3.

Introduction
• A solution is a homogeneous mixture because its composition
and properties are uniform.

• The solvent is the component that is present in the greatest

quantity or that determines the state of matter in which a
solution exists.

• Other solution components, called solutes, are said to be

dissolved in the solvent.

• A concentrated solution has a relatively large quantity of

dissolved solute(s), and a dilute solution has only a small
quantity.
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• Solution Concentration

• Concentration is a measure of the quantity of solute in a

given quantity of solvent (or solution).

• There are several methods of expressing concentration, each

of which serves a different purpose.
• Mass Percent, Volume Percent, and Mass/Volume Percent

3
• Note that the denominator in each of these expressions is the
mass or volume of solution rather than mass or volume of
solvent.
• Mass percent and volume percent do not depend on the units.

• For example, an aqueous solution that is 3.5% NaCl by mass

contains 3.5 g of NaCl in 100.0 g of solution.

• This solution can be prepared by dissolving 3.5 g of NaCl in

96.5 g of water (100.0 - 3.5 = 96.5).

• Q. How would you prepare 425 g of an aqueous solution

containing 5.50% by mass of sodium acetate, NaC2H3O2?

4
• Molarity (The most widely used)

• The mole concept is useful in expressing concentrations of

solutions, especially in analytical chemistry.

• A one-molar solution is defined as one that contains one mole of

solute in each liter of a solution.

• More generally, the molarity of a solution is expressed as moles

per liter or as millimoles per milliliter.

• Molar solution is abbreviated as M.

5
• E.g. An ethanol water solution is prepared by dissolving 10.00
mL of ethanol a density 0.789 g/mL, in a water to produce
100.0 mL of a solution with a density 0.982 g/mL.

• What is the concentration of ethanol in this solution expressed

as (a) mass percent; (b) volume percent; (c) mass/volume
percent; (d) molarity?

6
• Q. Calculate the concentration of potassium ion in grams per
liter after mixing 100 mL of 0.250 M KCl and 200 mL of
0.100 M K2SO4.

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• Parts per Million, Parts per Billion, and Parts per Trillion

• When the mass or volume percent of a component is very low,

we use other units to describe solution concentration.

• For example,
• 1 mg/L solution of a given solute mean 0.001 g/L of it.

• A solution that is very dilute will have the same density as

water, approximately 1 g/mL at 250 C.

• This means the concentration will be equal to 0.001 g/1000 g

of solution, and it is the same as 1 g/1,000,000 g

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• We can describe the solute concentration as 1 part per
million (ppm).

• For a solution with 1 μg/L of solution, the concentration of

the solution is 1.00 × 10−6 g of solute/1000g of solution or 1
g of solute/ 1.00 × 10−9 g of solution .

• Here, the solute concentration is 1 part per billion (ppb).

• Q. Use the same analogy to express part per trillion (ppt).

• E.g. What is the molar concentration of K+ in a solution that

contains 63.3 ppm of K3Fe(CN)6 (329.3 g/mol)?

9
• 63.3 ppm of K3Fe(CN)6 = 63.3 mg of K3Fe(CN)6/L of solution

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• Normality

• A one-normal solution contains one equivalent per liter.

• An equivalent represents the mass of material providing

Avogadro’s number of reacting units.

• A reacting unit is a proton or an electron.

• The number of equivalents is given by the number of moles

multiplied by the number of reacting units per molecule or atom.

• The equivalent weight is the formula weight divided by the

number of reacting units.
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• For acids and bases, the number of reacting units depends on
the number of protons (i.e., hydrogen ions) an acid will furnish
or a base will react with.

• For redox reactions it is based on the number of electrons

involved in the redox reaction.

• For example, sulfuric acid, H2SO4, has two hydrogen ions; that
is, there are two equivalents of protons in each mole.

• Therefore, Equivalent weight of H2SO4

98.08 𝑔/𝑚𝑜𝑙
= = 49.04 𝑔/𝑒𝑞
2 𝑒𝑞/𝑚𝑜𝑙

12
• So, the normality of a sulfuric acid solution is twice its
molarity, that is, N = (g/eq wt)/L.

• The number of equivalents is given by

• Just as we use millimoles (mmol) instead of moles, we cana

also use milliequivalents (meq) instead of equivalents

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• Calculate the equivalent weight and normality for a solution of
6.0 M H3PO4 given the following reactions:

a) H3PO4(aq) + 3OH–(aq) ⇌ PO43– (aq) + 3H 2 O( l )

b) H3PO4(aq) + 2NH3(aq) ⇌ HPO42– (aq) + 2NH4+(aq)

c) H3PO4(aq) + F–(aq) ⇌ H2PO4– (aq) + HF(aq)

• The number of H+ ions donated to the base for the reactions in

a), b), and c) are the number of equivalents and are equals to 3,
2, and 1, respectively.

