‘ANALYTICAL CHEMISTRY’

- A branch of chemistry that deals

with the separation, identification &
determination of analytes
(components) in a sample

-It involves the application of a

range of techniques and
methodologies to obtain and assess
qualitative, quantitative and
structural information on the nature
of matter.
Analyte is the substance to be identified, detected, or
separated in some manner/method.

Matrix is the medium in which the analyte is analyzed. Or

all other constituents in a sample except for the analyte

Sample : representative of the population or gross

sample
Type of sample can be anything… its depend
on things we are going to analyzed.
TYPES OF ANALYSIS

Qualitative analysis
is performed to identify what material/analyte
present in a sample.

Quantitative analysis
is an analysis to determine how much of a
material is present in a sample.
AREAS OF ANALYTICAL CHEMISTRY
Clinical analysis: blood, urine, feces, cellular fluids, etc., for use in
diagnosis.

Pharmaceutical analysis: establish the physical properties, toxicity,

metabolites, quality control, etc.

Environmental analysis: pollutants, soil and water analysis, pesticides.

Forensic analysis: analysis related to criminology; DNA finger printing,

finger print detection; blood analysis.

Industrial quality control: required by most companies to control product

quality.

Bioanalytical chemistry and analysis: detection and/or analysis of

biological components (i.e., proteins, DNA, RNA, carbohydrates).
ANALYTICAL CHEMIST/ANALYST?
A true analyst has several characteristics:
Has knowledge of the methods and instruments
used for analysis.
Understands the principles of analysis, so that
he/she can apply and if necessary modify analytical
methods to solve a particular problem.
Can develop new methods of analysis.
Can evaluate and interpret the result of a
quantitative analysis.

An analytical chemist is a skilled and

well-trained chemist and also known as
a problem solver.
CLASSIFICATION OF Analytical methods
Gravimetric Methods
Measure the mass of the analyte (or a compound chemically related to
the analyte).

Volumetric Methods
Measure the volume of a solution containing sufficient reagent to react
with the analyte (i.e., titration or gas analysis).

Separation Methods
Measure the peak areas of the separated components of a sample.

Spectroscopic Methods
Measuring the interaction between the analyte and electromagnetic
radiation (or the production of radiation by an analyte).

Electroanalytical Methods
Measure an electrical property (i.e., potential, current, amperes) which
is chemically related to the amount of analyte.
STEPS IN A QUANTITATIVE ANALYSIS

Define the problem

Select a method

sampling

Sample Preparation

Eliminate interferences

Perform the measurement

Calculate the results and report writing

Definition of the Problem
Learn as much as possible about the overall problem that is being
faced.
The analyst must know;
What is the problem? What needs to be found? (Qualitative
and/or quantitative?)
Who will use the information – to provide evidence for possible
future litigation, to help improve company profit or to satisfy a
customer.
When will the result be needed?
How many samples are to be analyzed?
What type of sample is to be analyzed (physical state of the
sample)?

After the problem is defined this will dictate to:

How accurate and precise does it have to be (how
sensitive the method must be?)?
What is the budget?
How the sample is to be obtained?
What are the physical or chemical properties of the
laboratory sample?
Is it required any preliminary treatment (what
separation may be required to eliminate
interferences?)
METHOD SELECTION.

Factors to consider include:

•Accuracy
•Detection limit
•Time
•Cost/number of analyses
•Complexity of sample - selectivity.
•Equipment
•Technical expertise
•Speed
•Does it need to be automated?
•Are methods available in the chemical literature?
•Analyst, Analytica Chimica Acta, Journal of Analytical Chemistry, Journal
of Chromatography.
•Standard methods available?
•Legality- how well an analytical method will stand up in court.

•CHOOSEN METHOD MUST BE VALID/CERTIFIED

•IF NOT VALID?
SAMPLING
Sampling is the process to get a representative and homogeneous
sample.
Representative means that content of analytical sample reflects content
of bulk sample.
Homogeneous means that the analytical sample has the same content
throughout.

Deciding how to obtain a sample for analysis depend on:

i. The size of the bulk to be sampled.
ii. The physical state of the fraction to be analyzed.
(solid, liquid, gas)
iii. The chemistry of the material to be assayed.
(Nothing can be done that would destroy or alter the identity or quantity
of the analyte)

Steps involved in sampling bulk material:

• Identify the population from which the sample is to be obtained.
• Collect a gross sample that is truly representative of the population
being sampled.
• Reduce the gross sample to a laboratory sample that is suitable for
analysis.
SAMPLING SOLIDS
•Inhomogeneity of the material, make sampling of solids more
difficult.

•The easiest way to sample a material is grab sample – the sample

taken at random and assumed to be representative.

•For reliable results, it is best to take 1/50 to 1/100 of the total bulk.
The larger the particle size, the larger the gross sample should be.

Examples:
•Stockpile of cereals: take increment from surface and interior.
•Compact solids (metals and alloys): obtained by random drilling
or by sawing across the metal at random intervals and collecting
the `sawdust’ as the sample.
•Obtaining a random sample from a bulky material (ore, grain, coal) can be
achieved while the material in motion (conveyor belt). Periodically transfer
portion into a sample container.

