CHM 219 ANALYTICAL CHEMISTRY I READING NOTE

ANALYTICAL CHEMISTRY I
UNIT ONE
• Meaning of Analytical Chemistry
Analytical chemistry is often described as the area of chemistry responsible for
characterizing the composition of matter, both qualitatively (what is present) and
quantitatively (how much is present). The craft of analytical chemistry is not in performing
a routine analysis on a routine sample which is more appropriately called (chemical
analysis), but in improving established methods, extending existing methods to new types
of samples, and developing new methods for measuring chemical phenomena. Here’s one
example of this distinction between analytical chemistry and chemical analysis. Mining
engineers evaluate the economic feasibility of extracting an ore by comparing the cost of
removing the ore with the value of its contents. To estimate its value, they analyze a sample
of the ore. The challenge of developing and validating the method providing this
information is the analytical chemist’s responsibility. Once developed, the routine, daily
application of the method becomes the job of the chemical analyst.

Analytical chemistry is a branch of chemistry concerned with the chemical characterization

of matter and answer two questions: what is it (Qualitative) and how much is it
(Quantitative). Chemicals make up everything we use or consume, and knowledge of the
chemical composition of many substances is important in our daily lives.

• Qualitative and Quantitative Analysis

Analysis is a process that provides chemical or physical information about the constituents
in the sample or the sample itself. Qualitative analysis establishes the chemical identity of
the species in the sample. Quantitative analysis determines the relative amounts of these
species, or analytes, in numerical terms. The former deals with the identification of
elements, ions or compounds present in a sample (we may be interested in whether only a
given substance is present), while the latter deals with the determination of how much of
one or more constituents are present. The sample may be solid, liquid, gas or mixture.
 CHM 219 ANALYTICAL CHEMISTRY I READING NOTE

Analytes are the components of a sample to be determined. The presence of gunpowder

residue on a hand of suspect generally requires only qualitative detection, not of how much
is there, but the price of coal will be determined by the percent of sulphur impurity present.
The analyte determined here is sulphur in coal sample.

Qualitative tests may be performed by selective chemical reaction or with the use of
instrumentation. A clear distinction between selective and specific is that:

• A selective reaction or test is one that can occur with other substances but exhibits
a degree of preference for the substance of interest.
• A specific reaction or test is one that occurs only with the substance of interest.
Unfortunately, few reactions are specific but many exhibit selectivity.

Importance of Analytical Chemistry

Analytical chemistry seeks ever improved means of measuring the chemical composition
of natural and artificial materials. The techniques of this science are used to identify the
substances which may be present in a material and to determine the exact amounts of the
identified substance. Analytical chemistry is applied throughout all fields of study as
represented in fig 1.1 below. Some of the fields are;

1. Chemistry and Biochemistry: Quantitative analytical measurements also play a vital

role in many research areas in chemistry and biochemistry. For example, quantitative
measurements of potassium, calcium, and sodium ions in the body fluids of animals
permit physiologists to study the role of these ions in nerve signal conduction as well
as muscle contraction and relaxation. Chemists unravel the mechanisms of chemical
reactions through reaction rate studies. The rate of consumption of reactants or
formation of products in a chemical reaction can be calculated from quantitative
measurements made at equal time intervals. Materials scientists rely heavily on
quantitative analyses of crystalline germanium and silicon in their studies of
semiconductor devices. Impurities in these devices are in the concentration range of 1
X 10-6 to 1 X 10-9 percent.
 CHM 219 ANALYTICAL CHEMISTRY I READING NOTE

2. Medicine: Analytical chemistry is the basis for clinical laboratory tests which help
physicians diagnose disease and chart progress in recovery.
3. Industry: It provides the means of testing raw materials and for assuring the quality of
finished products whose chemical composition is critical. Many household products,
fuels, paints, pharmaceuticals, etc. are analyzed by the procedures developed by
analytical chemists before being sold to the consumer.
4. Environmental Quality: This is often evaluated by testing for suspected contaminants
using the techniques of analytical chemistry.
5. Food and Nutrition: The nutritional value of food is determined by chemical analysis
for major components such as protein and carbohydrates and trace components such as
vitamins and minerals.
6. Forensic Science: Analytical chemistry techniques are needed to determine the
residues of narcotics, cannabis, barbiturates, and other hard drugs in criminals.
7. Archaeology: Archaeologists identify the source of volcanic glasses (obsidian) by
measuring concentrations of minor elements in samples taken from various locations.
This knowledge in turn makes it possible to trace prehistoric trade routes for tools and
weapons fashioned from obsidian.
8. Geology: The mineralogical composition of soil and rock is monitored using the
techniques developed by Analytical Chemistry.
 CHM 219 ANALYTICAL CHEMISTRY I READING NOTE

Expressions of Analytical Results

Analytical results are always reported as concentration based on weight (mass) or volume,
i.e. the quantity of analyte in a unit weight or unit volume of analyte.

Units of Measurements

The common units of mass/volume will be presented below. The basic unit of mass is
gram(g) in the metric system. It is the unit commonly used in macroanalysis. It has the
following subunits which are used for trace or ultra-trace constituents in samples;

Milligram (mg) = 10-3g

Microgram (µg) = 10-6g

Nanogram (ng) =10-9g or 10-6mg

 CHM 219 ANALYTICAL CHEMISTRY I READING NOTE

The basic unit of volume is Litre (L), its subunits include:

Millilitre (mL) = 10-3L

Microlitre (µL) = 10-6L

Nanolitre (nL) = 10-9L or 10-6mL

Other subunits for quantities used by scientists are the following prefixes in the table below.

❖ Percent Concentration
Chemists frequently express concentrations in terms of percent (parts per hundred).
Unfortunately, this practice can be a source of ambiguity because percent composition of
a solution can be expressed in several ways. Three common methods are weight solute

𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
Weight percent (w/w) = X 100%
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
Volume percent (v/v) = X 100%
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 (𝑔)

weight/volume percent (w/v) = X 100%
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 (𝑚𝐿)
 CHM 219 ANALYTICAL CHEMISTRY I READING NOTE

Note that the denominator in each of these expressions refers to the solution rather than to
the solvent. Note also that the first two expressions do not depend on the units employed
(provided, of course, that there is consistency between numerator and denominator). In the
third expression, units must be defined because the numerator and denominator have
different units that do not cancel. Of the three expressions, only weight percent has the
virtue of being temperature independent. Weight percent is frequently employed to express
the concentration of commercial aqueous reagents. For example, nitric acid is sold as a
70% solution, which means that the reagent contains 70 g of HN03 per 100 g of solution.

Volume percent is commonly used to specify the concentration of a solution prepared by

diluting a pure liquid compound with another liquid. For example, a 5% aqueous solution
of methanol usually describes a solution prepared by diluting 5.0 mL of pure methanol with
enough water to give 100-mL. Weight/volume percent is often employed to indicate the
composition of dilute aqueous solutions of solid reagents. For example, 5% aqueous silver
nitrate often refers to a solution prepared by dissolving 5 g of silver nitrate in sufficient
water to give 100 mL of solution.

❖ Parts per million: Micrograms of solute per gram of solution; for aqueous solutions
the units are often expressed as milligrams of solute per liter of solution (ppm). Parts
per billion: Nanograms of solute per gram of solution; for aqueous solutions the units
are often expressed as micrograms of solute per liter of solution (ppb).

