Fundamentals of Analytical chemistry (221)

CHAPTER-4

Solutions

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 1. Introduction

 Most of the materials around us are mixtures.

 Mixtures are combinations of two or more substances in which each substance

retains its own chemical identity and hence its own properties.
 There are two broad classes of mixtures, (homogeneous and heterogeneous

mixtures).

A. A homogeneous mixture is a mixture in which the composition of the

mixture is the same throughout.
 i.e., it has no visible boundaries because the components are mixed as individual

atoms, ions and molecules.

Example: when a spoonful of sugar dissolves in water, when sodium chloride is

dissolved in water
- Air is a gaseous solution, nitrogen and oxygen, which are physically mixed but
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not chemically combined.
 1. Introduction...

B. A heterogeneous mixture has one or more visible boundaries between

the components.
 Thus, its composition is not uniform.

 Can be detected by the naked eye or with a magnifying glass.

Example: sand mixed with iron filings, the sand grains and the iron filings
remain separate.
 A solution has two components namely, solute and solvent.

 A solute is: a substance that dissolves.

 a substance existing in small proportion and the most active component
chemically.
 A solvent is: A substance that does the dissolving process.
 A substance existing in larger proportion.
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 There are three types of solutions:

i. Gaseous solution: If the solvent is a gas, only gases are dissolved under
any given set of conditions.

ii. Liquid solution: If the solvent is a liquid, then gases, liquids and solids
can be dissolved.

iii. Solid solution: If the solvent is a solid, then gases, liquids, and solids
can be dissolved.

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 4.2 Types of solution...
Solute Solvent Types of solution Example
Solid solid Solid in solid Alloys
Liquid solid Solid in liquid Salt solution in water
Gas solid Solid in gas Iodine vapor in gas
Solid Liquid Liquid in solid Hydrated salts
Liquid Liquid Liquid in liquid Alcohol in water
Gas Liquid Liquid in gas Humidity in air
Solid Gas Gas in solid Dissolved gas in minerals
Liquid Gas Gas in Liquid Aerated drinks
Gas Gas Gas in Gas Air

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 4.3 The solution process
4.3.1 Liquid Solutions and Interparticle Forces of Attractions
 Particles of the solute mix with particles of the solvent.
 The tendency to mix is affected by the relative strengths of three
types of interaction. These are:
1. Solvent-solvent interaction: Strong forces of attraction between
solvent particles
 Tend to keep like particles close together and reduce the solubility
of solute in the solvent.
2.Solute-solute interaction: Strong forces of attraction between
solute particles also tend to keep like particles close together
3. Solvent-solute interaction: makes dissolving easier and helps to
6 keep particles in solution.
 4.3.1 Liquid Solutions and Interparticle Forces of Attractions...
 For simplicity, we can imagine the solution process
taking place in three distinct steps

 Figure 4.3: A molecular view of the solution process,

portrayed as taking place in three steps.
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4.3.1 Liquid Solutions and Interparticle Forces of Attractions...

 Step 1 – is the separation of solvent molecules from each other to

“make room” for the incoming solute particles;

 Step 2 – is the separation of solute molecules.

 These two steps require energy input to break attractive

intermolecular forces.
 Therefore, they are endothermic.

 In step 3 – the solvent and solute molecules mix.

 This process can be exothermic or endothermic.

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 Solution of liquids in liquids
Solubility is a measure of how much solute will
dissolve in a solvent at a specific temperature.
The “like dissolves like” principle is helpful in
predicting the solubility of a substance in a given
solvent.
Two substances with intermolecular forces of
similar type and magnitude are likely to be
soluble in each other.
Example: Ethanol mixes with water but oil does not.
benzene (C6H6) and carbon tetrachloride (CCl 4)

Figure 4.2: Solubility of ethanol and methanol in water through

9 hydrogen bonding.
 Solutions of Solids in Liquids
 Solids composed of polar molecules or ions, are insoluble in non-

polar solvents.
 Example: sugar is soluble in water;

 however, sugar is insoluble in solvents like oil;

 Solids whose crystals are held together by London forces are able to

dissolve to appreciable extents in non-polar solvents.

 Water and other polar molecules are attracted to ions.

 The electrostatic attraction between an ion and a molecule with a

dipole is called an ion-dipole attraction.

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 Solutions of Solids in Liquids

Figure 4.3: Ion-dipole force in dissolving an

ionic crystal.
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 Solutions of Solids in Liquids...
 When ionic compounds, such as KCl, dissolve in
water, the ions in the solid separate; because
water molecules surround and solvate the ions.
In general, when a solute particle becomes
surrounded by solvent molecules we say that it is
solvated.
When the solvent is water the process is called
hydration.

