 M solutions of: KNO3,
K2SO4, ZnSO4 and K4Fe(CN)6
Answer:
1
IKNO3 = [0.1 x(1)2 + 0.1x(-1)2] = 0.1 M
2

1
IK2SO4 = [0.2 x(1)2 + 0.1 x(-2)2] = 0.3 M
2

1
IZnSO4 = [0.1 x(2)2 + 0.1 x(-2)2] = 0.4 M
2

1
IK4Fe(CN)6 = 2 [0.4 x(1)2 + 0.1 x(-4)2] = 1.0 M

Note: K4Fe(CN)6 ⇌ 4K+ + Fe(CN)64-

Exercises
Example: What concentration of the following have the same ionic strength as
0.1 M NaCl?
CuSO4, Ni(NO3)2, Al2(SO4)3 and Na3PO4
1
Answer: INaCl= [0.1 x(1)2 + 0.1x(-1)2] = 0.1 M
2
1
CuSO4 ➔ ICuSO4 = [c x(2)2 + c x(-2)2] = 0.1 M
2
4c=0.1 → c=2.5x10-2 M
1
Ni(NO3)2 ➔ INi(NO3)2 = [c x(2)2 + 2c x(-1)2] = 0.1 M
2
3c=0.1 → c=3.3x10-2 M
1
Al2(SO4)3 ➔ IAl2(SO4)3 = 2 [2c x(3)2 + 3c x(-2)2] = 0.1 M
→c=6.7x10-3 M
1
Na3PO4 ➔ INa3PO4 = [3c x(1)2 + c x(-3)2] = 0.1 M
2
→c=1.7x10-2 M
Example: The solubility product of PbF2 at 25°C is 4.0x10-9 mol3.dm-9.
Assuming the DHLL to apply., calculate the solubility of PbF2 in:
A) Pure water B) 0.01 M NaF
Answer: A) in pure water assuming DHLL to apply.
PbF2 ⇌ Pb2+ + 2F- Ksp= [Pb2+][F-]2
At equ. s 2s ∴ Ksp= s (2s)2 = 4s3 = 4.0x10-9
s=1.0x10-3 M
1
IPbF2= [s (2)2 + 2s (-1)2] where s= 1.0x10-3
2
IPbF2= 3.0 x10-3 M
𝐥𝐨𝐠𝛄± = −𝟎. 𝟓𝟏 𝒁− 𝒁+ 𝑰 = -0.51 (2)(1) 3.0 × 10−3
γ± = 0.879290
Ksp= [Pb2+] γ+ [F-]2 γ-2 = s (2s)2 γ±3 = 4s3 γ±3 = 4.0x10-9
➔ s = 1.1 x 10-3 M
Answer: B) in 0.01 M NaF assuming DHLL to apply
In 0.01 M strong electrolyte NaF, we calculate the ionic strength ignoring the
ions from weak electrolyte PbF2
1
INaF= [0.01 (1)2 + 0.01 (-1)2] = 0.01 M
2

Then we calculate the mean activity coefficient for PbF2

𝐥𝐨𝐠𝛄± = −𝟎. 𝟓𝟏 𝒁− 𝒁+ 𝑰 = -0.51 (2)(1) 0.01
γ± = 0.790678

Solubility product expression as in part A is given by:

(This is called a common ion effect) use [F-] = 0.01 M
Ksp= [Pb2+] γ+ [F-]2 γ-2 = s x 0.012 γ±3 = 4.0x10-9
➔ s = 8.1 x 10-5 M
Example: Calculate the mean activity coefficient for the Ba2+ and
SO42- ions in a saturated solution of BaSO4 (Ksp=9.2x10-11) in 0.2 M
K2SO4.
Answer: Ionic strength is obtained from the strong electrolyte K2SO4
.
1
IK2SO4 = [0.4 (1)2 + 0.2 (-2)2] = 0.6 M
2

𝐥𝐨𝐠𝛄± = −𝟎. 𝟓𝟏 𝒁− 𝒁+ 𝑰 = -0.51 (2)(2) 0.6

→ γ± = 2.6x10-2
Example: The solubility of AgCl in water is 1.274x10-5 M. On the
assumption that DHLL applies:
A) Calculate the ionic strength I
B) Calculate the mean activity coefficient γ±
C) Calculate the solubility product Ksp
D) Calculate ΔG° for the process AgCl(s)⇄Ag+(aq) + Cl -(aq)

Answer: A) Ionic strength comes from the Ag+ and Cl- ions in solution,
therefore:
AgCl(s)⇄Ag+(aq) + Cl -(aq)
s s (s=1.274x10-5 M as given in question)

1
IAgCl = [s (1)2 + s (-1)2] = 1.274x10-5 M
2
B) To calculate the mean activity coefficient for the Ag+ and Cl- ions, we
use the DHLL equation:

𝐥𝐨𝐠𝛄± = −𝟎. 𝟓𝟏 𝒁− 𝒁+ 𝑰 = -0.51 (1)(1) 1.274x10−5

→ γ± = 0.995

C) Calculate the solubility product Ksp:

AgCl⇄Ag+ + Cl –
s s (s=1.274x10-5 M as given in question)
Ksp = [Ag+][Cl–] γ±2 = s2 γ±2 = (1.274x10-5) 2 (0.995)2
→Ksp = 1.609x10-10
C)
ΔGo = -RTlnKsp
= - (8.314)(298.15)ln(1.609x10-10)
= 55900.51 J/mol
ΔGo = 55.90 kJ/mol
End of Chapter 7