Analytical Chemistry

Chapter 3. Solutions and Solution Preparation

Course Title: Analytical Chemistry

Course Code: Iche2031
Module Code: M03
Credit Hrs: 2
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3. Introduction
 A mixture is a substance made by combining two or more different
materials in such a way that no chemical reaction occurs.
 It is a combination of two or more substances that do not combine
chemically, but remain the same individual substances; can be
separated by physical means.
• The objects do not bond together in a mixture.
• A mixture can usually be separated back into its original
components.
Mixtures

Homogeneous Heterogeneous
“Homo” means the same “Hetero” means “different”
has the same uniform appearance and Consists of visibly different substances
composition throughout; maintain one or phases (solid, liquid, gas)
phase (solid, liquid, gas). Commonly
referred to as solutions Can be separated by filtering 2
 A solution is a homogenous mixture composed of two or more
substances.
 In such a mixture, a solute is dissolved in another substance, known as
a solvent. Usually, the solvent is the most abundant component.
 A common example is a solid, such as salt or sugar, dissolved in water,
a liquid.
 There are many ways to separate mixtures into their components.

distillation filtering chromatography Magnetic

separation
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3.2. Types of Solutions
 Gas in liquid
Example – soda water
• Solute: carbon dioxide (gas)
• Solvent: water (liquid)

 Solid in solid
Example – Steel
• Solute: carbon
• Solvent: iron

 Gas in gas
Example - Air
• Solute: Oxygen
• Solvent: Nitrogen
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 Liquid in liquid
Example – Vinegar
• Solute: Acetic acid
• Solvent: Water

 Solid in liquid
Example – Ocean Water
• Solute: Sodium Chloride (solid)
• Solvent: Water (liquid)

Aqueous Solution
 Any mixture where water is the solvent.
• Something is dissolved in water

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 A solution may exist as a solid, liquid or gas depending on the state of the
solvent.
Gas Solutions: The solvent is a gas
 If the solvent is a gas, then gases, liquids and solids can be dissolved.
• Gas in gas: a gaseous solution is air
• Liquid in gas: Humidity in air
• Solid in gas: Iodine vapours in air

Liquid Solutions: The solvent is a liquid

 If the solvent is a liquid, then gases, liquids and solids can be dissolved.
• Gas in liquid: O2 in water
• Liquid in liquid: ethanol in water
• Solid in liquid: Sucrose (table sugar) in water

Solid Solutions: The solvent is a solid

 If the solvent is a solid, then gases, liquids, and solids can be dissolved.
• Gas in solid: H2 dissolves in palladium (used as a means of H2 storage).
• Liquid in solid: Mercury in gold (forming an amalgam)
• Solid in solid: Steel, carbon atoms in a crystalline matrix of Fe atoms.
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Summary

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3.3. Solubility
 Solubility: The maximum amount of solute that will dissolve in a given
quantity of solvent at a specific temperature and pressure to produce a
saturated solution.
• Immiscible - two liquids that are insoluble in each other.
• Insoluble - a substance that does not dissolve in another substance.
• Miscible - two liquids that are soluble in each other.
• Soluble - a substance that dissolves in another substance.
 Substances that exhibit similar types of intermolecular force dissolve
in each other. This is often expressed by saying “like dissolves in like.”
 Example: Alcohols are organic compounds that have dual polarity.
The general formula for an alcohol is CH3(CH2)nOH.
• Polar: The –OH group of an alcohol.
– It interacts with water through H-bonds and
– It interacts with hexane by through weak dipole-induced dipole forces.
• Nonpolar: The hydrocarbon portion.
– It interacts through weak dipole-induced dipole forces with water
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– It interacts with hexane by dispersion forces.
Types of intermolecular forces in solutions
Ion-dipole Ion-induced dipole
(40-600) (3-15)
H2O

H-bond Dipole-induced dipole

(10-40) (2-10)

Dispersion
(0.05-40)
Dipole-dipole
(5-25)

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Solubility* of a Series of Alcohols in Water and Hexane.
Solubility Solubility
Alcohol Model in Water in Hexane
CH3OH ∞ 1.2
(methanol)
CH3CH2OH ∞ ∞
(ethanol)
CH3(CH2)2OH ∞ ∞
(propanol)
(CH3(CH2)3OH 1.1 ∞
(1-butanol)
(CH3(CH2)4OH 0.30 ∞
(1-pentanol)
(CH3(CH2)5OH 0.058 ∞
(1-hexanol)