For concentration in parts per million and parts per billion (w/w);

𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 (𝑔) µ𝑔 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑚𝑔 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑛𝑔 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒

Conc. (ppm) = × 106 = = =
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 (𝑔) 𝑔 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝐾𝑔 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑚𝑔 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 (𝑔) 𝑛𝑔 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 µ𝑔 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑝𝑔 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒

Conc. (ppb) = × 109 = = =
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 (𝑔) 𝑔 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝐾𝑔 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑚𝑔 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

For concentration in parts per million (w/v);

𝑚𝑔 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 µ𝑔 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑛𝑔 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒

Conc. (ppm) = = =
𝐿 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑚𝐿 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 µ𝐿 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
 CHM 219 ANALYTICAL CHEMISTRY I READING NOTE

µ𝑔 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑛𝑔 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑝𝑔 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒

Conc. (ppb) = = =
𝐿 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑚𝐿 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 µ𝐿 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

Parts per million (ppm) and parts per billion (ppb) are mass ratios of grams of solute to
one million or one billion grams of sample, respectively. For example, a steel that is 450
ppm in Mn contains 450 mg of Mn for every gram of steel. If we approximate the density
of an aqueous solution as 1.00 g/mL, then solution concentrations can be expressed in parts
per million or parts per billion using the following relationships. For gases a part per
million usually is a volume ratio. Thus, a helium concentration of 6.3ppm means that one
liter of air contains 6.3 mL of He.

❖ Molarity: The number of moles of solute per litre of solution (M). Molarity is the
concentration of a particular chemical species in solution.

𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒆
Molarity =
𝑳𝒊𝒕𝒓𝒆𝒔 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏

❖ Normality: The number of equivalents of solute per liter of solution (N). Normality
makes use of the chemical equivalent, which is the amount of one chemical species
reacting stoichiometrically with another chemical species. Note that this definition
makes an equivalent, and thus normality, a function of the chemical reaction in which
the species participates. Although a solution of H2SO4 has a fixed molarity, its normality
depends on how it reacts. The number of equivalents, n, is based on a reaction unit,
which is that part of a chemical species involved in a reaction. In a precipitation
reaction, for example, the reaction unit is the charge of the cation or anion involved in
the reaction; thus for the reaction

Pb2+(aq) + 2I–(aq) PbI2(s)

n = 2 for Pb2+and n = 1 for I–. In an acid–base reaction, the reaction unit is the number of
H+ ions donated by an acid or accepted by a base. For the reaction between sulfuric acid
and ammonia
 CHM 219 ANALYTICAL CHEMISTRY I READING NOTE

H2SO4(aq) + 2NH3(aq) 2NH4+(aq)+ SO42–(aq)

we find that n = 2 for H2SO4 and n = 1 for NH3.

𝑵𝒐 𝒐𝒇 𝑬𝒒𝒖𝒊𝒗𝒂𝒍𝒆𝒏𝒕 𝒘𝒆𝒊𝒈𝒉𝒕𝒔 𝒔𝒐𝒍𝒖𝒕𝒆

Normality =
𝑳𝒊𝒕𝒓𝒆𝒔 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏

Equivalent weight: The mass of a compound containing one equivalent (EW). Formula
weight: The mass of a compound containing one mole (FW).

𝑾𝒆𝒊𝒈𝒉𝒕 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒆
No of EWs solute =
𝑬𝒒𝒖𝒊𝒗𝒂𝒍𝒆𝒏𝒕 𝒘𝒆𝒊𝒈𝒉𝒕

𝑭𝒐𝒓𝒎𝒖𝒍𝒂 𝒘𝒆𝒊𝒈𝒉𝒕 (𝑭𝑾)

Equivalent weight =
𝑵𝒐 𝒐𝒇 𝒗𝒂𝒍𝒆𝒏𝒄𝒚 (𝒏)

𝑾𝒆𝒊𝒈𝒉𝒕 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒆
Normality = ×n
𝑭𝒐𝒓𝒎𝒖𝒍𝒂 𝒘𝒆𝒊𝒈𝒉𝒕 × 𝑳𝒊𝒕𝒓𝒆𝒔 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏

Consequently, the following simple relationship exists between normality and molarity.

N = n×M

❖ Molality: The number of moles of solute per kilogram of solvent (m). This is given by
number of moles of solute per 1000grams of the solvent.

𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒆 𝒐𝒓 𝒏
Molality (m) = ×1000
𝑲𝒊𝒍𝒐𝒈𝒓𝒂𝒎 𝒐𝒇 𝒔𝒐𝒍𝒗𝒆𝒏𝒕 𝒐𝒓 𝑾

Simple Class Exercise

1. What is the molarity of a solution made by dissolving 2.355 g of sulfuric acid in water
and diluting to a final volume of 50.0 mL?
2. Hydrochloric acid is sold commercially as a 12.0 M solution. How many moles of HCl
are in 300.0 mL of 12.0 M solution?
3. 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) + 3H2O(l)
(b) H3PO4(aq) + 2NH3(aq) HPO42–(aq) + 2NH4+(aq)
 CHM 219 ANALYTICAL CHEMISTRY I READING NOTE

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

4. In standard method for Alkalinity measurement, a solution of 0.05N of Na2CO3 should

be prepared based on the following titration reaction with sulfuric acid:
Na2CO3(aq) + H2SO4 [H2CO3] + Na2SO4(aq) H2O(aq) + CO2(gas) + Na2SO4(aq)
The part [H2CO3] is an intermediate which is directly converted to H2O and CO2 gas.
How many grams of Na2CO3 required to prepare 1.0 Liter of 0.05N solution?
5. What is the molality of solution made by dissolve 25 g of NaCl in to 2.0 Liter of water.
Assume the density of water d = 1.0 g/mL (= kg/L).
6. How many grams of NaCl required to prepare each of the following solutions:
a) 2500 ppm (w/v) NaCl 250 mL solution.
b) 10% (w/v) NaCl in 250 mL solution.
c) 20% (w/w) NaCl in 250 g solution.
7. What is the concentration of MgSO4 the following prepared solution, express
concentrations in ppm, %(w/v) and (w/w) concentrations units. Assume solution
density is 1.0 g/mL 30 g of MgSO4 dissolved in 500 mL distilled water.
8. A 2.6-g sample of Nile tilapia fish tissue was analyzed and found to contain 3.6µg lead
(Pb). What is the concentration of Pb in the fish in ppm? In ppb?
9. The maximum allowed concentration of chloride in a municipal drinking water supply
is 2.50×102ppm Cl–. When the supply of water exceeds this limit, it often has a
distinctive salty taste. What is this concentration in moles Cl–/liter?
10. Determine the molarity of a solution containing 86.53grams of sodium carbonate
(Na2CO3)(MM-105.99) per litre of the solution in water at 20ºc. The density of the
solution at this temperature is 1.0816g/ml. Also, find the molality of the solution?

Preparation of Solutions

Preparing a solution of known concentration is perhaps the most common activity in any
analytical lab. The method for measuring out the solute and solvent depend on the desired
concentration units, and how exact the solution’s concentration needs to be known. Pipets
 CHM 219 ANALYTICAL CHEMISTRY I READING NOTE

and volumetric flasks are used when a solution’s concentration must be exact; graduated
cylinders, beakers, and reagent bottles suffice when concentrations need only be
approximate. Two methods for preparing solutions are described in this section.