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• Thus, the calculated equivalent weights and normalities are

• Preparation of Solutions

• To prepare a solution with a desired concentration from a pure

solid or liquid, we measure out the correct mass of reagent.

• Then dissolve it in a volumetric flask with distilled or

deionized water.
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• Distilled water is water that has been boiled into vapor and
condensed back into liquid in a separate container.

• Deionized water is water that has been treated to remove all

ions which means all of the dissolved mineral salts..

• Dilution
• A dilute solution can be prepared from a more concentrated
solution.

• The number of moles of reagent remains unchanged.

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• E.g. The molarity of “concentrated” HCl is approximately 12.1
M. How many milliliters of this reagent should be diluted to 1.0
L to make 0.1 M HCl?

• From the formula Mcon·Vcon = Mdil·Vdil

(12.1 M) · (x mL) = (0.1 M) · (1000 mL)

x = 8.26 mL

• First place about 900 mL of water in a 1-L volumetric flask then

add 8.26 mL of concentrated HCl, and swirl to mix.

• Then dilute to 1.000 L with water and invert many times to mix
well.

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• E.g. A solution of ammonia in water is called “ammonium
hydroxide” because of the equilibrium
NH3 + H2O ⇌ NH4+ + OH−

• The density of concentrated ammonium hydroxide, which

contains 28.0 wt% NH3, is 0.899 g/mL. What volume of this
reagent should be diluted to 500.0 mL to make 0.250 M NH3?

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 4. Classical Methods of analysis
Volumetric or titrimetric analyses

• Volumetric or titrimetric analyses are among the most useful

analytical techniques, especially for millimole amounts of
analyte.

• They are generally used only in situations that require high

accuracy for relatively small numbers of samples.

• They are used, for analysis, calibration or method validation

of more routine instrumental methods.

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• In a titration, the test substance (analyte) reacts with an
added reagent of known concentration.

• The reagent of known concentration is referred to as a

standard solution.

• It is typically delivered from a buret; the solution delivered by

the buret is called the titrant.

• The volume of titrant required to just completely react with

the analyte is measured.

• Since we know the reagent concentration as well as the

reaction stoichiometry between the analyte and the reagent,
we can calculate the amount of analyte.

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• Sometimes the reverse may be carried out where a known
volume of the standard solution is taken and it is titrated with
the analyte of unknown concentration as the titrant.

• The requirements of a titration are

1. The reaction must be stoichiometric.

2. The reaction should be rapid.

3. There should be no side reactions i.e the reaction should be

specific.

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4. There should be a marked change in some property of the
solution when the reaction is complete.

5. The reaction should be quantitative. That is, the equilibrium of

the reaction should be far to the right.

• Standard solution

• A standard solution is prepared by dissolving an accurately

weighed quantity of a highly pure material called a primary
standard.

• If the material is not sufficiently pure, the solution is prepared

by approximating the desired concentration, and then
standardized by titrating it with a primary standard. 22
• A primary standard should fulfill these requirements:

1. It should be 100.00% pure, although 0.01 to 0.02% impurity

is tolerable if it is accurately known.

2. It should be stable to drying temperatures, and it should be

stable indefinitely at room temperature.

• The primary standard is always dried before weighing.

3. It should be readily and relatively inexpensively available.

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4. Although not essential, it should have a high formula
weight.

• This is so that a relatively large amount of it will have to be

weighed.

• The relative error in weighing a greater amount of material

will be smaller than that for a small amount.

5. If it is to be used in titration, it should possess the properties

required for a titration listed above.

• In particular, the equilibrium of the reaction should be far to

the right so that a sharp end point will be obtained.

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• Classification of volumetric methods.

• There are four general classes of volumetric or titrimetric

methods.

1. Acid–Base

• Many compounds, both inorganic and organic, are either acids

or bases and can be titrated with a standard solution of a
strong base or a strong acid.

• The end points of these titrations are easy to detect, either by

means of an indicator or by following the change in pH with a
pH meter.
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2. Precipitation
• In this method the titrant forms an insoluble product with the
analyte.

• An example is the titration of chloride ion with silver nitrate

solution to form silver chloride precipitate.

• An indicator can be used to detect the end point, or the potential

of the solution can be monitored electrically.

3. Complexometric

• In complexometric method the titrant is a reagent that forms a

water-soluble complex with the analyte, a metal ion.
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• Ethylenediaminetetraacetic acid (EDTA) is one of the most
useful chelating agents used for titration.