*Expressed in mol alcohol/1000 g solvent at 20°C. 10

Factors Affecting Solubility
The nature of the solute and solvent:
• Different substances have different solubilities “Like Dissolves Like”.
• Polar solvents dissolve polar compounds, and non polar solvents
dissolve non polar compounds.
Temperature:
• Many solids substances become more soluble as the temp of a solvent
increases;
• However, gases are less soluble in liquids at higher temps.
Pressure:
• Only affects the solubility of gases.
• As pressure increases, the solubility of gases increases.

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Relation between solubility and temperature for several ionic
compounds.

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The effect of pressure on gas solubility.

• As the pressure is increased, more gas particles collide with the liquid
surface.
• More gas particles dissolve until equilibrium is re-established.

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Henry’s Law
The solubility of a gas (Sgas) is directly proportional to the partial
pressure of the gas (Pgas) above the solution.
Sgas = kH X Pgas
Example: The partial pressure of carbon dioxide gas inside a bottle of cola
is 4 atm at 25oC. What is the solubility of CO2? The Henry’s law constant
for CO2 dissolved in water is 3.3 x102 mol/L·atm at 25oC.
SOLUTION
We know P for CO2 (4 atm) and the value of kH, so we substitute these
into the Henry’s law equation.
SCO2 = (3.3 x 10−2 mol/L·atm)(4 atm) = 0.1 mol/L

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3.4. Concentration of solutions
 Concentration: The measure of the amount of solute dissolved in a
given quantity of solvent
 There are a number of ways to express the relative amounts of solute
and solvent in a solution.
 Which one we choose to use often depends on convenience (E.g, it is
sometimes easier to measure the volume of a solution rather than the
mass of the solution).