•The gross sample must be reduced in size to obtain a laboratory sample.

•The sample is crushed and mixed to form a conical pile. This pile is
flattened and cut into equal quarters, and two opposite quarters are
chosen at random. The procedure is called coning and quartering. This
process is continued until the gross sample is small enough to be
transported to the laboratory.
SAMPLING LIQUIDS
•Liquid samples are homogeneous and are much easier to sample.
•The gross sample can be relatively small.
•If liquid samples are not homogeneous, and have only small quantity, they
can be shaken and sampled immediately.
•Sampling techniques will depend on the types of liquid.
Example:
Large volume of liquids (impossible to mix)
Sampled after transfer (during discharge) or if in a pipe, sampled after
passing through a pump or at different points in pipe system.
Large stationary liquids (lakes, rivers)
Samples may be obtained at different depths using a sample thief (a bottle
that can be opened and filled at any desired location in the solution). The
separate aliquots of liquids can be analyzed individually or can be combined
into one gross sample (composite sample) and replicate analyses
performed.

Biological fluids
The timing of sampling is very important. For example, the composition of
blood varies before and after meal. The sample is collected after the patient
has fasted for a number of hours.
SAMPLING GASES
•Tend to be homogeneous.

•Large volume of samples is required because of their low density.

•Examples:

•Air analysis: Use a `Hi-Vol’ sampler that is containing filters to collect

particulates.

•Liquid displacement method: The sample must has little solubility in

the liquid and does not react with the liquid

•Breath sample: The subject could blow into evacuated bag.

SAMPLE STORAGE AND PRESERVATION
An important aspect of the sampling process.

Objective:
To make analyte contains in the sample as same as
during the sampling process.

MECHANISM OF PREVENTION:
•Decomposition of biological samples through the action of
bacteria. Refrigerated after collection until the time of analysis.
•Precipitation of metals from water samples. Acidified (10% HNO3)
immediately upon collection.
•Loss of water from hygroscopic material.
•Loss of volatile analytes from water samples.
•Use an appropriate container to store the sample e.g. glass is not
suitable for inorganic trace analyses, low molecular weight
polyethylene is not suitable for hydrocarbon samples.
PREPARING A LABORATORY SAMPLE
•Converting the sample to a useful form:
•Solids are usually ground to a suitable particulate size to get a
homogeneous sample.
•Dry the samples to get rid of absorption water. (Drying at 110 to 120C for 1
hour and cooled in dessicator before weighing).
DEFINING REPLICATE SAMPLES
•Replicate samples are always performed unless the quantity of the analyte,
expense or other factors prohibit.
•Replicate samples are portion of a material of approximately the same size
that is carried through an analytical procedure at the same time and the
same way.

PREPARING SOLUTIONS OF THE SAMPLE

•Most analyses are performed on solutions.
•A solvent is chosen that dissolves the whole sample without decomposing
the analyte.
•Several sources of error are encountered in the sample dissolution step:
•Incomplete dissolution of the analyte.
•Losses of analyte by the volatilization.
•Introduction of analyte as a solvent contamination.
•Contamination from the reaction of the solvent with vessel walls.
SAMPLE PREPARATION AND DISSOLUTION

Decomposition and Dissolution of Inorganic Solids

•Simple Dissolution
Dissolution by water.

Acid Treatment
Hydrochloric acid, nitric acid, perchloric acid.

•Fusion Techniques
The sample is mixed with flux (1:10), heated
(300 – 1000C) in the crucible until molten. Then dissolve in dilute acid
or water.
Base flux (carbonates, hydroxides of alkaline metal)
Acid flux (pirosulfates, boric oxide, fluoride acids)
Decomposition of Organic Matrices for Elemental Analysis

Dry Ashing
•The method consists of preparing an ash by using heat and
water/nitric acid to decompose the organic matter, and dissolving
the inorganic residue in an appropriate volume of dilute
hydrochloric acid.
•The sample is place in crucible and heat in furnace up to 450C.

Wet Digestion
•HCl: Carbonates, phosphates, oxides
•H2SO4: Organic material at 300C
•HNO3: Any metals not dissolve by HCl
•HClO4: Steel
•HF: Silica
•Aqua Regia (HCl:HNO3, 3:1): Not stable
•HNO3:HCl:HF (5:15:3): Alloys
MICROWAVE DECOMPOSITION

•The best method for converting the liquid or solid sample into
solution.

•The advantages of microwave digestion include:

•Sample contained within the digestion vessel.

•Highly efficient.

•Mostly any sample can be digested.

•Volatile elements are retained in the reaction vessel.

•Easy to automate: a computer controls the pressure and the

temperature.
ELIMINATING INTERFERENCES
Interferences are substances that prevent direct measurement of the
analyte and must be removed.

CALIBRATION AND MEASUREMENT

•The physical or chemical property proportional to the analyte
concentration is measured.

•Suitable standards must be measured to determine the relationship

between analyte quantity and the physical/chemical property being
measured (i.e., calibration).
CALCULATING RESULTS
This requires using the raw data, stoichiometry of the reaction(s) and
instrumental factors to calculate the analyte concentration.
Evaluating the results and estimating their reliability. This requires
appropriate use of statistics.

