Analytical Chemistry

(Chem2021)
Chapter 4

Solutions and their concentrations

July, 2021
1
[email protected]
 4.1. Types of solutions
• A solution is a homogeneous mixture of two or more
substances of molecular dimensions, whose composition can
be varied within certain limits.
• A solution has two components namely, solute and solvent.
Solute Solvent
A substance that  A substance that does the dissolving
dissolves process
 A substance existing in  A substance existing in larger
small proportion proportion
 The most active  A substance whose physical state
component chemically doesn’t change during the solution
process.
 The least active component
chemically
2
There are 9 types of solutions, based on the solute (1st) and the
solvent (2nd)
Table 4.1: types of solutions with example:
Solute Solvent Solution
Gas Gas Air
Gas Liquid soda water
Gas Solid hydrogen in Pt
Liquid Gas water vapor in air
Liquid Liquid alcohol in water
Liquid Liquid silver amalgam
Solid Gas sulfur vapor in air
Solid Liquid sugar in water
Solid Solid brass
3
• Based on the relative amount of solute in the solution,
solutions may be dilute or concentrated; unsaturated,
saturated, or supersaturated.
• Degree of saturation is dependent on temperature; eg,
more sugar will dissolve when tea is hot).

4
 4.2. Different ways of expressing concentration
 The quantity of a solute in a given quantity (weight or
volume) of the solvent or solution is known as
concentration of a solution.
 When we want to compare in a qualitative way the
concentration of solutions, we use terms dilute and
concentrated.
 Quantitatively the concentration of solution is expressed in
terms of molarity, normality, molality, mole fraction,
percent by mass and volume, ppm, etc.

5
• Molarity (M): The most common unit of solution
concentration is molarity (M). Molarity is defined as the
number of moles of a solute per liter of solution.
Molarity =
Examples:
1. Calculate the number of moles and number of grams of
KMnO4 (F.Wt =158) in 3.0 L of a 0.25 M solution.
Solution:
The number of moles (n) = molarity x volume
= 0.25 mol/L x 3.0 L = 0.750 mol
The mass in gram (m) = no of moles x formula weight (F.Wt)
= 0.750 mol x 158.0 g/mol = 118.5 g
6
Exercise
i. Explain how you would prepare 250 mL of 0.600 M aqueous KBr
solution.
ii. How many moles of each kind of ions are present in
a. 135 mL of 0.82 M (NH4)2SO4?
b. 75 mL of 0.250 M Al2(SO4)3
 Formality (F)
 Formality and molarity become equivalent terms when the formula
weight is the same as molecular weight.
F = gram-formula weight/ volume of solution = m / (M x V)
Where: m is mass of the solute;
M is gram-formula weight of the solute and
V is volume of the solution.
7
 Normality (N): Normality is defined as the number of
equivalents per liter of solution.
Normality (N) =
But number of equivalents = mass (m)/equivalent weight (E).
Therefore,
Normality (N) = No of equivalents/Liter of solution
= m/(E x V)
Where: E is equivalent weight of the solute.
• For preparation of solution of any desired normality (ND) and
volume (VD):
• Grams of solute to measure = VD X ND X Equ. Wtsolute
8
• Concept of Equivalent:
• The equivalent of a substance is that part of a mole which reacts on a
one-to-one basis with another substance. Equivalents always react in
one-to one ratio.
• Methods for determining the equivalent weights are defined according
to the reaction types:
i. For Acid/Base reactions: The equivalent weight of an acid is
molecular weight divided by the number of hydrogen donated (ionized
or replaced) per molecule in the reaction. And that of a base is
molecular weight divided by the number of hydroxyl ion supplied per
molecule.
• ii. For Redox reactions: For oxidizing and reducing agents, the
equivalent weight is the formula weight of the substance divided by the
number of electrons gained or lost per mole of the substance. 9
  Molality (m)
 Molality is the mole of the solute per kilogram of the solvent.
m = mole of solute /kg of solvent.
Molality can be used for working problems related to colligative
properties of solutions.
Note: There is a very simple relationship between molarity and
normality.
• The normality is always an integral multiple of molarity. The
normality of a substance is never less than its molarity.
• N = M x n where n is the total positive valence, or the number
of electrons lost or gained during redox reaction per formula
unit.

10
 Percent by mass and volume:
 Percentage composition may be the percentage of the solute
relative to the final solution on either weigh-by-weight or
volume- by- volume basis.
 Three different percent units are known.
i. volume/volume (v/v) percent = x 100
 For preparation:
Volume to measure = (% desired/100) X solution volume desired
ii. weight/weight (w/w) percent = x 100
• For preparation:
• Weight to measure = (% desired/100) x solution weight desired
iii. weight/volume (w/v) percent = x 100
• For preparation:
Weight to measure = (% desired/100) x solution volume desired
11
Examples:

1) 70% (w/w) HNO3 means 70 g HNO3 per 100 g of solution.

2) 5% (v/v) aqueous CH3OH ⇒ 5.0 mL of CH3OH with

enough water to give 100 mL of solution.

3) 5% (w/v) aqueous AgNO3 5 g of AgNO3 in sufficient water

to give 100 mL of solution.

12
 Activities
1. What is the percentage concentration of 75.0 g
of ethanol dissolved in 500.0 g of water?
2. A chemist dissolves 3.50 g of potassium
iodate and 6.23 g of potassium hydroxide
in 805.05 g of water. What is the percentage
concentration of each solute in the solution?
3. A student wants to make a 5.00% solution of
rubidium chloride using 0.377 g of the sub
stance. What mass of water will be needed to
make the solution?
13
4. What is the % W/W if 8.0 g copper is added to enough zinc
to produce 100 g of an alloy?
5. What is approximate % V/V if 30 mL of pure ethanol is
added to 250 mL of water?
6. What is the % W/W of copper in an alloy when 10 g of Cu
is mixed with 250 g of Zn?