Preparing Stock Standard Solution

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. For example, to
prepare a solution with a desired molarity you would weigh out an appropriate mass of the
reagent, dissolve it in a portion of solvent, and bring to the desired volume. To prepare a
solution where the solute’s concentration is given as a volume percent, you would measure
out an appropriate volume of solute and add sufficient solvent to obtain the desired total
volume. A standard solution is a solution which contains a known mass of a solution. It is
in a known volume of solution. It is also defined as a solution of known concentration. The
concentration of a standard solution can be expressed as follows

𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠
Molar concentration =
𝑉𝑜𝑙𝑢𝑚𝑒 (𝑑𝑚3 𝑜𝑟 𝐿)

𝑔
𝑀𝑎𝑠𝑠 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 (𝑑𝑚3)
Molar concentration =
𝑀𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 (𝑔/𝑚𝑜𝑙)

Also, mass concentration (g/dm3) =molar concentration X Molar mass. Therefore, standard
solution can be prepared in moldm-3 or gdm-3.

To prepare a standard solution, a definite mass of the standard substance, e.g

Na2CO3 is weighed and dissolved in distilled water to from a known volume of solution.
Solution prepared as above is known as primary standard solution.

Example 1

Describe the preparation of 500cm3 solution of 0.5 moldm-3 (0.5M) of solution hydroxide
solution.
 CHM 219 ANALYTICAL CHEMISTRY I READING NOTE

Solution

𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠
Molar concentration =
𝑉𝑜𝑙𝑢𝑚𝑒 (𝑑𝑚3 𝑜𝑟 𝐿)

Moles concentration = molar x volume in dm3

= 0.5 moldm-3 x 5000x10-dm3 = 0.25 mol

𝑚𝑎𝑠𝑠 𝑜𝑓 𝑁𝑎𝑂𝐻
Mole =
𝑀𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑁𝑎𝑂𝐻

Molar mass of NaOH = 23+16+1= 40gmol-1

Mass of NaOH = mole x molar mass

= 0.25mol x 40gmol-1 = l0g

Hence, to prepare 500mL of 0.5 solution of NaOH, weigh accurately 10g of NaOH and
dissolve distilled water of 500mL of volumetric flask. The beaker is rinsed repeatedly with
small portions of water, which are added to the volumetric flask. This process, which is
called a quantitative transfer, ensures that the NaOH is completely transferred to the
volumetric flask. Finally, additional water is added to the volumetric flask’s calibration
mark.

Preparation of standard solution from concentrated reagent

The concentrated solution is however relative as the percentage of most mineral

acids in the commercial aqueous reagent is always is less than 100% weight percent,
relative density is frequently used to express the concentration of commercial aqueous
reagents. The molar concentration is usually not given but this can be worked out.

Example 2

Describe the preparation of 500cm3 of 3M H2SO4 from the consented reagent the labeled
on the bottle states that the reagent is 95% H2SO4 has a specific gravity of 1.84?
 CHM 219 ANALYTICAL CHEMISTRY I READING NOTE

Solution

The specific gravity (or density) of 1.84g H2SO4 if it 98% pure H2SO4

98 × 1.84𝑔
∴ 1cm3 of the acid will contain = 1.80g of H2SO4
100

Convert the mass of H2SO4 to molar mass of H2SO4 = 98gmol-1

1.80𝑔
∴ 1cm3 of the acid contains = 0.0184 mol of H2SO4
98𝑔/𝑚𝑜𝑙

1000cm3 (1dm3) of the acid will contain 0.0184x1000 =18.4mol

The concentration of the concentrated reagent of H2SO4 is 18.4 moldm-3 or 18.4M

Using dilution law,

CiVi = CfVf

Ci = initial concentration Cf = final concentration

Vi = initial volume Vf = final volume;

3𝑀 ×500𝑚𝐿
Vi = = 81.52mL
18.4 𝑀

Hence, to prepare 3M H2SO4 take 81.52cm3 of the concentrated reagent and dilute to
500mL with distilled water.

Example 3

How to prepare approximately a 0.5moldm-3 of hydrochloric acid form the commercial

reagent that is 37%HCl and relative density of 1.18?

Solution

To find the concentration of the concentrated acid in the bottle, we start from the
information we have;
 CHM 219 ANALYTICAL CHEMISTRY I READING NOTE

Density = 1.18g/cm3, M. Mt = 36.5g/mol, 37% (w/w)

37𝑔 𝑜𝑓 𝐻𝐶𝑙
37% (w/w) =
100𝑔 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

37𝑔 𝑜𝑓 𝐻𝐶𝑙 1.18𝑔 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 1000𝑚𝐿 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 1𝑚𝑜𝑙 𝐻𝐶𝑙

× × × = 12molL-1 or 12
100𝑔 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 1𝑚𝐿 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 1𝐿 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 36.5𝑔/𝑚𝑜𝑙

The concentration of the HCl stock solution is 12moldm-3 or 12M

using dilution law,

CiVi = Cf Vf

12M x Vi = 0.5M x1000cm3

0.5𝑀 ×1000𝑚𝐿
Vi = =41.7cm3
12𝑀

Hence, to prepare 0.5M HCl, take 41.7cm3 of the concentrated reagent and dilute to
1000cm3 (1dm3) with distilled water.

Preparing Solutions by Dilution

Solutions with 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. Dilution is e process of preparing a less concentrated solution
from a more concentrated solution. For convenience, chemicals are sometimes bought and
stored as concentrated solutions that must be diluted before use. Aqueous hydrochloric
acid, for example, is sold commercially as a 12.0M solution, yet it is most commonly used
in the laboratory after dilution with water to a final concentration of 6.0M or 1.0M.

Concentrated Solution + Solvent Diluted Solution

Since the total amount of solute is the same before and after dilution, we know that

Ci × Vi = Cf × Vf
 CHM 219 ANALYTICAL CHEMISTRY I READING NOTE

where Ci is the concentration of the stock solution, Vi is the volume of the stock solution
being diluted, Cf is the concentration of the dilute solution, and Vf is the volume of the
dilute solution. Again, the type of glassware used to measure Vi and Vf depends on how
exact the solution’s concentration must be known. Rearranging this equation into a more
useful form shows that the molar concentration after dilution (Cf) can be found by
multiplying the initial concentration (Ci) by the ratio of initial and final volumes (Vi/Vf):

𝑉𝑖
Cf = Ci ×
𝑉𝑓

Part (Vf/Vi) called dilution factor:

𝐶𝑖
Cf = Ci = Cf × DF
𝐷𝐹

𝑉𝑖 𝑀𝑖
Where DF (Dilution Factor) = =
𝑉𝑓 𝑀𝑓

Suppose, for example, that we dilute 50.0 mL of a solution of 2.00 M to a volume of 200.0
mL. The solution volume increases by a factor of four (from 50 mL to 200 mL), so the
concentration of the solution must decrease by a factor of four (from 2.00 M to 0.500 M):

50.0𝑚𝐿
Cf = 2.00M × = 0.500M
200.0𝑚𝐿

𝑉𝑓 200.0𝑚𝐿
Dilution Factor DF = = =4
𝑉𝑖 50.0𝑚𝐿

Exercise

1. How would you prepare 500.0 mL of 0.2500 M NaOH solution starting from a
concentration of 1.000 M?
2. Describe how you would prepare the following three solutions: (a) 500 mL of
approximately 0.20 M NaOH using solid NaOH; (b) 1 L of 150.0 ppm Cu2+ using Cu
metal; and (c) 2 L of 4% v/v acetic acid using concentrated glacial acetic acid?
 CHM 219 ANALYTICAL CHEMISTRY I READING NOTE