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Different ways of expressing concentration
Expression of Concentration Semi-quantitatively
 There are a number of ways to express the relative amounts of solute
and solvent in a solution.
• Dilute: a solution that contains a small proportion of solute relative
to solvent.
• Concentrated: a solution that contains a large proportion of solute
relative to solvent.
• Unsaturated: a solution in which more solute will dissolve at a
given temperature.
• Saturated: a solution in which no more solute will dissolve at a
given temperature. Undissolved solute is in equilibrium with
dissolved solute. Solute (undissolved) ↔ solute (dissolved)
• Supersaturated: a solution in which more solute dissolved than it
can dissolve at a given temperature. It is unstable and any
disturbance will cause excess solute to crystallize immediately.
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Expression of Concentration Quantitatively
 The relative amount of solute per unit volume or unit mass of solution.
 Molarity (M): the number of moles of solute in exactly one liter of a
solution.
moles of solute
M=
liter of solution
mass of solute
moles of solute =
formula weight of solute
 Normality (N): the number of equivalent weights (EW) per unit
volume. N makes use of the chemical equivalent that is the amount of
one chemical species reacting stoichiometrically with another species.
number of equivalent of solute
N=
liter of solution
mass of solute
No. of equiv. of solute =
equivalents weight EW of solute
formula weight FW
EW = =
number of of its equivalent n 17
 Number of equivalents (n) is based on a reaction unit, which is that part of
a chemical species involved in a reaction.
 Acid–base reaction: n is the number of H+ ions donated by an acid or
accepted by a base.
H2SO4(aq) + 2NH3(aq) ⇋ 2NH4+(aq) + SO42–(aq) (n = 2 for H2SO4 & n
= 1 for NH3).
 Precipitation reaction: n is the charge of the cation or anion involved
in the reaction.
Pb2+(aq) + 2I–(aq) ⇋ PbI2(s) (n = 2 for Pb2+ & n = 1 for I–).
 Oxidation–reduction reaction: n is the number of electrons released
by the reducing agent or accepted by the oxidizing agent.
2Fe3+(aq) + Sn2+(aq) ⇋ Sn4+(aq) + 2Fe2+(aq) (n = 1 for Fe3+ & n = 2 for
Sn2+).
 Complexation reaction: n is the number of electron pairs that can be
accepted by the metal or donated by the ligand.
Ag+(aq) + 2NH3(aq) ⇋ Ag(NH3)2+(aq) (n = 2 for Ag+&n = 1 for NH3 ).
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 Example: Calculate the molarity of a solution of 3.6 g of NaOH in 300 mL of
solution. Given: M. Wt. of NaOH = 40.0 g/mole
Solution: 300 mL = 0.300 L
3.6 g
moles of NaOH = = 0.090 mole
40.0 g/mole
0.090 mole
M= = 0.30 M
0.300 L
 Example: Calculate the equivalent weight and normality for a solution of 6.0 M
H3PO4 given in the following reactions:
(a) H3PO4(aq) + 3OH–(aq) ⇋ PO43–(aq) + 3H2O(l)
(b) H3PO4(aq) + 2NH3(aq) ⇋ HPO4 2–(aq) + 2NH4+(aq)
(c) H3PO4(aq) + F–(aq) ⇋ H2PO4–(aq) + HF(aq)
Solution: For H3PO4, the number of equivalents (n) is the number of H+ ions
donated to the base.
FW 97.994
(a) EW = = = 32.665 N = n x M = 3  6.0 = 18 N
n 3
FW 97.994
(b) EW = = = 48.997 N = n x M = 2  6.0 = 12 N
n 2
FW 97.994
(c) EW = = = 97.994 N = n x M = 1  6.0 = 6.0 N 19
n 1
 Molality (m) is the number of moles of solute dissolved in exactly one
kilogram of solvent.
moles of solute
m=
mass of solvent in Kgs
 Mole Fraction (x) is the ratio of the number of moles of a component
to the total number of moles of all components in the solution. The
mole fraction of A (xA) in a solution consisting of A, B, C ... is calculated
using the equation:
moles of A
xA =
moles of A + moles of B + Moles of C
 Percent by mass (% w/w) is the mass of the solute in the solution per the
mass of the solution.
mass of solute
Percent by mass =  100
mass of solution
 Percent by volume (% v/v) is the volume of the solute in the solution per the
volume of the solution.
volume of solute
Percent by volume =  100
volume of solution 20
Summary.
Name Unitsa Symbol
Molarity moles solute / liters solution M
Formality number FWs solute / liters solution F
Normality number EWs solute / liters solution N
Molality moles solute / kg solvent m
% by weight (g solute/g solution) x 100 %w/w
% by volume (mL solute/mL solution) x 100 %v/v
% by weight-to-volume (g solute/mL solution) x100 %w/v
Parts per million (g solute/g solution) x 106 ppm
Parts per billion (g solute/g solution) x 109 ppb

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Interconverting of Concentration Units
 To convert a term based on amount (mol) to one based on mass, you
need the molar mass.
m = n x M x Wt
 To convert a term based on mass to one based on volume, you need the
solution density.
ρ = m/V
 Molality involves quantity of solvent, whereas the other concentration
terms involve quantity of solution.
 The following simple relationship exists between normality and
molarity.
N=nM

