C H A P T E R II : Generalities on Aqueous Solutions

plan
II.1. Study of solutions: classification of solutions
II.2. The concentrations and fractions: molarity, molality, osmolarity,
equivalent concentration, mass and molar fractions.
II.3. Solubility
II.4. Electrolyte solutions: electrical conductivity, physical and chemical
properties of electrolytes
Objective
1. Recognize basic notions about aqueous solutions
2. Learn how to calculate:
3. Concentrations
4. Fractions
5. Conductivity

II.1. STUDY OF SOLUTIONS

1.1. Introduction

An electrolytic solution is a homogeneous mixture (consisting of a single phase) resulting

from the dissolution of one or more solute (s) (dissolved chemical species) in a solvent. The
molecules (or ions) of solute are then solvated and dispersed in the solvent.

 Solvent: the material that exists in greater quantity.

 Solute: the material (materials) that exists in small quantities. If the solvent is water, the
solution obtained is called an aqueous solution.

It is noted that all the properties and the physicochemical characteristics of the aqueous
solutions are dependent on the nature of these substances.

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1.2. Classification of solutions

Solutions can be classified in several ways depending on the physical state, concentration,
solvent type and electrical behavior.

1. Based on Physical State of Solvent

 Gaseous solutions: Solute and solvent are gases. Example: Air (O₂, CO₂, etc. dissolved in
N₂).

 Liquid solutions: Solvent is liquid. Example: Salt in water, alcohol in water.

 Solid solutions: Solvent is solid. Example: Alloys (brass = Cu + Zn).

2. Based on Concentration of Solute

 Dilute solution: Contains small amount of solute relative to solvent.

 Saturated solution: Contains maximum solute at a given temperature.

 Unsaturated solution: Contains less solute than its solubility limit.

 Supersaturated solution: Contains more solute than theoretically possible; unstable.

3. Based on Solvent Type

 Aqueous solutions: Water is the solvent (e.g., NaCl in water).

 Non-aqueous solutions: Solvent is not water (e.g., iodine in alcohol).

4. Based on Electrical Conductivity

 Electrolytic solutions: Conduct electricity.

 Strong electrolytes: Fully ionize (e.g., NaCl in water).

 Weak electrolytes: Partially ionize (e.g., CH₃COOH in water).

 Non-electrolytic solutions: Do not conduct electricity (e.g., sugar in water).

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II. 2. Quantitative characteristics of solutions (concentration and
fraction)

A solution is obtained by dissolving one or more chemical species, called solutes, in a

solvent (usually water). The solute can be solid, liquid or gaseous, molecular or ionic.

2.1. Mass Concentration (Cmass)

The mass concentration of a solute in a solution is defined as the mass of solute per unit
volume of solution. It expresses how many grams of solute are present in a certain volume of
solution.
𝑚
𝐶 = … … … … … … … . (𝐼𝐼. 1)
𝑉

(msolute in g and V T in l)

2.2. Molar Concentration – molarity (Cmol)

The molar concentration (also called molarity) of a solution is defined as the amount of
substance (in moles) of solute per unit volume of solution.

𝑛
𝐶 = … … … … … … … . (𝐼𝐼. 2)
𝑉

Cmol : molar concentration (mol/l)

nsolute : number of moles of solute (mol)

VT : volume of solution (l)

Since the number of moles is related to the solute’s mass and molar mass:

𝑚
𝑛 = … … … … … … … … … … … (𝐼𝐼. 3)
𝑀

we can also write: 𝐶 =𝐶 𝑋𝑀 … … … . (𝐼𝐼. 4)

(C ma ss in g.l-1, C mo l in mol.l-1 et Ms o l u e in [Link]-1)

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2.3. Molal Concentration – molality (Cmolal)

It represents the amount of material of the dissolved chemical species per unit mass of solvent.
It is expressed in mol. Kg-1.

𝑛
𝐶 = … … … … … … … . (𝐼𝐼. 5)
𝑚

Example: (The solution during the lecture)

A solution contains 15 g of KOH (molar mass M=56 g/mol) dissolved in 500 ml of water.