3. 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)?
4. A sample of an ore was analyzed for Cu2+ as follows. A 1.25-g sample of the ore was
dissolved in acid and diluted to volume in a 250-mL volumetric flask. A 20-mL portion
of the resulting solution was transferred by pipet to a 50-mL volumetric flask and
diluted to volume. An analysis showed that the concentration of Cu2+ in the final
solution was 4.62 ppm. What is the weight percent of Cu in the original ore?
5. How many grams of Sodium Persulfate (Na2S2O8) required to prepare a 1 L solution of
Sodium Persulfate with concentration of 10% (w/v). This solution is widely used as
oxidizing reagent for Total Organic Carbon analyzer (TOC)?
6. How to prepare a 500 mL solution of 2.0 N Sulfuric acid (H2SO4) from concentrated
bottle of Sulfuric acid. If the following information written on Sulfuric acid bottle:
M.Wt = 98.08 g/mol, d= 1.84 g/cm3 , 97% (w/w).
7. If we need to prepare a solution of NaOH with concentration of 20% (w/w) with total
weight of solution equals to 2.0 Kg, how many grams of Sodium Hydroxide required.
8. A Total Petroleum Hydrocarbon (TPH) standard solution is prepared by dissolving
amount of mineral oil (motor oil) in organic solvent like n-hexane or chloroform.
Explain how to prepare TPH standard in 100 mL volume with concentration of 50,000
ppm (w/v).
9. How to prepare 500 g solution of 5 % (w/w) NaOH starting from 50% (w/w) NaOH
solution.
10. Blank solution for metals analysis on ICP-OES is normally 2% Nitric acid (HNO3)
solution, how to prepare 1 liter of the blank solution from concentrated bottle of Nitric
acid if the following information appear on the concentrated bottle. 69% (w/w),
d=1.408 g/cm3 , M.W = 63.01288 g/mol.
11. The concentration of sugar (glucose, C6H12O6) in human blood ranges from about 80
mg/100 mL before meals up to 120 mg/100 mL after eating. Find the molarity of
glucose in blood before and after eating.
 CHM 219 ANALYTICAL CHEMISTRY I READING NOTE

12. Express the following solution concentrations in % (w/v):

a) 5 N of NaOH solution b) 2000 ppm of NaCl c) 3 M of Na2CO3
13. How to prepare 200 mL of solution with concentration of 1% (w/v) NaOH starting from
NaOH 20 %?
14. A student has got three stock standard solutions of 3 different elements, zinc (Zn) 2000
ppm, cadmium (Cd) 1500 ppm and lead (Pb) 1000 ppm. A student took 10 mL from
each solution and transfers it to 200 mL volumetric flask then completed to total volume
with solvent. What is the final concentration of each element in the diluted mix
solution?

UNIT TWO

ERROR AND STATISTICAL TREATMENT OF ANALYTICAL DATA

The whole essence of chemical analysis is to have good accuracy and good precision.
Measurements invariably involve errors and uncertainties. Only a few of these are due to
mistakes on the part of the experimenter. More commonly, errors are caused by faulty
calibrations or standardizations or random variations and uncertainties in results. Frequent
calibrations, standardizations, and analyses of known samples can sometimes be used to
lessen all but the random errors and uncertainties. In the limit, however, measurement
errors are an inherent part of the quantized world in which we live. Because of this, it is
impossible to perform a chemical analysis that is totally free of errors or uncertainties. We
can only hope to minimize errors and estimate their size with acceptable accuracy. In this
unit, we explore the nature of experimental errors and their effects on the results of
chemical analyses.

Concept of Errors

The term error has two slightly different meanings. First, error refers to the difference
between a measured value and the "true" or "known" value. Second, error often denotes
the estimated uncertainty in a measurement or experiment.
 CHM 219 ANALYTICAL CHEMISTRY I READING NOTE

• Error is a measure of bias in a result or measurement. It is the difference between a

single measurement or mean result and its true value.
• Uncertainty is the range of possible values for a measurement. It expresses the range
of possible values that a measurement or result might reasonably be expected to
have.

Errors are normal in science or chemical analysis. Every measurement has an associated
error that can be quantified or determined and can be avoided. Although, some errors are
inherent in analysis and cannot be eliminated but can be minimized.

Some Important Terms in Chemical Analysis

➢ Accuracy is the degree of closeness or agreement between the measured value or

analytical result and the accepted true value. An absolute true value is seldom
known. We can by good analytical technique, such as making comparisons against
known standard sample of similar composition, arrive at a reasonable assumption
of about the accuracy of a method, within the limitations of the knowledge of the
“known” sample (and of measurements).
➢ Precision is defined as the degree of closeness or agreement among replicate
measurements or results obtained from replicate analysis of the same sample. That
is, it is the repeatability of a result. The precision may be expressed as the standard
deviation, the coefficient of variation, the range of the data, or as a confidence
interval (e.g., 95%) about the mean value. Good precision does not assure good
accuracy. On the other hand, the precision can be relatively poor and the accuracy,
more or less by chance, may be good. Since all real analyses are unknown, the higher
the degree of precision, the greater the chance of obtaining the true value (good
accuracy).
➢ Repeatability is the precision that is associated with replicate analysis of a sample
by an analyst over a short period under the same laboratory condition. It is the
precision obtained when all measurements are made by the same analyst during a
single period of laboratory work, using the same solutions and equipment. This is
 CHM 219 ANALYTICAL CHEMISTRY I READING NOTE

the precision of an analysis in which the only source of variability (spread) is the
analysis of replicate samples.
➢ Reproducibility is the precision that is associated with replicate analysis of a
sample over a long period of time often in different laboratory conditions. It is the
precision obtained under any other set of conditions, including that between
analysts, or between laboratory sessions for a single analyst. The precision when
comparing results for several samples, for several analysts, or several methods.
➢ Replicates are samples of about the same size that are carried through an analysis
in exactly the same way.
➢ Analytes: The components or constituents of interest in a sample.
➢ Matrix: All other constituents in a sample except for the analytes.

Types of Errors

There are at least two types of error that can affect the accuracy or precision of a measured
quantity. They are Determinate and Indeterminate errors.

❖ Determinate/Systematic errors are those that, as the name implies, are determinable
and that are presumably can be either avoided or corrected. They may be constant, as
in the case of an uncalibrated weight or glassware that is used in all weighing and
measurements. Or, they may be variable but of such a nature that they can be accounted
 CHM 219 ANALYTICAL CHEMISTRY I READING NOTE

for and corrected, such as a burette whose volume readings are in error by different
amounts at different volumes. Such measurable determinate errors are classed as
systematic errors. Some of the common determinate errors are:

1. Personal/operative errors: These errors result from personal or the operator of the
instrument or due to carelessness on the part of the analyst. Also, analyst inability
to differentiate between colour changes at the end point during titration due to colour
blindness, mathematical errors in calculation and prejudice in estimating
measurements.

2. Instrumental errors: These include faulty equipment, uncalibrated weights, and

uncalibrated glassware.

3. Reagent error: These errors arise from presence of impurities in a reagent used in
the analysis. A high purity reagent should be used to give good yield of the analysis.

