Analytical Chemistry

Dr. Lamia Lafta

JANUARY 1, 2018
Department of Chemistry, College of Science,
Mustansiriyah University, Baghdad, Iraq
Analytical Chemistry Dr. Lamia Lafta

Analytical chemistry
Is a measurement science consisting of a set of powerful ideas and
methods that are useful in all fields of science, engineering, and
medicine.

Analytical chemistry consists of:

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.

Analytes:
Are the components of a sample that are determined.

Quantitative Analytical Methods

1- Gravimetric methods
We determine the mass of the analyte or some compound chemically
related to it.

2- Volumetric method
We measure the volume of a solution containing sufficient

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Analytical Chemistry Dr. Lamia Lafta

reagent to react completely with the analyte.

3- Instrumental analysis:
They are based on the measurement of a physical property of the
sample, for example, an electrical property or the absorption of
electromagnetic radiation, this method involves:

A- Electroanalytical methods
We measure electrical properties such as potential, current,
resistance, and quantity of electrical charge.

Example: potentiometric technique and amperometric technique.

B- Spectroscopic methods
We explore the interaction between electromagnetic radiation and
analyte atoms or molecules or the emission of radiation by analytes.

Examples: (ultraviolet, visible, or infrared), fluorimetry, atomic

spectroscopy (absorption, emission), mass spectrometry, nuclear
magnetic resonance spectrometry (NMR), X-ray spectroscopy.

Calculations Used in Analytical Chemistry

1- Calculating the Amount of a Substance in Moles or Millimoles

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Analytical Chemistry Dr. Lamia Lafta

Sometimes it is more convenient to make calculations with millimoles

(mmol) rather than moles. The millimole is 10-3 of a mole.

wt g
The number of moles (n) = = = mol
M.wt g/mol
wt g
The number of millimoles (mn) = = = mmol
M.wt g/mmol

Example:

The number of moles (n) = wt/(M.wt) = 2/122=0.0163 mol

g g mol
M.wt = = mol x 1000 mmol = 0.122g/mmol
mol

The number of millimoles (mn) = wt/(M.wt) = 2 g/0.122 g/mmol

=16.38 mmol

Calculations Used in Analytical Chemistry

Concentration of Solutions:

1- Molar Concentration
2- Normal Concentration
3- Density and Specific Gravity of Solutions

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Analytical Chemistry Dr. Lamia Lafta

4- Percent Concentration
5- Parts per Million and Parts per Billion
6- Solution-Diluent Volume Ratios
7- p-Functions

1- Molar Concentration

Is the number of moles of that species that is contained in 1 liter of

the solution (not 1 L of the solvent)

The unit of molar concentration is molar, symbolized by M, which has

the dimensions of mol/L, or mol L-1.
The millimolar mass (mM) is 10-3 of the molar mass.
Molar concentration is also the number of millimoles of solute per
millilitre of solution.
Example
Calculate the molar concentration of ethanol in an aqueous solution
that contains 2.30 g of C2H5OH (46.07 g/mol) in 3.50 L of solution.

Solution
To calculate molar concentration, we must find both the amount of
ethanol and the volume of the solution. The volume is given as 3.50 L,
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Analytical Chemistry Dr. Lamia Lafta

so all we need to do is convert the mass of ethanol to the

corresponding amount of ethanol in moles.

wt(g) 2.30 g
No. of moles (n) = = = 0.0499 mol
M. wt 46.07

0.0499
Molar concentration = = 0.0142 𝑀
3.5

Example
Describe the preparation of 500 mL of 0.0740 M Cl-1 solution from
solid BaCl2 .2H2O (244.3 g/mol).
Solution:
wt(g) 1000
M= x
M. wt Vml

0.074 wt(g) 1000 , Wt. of BaCl2 = 4.52 g

= x
2 244.3 500 ml

2- Normal Concentration (N)

Is the number of equivalents of solute contained in 1 L of solution or
the number of milliequivalents in 1 mL of solution (not 1 L of the
solvent).