Figure4.4: K+ and Cl– surrounded by

H2O molecules.
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 1.3.2 The Rate of Dissolution
 The rate of dissolution is the speed with which a solute goes into

solution.
 This largely depends upon the inter-particle forces and, to a lesser

extent, on conditions such as:

1) The surface area of the solid solute,

2) The temperature and

3) The pressure of the system.

 Increasing surface area will increase the rate of dissolution;

 because it increases the number of solute particles in contact with the

solvent.
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 4.3.3 Energy Changes in the Solution Process
 Heat of Solution

 The amount of energy that is absorbed or released when one mole of a

substance enters solution is called the heat of solution;

 is given by the symbol H°Sol, which is the sum of the enthalpies associated

with the three steps in the solution process;

 The separation of solute particles (step 1) and solvent particles (step 2) is

endothermic;
 Each solute particle is surrounded by a layer or “cage” of solvent molecules

that is attracted to it by intermolecular forces.

 This step 3 can be endothermic or exothermic, and is referred to as solvation.

 The heat of solution HoSol

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 Hydration of Ionic Solids in Water

 Hydration of ions favours the dissolution of an ionic solid in

water.
 Lattice energy works against the solution process;

 Lattice energies depend on the charge on the ions and also the

distance between the centres of the neighbouring positive and

negative ions.
 As the magnitude of the charge on the ions increases the lattice

energy also increases.

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 4.5 SOLUBILITY AS AN EQUILIBRIUM PROCESS
When an ionic solid dissolves, ions leave the solid and
become dispersed in the solvent.
Eventually, ions from the solid are dissolved at the
same rate as the ions in the solution are crystallized.
Eventually again, a dynamic equilibrium is reached in
which the rate at which ions leave the crystals equals
the rate at which ions return to the crystals.
At this point, even though dissolution and
crystallization continue, there is no further change in
the concentration over time.
The system has reached equilibrium.
That is, excess undissolved solute is in equilibrium
with the dissolved solute.
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 4.5 SOLUBILITY AS AN EQUILIBRIUM PROCESS...
After equilibrium is established, no more solid
dissolves.
Such a solution is said to be saturated.
A saturated solution is a solution in which the
dissolved and undissolved solutes are in dynamic
equilibrium;
Before equilibrium is reached, the solution is said
to be unsaturated.
An unsaturated solution is a solution that can
dissolve more solute at a given temperature.
The solubility of many ionic solids in water
increases as temperature increases.
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 4.5 SOLUBILITY AS AN EQUILIBRIUM PROCESS...
 They form supersaturated solutions, which actually contain larger

amounts of solute than in saturated solutions.

 Supersaturated solutions can sometimes be prepared by saturating a

solution at a high temperature.

 Example: Honey is naturally occurring supersaturated solution.

 It contains glucose, as a solute, and water, as a solvent.

 If honey is left to stand, the glucose eventually crystallizes.

 Supersaturated solutions are unstable, and addition of a “seed” crystal of

solute will generally cause all of the excess solute to suddenly

18crystallize.
 4.5 SOLUBILITY AS AN EQUILIBRIUM PROCESS...

 A saturated solution is, a solution that is in equilibrium with

respect to a given dissolved substance.

 An unsaturated solution, a solution not in equilibrium with respect

to a given dissolved substance and in which more of the substance

can dissolve.
 A supersaturated solution, a solution that contains more dissolved

substance than a saturated solution does.

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 Effects of Temperature and Pressure on Solubility
 Temperature Change

 Most gases become less soluble in water at higher temperatures.

 The first bubbles that appear when tap water is heated are bubbles of air

released as the increasing temperature reduces the solubility of air in water.

 In contrast, most ionic solids become more soluble in water with rising

temperature.

The solubilities of the salts NaCl, KNO3, and CuSO4 rise with increasing
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temperature, as is the case with most ionic solids. The solubility of
 The Effect of Pressure on Solubility
 Since liquids and solids are almost incompressible, pressure has

little effect on their solubility,

 The solubility of gases always increases with increasing pressure.

 The solubility of a gas in a liquid is directly proportional to the

partial pressure of the gas over the solution.

 The quantitative relationship between gas solubility and pressure is

given by Henry’s law,

 which states that “at a given temperature the solubility of a gas in a

liquid is directly proportional to the partial pressure of the gas over

21 the solution”. Cg = KH. Pg
 The Effect of Pressure on Solubility...

If the pressure is increased to, the volume of the gas decreases.

 As a result, the collisions with the surface increases, and more gas
22 molecules enter the solution when equilibrium is re–established.
 The Effect of Pressure on Solubility...

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 4.6 Ways of expressing concentration
 Measures of concentration

 The concentration is a measure of the amount of solute that has been

dissolved in a given amount of solvent or solution.