4. Method error: These are the most serious errors of an analysis. Most of the above
errors can be minimized or corrected for, but errors that are inherent in the method
cannot be changed unless the conditions of the determination are altered. Some
sources of methodic errors include coprecipitation of impurities, slight solubility of
a precipitate, side reactions, incomplete reactions and impurities. Sometimes
correction can be relatively simple for example, by running a reagent blank.

5. Sampling Errors: We introduce determinate sampling errors when our sampling

strategy fails to provide a representative sample. This is especially important when
sampling heterogeneous materials. For example, determining the environmental
quality of a lake by sampling a single location near a point source of pollution, such
as an outlet for industrial effluent, gives misleading results. In determining the mass
of a U.S. penny, the strategy for selecting pennies must ensure that pennies from
other countries are not inadvertently included in the sample.

6. Measurement Errors: Analytical instruments and equipment, such as glassware and

balances, are usually supplied by the manufacturer with a statement of the item’s
 CHM 219 ANALYTICAL CHEMISTRY I READING NOTE

maximum measurement error, or tolerance. For example, a 25-mL volumetric

flask might have a maximum error of ±0.03 mL, meaning that the actual volume
contained by the flask lies within the range of 24.97–25.03-mL. Although expressed
as a range, the error is determinate; thus, the flask’s true volume is a fixed value
within the stated range.

❖ Indeterminate errors: These errors are often called accidental or random errors,
which represent the experimental uncertainty that occurs in any measurement. These
errors are revealed by small differences in successive measurements made by analyst
under virtually identical conditions and they cannot be predicted or estimated.

Sources of Indeterminate Error

Indeterminate errors can be traced to several sources, including the collection of samples,
the manipulation of samples during the analysis, and the making of measurement. When
collecting a sample, for instance, only a small portion of the available material is taken,
increasing the likelihood that small-scale inhomogeneities in the sample will affect the
repeatability of the analysis. Individual pennies, for example, are expected to show
variation from several sources, including the manufacturing process, and the loss of small
amounts of metal or the addition of dirt during circulation. These variations are sources of
indeterminate error associated with the sampling process. During the analysis numerous
opportunities arise for random variations in the way individual samples are treated. In
determining the mass of a penny, for example, each penny should be handled in the same
manner. Cleaning some pennies but not cleaning others introduces an indeterminate error.

Evaluating Indeterminate Error

Although it is impossible to eliminate indeterminate error, its effect can be minimized if

the sources and relative magnitudes of the indeterminate error are known. Indeterminate
errors may be estimated by an appropriate measure of spread. Typically, a standard
deviation is used, although in some cases estimated values are used. The contribution from
 CHM 219 ANALYTICAL CHEMISTRY I READING NOTE

analytical instruments and equipment are easily measured or estimated. Indeterminate

errors introduced by the analyst, such as inconsistencies in the treatment of individual
samples, are more difficult to estimate.

Characteristics of Systematic and Random Errors

Systematic Error Random Error

1. Determinate error usually large in Indeterminate error generally small in
magnitude magnitude
2. They are unidirectional and fixed in They usually occur as fluctuation on
magnitude both sides of a position (+ve and -ve) i.e.
not unidirectional.
3. It can be predicted or predetermined. The value cannot be predicted.
4. Most systematic error can be avoided Random error cannot be avoided
5. Systematic errors affect accuracy Random error affects precision.
6. The magnitude is not constant.

Estimate of Accuracy and precision

The accuracy of measurements or methods can be estimated using the absolute error or
relative absolute error, RAE.

• Absolute Error (Bias) is calculated as µ-x, where µ is the accepted true value and
x is the mean value of the measurement. It gives the bias that occurred between the
values.

• Relative Absolute Error: It is also referred to as ACCURACY. Good accuracy is

the same as high accuracy, but the relative absolute error should be low. Relative
error can be expressed in percentage (%) or in parts per thousand (ppt) as follows:

µ−𝑋 µ−𝑋
R.A.E = × 100% or = × 1000‰
µ µ
 CHM 219 ANALYTICAL CHEMISTRY I READING NOTE

Also, the precision of the measurements can be evaluated using standard deviation, relative
standard deviation or coefficient of variation, standard error, etc.

• Standard deviation: It is related to stated mean (X), the higher the standard
deviation is equal to poor precision. The absolute standard deviation, s, describes
the spread of individual measurements about the mean and is given as

Sd = Σ(x-xi)2

n-1

Sd = standard deviation of a sample (n≤10) δn-1 or δn when n>10, where Xi is one of

n individual measurements, and X is the mean.

• Relative Standard deviation: It is called coefficient of variation and otherwise

called precision. The higher the coefficient of variation, the poorer is the precision,
but low coefficient of variation will give good precision. Precision is

𝑆 𝑆
Rsd = ×100% or ×1000‰
𝑋 𝑋

• Standard Error: It is sometimes referred to standard deviation of the mean Smean, and
is calculated

Smean = S
√N
Class Exercise

1. A sample of soil was analysed in replicate for its organic carbon content. The following
results were obtained:
2.34, 2.44, 2.29, 2.45, 2.53, 2.42, 2.42, 2.33, 2.51, 2.30 (%)
The organic carbon content had been previously established to be 2.56%. How
accurate is the result?
2. A plant sample was analysed in replicate for the concentration of phosphate-
phosphorus. The following results were obtained:
 CHM 219 ANALYTICAL CHEMISTRY I READING NOTE

14.5, 14.4, 14.7, 14.0, 14.1, 14.3, 14.5, 14.7 mg/kg

i. What is the coefficient of variation?
ii. What is the standard error of the mean?
iii. What is the bias, given a true value of 14.7 mg/kg?
iv. Estimate the accuracy and relative standard deviation in percentage and parts
per thousand?
3. A sample of pure potassium chlorate was analyzed for chloride ion using
conductometric titrations. The following results in percentage were obtained:
27.24, 27.18, 27.31, 27.29, 27.38, 27.42, 27.22, 27.42, 27.62, 27.50
Use the above information to calculate:
a) (i) Standard error of the mean
(ii) coefficient of variation
(iii) variance
b) What are the absolute and percentage relative errors of the mean composition of
chloride when compared with the theoretical percentage composition of chloride
ion in KClO3? [K = 39, Cl = 35.5, O = 16]
4. The following is a list of common errors encountered in research laboratories.
Categorize each as a determinate and indeterminate errors, and further categorize
determinate errors as instrumental, personal or methodical errors.
a) Solubility of the precipitate in the wash liquid.
b) A tip of the pipette used in the titrimetric analysis is broken.
c) A radioactive substance being counted by scintillation counter repeatedly without
any change in conditions yields a slightly different count rate at each trial.
d) Leaving funnel on top of the burette during acid-base titration.
e) A student claimed not to observe any colour change with methyl orange indicator
during acid-base titration.
f) During acid-base titration, an analyst who is expected to put the acid in the burette
and base in the conical flask did the reverse of this.
 CHM 219 ANALYTICAL CHEMISTRY I READING NOTE

5. The concentration of Nickel in Nigerian coin was determined spectrophotometrically

with visible spectrophotometer, and the following results (µg g-1) were obtained: 3.65,
4.11, 3.59, 7.51, 3.95, 3.87, 4.06, 1.48, 3.60, 3.76 and 3.99. If the true concentration of
nickel in the coin as determined by atomic absorption and inductively coupled plasma
atomic emission spectrophotometers was 3.92µg g-1. Use this to determine:

i. Absolute error

ii. Percentage relative error

iii. Average deviation

iv. Standard deviation

v. Coefficient of variation

vi. Standard error

vii. Variance

viii. Relative accuracy in parts per thousand.