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Analytical Chemistry Dr. Lamia Lafta

no. eq
N=
volume in liters
no. meq
N=
volume in mL
wt (g)
number of equivalents (no. eq) =
eqwt(g/eq)

M. wt
eqwt =
no. of valence electrons

wt (g)
number of milliequivalents (no. meq) =
eqwt(g/meq)
equivalents weight = M.wt / a
a = number of reacting units:
1- Equivalent Weights in Neutralization Reactions
For example, the equivalent weights of KOH, HCl, and CH3COOH are
equal to their molar masses because each has a single reactive
hydrogen ion or hydroxide ion. Barium hydroxide, which contains two
identical hydroxide ions, reacts with two hydrogen ions in any
acid/base reaction, and so:
Eq.wt Ba(OH)2 = M.wt Ba(OH)2/2

2- Equivalent Weights in Oxidation/Reduction Reactions

5C2O4 -2 + 2MnO4 - + 16H 10CO2 + 2Mn+2 + 8H2O

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Analytical Chemistry Dr. Lamia Lafta

In this reaction, the change in oxidation number of manganese is 5

because the element passes from the +7 to the +2 state; the
equivalent weights for MnO4-2 are thus one fifth their molar masses

3- Equivalent Weights in Precipitation and Complex Formation

Reactions: eqw AlCl3 = M.wt AlCl3 / 3

The unit of normal concentration is normal, symbolized by N, which

has the dimensions of eq/L, or eq L-1.
Normal concentration is also the number of millieqivalents of solute
per milliliter of solution.

1N = 1 eq L-1 = 1eq = 1meq

L mL

for a solution of the species A, the normality N(A) is given by:

no. eq A = V (L) x N(A)(eq/L)

no. meq A = V (mL) x N(A)(meq/mL)

Example
Describe the preparation of 500 mL of 0.0740 N Cl-1 solution from solid
BaCl2 .2H2O (244.3 g/mol).
Solution: wt(g) 1000
N= x
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𝑒𝑞𝑤𝑡 Vml
Analytical Chemistry Dr. Lamia Lafta

M. wt
eqwt =
no. of valence electrons

0.074 wt(g) 1000

= x
2 244.3 500 ml
2

Wt. of BaCl2 = 2.25 g

The relationship between the normality and molarity:

N=aM
N= normal concentration
M= molar concentration
a = no. of equivalent es

3- Density and Specific Gravity of Solutions:

Density expresses the mass of a substance per unit volume. In SI units,

density is expressed in units of kg/L or alternatively g/mL.
Specific gravity is the ratio of the mass of a substance to the mass of
an equal volume of water.

% × 𝐬𝐩.𝐠𝐫 × 𝟏𝟎 % × 𝐝 × 𝟏𝟎
𝐌= , 𝐌=
𝐌.𝐰𝐭 𝐌.𝐰𝐭

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Analytical Chemistry Dr. Lamia Lafta

M= molarity, sp.gr = specific gravity, M.wt = molecular weight, % =

percentage,
d= density, no. of valence electrons es = number of valence electrons

% × 𝐬𝐩.𝐠𝐫 × 𝟏𝟎 % × 𝐝 × 𝟏𝟎
𝐍= , 𝐍=
𝐞𝐪𝐰𝐭 𝐞𝐪𝐰𝐭

M. wt
eqwt =
no. of valence electrons

Example
Calculate the molar concentration of HNO3 (63 g/mol) in a solution
that has a specific gravity of 1.42 and is 70.5% HNO3 (w/w).
Solution:
% × 𝐬𝐩. 𝐠𝐫 × 𝟏𝟎
𝐌=
𝐌. 𝐰𝐭
70.5 × 1.42 × 10
M=
63.0
M= 15.89  16 M

Example
Describe the preparation of 100 mL of 6.0 M HCl from a concentrated
solution that has a specific gravity of 1.18 and is 37% (w/w) HCl (36.5
g/mol).

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Analytical Chemistry Dr. Lamia Lafta

% × 𝐬𝐩.𝐠𝐫 × 𝟏𝟎
Solution: 𝐌=
𝐌.𝐰𝐭

𝟑𝟕 × 𝟏.𝟏𝟖 × 𝟏𝟎
𝐌= , M = 11.96
𝟑𝟔.𝟓
M 1 x V1 = M2 x V2
11.96 x V = 6 x 100
V = 50.16 mL

4- Percent Concentration
Three common methods are used to express concentrations in terms
of percent (parts per hundred):

Solution = Solute + Solvent

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Analytical Chemistry Dr. Lamia Lafta

Note:
The denominator in each of these expressions is the mass or volume
of solution rather than mass or volume of solvent.
Note:
The first two expressions do not depend on the units used for weight
(mass) or volume as long as the same units are used in the
numerator and the denominator.
Note:
The third expression, units must be defined because the numerator
and denominator have different units that do not cancel.

