CHM256

Chapter 1
Introduction to Analytical
Chemistry
 SUBTOPICS
 Types and steps in analysis
 Review the terms:
 moles, molarity and concentration. Other
expressions of concentration: % (w/w), % (w/v), %
(v/v), ppm, ppt, ppb.
 Calculations involving different expressions of
concentrations
 Dilution
 Preparation of standard solution
1. Types and steps in analysis
 CHEMICAL ANALYSIS

 Chemical analysis is more than just detecting or

determining the general composition or a specific
component of a sample.

 Related to the measurements and characterization of a

chemical species that contain in a sample.

 Determine WHAT and HOW MUCH specific chemical

contain in a sample.
SOME APPLICATIONS OF CHEMICAL
ANALYSIS

 Analysis of carbon monoxide in air.

 Determination of glucose in blood.

 Determination of heavy metals in river water.

 Determination of pesticide residues in food.

DISCIPLINE OF ANALYTICAL CHEMISTRY
Qualitative Quantitative
To determine the presence or Indicates the amount of
absence of a particular particular compound in the
compound in a sample. sample.
Qualitative Analysis Quantitative Analysis
 STEPS IN AN ANALYSIS
Defining the problem

Selecting the method

Obtain a representative sample

Prepare the sample for analysis

Performing the measurements

Conducting the experiment and gathering the data

 1) Defining Problem
• The goal of every chemical analysis is to obtain the
required information within a period of time acceptable
to the customer.

• Many problem do not require complete identification

and many cases require only a general classification.

• It is important for the analyst to determine the

information required by the client.

• For example, in water analysis.

 2) SELECTING METHOD

• Should know the origin of the sample.

• Sample history include information on how, where,

and when the sample were collected, transported and
stored.

• Analyst will use the sample history to maximize

advantage in solving the problem.
1) Literature search
2) Patent or commercial literature.
3) Books
4) Journals or review articles
5) Electronic media
6) Standard organization (e.g AOAC- Association of
Analytical Communities)
 3) OBTAIN A REPRESENTATIVE SAMPLE

o Sampling: Process to get a representative and

homogeneous sample

o Chemical analysis usually performed on only a small

portion of the material.

o That sample must represent the bulk of sample.

o The suitable sampling method differ from one

substance to another depending on homogeneity.
• Homogeneous: Substance that has the same composition
throughout the sample.
• Heterogeneous: Substance that has different composition
from one reagent to another reagent. Its parts can be
distinguish visually or with the aid of microscope.

Homogeneous Heterogeneous

• Proper procedure must be used to store both samples and

standards.
• All sample must be properly labeled and recorded.
 4) SAMPLE PREPARATION

Steps of sampling bulk materials

1. Bulk sample must be reduced in size to obtain a

laboratory sample of several grams from which a
few grams to milligrams will be taken to be analyzed
(analysis sample).

2. Size reduction may require taking portions (e.g. two

quarters) and mixing, in several steps, as well as
crushing and sieving to obtain a uniform powder for
analysis.
Why sample pre-treatment is important????

Laboratory samples are often subjected to physical or

chemical pretreatment where it is converted to a form
that is suitable for the measurement.

During pretreatment:
i) reduce and remove interferences
ii) adjust analyte concentrations to a range suitable
for measurement
iii) produce species from analyte that have
quantitatively measurable properties.
 5) PERFORMING THE MEASUREMENT

• Analysis: Incorporates the measurement of the

concentration of the analyte in replicates and
comparing with standards.

• Replicates: A portion of a materials of approximately

the same size or quantity that undergo the same
analysis/ method at the same time and same place.

• Replicate measurements are necessary to obtain the

measurement uncertainty.

• Uncertainty is important as it indicates the reliability

of the measurements.
 6) CONDUCTING EXPERIMENTS & ANALYSING DATA

• Performed the experiments on the prepared samples based

on method define.

• Performed a blank analysis.

-A blank contains the reagents and solvents use in analysis, (no
analyte)

• Run a statistical analysis (e.g. Standard deviation)

• Deliver a clearly written, complete report and their

limitations.