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 To convert a term based on mass to one based on volume, you need the
solution density (ρ = m/V).
 Molarity  Percent Concentration (mol/L  g/100 g)
• The volume (V = 1 L) must be converted to the mass (m) of the
solution using its density ρ (ρ = m/V).
• The substance amount can be then expressed as the number of moles
found in 100 g of the solution.
• The substance amount is finally converted to the mass of a substance
using molar weight (m = n  M.Wt.)
 Percent Concentration  Molarity (g/100 g  mol/L)
• The mass of the solution (m = 100 g) must be converted to volume (V)
using its density ρ (ρ = m/V).
• The mass of a substance can be then expressed as the mass found in 1
L of the solution.
• The mass of the substance is finally converted to the substance amount
(n) using MW (m = n x M.Wt.).
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 Example: What is the concentration of NaOH (in ppm) if 10 grams of
NaOH is dissolved in enough water to make 2 L of solution?
Since density of water (ρw) is 1g/mL, mass of 2 L (2000 mL) can be
calculated as
m = ρw Vw = (1g mL) 2000 mL = 2000 g
mass of solute
ppm =  106
mass of solution
10 g NaOH
ppm =  106 = 5000 ppm NaOH
2000 g solution
 Example: Calculate mass of NaCl and mass of water which are needed
for preparation of 600 g of 5% (w/w) solution.
5 g of NaCl in 100 g of its solution
x g of NaCl in 600 g of its solution
x = (600/100) x 5
x = 30 g of NaCl (Mass of water = 600 - 30 = 570 g of water)
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 Example: Calculate the percent concentration (%w/w) of 5.62 M solution of
HNO3 (ρ = 1.18 g/mL, M.Wt. = 63 g/mol)
1) the volume 1 L is converted to the mass of the solution using the density:
ρ = m/V, m = ρ  V = 1.18 g/mL  1000 mL = 1180 g
5.62 mol of HNO3 are found in 1 L of the solution
5.62 mol of HNO3 are found in 1180 g of the solution
2) the substance amount is expressed as number of moles found in 100 g of the
solution
5.62 mol of HNO3 are found in 1180 g of the solution
x mol of HNO3 are found in 100 g of the solution
x/5.62 = 100/1180
x = (100/1180) x 5.62 = 0.476
3) the substance amount is converted to the mass using the value of M.Wt.
63 g = 1 mol
x g = 0.476 mol
x/63 = 0.476/1
x = (0.476/1) x 63 = 29.988 ≈ 30.0 g
30 g of HNO3 are found in 100 g of the solution
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4) Percent by mass = 30 g /100 g = 30%
Example. Hydrogen peroxide is a powerful oxidizing agent used in
concentrated solution in rocket fuels and in dilute solution as a hair bleach.
An aqueous solution H2O2 is 30.0% by mass and has a density of 1.11
g/mL. Calculate its
(a) Molarity
(b) Molality
(c) Mole fraction of H2O2
Solution
(a) Use the density to find the volume of the solution.
(b) To find the mass of solvent we assume the % is per 100 g of
solution. Take the difference in the mass of the solute and solution
for the mass of peroxide.
(c) Convert g of solute and solvent to moles before finding mole
fraction.