UNIT THREE

INTRODUCTION TO THEORY OF SAMPLING AND CHEMICAL METHODS

OF ANALYSIS

Sampling is one of the most important operations in a chemical analysis analyses use only
a small fraction of the available sample. Knowing how much sample to collect and to
further subdivide the collected sample to obtain a laboratory sample is vital in the analytical
process. The sampling process involves obtaining a small amount of material that
accurately represents the bulk of the material being analyzed. Acquiring a representative
sample is a statistical process. A chemical analysis is most often performed on only a small
fraction of the material whose composition is of interest. Clearly, the composition of this
 CHM 219 ANALYTICAL CHEMISTRY I READING NOTE

fraction must reflect as closely as possible the average composition of the bulk of the
material if the results are to have value. The process by which a representative fraction is
acquired is termed sampling. Often, sampling is the most difficult step in the entire
analytical process and the step that limits the accuracy of the procedure. This statement is
particularly true when the material to be analyzed is a large and inhomogeneous liquid,
such as a lake, or an inhomogeneous solid, such as an ore, a soil, or a piece of animal tissue.

Sampling is the process by which a sample population is reduced in size to an amount of

homogeneous material that can be conveniently handled in the laboratory and whose
composition is representative of the population. For analysis in the laboratory, the gross
sample is usually reduced in size and made homogeneous to become the laboratory sample.
In some cases, such as sampling powders, liquids, and gases, we do not have obvious
discrete items. Such materials may not be homogeneous because they may consist of
microscopic particles of different compositions or, in the case of fluids, zones where
concentrations differ. With these materials, we can assure a representative sample by taking
our sample increments from different regions of the bulk material.

Types of Sampling Plan in Analytical Chemistry

1. Random Sampling: A sample collected at random from the target population. The ideal
sampling plan provides an unbiased estimate of the target population’s properties. This
requirement is satisfied if the sample is collected at random from the target population.
Despite its apparent simplicity, a true random sample is difficult to obtain. Haphazard
 CHM 219 ANALYTICAL CHEMISTRY I READING NOTE

sampling, in which samples are collected without a sampling plan, is not random and
may reflect an analyst’s unintentional biases. The best method for ensuring the
collection of a random sample is to divide the target population into equal units, assign
a unique number to each unit, and use a random number table to select the units from
which to sample. A randomly collected sample makes no assumptions about the target
population, making it the least biased approach to sampling. On the other hand, random
sampling requires more time and expense than other sampling methods since a greater
number of samples are needed to characterize the target population.
2. Judgmental Sampling: The opposite of random sampling is selective, or judgmental
sampling, in which we use available information about analyte distribution in the target
population to help select samples. Because assumptions about the target population are
included in the sampling plan, judgmental sampling is more biased than random
sampling; however, fewer samples are required. Judgmental sampling is common when
we wish to limit the number of independent variables influencing the results of an
analysis. For example, a researcher studying the bioaccumulation of polychlorinated
biphenyls (PCBs) in fish may choose to exclude fish that are too small or that appear
diseased.
3. Systematic Sampling: Random sampling and judgmental sampling represent extremes
in bias and the number of samples needed to accurately characterize the target
population. Systematic sampling falls in between these extremes. In systematic
sampling the target population is sampled at regular intervals in space or time. For a
system exhibiting a spatial heterogeneity, such as the distribution of dissolved O2 in a
lake, samples can be systematically collected by dividing the system into discrete units
using a two- or three-dimensional grid pattern. Samples are collected from the center
of each unit, or at the intersection of grid lines. When a heterogeneity is time-dependent,
as is common in clinical studies, samples are drawn at regular intervals.
4. Systematic-Judgmental sampling: A sampling plan that combines judgmental
sampling with systematic sampling. This is encountered in environmental studies when
a spatial or temporal distribution of pollutants is anticipated. For example, a plume of
 CHM 219 ANALYTICAL CHEMISTRY I READING NOTE

waste leaching from a landfill can reasonably be expected to move in the same direction
as the flow of groundwater. The systematic–judgmental sampling plan includes a
rectangular grid for systematic sampling and linear transects extending the sampling
along the plume’s suspected major and minor axes.
5. Stratified Sampling: A sampling plan that divides the population into distinct strata
from which random samples are collected. Another combination of the three primary
approaches to sampling is judgmental–random, or stratified sampling. Many target
populations are conveniently subdivided into distinct units, or strata. For example, in
determining the concentration of particulate Pb in urban air, the target population can
be subdivided by particle size. In this case samples can be collected in two ways. In a
random sampling, differences in the strata are ignored, and individual samples are
collected at random from the entire target population. In a stratified sampling the target
population is divided into strata, and random samples are collected from within each
stratum. Strata are analyzed separately, and their respective means are pooled to give
an overall mean for the target population. The advantage of stratified sampling is that
the composition of each stratum is often more homogeneous than that of the entire target
population.

Types of Samples to Collect

Three methods are commonly used to obtain samples: grab sampling, composite sampling,
and in situ sampling.

• Grab sample: A single sample removed from the target population at a given time and
location in space. A grab sample, therefore, provides a “snapshot” of the target
population. Grab sampling is easily adapted to any of the sampling schemes discussed
in the previous section. A systematic sampling using grab samples can be used to
characterize a target population whose composition varies over time or space. Grab
sampling is carried out on homogeneous materials especially for small size
homogeneous. We homogenize a small bulk of small size heterogenous sample. It can
be done grinding, blending, crushing, stirring, mixing and then carry out grab sampling.
 CHM 219 ANALYTICAL CHEMISTRY I READING NOTE

Large size homogeneous can not be converted to small size homogeneous, therefore,
we do compositing.
• Composite Sample: A composite sample consists of a set of grab samples that are
combined to form a single sample. After thoroughly mixing, the composite sample is
analyzed. Because information is lost when individual samples are combined, it is
normally desirable to analyze each grab sample separately. In some situations, however,
there are advantages to working with composite samples. One such situation is in
determining a target population’s average composition over time or space. For example,
wastewater treatment plants are required to monitor and report the average composition
of treated water released to the environment. One approach is to analyze a series of
individual grab samples, collected using a systematic sampling plan, and average the
results. Alternatively, the individual grab samples can be combined to form a single
composite sample. Analyzing a single composite sample instead of many individual
grab samples, provides an appreciable savings in time and cost. Composite sampling is
also useful when a single sample cannot supply sufficient material for an analysis. For
example, methods for determining PCBs in fish often require as much as 50 g of tissue,
an amount that may be difficult to obtain from a single fish. Tissue samples from several
fish can be combined and homogenized, and a 50-g portion of the composite sample
taken for analysis.
• In situ Sampling: An analytical sensor is placed directly in the target population,
allows continuous monitoring without removing individual grab samples. For example,
the pH of a solution moving through an industrial production line can be continually
monitored by immersing a pH electrode within the solution’s flow.