• Analyst should critically evaluate whether the results are

reasonable and relate to the analytical problem.
2. Review the terms:
• moles, molarity and concentration.
• Other expressions of concentration: % (w/w), %
(w/v), % (v/v), ppm, ppt, ppb.
• Calculations involving different expressions of
concentrations
• Dilutions
 1) Moles
No of moles = mass (g)
relative molecular mass (g/mol)
Relative molecular mass (RMM) = Molecular Weight (MW) = Molar Mass

Example:
Calculate the number of moles in 500 mg Na2SO4

Convert 500 mg to g
= 500 mg x 1 g = 0.5 g
1 1000 mg

Moles = 0.5 g
132 g/mol
= 3.79 x 10-3 mol
 2) Concentration
 Molarity (M)
- No. of moles of the solute in 1 L of solution

Molarity = no. of mole of solute

Volume of solution in L

Molality (m)
- No. of moles of the substance per kilograms of the
solvent.

m = no. of mol solute

kg solution
 2) Concentration
 Weight percent, %w/w = Weight solute (g) x 100
Weight of sample (g)

 ppm = weight solute (g) x 106

weight sample (g)

 ppb = weight solute (g) x 109

weight sample (g)

 ppt = weight solute (g) x 1012

weight sample (g)
 2) Concentration
 %w/v = Weight solute (g) x 100
Volume of sample (mL)

 ppm = weight solute (g) x 106

volume of sample (mL)

 ppb = weight solute (g) x 109

volume of sample (mL)

 ppt = weight solute (g) x 1012

volume of sample (mL)
 2) Concentration

 %v/v = Volume of solute (mL) x 100

Volume of sample (mL)

 3) DENSITY
• Concentration of many fairly concentrated commercial
acids and bases are usually given in terms of percent by
weight.
• It is necessary to prepare solutions of a given
approximate molarity from these substances.
• Must know the density in order to calculate molarity.
Density = Mass
Volume

• Density of a solution correlates with the concentration

of the dissolved substance.
 4) Specific gravity (SG)
• Specific gravity usually refers to the ratio between the
density of a given substance and the density of a
reference substance at the same temperature. More
often than not, that reference substance is water.

Specific gravity, SG = ρ substance

ρ water
ρ = density

• Since no mention of temperature was made, you can

assume the density of water to be equal to 1.00 g/mL.
 4) Specific gravity (SG)
• For example, HCl solution has specific gravity of 1.08. In this
context, hydrochloric acid's specific gravity tells you what the
density of a specific hydrochloric acid solution is compared with
that of water.

• The density of hydrochloric acid solution will be equal to

SG = ρ HCl ⇒ ρ HCl = SG × ρ water

ρ water

ρ water = 1.00 g/mL

So,
ρ HCl = 1.08 × 1.00 g/mL = 1.08 g/mL
 Common unit to express content

Expression Abbreviation Units

w/w w/v v/v
Parts per ppm µg/g µg/mL nL/mL
million
mg/kg mg/L µL/L

Parts per ppb ng/g ng/mL nL/L

billion
µg/kg µg/L
 Example 1

Find the molarity of a solution of 0.60 g NaCl in 100 mL

of solution (MW NaCl = 58.5 g/mol)

No. of mol = 0.60 g

58.5 g/mol
= 0.0102 mol

Molarity = 0.0102 mol

0.1 L
= 0.102 mol/L or M
 Example 2
A 4 g sugar cube (Sucrose: C12H22O11) is dissolved in a 350 ml
teacup of 80°C water. What is the molality of the sugar solution?
Given: Density of water at 80° = 0.975 g/mL; MW C12H22O11 = 342
g/mol.
Solution:
1. No. of moles of sucrose = 4 g/342 gmol-1
= 0.0117 mol