14
 Part per Million/Billion (ppm/ ppb)
• ppm: is most often assumed to mean milligrams of the solute
per liter of solution (mg/liter)
• ppb: is to mean micrograms of solute per liter (μg/liter).
• The grams to be measured (when the solute is a pure solid or
liquid) are calculated as follows.
Gram to be measured =
Gram to be measured =
• in which VD is the liters (volume)desired, ppmD and ppbD
represent the concentrations desired, and 1000 and 106 are
conversion factors which convert milligrams and
micrograms.
15
 Mole fraction (x):
 Mole fraction is the ratio of the number of mole of a given
solute to the total number of moles in a solution.
 For a two component system consisting of species i and j,

xi =
• where the n’s refer to the moles of the components.
• The sum of all mole fractions is unity. In general for
multicomponent system,
Xi = where nt is the total number of moles of all components.

16
 Properties and preparations of solutions
•Solutions have many special properties or qualities, besides their
chemical behavior, which may be classified into general types.
These general types include:
1.Specific properties: are physical properties of a solution, which
depend upon the nature of the solute particles.
•Examples: viscosity, density, surface tension, refractive index,
boiling point, etc.
2. Electrical properties: are dependent upon the number and
nature of the charged particles within the solution, which move
between the electrodes under the influences of an electric current.
Example: electrical conductivity of solution, resistance, etc.
17
 Preparations of solutions
• Preparing a solution of known concentration is most
common activity in any analytical lab.
• 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.

18
Preparations of solutions

19
 Preparations of solutions.
Dilution- the procedure for preparing a less
concentrated solution from a more concentrated one.
Aliquot: a measured sub-volume of original sample.
Diluent: material with which the sample is diluted.
Dilution factor (DF): ratio of final volume/aliquot
volume (Final volume= Aliquot + Diluent).
During dilution number of moles never change.

20
Dilution

21
 Dilution
• Since moles are constant before and after dilution, we can
use the following formula for calculations: CiVi = CfVf
• In a serial dilution the total dilution factor at any point is
the product of the individual dilution factors in each step
up to it.
• Final Dilution Factor {DF) = DFl x DF2 x DF3...
Example
1. Describe how you would prepare 800mL of a 2.0M
H2SO4 solution, starting with a 6.0M stock solution of
H2SO4
22
2. How many mL of water must be added to 200 mL of
0.65 M HCl to dilute the solution to 0.20 M.
3. A series of dilute NaCl solutions is prepared, starting
with an initial stock solution of 1.0 M NaCl. Solution A
is prepared by pipetting 10 mL of the stock solution into
a 250-mL volumetric flask and diluting to volume.
Solution B is prepared by pipetting 25 mL of solution A
into a 100-mL volumetric flask and diluting to volume.
Solution C is prepared by pipetting 20 mL of solution B
into a 500-mL volumetric flask and diluting to volume.
What is the molar concentration of NaCl in solution C.
23
 Activity and activity coefficient
• It has been already pointed out that the effective
concentration of ionized ions is less than the actual
concentration.
• The decrease in effective concentration is due to the
interionic attraction.
• The factor that is used to convert actual concentration to
effective concentration (activity) is called activity
coefficient.
• If the actual concentration is C, the effective concentration
is a, and activity coefficient is f, the mathematical
relationship among the three factors is given by a = fC.
24
• The ionic strength of a solution (m) is defined as half the
sum of the products of the concentration of all the ions
present in solution by the square of the charge of the
given ion:

• where; Ci is the molar concentration of the ion and zi is

the charge on the ion.
• For a solution that contains two or more components that
don’t interact the ionic strength is given by:
= ½( + + + ...+ )
where C1, C2, ... Cn stands for the concentrations of ion 1, 2, 3,
…, n present in the solution and zn is their respective charges.
25
• At 25oC mean activity coefficient is given by

-log f = 0.509z+z−
where of z+ and z− are charges on the positive and negative
ions respectively obtained by the dissociation of the salt.

26
Examples:
1. Calculate the ionic strength of 0.1 M solution of NaCl.
• Solution: NaCl is a strong electrolyte that dissociates almost
completely. Hence, the concentrations of sodium and chloride
ions in solution are approximated to be 0.1 M.
• Thus = [ + ] = ½[0.1(1)2 + 0.1(-1)2] = 0.1
2. What is the ionic strength of a solution containing in 1 liter
0.01 mol of K2SO4 and 0.01 mol Al2(SO4)3.
• Solution: First calculate molarity of the two salts. Molarity
is the number of moles of the solute per liter of the solution.
Hence, molarities of K2SO4 and Al2(SO4)3 are each 0.01M.
Assuming both salts dissociate almost completely,
27
 Assuming both salts dissociate almost completely,
K2SO4 2K+ + SO4-2
0.01M 2(0.01M) 0.01 M
Al2(SO4)3 2Al+3 + 3SO4-2
0.01 M 2(0.01 M) 3(0.01 M)
=[+ +
= [(0.02)( 1)2 + (0.02)( 3)2 + (0.04)( 2)2] = 0.18

Note that the concentration of the sulphate ion is the sum of

the concentrations resulting from the dissociation of the two
salts.

28