CHEMICAL METHODS OF ANALYSIS

The term titrimetry or volumetry referrers to quantitative chemical analysis carried out
by determining the volume of a solution of accurately known concentration which is
required to react quantitatively with a measured volume of a solution of a substance to be
 CHM 219 ANALYTICAL CHEMISTRY I READING NOTE

determined. Volumetric methods are much more easily used than gravimetry because they
are more rapid and convenient, but very good accuracy can be obtained with gravimetric
analysis.

Titrimetric methods are classified into four groups based on the type of reaction involved.
These groups are:

• Acid-Base titrations: This is a titration in which an acidic or basic titrant reacts with
an analyte that is a base or an acid.
• Complexometric titrations: This involving a metal–ligand complexation reaction.
• Redox titrations: This is where the titrant is an oxidizing or reducing agent.
• Precipitation titrations: This involves the analyte and titrant react to form a
precipitate.

Terms used in Volumetric Titrimetry

• Standard solution: A standard solution is a reagent of exactly known concentration

that is used in a titrimetric analysis.
• Titration: Titration is a process in which a standard reagent is added to a solution of an
analyte until the reaction between the analyte and reagent is judged to be complete. A
titration is performed by slowly adding a standard solution from a burette or other
liquid-dispensing device to a solution of the analyte until the reaction between the two
is judged complete. The volume or mass of reagent needed to complete the titration is
determined from the difference between the initial and final readings.
• Equivalence point: The equivalence point in a titration is a theoretical point reached
when the amount of added titrant is chemically equivalent to the amount of analyte in
the sample. For example, the equivalence point in the titration of sodium chloride with
silver nitrate occurs after exactly I mol of silver ion has been added for each mole of
chloride ion in the sample. The equivalence point in the titration of sulfuric acid with
sodium hydroxide is reached after introduction of 2 mol of base for each mole of acid.
 CHM 219 ANALYTICAL CHEMISTRY I READING NOTE

• End point: The end point is the point in a titration when a physical change occurs that
is associated with the condition of chemical equivalence. We cannot determine the
equivalence point of a titration experimentally. Instead, we can only estimate its
position by observing some physical change associated with the condition of
equivalence. This change is called the end point for the titration. The difference in
volume or mass between the equivalence point and the end point is the titration error.
• Indicators: Indicator is mostly used in volumetric analysis. An indicator is a compound
that has physical properties usually colour or electrical signal that changes abruptly near
the equivalence point. The change is caused by the sudden disappearance of analyte or
appearance of titrant at the equivalence point. Examples of acid-base indicators shown
in table 9.4.
• Back titration: Back-titration is a process in which the excess of a standard solution
used to consume an analyte is determined by titration with a second standard solution.
Back-titrations are often required when the rate of reaction between the analyte and
reagent is slow or when the standard solution lacks stability. For example, the amount
of phosphate in a sample can be determined by adding a measured excess of standard
silver nitrate to a solution of the sample, which leads to the formation of insoluble silver
phosphate:
Ag+ + PO43- Ag3PO4(s)
The excess silver nitrate is then back-titrated with a standard solution of potassium
thiocyanate:
Ag+ + SCN- AgSCN(s)
Here, the amount of silver nitrate is chemically equivalent to the amount of phosphate
ion plus the amount of thiocyanate used for the back-titration.

Primary Standards

A primary standard is a highly purified (ultrapure) compound that serves as a reference

material in volumetric and mass titrimetric methods. The accuracy of a method is critically
 CHM 219 ANALYTICAL CHEMISTRY I READING NOTE

dependent on the properties of this compound. Important requirements for a primary

standard are the following:

i. High purity: It should be 100% pure, although 0.01 – 0.02% impurities is tolerable.
ii. Atmospheric Stability: The primary standard is stable to dry temperature.
iii. Absence of hydrated water so that the composition of the solid does not change with
variations in humidity.
iv. Readily available at a modest cost.
v. Reasonablely large molar mass so that the relative error associated with weighing the
standard is minimized.
vi. Equilibrium to the reaction should be far to the right.
Very few compounds meet or even approach these criteria, and only a limited number
of primary-standard substances are available commercially. As a consequence, less pure
compounds must sometimes be used in place of a primary standard. The purity of such
a secondary standard must be established by careful analysis. A secondary standard
is a compound whose purity has been established by chemical analysis and that serves
as the reference material for a titrimetric method of analysis.

The Requirement of a Volumetric Analysis for any Determination

For titrimetric or volumetric analysis to be applied or be used, the reaction between the
titrant and sample solution (analyte) must fulfilled the following conditions:

1. The reaction should be stoichiometric (i.e., well-defined and known reaction between
the analyte and titrant).
2. The reaction should be fast or rapid.
3. There should be no side reaction.
4. The reaction should be specific.
5. There should be a marked change in the properties or in some electrical or other
physical properties of the solution.
 CHM 219 ANALYTICAL CHEMISTRY I READING NOTE

6. The reaction should be quantitative (i.e., the equilibrium to the reaction should proceed
forward, i.e., irreversible).

Volumetric Calculations Exercise

1. A 50.00-mL portion of an HC] solution required 29.71-mL of 0.01963M Ba(OH)2 to

reach an end point with bromocresol green indicator. Calculate the molarity of the HCl.
2. A 0.4512-g sample of primary-standard-grade Na2CO3 required 36.44 mL of an H2SO4
solution to reach the end point in the reaction. What is the molarity of the H2SO4?
3. A hydrochloric acid solution is standardized by titrating 0.2329g of primary standard
sodium carbonate to a methyl red end point by boiling the carbonate solution near the
end point to remove carbon dioxide. If 42.87mL acid is required for the titration. What
is its molarity?
4. A sodium hydroxide solution is standardized by titrating 0.8592g of primary standard
potassium acid phthalate to a phenolphthalein endpoint, requiring 32.67mL. What is
the molarity of the base?
 CHM 219 ANALYTICAL CHEMISTRY I READING NOTE

5. 45.7cm3 of 0.500moldm-3 H2SO4 are required to react completely with 20.0cm3 sample
of NaOH solution. H2SO4(aq) + 2NaOH(aq) 2H2O(l) + Na2SO4(aq). What is the
concentration of NaOH solution in: (i.) moldm-3 (ii.) gdm-3.

Gravimetric Analysis

Gravimetric methods are quantitative methods that are based on determining the mass of a
pure compound to which the analyte is chemically related. This method is one of the most
accurate and precise method of macro-quantitative analysis. In this process, the analyte is
selectively converted to an insoluble form. The separated precipitate is dried or ignited,
possibly to another form and is accurately weighed. From the weight of the precipitate and
knowledge of its chemical composition, we can calculate the weight of analyte in the
desired form. There are several methods of gravimetric analysis;

1. Precipitation gravimetry 4. Thermogravimetry

2. Evaporation gravimetry 5. Electrogravimetry
3. Combustion gravimetry 6. Volatilization gravimetry

Precipitation Gravimetry

In precipitation gravimetry, the analyte is converted to a sparingly soluble precipitate. This

precipitate is then filtered, washed free of impurities, converted to a product of known
composition by suitable heat treatment, and weighed. For example, a precipitation method
for determining calcium in natural waters is recommended by the Association of Official
Analytical Chemists. Here, an excess of oxalic acid, H2C2O4, is added to an aqueous
solution of the sample. Ammonia is then added, which neutralizes the acid and causes
essentially all of the calcium in the sample to precipitate as calcium oxalate. The reactions
are

2NH3 + H2C2O4 2NH4+ + C2O42-

Ca2+(aq) + C2O22-(aq) CaC2O4(s)

 CHM 219 ANALYTICAL CHEMISTRY I READING NOTE

The precipitate is filtered using a weighed filtering crucible, then dried and ignited. This
process converts the precipitate entirely to calcium oxide. The reaction is

CaC2O4(s) ∆ CaO(s) + CO(g) + CO2(g)

After cooling, the crucible and precipitate are weighed, and the mass of calcium oxide is
determined by subtracting the known mass of the crucible. The calcium content of the
sample is then computed as will be shown later.