2. Mass of solution (water) in kg 3. Molality = mol solute / kg solution

density = mass/volume molality = 0.0117 mol /0.341 kg

mass = density x volume molality = 0.034 mol/kg
mass = 0.975 g/ml x 350 ml
mass = 341.25 g
mass = 0.341 kg
 Example 3
The density of ethanoic acid, CH3COOH is 1.049
g/mL. If 23.5 mL of ethanoic acid is dissolved in
distilled water to a volume of 0.5 L, calculate the
concentration of ethanoic acid in

i. % v/v
ii. % w/v
iii. ppm
iv. Molarity
 Answer
density of ethanoic acid = 1.049 g/mL
Volume ethanoic acid (solute) = 23.5 mL
volume solution/sample = 0.5 L → 500 mL

i. % v/v
% v/v = volume of solute (mL) x 100
volume of solution (mL)

= 23.5 mL x 100
500 mL
= 4.7%
 Answer
density of ethanoic acid = 1.049 g/mL
volume ethanoic acid (solute) = 23.5 mL
volume solution/sample = 0.5 L → 500 mL

ii. % w/v
% w/v = weight of solute (g) x 100
volume of solution (mL)

Density (g/mL) = mass (g)

volume (mL)
1.049 g/mL = mass (g)
23.5 mL
mass = 1.049 g/mL x 23.5 mL = 24.65 g

% w/v = 24.65 g x 100 = 49.3%

500 mL
 Answer
volume solution/sample = 0.5 L → 500 mL
mass ethanoic acid = 1.049 g/mL x 23.5 mL = 24.65 g

iii. ppm

ppm = weight of solute (g) x 106

volume of solution (mL)

ppm = 24.65 g x 106 = 49300 ppm

500 mL
 Answer
volume solution/sample = 0.5 L
mass ethanoic acid = 1.049 g/mL x 23.5 mL = 24.65 g
RMM ethanoic acid = 60 g/mol
Mol of ethanoic acid = 24.65 g/60 g/mol = 0.41 mol

iv. Molarity

Molarity = no. of moles of solute (mol)

volume of solution (L)

= 0.41 mol
0.5 L
= 0.82 mol/L @ M
 Example 4

Calculate molarity of
commercial concentrated
H3PO4 if it have purity
85%w/w and specific gravity
of 1.69.
RMM H3PO4 = 98.004 g/mol

commercial
concentrated H3PO4
 Answer

1. SG = density H3PO4 density H2O = 1 g/mL

density H2O
1.69 = density H3PO4
1 g/mL
Density H3PO4 = 1.69 x 1 = 1.69 g/mL

2. Density H3PO4 = mass (g)

Volume (mL)

* Note: Volume assumed to be 1 L @ 1000 mL (based on definition

of Molarity)
1.69 g/mL = mass x 1000 mL
Mass of H3PO4 = 1690 g purity 100%
3. Determine mass of H3PO4 at purity 85%w/w

Mass H3PO4 at purity 85%w/w = 85 x 1690 g = 1436.5 g

100

4. Molarity = no. of moles of H3PO4

Volume of solution (L)

No. of moles of H3PO4 = 1436.5 g / 98.004 g/mol = 14.66 mol

Molarity = 14.66 mol

1L
= 14.66 mol/L @ M
 Example 5
Perform this following conversions:
i. 2.5 mg/L to ppm
ii. 1.5 g/L to ppm
iii. 3.2 mL/L to ppb

Answer

i. 2.5 mg/L to ppm

1 ppm = 1 mg/L
So, 2.5 mg/L = 2.5 ppm
 Answer
ii. 1.5 g/L to ppm
1 ppm = 1 mg/L

convert g/L to mg/L

= 1.5 g x 1 mg = 1500 mg/L = 1500 ppm
L 10-3 g

iii. 3.2 mL/L to ppb

1 ppb = 1 nL/L

convert mL/L to nL/L

= 3.2 mL x 1 L x 1 nL = 3200000 nL/L = 3200000 ppb
L 103 mL 10-9 L
 5) Dilution
Definition: Process of decreasing the concentration of a
solution by adding more solvent.
Dilute solution (with low concentration) can be prepared from
a more concentrated solution.
A known volume of the concentrated solution can be
transferred into a new flask and diluted to the required
volume or weight.