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(a) From mass % and density to molarity:
1 mL
volume (mL) of solution = 100.0 g x = 90.1 mL
1.11 g
mol H2O2 0.882 mol H2O2
molarity = = = 9.79 M H2O2
L soln 1 L soln
90.1 mL x 3
10 mL
(a) From mass % to molality:
g of H2O = 100. g solution − 30.0 g H2O2 = 70.0 g H2O
1 mol H2O2
mol H2O2 = 30.0 g H2O2 x = = 0.882 mol H2O2
34.02 g H2O2
0.882 mol H2O2
molality = = = 12.6 m H2O2
1 kg
70.0 g x 3
10 g
(b) From mass % to mole fraction:
1 mol H2O
mol H2O =70.0 g H2O x = = 3.88 mol H2O
18.02 g H2O
0.882 mol H2O2
𝑋H O = = 0.185
2 2 3.88 mol H2O + 0.882 mol H2O2 27
3.5. Preparation of solutions
Preparation of stock solution
 A stock solution can be prepared from pure solid or liquid reagents.
 A stock solution is prepared from pure solid reagents by weighing out
an appropriate portion of the solid and dissolving in suitable solvent
and then diluting to a definite volume.
 A stock solution can also prepared from pure liquid reagents by
measuring out an appropriate volume of a pure liquid and diluting to a
definite volume using suitable solvent.
 Example : Describe how you would prepare 500 mL of approximately 0.20
M NaOH using solid NaOH.
Solution: The desired mass of NaOH is
0.20 mol L x 40.0 g mol x 0.50 L = 4.0 g
To prepare the solution we place 4.0 g of NaOH, weighed to the nearest
tenth of a gram, and dissolve in a 500 mL volumetric flask with sufficient
reagent water and finally dilute to the mark.
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Preparation of working solutions
 Working solutions (solutions with relatively small concentrations) are often
prepared by diluting a more concentrated stock solution.
 A known volume of the stock solution is transferred to a new container and
brought to a new volume.
 Since the total amount of solute is the same before and after dilution
Moles of a solute = 𝐂𝟎 𝐕𝟎 = 𝐂𝐝 𝐕𝐝
Where Co is the concentration of the stock solution, Vo is the volume of the
stock solution being diluted, Cd is the concentration of the dilute solution, and
Vd is the volume of the dilute solution.
 Exercise 7: Describe how you would prepare 250 mL of an approximately 0.10
M solution of NH3 using a stock solution of NH3 (14.8 M).
Solution:
14.8 M x Vo = 0.10 M x 0.25 L
Solving for Vo gives 1.69 x 10–3 L, or 1.7 mL.
We can measure the appropriate amount of concentrated NH3 using a
graduated cylinder, transfer the NH3 to a 250 mL volumetric flask, and add
sufficient water to bring the total solution volume to the mark. 29
Diluting a solution reduces the number of moles of
solute per unit volume, but the total number of moles
of solute in solution does not change.
The total number of moles of solute remains
unchanged upon dilution, so you can write this
equation.
𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑎 𝑠𝑜𝑙𝑢𝑡𝑒 = 𝐶0 𝑉0 = 𝐶𝑑 𝑉𝑑
M0 and V0 are the molarity and volume of the initial
solution, and Md and Vd are the molarity and volume of
the diluted solution. 30
3.6. Activity and activity coefficient
 In the deduction of the Law of Mass Action, it was assumed that the effective
concentrations or active masses of the components could be expressed by
the stoichiometric concentrations.
 According to thermodynamics, this is not strictly true. The rigorous
equilibrium equation for, say, a binary electrolyte:
a a
AB ⇋ A+ + B- K t = A+ B−
aAB
Where aA+, aB- and aAB represent the activities of A+, B-, and AB respectively,
and Kt is the true or thermodynamic dissociation constant.
 Chemists use a term called activity (a) to account for the effects of
electrolytes on chemical equilibria.
 The activity, or effective concentration, of species X depends on the ionic
strength of the medium and is defined by
ax = [X]γx
where ax is the activity of the species X, [X] is its molar concentration, and 𝛾x
is a dimensionless quantity called the activity coefficient.
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 The activity coefficient (𝛾x) varies with the concentration.
 For ions, 𝛾x also varies with the ionic charge, and is the same for all dilute
solutions having the same ionic strength (I).
 I is a measure of the electrical field existing in the solution.
 I is equal to one half of the sum of the products of the concentration of each
ion multiplied by the square of its charge
I =0.5∑cizi2
where ci is the ionic concentration in moles per liter of solution and zi is the
charge number of the ion concerned.
 Exercise 8: What is the ionic strength of 0.1 M HNO3, solution containing
0.2M Ba(NO3)2 ?
Solution
I= 0.5{0.1 x 12 (for H+) + 0.1 x 12(for NO3-) + 0.2 x 22 (for Ba+2) +
0.4 x 12 (for NO3-)
I = 0.5 {1.4} = 0.7

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The Debye-Hückel Equation
 P. Debye and E. Hückel used the ionic atmosphere model to derive an
equation that permits the calculation of activity coefficients of ions from
their charge and their average size.
 This equation, which has become known as the Debye-Hückel equation:
0.51Zx 2 I
−logγx =
1 + 3.3αx I
where Zx = charge on the species X, and αx = effective diameter of the
hydrated ion X in nanometers (10-9 m). The constants (αx ) 0.51 and 3.3 are
applicable to aqueous solutions at 25°C.
Example: What is the activity coefficient for Hg2+ in a solution that has an ionic
strength of 0.085 M? Use 0.5 nm for the αx of the ion.
Solution
0.51Zx 2 I 0.51(2)2 0.085
−logγx = = −logγHg2+ = = 0.4016
1 + 3.3αx I 1 + 3.3)(0.5) 0.085
γHg2+ = 10−0.4016 = 0.397 ≈ 0.4 33
Properties of activity coefficients
 In very dilute solutions, in which the ionic strength is minimal, this
effectiveness becomes constant, and the activity coefficient is unity.
As I→0, 𝛾x→1, and ax→ [X]
 In solutions that are not too concentrated, the activity coefficient for a
given species is independent of the nature of the electrolyte and
dependent only on the ionic strength.
 For a given ionic strength, the activity coefficient of an ion departs
farther from unity as the charge carried by the species increases.
 The activity coefficient of an uncharged molecule is approximately
unity, regardless of ionic strength.
 At any given ionic strength, the activity coefficients of ions of the same
charge are approximately equal.

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End of Chapter 3

Thank you!

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