In gravimetric analysis, two experimental measurements are required. First, the mass of
the sample taken (natural water containing calcium), and secondly the mass of a product
of known composition derived from the sample (precipitate). Ordinarily, these data are
converted to a percentage of analyte by a simple mathematical manipulation.

If A is the Analyte, we may write,

𝑚𝑎𝑠𝑠 𝑜𝑓 𝐴
%A= × 100%
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒

The species that is actually isolated and weighed either contains A or can be chemically
related to A. In either case, gravimetric factor (G.F.) is needed to convert the mass of the
precipitate to the corresponding mass of A.

𝑎 𝐹.𝑀.𝑜𝑓 𝑡ℎ𝑒 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒 𝑠𝑜𝑢𝑔ℎ𝑡 (𝐴)

G.F. = ×
𝑏 𝐹.𝑀.𝑜𝑓 𝑡ℎ𝑒 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒 𝑤𝑒𝑖𝑔ℎ𝑡𝑒𝑑 (𝑝𝑝𝑡)

Where a and b are small integers that take such values as necessary to make the number of
formula mass in the numerator and denominator chemically equivalent. The equation can
now be converted to the more useful form:

𝑎 𝐹.𝑀. 𝑜𝑓 𝐴
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑝𝑝𝑡 × 𝑏 𝐹.𝑀. 𝑜𝑓 𝑝𝑝𝑡 ×100%
%A =
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒

𝑚𝑎𝑠𝑠 𝑜𝑓 𝑝𝑝𝑡 ×𝐺.𝐹 ×100%

Or %A =
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑎𝑚𝑝𝑙𝑒
 CHM 219 ANALYTICAL CHEMISTRY I READING NOTE

Gravimetric Analysis Exercise

1. 0.703-gram sample of a commercial detergent was ignited at a red heat to destroy the
organic matter. The residue was then taken up in hot HCl which converted the P to
H3PO4. The phosphate was precipitated as MgNH4PO4.6H2O by addition of Mg2+
followed by aqueous NH3. After being filtered and washed, the precipitate was
converted to Mg2P2O7 (formula mass = 222.6) by ignition at 100℃. This residue
weighed 0.432-gram. Calculate the percentage of phosphorus, P (formula mass = 30.97)
in the sample.
2. 1.236 grams of an herbicide was decomposed with metallic sodium in alcohol. The
chloride ion liberated by this treatment was precipitated as AgCl and found to weigh
0.1840g. Calculate the percentage of 2,4-dichlorophenoxyacetic acid (C8H6O3Cl2,
formula mass = 221) in the sample.
3. The aluminum in a 0.910-g sample of impure ammonium aluminum sulfate was
precipitated with aqueous ammonia as the hydrous Al2O3.xH2O. The precipitate was
filtered and ignited at 1000°C to give anhydrous A12O3, which weighed 0.2001 g.
Express the result of this analysis in terms of
(a) % NH4Al(SO4)2 (b) % A12O3 (c) % Al

UNIT FOUR
CHROMATOGRAPHY
Chromatography refers to continuous equilibration of solute between two phases
(mobile and stationary). The mobile phase can be a liquid or a gas while the stationary
phase solid or liquid. The main purpose of mobile phase is to carry the solute through
the chromatographic column. The main factor causing the separation of a solute in the
stationary phase is distribution coefficient. The interaction of solute on the stationary
phase may either be adsorption, dissolution, ion-exchange, molecular size and/or
partition. Each type of interaction give rise to a distinct type of chromatography.
 CHM 219 ANALYTICAL CHEMISTRY I READING NOTE

Classification of Chromatography
Chromatographic process can be classified according to the equilibration process
involved. This is governed by the type of stationary phases used and equilibration are
base on.
1. Adsorption chromatography: In adsorption chromatography, the stationary phase
is solid on which sample components are adsorbed. The mobile phase maybe a liquid
(liquid-solid chromatography) or gas (gas-solid chromatography). The components
or solutes distribute between two phases through a combination of sorption and
desorption processes. Thin-layer chromatography (TLC) is a special example of
sorption chromatography in which the stationary phase is a “plane” in the form of
solid support on an inert plate, and the mobile phase is a liquid.
2. Partition chromatography: The stationary phase of a partition chromatography is
a liquid supported by an inert solid. Again, the mobile phase maybe a liquid (liq.-liq.
partition chromatography) or a gas (gas-liquid chromatography). Example is a paper
chromatography in which the stationary phase is a layer of water adsorbed on a sheet
of paper. In the normal mode of operations of liquid-liquid partition chromatography,
a polar stationary phase (e.g., methanol on silica) is used with a non-polar mobile
phase (e.g. hexane). This combination of polar and non-polar phases in liquid form
favours the retention of polar compounds and elution of non-polar compounds and
the process is called Normal Phase Chromatography. If a non-polar stationary phase
is used with a polar mobile phase, then the non-polar solutes are retained more and
polar solutes are readily eluted. This process is called Reverse Phase
Chromatography.
3. Ion-exchange and Size exclusion chromatography: Ion-exchange
chromatography uses ion-exchange resins. The mechanism of ion-exchange
chromatography is based on ion-exchange equilibria. In pore-penetration or size
exclusion chromatography, solvated molecules are separated according to their sizes
by their ability to penetrate a sieve-like structure (stationary phase).
 CHM 219 ANALYTICAL CHEMISTRY I READING NOTE

INTRODUCTION TO ANALYTICAL SEPARATION TECHNIQUES

Separations are extremely important in synthesis, industrial chemistry, the biomedical

sciences, and chemical analyses. Few, if any, measurement techniques used for chemical
analysis are specific for a single chemical species; as a consequence, an important part of
most analyses is dealing with foreign species that either attenuate the signal from the
analyte or produce a signal that is indistinguishable from that of the analyte. A chemical
species that affects an analytical signal or the background causing systematic error is called
an interference or an interferent. Several methods can be used to deal with interferences
in analytical procedures and separations isolate the analyte from potentially interfering
constituents. The basic principles of a separation are depicted in Figure below.

Separation methods that are common in use to separate analyte from interferents are:

• Precipitation: Separations by precipitation require large solubility differences between

analyte and potential interferences. The theoretical feasibility of this type of separation
can be determined by solubility product calculations, Ksp. Unfortunately, several other
 CHM 219 ANALYTICAL CHEMISTRY I READING NOTE

factors may preclude the use of precipitation to achieve a separation. For example, the
various coprecipitation phenomena may cause extensive contamination of a precipitate
by an unwanted component, even though the solubility product of the contaminant has
not been exceeded. Likewise, the rate of an otherwise feasible precipitation may be too
slow to be useful for a separation. Finally, when precipitates form as colloidal
suspensions, coagulation may be difficult and slow, particularly when the isolation of a
small quantity of a solid phase is attempted.