Moles of solute Moles of solute

before dilution (1) = after dilution (2)

M1V1 = M2V2
 EXAMPLE
Find the volume of 1.0 M hydrochloric acid to be used to
prepare 100 cm3 of hydrochloric acid at 0.1 M.

Answer:

M1V1 = M2V2

1.0 M x V1 = 0.1 M x 100 cm3

Note: 1 cm3 = 1 mL
V1= 0.1 x 100
1 dm3 = 1 L
1.0
= 10 cm3
3. Preparation of standard solution
 Standard solution
is a solution of which the
concentration can be determined
from the calculation of the mole of
solute and the volume of the solution
 Example 1: Preparation of 0.100 M HCl solution from
12.1 M HCl

 The laboratory grade concentrated HCl has a

concentration of 12.1 M. Briefly explain how to prepare

500 mL of 0.100 M HCl.

 Solution:
Calculate V1 (volume HCl needed to be taken from
concentrated solution, M1)
M1V1 = M2V2
(12.1 M) x V1 = (0.100 M) x 500 mL
V1 = (50.0) / 12.1 = 4.13 mL
• Procedures:
1. Transfer 4.13 mL of concentrated HCl into 500 mL
volumetric flask that already contain small amount of
distilled water.
2. Add distilled water until calibration mark.
3. Invert the flask several times to ensure complete mixing.

4.13 mL HCl

500 mL volumetric flask

 Example 2: Preparation of 250 mL 0.5 M H3PO4 from a
commercial reagent

Briefly explain how to prepare 250 mL 0.5 M H3PO4 from

a commercial reagent at 85%w/w purity and specific
gravity of 1.69.

M1 = ?
V1 = ? dilution
0.5 M
(dilute solution, M2)

V2 = volume of
diluted/prepared
Commercial reagent solution
Solution:
1. Determine concentration of H3PO4 from commercial reagent
(refer example 4) → M1

Concentration of H3PO4 from commercial reagent, M1 = 14.66 M

2. Determine volume of H3PO4 that has to be taken from

concentrated/commercial reagent (V1)

M1V1 = M2V2
(14.66 M)(V1) = (0.5 M)(250 mL)
V1 = 8.53 mL
3. Procedure:
i. Transfer 8.53 mL of the concentrated H3PO4 into a 250 mL
volumetric flask that already contain small amount of
distilled water.
ii. Then add distilled water until calibration mark.
iii. Invert the volumetric flask several times to ensure
complete mixing.

8.53 mL
 Example 3: Preparation of 100 mL 26%v/v of ethanoic
acid

1. Determine volume of ethanoic acid

26% = volume of solute (mL) x 100

100 mL
volume of solute = 26 mL

2. Procedure:
i. Transfer 26 mL of ethanoic acid into a 100 mL volumetric flask
that already contain small amount of distilled water.
ii. Then add distilled water until calibration mark.
iii. Invert the volumetric flask several times to ensure complete
mixing.
 Example 4: Preparation of solution from solid

Briefly describe how to prepare 500 mL 0.2 M KCl.

(RMM KCl: 75 g/mol)
1. Determine mass of KCl needed to prepare solution
500 mL = 0.5 L

Molarity = no. of moles of KCl

Volume of solution (L)
0.2 = no. of moles
0.5 L
no. of moles = 0.1 mol

mass KCl = 0.1 mol x 75 g/mol = 7.5 g

2. Procedure:

i. Weigh 7.5 g of KCl into a beaker.

ii. Dissolve KCl in small amount of distilled water. Stir the
solution until all KCl was dissolve.
iii. Transfer the KCl solution into 500 mL volumetric flask.
iv. Add distilled water until calibration mark.
v. Invert the volumetric flask several times to ensure
complete mixing.
Procedure to make standard solution from solid solute

(iii)
(i) (ii)

Invert the
flask

(v) (iv) (iii)