• EDTA reacts with a large number of metal ions, and the

reactions can be controlled by adjustment of pH.

• Indicators can be used to form a highly colored complex with

the metal ion.

4. Reduction–Oxidation

• These “redox” titrations involve the titration of an oxidizing

agent with a reducing agent, or vice versa.

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• An oxidizing agent gains electrons and a reducing agent loses
electrons in a reaction between them.

• There must be a sufficiently large difference between the

oxidizing and reducing capabilities for the reaction to go to
completion and give a sharp end point.

• That is, one should be a fairly strong oxidizing agent (strong

tendency to gain electrons) and the other a fairly strong
reducing agent (strong tendency to lose electrons).

• Appropriate indicators for these titrations are available;

various electrometric means to detect the end point may also
be used.

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• Volumetric Calculations

• We will use molarity for volumetric calculations.

• For analyte A that react with a titrant T to produce a product P

as shown below
aA + tT → pP

number of mole of A number of mole of T

• At equilibrium =
𝑎 𝑡

• Where a and t are the stoichiometric factor N.B the equation

must be balanced.

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• E.g.
• A 0.4671-g sample containing bicarbonate was dissolved and
titrated with standard 0.1067 M hydrochloric acid solution,
requiring 40.72 mL. The reaction is HCO3− + H+→ H2O + CO2
Calculate the percent sodium bicarbonate in the sample.

• Solution

• The millimoles of bicarbonate are equal to the millimoles of

acid used to titrate it, since they react in a 1:1 ratio.

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 𝑚𝑚𝑜𝑙𝐻𝑐𝑙 = 𝑚𝑚𝑜𝑙𝐻𝐶𝑂3
𝑚𝑚𝑜𝑙𝐻𝐶𝑂3 = 0.1067 𝑚𝑚𝑜𝑙/mL × 40.72 mL
=4.345 mmol
𝑚𝑔𝐻𝐶𝑂3 = 4.345 𝑚𝑚𝑜𝑙 × 84.01 g/mol
=365.02 mg
365.02 𝑚𝑔
% HCO3− = × 100%
467.1 𝑚𝑔
=78.15%
• Or, combining all the steps,

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• E.g. How many milliliters of 0.25 M solution of H2SO4 will
react with 10 mL of a 0.25 M solution of NaOH?

• Solution
• The reaction is H2SO4 + 2NaOH → Na2SO4 + 2H2O

• 𝑀H SO × 𝑚𝐿H SO = 𝑀NaOH × 𝑚𝐿NaOH × ½

2 4 2 4

• Therefore,

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• Standardization

• When a titrant material of high or known purity is not

available, the concentration of the approximately prepared
titrant solution must be determined by standardization.

• From the volume of titrant used to titrate the primary standard,

we can calculate the molar concentration of the titrant.

• E.g. An approximate 0.1 M hydrochloric acid solution is

prepared by the dilution of concentrated hydrochloric acid. It
is standardized by titrating 0.1876 g of dried primary standard
sodium carbonate: The titration required 35.86 mL acid.
Calculate the molar concentration of the hydrochloric acid.
CO32− + 2H+ → H2O + CO2
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• Solution

• The millimoles of hydrochloric acid are equal to twice the

millimoles of sodium carbonate titrated.

• Or, combining all steps at once,

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• Gravimetric Method

• In gravimetric analysis, the analyte is converted to an insoluble

form, which is weighed.

• From the weight of the precipitate formed and the weight

relationship between the analyte and the precipitate, we can
calculate the weight of analyte.

• The analyte is almost always weighed in a different from what

we wish to report.

• Therefore, the weight of the desired substance from the weight

of the gravimetric precipitate must be calculated.
35
• This is done by using a direct proportion.

• Example, if we are calculating the weight of Cl2 that was

precipitated by Ag would proceed as

• We derive two moles of AgCl from each mole of Cl2, so

• and

• Or
36
• The gravimetric factor (GF) is the appropriate ratio of the
formula weight of the substance sought to that of the
substance weighed.

• The gravimetric factor is the weight of analyte per unit

weight of precipitate.

• where a and b are integers that make the formula weights in

the numerator and denominator chemically equivalent.

37
• E.g. Calculate the weight of barium and the weight of Cl
present in 25.0 g BaCl2.

• Solution

38
• E.g. Aluminum in an ore sample is determined by dissolving it
and then precipitating with base as Al(OH)3 and igniting to
Al2O3, which is weighed. What weight of aluminum was in the
sample if the ignited precipitate weighed 0.2385 g?

• Solution

• The gravimetric factor is

39