Calculate:

1. The molar concentration Cmol.

2. The mass concentration Cmass.

3. The molality Cmolal (assuming the mass of water is 500 g).

2.4. Particulate molar concentration - Osmolarity (W)

The osmolarity of a solution is a measure of the total concentration of dissolved particles (ions
or molecules) in a solution. It is given by the number of particulate moles (non-dissociable
molecules or ions) per liter of solution:

𝑛
𝑊= ( 𝑂𝑠𝑚𝑜𝑙. 𝑙 ) … … … … … … … . (𝐼𝐼. 6)
𝑉

If the solute dissociates into several ions, osmolarity is calculated as:

𝑤=𝑖𝐶 … … … … … … … … (𝐼𝐼. 7)

W: osmolarity (osmol/l)

Cmol: molar concentration of solute (mol/l)

i: van’t Hoff factor (number of particles produced per formula unit of solute after dissociation). The
van't Hoff factor, i, can be connected with the degree of dissociation, α, in the following way.

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 𝑖 = 1 + 𝛼(𝛽 − 1)……………..(II.8)

where

𝛽: number of ions formed if dissociation were complete.

𝛼: Degree of Dissociation

The degree of dissociation α is the fraction of solute molecules that actually dissociate into
ions in solution.

𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑑𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑒𝑑 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠

𝛼= … … … … … … … . (𝐼𝐼. 9)
𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠

So:

 If α=0: no dissociation (non-electrolyte).

 If α=1: complete dissociation (strong electrolyte).

 If 0<α<1: partial dissociation (weak electrolyte).

Example 1: NaCl (strong electrolyte)

NaCl → Na⁺ + Cl⁻ → 𝛽=2.

For complete dissociation (α=1):

i=1+1(2−1) =2

Example 2: CH₃COOH (weak acid)

CH₃COOH ⇌ CH₃COO⁻ + H⁺ → 𝛽=2.

If only 30% dissociation (α=0.3):

i=1+0.3(2−1)=1.3

2.5. Equivalent concentration (Ceq)

The equivalent concentration (also called normality) is defined as the number of equivalents

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of solute per unit volume of solution.

𝑛
𝐶 = ( 𝐸𝑞. 𝑙 ) … … … … … … … . (𝐼𝐼. 10)
𝑉

𝑛 =𝑛 × 𝑍 … … … … … . . (𝐼𝐼. 11)

Z: depends on the reaction:

 For acid–base: number of H⁺ (or OH⁻) exchanged per mole.

 For redox: number of electrons transferred per mole in the reaction considered.

 For ions forming charge: can be the ionic charge when counting charge balancing (use with
care).

𝐶 (𝑖) = 𝐶 (𝑖). |𝑍 | (𝑒𝑞. 𝑙 ) … … … … … … … (𝐼𝐼. 12)

Cmol (i) is the molar concentration of the ion i in mol.l-1 and Zi is the valence of the ion i.
For a solution containing N ions, its equivalent concentration is:

𝐶 = 𝐶 (𝑖). |𝑍 | (𝑒𝑞. 𝑙 ) … … … … … … … (𝐼𝐼. 13)

Example: (The solution during the lecture)

Dissolve 4.90 g of NaOH (M = 40 g·mol⁻¹) in water to make 250 mL solution. Find the
normality (Ceq).

2.6. Fractions

1. Molar fraction

The molar fraction (fi) of a component (i) is expressed by the ratio of the number of molecular
moles (ni) of this component to the total number of moles (ntot) of the solution.

𝑛
𝑓 = … … … … … … … . (𝐼𝐼 . 14)
∑𝑛

𝑤ℎ𝑒𝑟𝑒 ∑ 𝒇𝒊 = 𝟏 (𝑤𝑖𝑡ℎ𝑜𝑢𝑡 𝑑𝑖𝑚𝑒𝑛𝑠𝑖𝑜𝑛)

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2. Mass fraction

If (mi) the mass of a constituent (i) of the solution. The mass fraction (wi) of this constituent is
given by the ratio of its mass to the total mass (mtot) of the solution.

𝑚
𝑤 = … … … … … … … . (𝐼𝐼 . 15)
∑𝑚

𝑤ℎ𝑒𝑟𝑒 ∑ w𝒊 = 𝟏 (𝑤𝑖𝑡ℎ𝑜𝑢𝑡 𝑑𝑖𝑚𝑒𝑛𝑠𝑖𝑜𝑛)

Example: (The solution during the lecture)

A solution is made by dissolving 20 g of NaOH (M = 40 g/mol) in 180 g of water.
1. Find the mole fractions of solute and solvent.
2. Find the mass fractions of solute and solvent.