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 4.6 Ways of expressing concentration...
 Emphasizing the amounts of solute in solution

 The amount of solute that has been dissolved in a given amount of solvent

or solution can be expressed either qualitatively (diluted and

concentrated) and quantitatively.
 A solution with a relatively small amount of solute is said to be dilute

 One with a large amount of the solutes is said to be concentrated

 Several quantitative expressions of solution concentration are used in

chemistry including:
a) Percent by mass
b) Parts per million and parts per billion
c) Molarity and Molality
25 d) Mole fraction
 4.6 Ways of expressing concentration...
 Percent by mass

 The percent by mass is the ratio of the mass of a solute to the mass of the

solution, multiplied by 100.

Example: What is the mass percentage of Fe in a piece of metal with

87.9 g of Fe in a 113 g sample?

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 4.6 Ways of expressing concentration...
 Parts per million (ppm): When the mass of solute in the solution is very

small, a widely used expression is parts per million (ppm).

Example: A 2.5 g sample of ground water was found to contain 5.4 µg of

Zn2+. What is the concentration of Zn2+, in parts per million?

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 4.6 Ways of expressing concentration...
 For solutions that are even more dilute, parts per billion (ppb) is used.

 A concentration of 1 ppb represents 1 g of solute per billion (10 9) grams of

solution

 Molarity (M)

 Molarity or molar concentration is the number of moles of solute in 1 L of

solution

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 4.6 Ways of expressing concentration...
Example: What is the molar concentration of a solution containing
16.0 g of CH3OH in 200 mL of solution?

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 4.6 Ways of expressing concentration...
 Molality (m)

 The molality of a solution is the number of moles of solute per kilogram

of solvent contained in a solution

Example: What is molality of a solution prepared by dissolving 32.0 g

of CaCl2 in 271 g of water?

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 4.6 Ways of expressing concentration...
 Mole fractions (X)

Example: What is the mole fraction of I2 in a solution containing 30 g of I2

in 400 g of CCl4 ?

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 4.7 Preparation of solutions

 How do you prepare a solution of known concentration?

A common task in school, medical, industrial and other

chemical laboratories is the preparation of solutions of known
concentrations. For aqueous solutions, distilled, de-mineralized
order-ionized water is used

Preparing Stock Solutions

 A stock solution is prepared by weighing out an appropriate

portion of a pure solid or by measuring out an appropriate

volume of a pure liquid and diluting to a known volume.
 Exactly how this is done depends on the required
concentration units.
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  If starting with a solid, use the following procedure:

Calculate the amount of solid required

Weigh out the solid

Place in an appropriate volumetric flask

Fill flask about half full with water and mix (shake).

Fill to the mark with water and invert to mix.

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 4.7 Preparation of solutions...
 Grams of solute to measure = VD X MD X M solute

 Where, VD-desired volume, MD - molarity Msolute- molecular weight of

solute

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 4.7 Preparation of solutions...
Describe how you would prepare the solutions:

(a) 500 mL of approximately 0.20 M NaOH using solid NaOH;

Solution
(a). Since the concentration only needs to be known to two significant
figures, the mass of NaOH and volume of solution do not need to be
measured exactly. The desired mass of NaOH is:
Given: VD = 500 ml =0.5L
Molarity = 0.2 M = 0.2 mol/L
Molar mass = 40g/mol
 Grams of solute to measure = 0.5 L x 0.2 mol/L x 40g/mol = 4gm.
 Therefore; to prepare the solution we place 4.0 g of NaOH, in a bottle or
beaker and add approximately 500 mL of water.

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 4.7 Preparation of solutions...
Preparing Solutions by Dilution

Dilution is the procedure for preparing a less-

concentrated solution from a more concentrated one.
CB x VB = CA x VA .......................Dilution Law

Where :

 CB is the concentration of the stock solution,

 VB is the volume of the stock solution being diluted (before dilution),

 CA is the concentration of the dilute solution, and

 VA is the volume of the solution after dilution.

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NB: The total amount of solute is the same before and after dilution
 4.7 Preparation of solutions...
A laboratory procedure calls for 250 mL of an approximately 0.10 M solution of
NH3. Describe how you would prepare this solution using a stock solution of

concentrated NH3 (14.8 M).

Given : CB = 14.8 M, CA = 0.1 M, VA= 250 ml, required VB =?

Solution:

 Substituting known volumes in above equation, 14.8 M x VB = 0.10 M x 0.25

Since we are trying to make a solution that is approximately 0.10 M NH3, we can

measure the appropriate amount of concentrated NH3 using a graduated cylinder,

transfer the NH3 to a beaker, and add sufficient water to bring the total solution
volume
37 to approximately 250 mL.
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