Q1/
15 g of NaCl was dissolved in 225 g of water. What is the mass percent
of NaCI in the solution?
Solution:
Solute + Solvent = Solution
NaCl + H2O =
mass of solute
Mass % = × 100
mass of solution
15 g
Mass % = × 100 = 6.25 %
240 g

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Analytical Chemistry Dr. Lamia Lafta

Q2/ 25 mL of Methanol ( d= 0.792 g/cm3) is mixed with 150 mL of

Ethanol (d= 0.789 g/ cm3). What is the mass percent of Methanol in
the solution? What is the volume percent of Methanol?
Solution:
Cm3 = mL , solute= methanol (CH3OH), solvent = ethanol (C2H5OH)
Mass of methanol
d of Methanol =
volume of methanol
Mass of methanol
0.792g/mL = = 19.8 g mass of CH3OH
25 mL

Mass of ethanol
d of Eethanol =
volume of ethanol
Mass of ethanol
0.789 g/mL = = 118.35 g mass of C2H5OH
150 mL

Mass of solution = 19.8 g + 118.35 g = 138.15 g

19.8
% Methanol = 𝑥 100 = 143 %
138.15

25 mL
% V of methanol = × 100 = 14.3 %
175 mL

Q3/
What is the weight/volume percentage concentration of 500 mL of
aqueous sodium chloride solution containing 2 g NaCI?
Solution:
Solute = Sodium chloride= NaCI , Mass of solute = 2 g

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Analytical Chemistry Dr. Lamia Lafta

Volume of solution = 500 mL

2g
W/V(%) = x 100 = 0.4g/100 mL
500 mL

Q4/
10 g of BaCI2 is dissolved in 90 g of water. The density of the solution
is 1.09 g/mL. Calculate the weight/volume of the solution.
Solution:
Solute = BaCI2 , Mass of BaCl2 = 10 g
Solvent = water = H2O , Mass of solvent = 90 g
Mass of solution = mass of solute + mass of solvent = 10 + 90 = 100 g
Volume of solution?
Density = mass (solution) / volume (solution)
100g
1.09 g/mL = Volume (solution) = 91.74 mL volume of solution

10 g
= × 100 = 10.90 g /100 mL
91.74 mL

Q5/
The density of a 0.75 M NaOH solution is 1.1 g/mL. Calculate the
mass percent of NaOH in the solution.
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Analytical Chemistry Dr. Lamia Lafta

Solution:
% × d × 10
M=
M. wt
% × 1.1 × 10
0.75 =
40
mass % = 2.727  2.73 %

Q6/
20 mL of methanol was diluted with water to 80 ml, calculate the
volume percent of methanol in the solution?
Solution: Volume of solute = 20 , Volume of solution = 80

20 mL
V/V% = x 100 = 25%
80 mL

5- Parts per Million and Parts per Billion

Note:
The units of mass in the numerator and denominator must agree so
that they cancel.

mass of solute, g
Parts per thousand (ppt w/w) = x 103
mass of solution, g

mass of solute, g
Parts per million (ppm w/w) = x 106
mass of solution, g

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Analytical Chemistry Dr. Lamia Lafta

mg
(ppm w/w) =
Kg
µg
(ppm w/w) =
g

mass of solute, g
Parts per billion (ppb w/w) = x 109
mass of solution, g
µg
(ppb w/w) =
Kg
ng
(ppb w/w) =
g

Kg = 103 g , mg= 10-3 g , µg = 10-6 g , ng = 10-9 g

Example:
What is the ppm of calcium in a 15 grams soil sample if it is found that
there is 98 µg of calcium in the sample? (1 g = 106 µg)

mass of solute, µg
(ppm w/w) =
mass of solution, g

98 µg
ppm =
15 g

ppm of Ca+2 = 6.53

1- Parts per thousand

The term parts per thousand (ppt) is used to express the

concentration.
mass of solute, g
Parts per thousand (ppt w/v) = x 103
volume of solution, mL
g
ppt = mL
x 103

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