II.3. SOLUBILITY

3.1. Definition

Solubility is the property of a solid, liquid or gaseous chemical substance called solute to
dissolve in a solid, liquid or gaseous solvent. The solubility of a substance fundamentally depends
on the physical and chemical properties of the solute and solvent as well as on temperature,
pressure and presence of other chemicals (including changes to the pH) of the solution.

The extent of the solubility of a substance in a specific solvent is measured as the saturation
concentration, where adding more solute does not increase the concentration of the solution and
begins to precipitate the excess amount of solute. Insolubility is the inability to dissolve in a solid,
liquid or gaseous solvent.

3.2. Ways of expressing solubility

 Mass solubility (Smass)

𝑚
𝑆 = … … … … … … … … … . (𝐼𝐼. 16)
𝑚

Expressed as g of solute per 100 g of solvent or g/L of solution.

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 Molar solubility (S)

𝑛
𝑆= … … … … … … … … … . (𝐼𝐼. 17)
𝑉
Expressed as mol/L.

Examples

 NaCl in water: highly soluble → about 360 g/l at 25 °C.

 CaCO3 in water: very low solubility → about 0.013 g/l at 25 °C.

 Oxygen in water (gas): ~ 8.3 mg/l at 25 °C and 1 atm.

 Relation with Molar Solubility

Molar solubility (S) = number of moles of solute that dissolve per liter of solution.

Mass solubility (Smass) = molar solubility × molar mass

𝑆 = 𝑆 × 𝑀 … … … … … … … … . (𝐼𝐼. 18)

3.3. Factors Affecting Solubility

The solubility of a substance (solid, liquid, or gas) in a solvent depends on several factors:

1. Nature of the Solute and Solvent

• “Like dissolves like”: Polar solutes tend to dissolve in polar solvents (e.g., NaCl in water),
while non-polar solutes dissolve in non-polar solvents (e.g., iodine in benzene).

2. Temperature

• For most solids in liquids, solubility increases with temperature (endothermic dissolution).

• For some salts, solubility decreases with temperature (exothermic dissolution, e.g.,
Ce₂(SO₄)₃).

• For gases in liquids, solubility decreases with increasing temperature (because gases escape
more easily).

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3. Pressure

• Pressure has little effect on solids and liquids.

• For gases in liquids, solubility increases with pressure, as described by Henry’s Law:

S = K.P……………………… ( II.19)

where S is the solubility, K the Henry’s constant, and P the partial pressure of the gas.

4. Common Ion Effect

 In ionic compounds, solubility decreases when a solution already contains a common ion.

 Example: Solubility of AgCl decreases in a NaCl solution because both provide Cl⁻ ions.

5. pH of the Solution

Solubility of salts of weak acids (e.g., carbonates, phosphates) increases in acidic solutions
because H⁺ ions react with the anions (CO₃²⁻, PO₄³⁻), reducing their concentration and shifting
equilibrium.

6. Presence of Complexing Agents

Solubility of certain salts increases in the presence of ligands that form soluble complexes.

Example: AgCl dissolves in NH₃ solution due to the formation of [Ag(NH₃)₂]⁺.

II.4. ELECTROLYTE SOLUTIONS

An electrolyte solution is a solution that generally contains ions, atoms or molecules that
have lost or gained electrons, and is electrically conductive. For this reason, they are often called
ionic solutions, however there are some cases where the electrolytes are not ions. For this
discussion we will only consider solutions of ions.

Examples of electrolytic substances: acids, bases, and salts.

A non-electrolyte substance is one that, when in solution, does not allow an electric current
to pass through it.

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Examples of non-electrolyte substances include sugar and alcohol.

There are two types of electrolytes: strong and weak:

 Strong electrolytes: Substances that dissociate completely in water, producing ions with good
electrical conductivity.

 Weak electrolytes: Substances that partially dissociate in water, producing ions with poor
electrical conductivity. Examples include weak acids and weak bases.

 Properties of Solutions of Electrolytes

Electrolysis: When a direct electric current flows through an electrolytic cell, a chemical
reaction occurs. This process is known as electrolysis.

Electrons enter the cell from the battery or generator at the cathode, they combine with
positive ions or cations, in the solution, and the cations are accordingly reduced.

The negative ions, or anions, carry electrons through the solution and discharge them at the
anode, and the anions are accordingly oxidized.

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 Reduction is the addition of electrons to a chemical species

oxidation is removal of electrons from a species.

The current in a solution consists of a flow of positive and negative ions toward the
electrodes,

Fig. II.3. Relationship between specific conductance and equivalent conductance.

The resistance, R, in ohms of any uniform metallic or electrolytic conductor is directly proportional
to its length, l, in cm and inversely proportional to its cross-sectional area, A, in cm2,

𝑙
𝑅 = 𝜌 … … … … … … … … … … … … … … … . . (𝐼𝐼. 20)
𝐴

where ρ is the resistance between opposite faces of a unit cube of the conductor and is known as the
specific resistance.

The conductance, G, is the reciprocal of resistance,

1
𝐺= … … … … … … … … … … … … . (𝐼𝐼. 21)
𝑅

and hence can be considered as a measure of the ease with which current can pass through the
conductor. It is expressed in reciprocal ohms or mhos. From equation (II.20):

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 1 1 𝐴
𝐺= = × … … … … … … … … … … … (𝐼𝐼. 22)
𝑅 𝜌 𝑙

The specific conductance (also called conductivity, symbol 𝜎) is defined as the reciprocal of the
specific resistance (resistivity, ρ).
1
𝜎= … … … … … … … … . (𝐼𝐼. 23)
𝜌

The relationship between specific conductance and conductance or resistance is obtained by

combining equations (II.22) and (II.23):

𝑙 1 𝑙
𝜎=𝐺 = × … … … … … … … … … … … … . (𝐼𝐼. 24)
𝐴 𝑅 𝐴

For a solution containing the anion Ax- at the concentration C– and the cation By+ at the
concentration C+ and if A represents the surface of the electrodes, it is shown that the intensity of the
current which passes through such an electrolyte is given by:

𝐼= …………………………….(II.25)

If we denote by 𝐽⃑ the current density vector and by 𝜌 the electrical conductivity of the solution,
we show that:

𝐽⃑ = 𝜌 × 𝑣⃑ … … … … … … … … (𝐼𝐼. 26)

𝜌: the volume density of charge

𝑣⃑ : the moving speed of charge

In the case of several ions, if we denote Zi the valence of the species Ai, Ci its concentration and
μi its mobility, then:

𝐽⃑ = 𝜌 × 𝑣⃑ … … … … … … … … (𝐼𝐼. 27)

𝐽⃑ = (𝑍 × 𝐶 × 𝜇 ) × … … … … … … … … (𝐼𝐼. 28)

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We can also write that the total conductivity is equal to the contributions sum of all the ions:

𝜎= 𝜎 = |𝑍 | × 𝐶 × 𝜆 … … … … … … . (𝐼𝐼. 29)

where ( 𝜆 ) represents the molar conductivity of the ion "i"

In the system S.I.: 𝜎 is expressed in S.m-1, Ci in mol.m-3 and 𝜆i in [Link]-1.

Molar conductivity (𝝀) is the conductivity of a solution containing one mole of electrolyte, placed
between two electrodes of unit area and unit distance.

𝜎 × 1000
𝜆= … … … … … … … … (𝐼𝐼. 30)
𝐶

where:
 𝜎: specific conductivity (S·cm⁻¹),
 𝐶: molar concentration of the electrolyte (mol·l⁻¹),
 𝜆: molar conductivity (S·cm²·mol⁻¹).

Example: (The solution during the lecture)

Consider the sodium chloride solution NaCl obtained after dissolving a mass m = 10 g of NaCl
salt in 100 ml of water.
1) What is the molar concentration of the solution?
2) What is the molar concentration of the solution in sodium (Na+) and chlorine (Cl-) ions?
3) Find the conductivity of the NaCl sodium chloride solution.
Ionic molar conductivities are given:
λNa+ =5 [Link]−1 and λCl−= 7.6 [Link]−1.

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