REPORT
Report results with limitation/accuracy information.
A professional chemist/charted chemist should verify the report.
VALIDATION OF ANALYTICAL METHOD

•The Analysis of Standard Samples

(A sample whose analyte concentration is known)
The standard reference samples (SRM) can be obtained from The National
Institute Of Standard and Technology (NIST).
The analyte concentration in the SRM has been certified by the institute.
Compare the data obtained from the method with the certified value.

•Analysis by Other Methods

The result of the analytical method can be evaluated by comparison with
data obtained from a different method.

•Standard Addition to the Sample

The known amount of the analyte is added to the sample and then
analyzed by the proposed method. The effectiveness of the method can be
established by evaluating the recovery of the added quantity.
The standard addition method will reveal errors arising from the way the
sample was treated or from the presence of the other compounds in the
matrix.
 EXPRESSIONS OF CONCENTRATION

Concentration is the amount of solute in a known

amount of solution
Concentration = Amount of solute
Amount of solution

 Molarity (M)  Formality (F)

 Normality (N)  Molality (m)
 Part per thousand (ppt)
 Parts per million (ppm)
 Parts per billion (ppb)
 Percent concentration (%w/w, %w/v, %v/v)
  Molarity (M) = # moles solute
# liters of solution
This unit describes what exists at equilibrium

• Molality (m) = #moles of solute

#kilograms of solvent

 Formality (F) = # moles solute

# liters of solution
This unit describes how to make a solution, not
what exists at equilibrium (aka analytical molarity)
• For substances that ionize in solution, such as NaCl, molarity and formality
are different.

NaCl (aq) → Na+ + Cl–

initial 0.1 mol - -
final 0.0 0.1 mol 0.1 mol

The molarity of NaCl, therefore, is zero since there is essentially no

undissociated NaCl in solution. The solution, instead, is 0.1 M in Na+ and
0.1 M in Cl–. The formality of NaCl, however, is 0.1 F because it represents
the total amount of NaCl in solution.
. When we state that a solution is 0.1 M NaCl we understand it to consist of
Na+ and Cl– ions.
The unit of formality is used only when it provides a clearer description
• of solution chemistry.
• The definition of molarity, for better or worse, is largely ignored in the
current literature.

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 Normality (N) = # equivalents solute
# liters of solution
Equivalents = Weight  equivalent weight
Equivalent weight = formula weight  n
where, n is the number of e or H+ ions or OH- ions
N = (Formality) x (#electrons transferred) or
= (Formality) x (#H+ neutralized) or
= (Formality) x (#OH- neutralized)

Eg. 0.100 N Na2CO3 solution

The solution contains 0.100 equivalents Na2CO3
Rxn with H+ : CO32- + 2H+ H2O + CO2
1 L solution contains 0.1 equivalents Na2CO3
0.10 equivalent Na2CO3  0.050 mol Na2CO3
• 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.

H2SO4(aq) + 2NH3(aq) → 2NH+4 (aq) + SO42– (aq)

n = 2 for H2SO4 and n = 1 for NH3.

For a complexation reaction, the reaction unit is the number of

electron pairs that can be accepted by the metal or donated by the
ligand. In the reaction between Ag+ and NH3
Ag+(aq) + 2NH3(aq) → Ag(NH3)2+(aq)
the value of n for Ag+ is 2 and that for NH3 is 1.
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In an oxidation–reduction reaction the reaction unit is the number
of electrons released by the reducing agent or accepted by the
oxidizing agent; thus, for the reaction
2Fe3+(aq) + Sn2+(aq) → Sn4+ (aq) + 2Fe2+ (aq)
n = 1 for Fe3+ and n = 2 for Sn2+ .

• Clearly, determining the number of equivalents for a chemical

species requires an understanding of how it reacts.

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32
• Parts per thousand (ppt ) = g solute
103 g solution

• Parts per million (ppm) = g solute

106 g solution
(mg mL-1) = mg solute
Liter solution
For dilute aqueous solutions,
1 ppm = 1 g solute  106 mL solution
= 1 g solute  mL solution = 1 mg/L

• Parts per billion (ppb) = g solute

109 g solution
For dilute aqueous solutions,
1 ppb = 1 g solute  109 mL solution
= 1 ng solute  mL solution = 1 ng/L
• Weight percent = Weight of solute x 100%
(%w/w) Weight of solution
• Volume percent = Volume of solute x 100%
(%v/v) Volume of solution
• Weight-volume = Weight of solute x 100%
(%w/v) Volume of solution

Commercial aqueous reagents are usually

sold in (%w/w)
Example: 37% is labeled on a HCl reagent
bottle. This means that it contains 37 g HCl per
100 g solution
• Density = mass of substance
volume of substance
(g mL-1 is the most usual unit for density)

• Specific Gravity
= Mass of substance
Mass of equal volume of water
= Density of substance
Density of water
Specific gravity is more often used in
commercial reagents than density
(The temperature must be specified)
• A concentrated solution of aqueous ammonia is 28.0% w/w NH3
and has a density of 0.899 g/mL. What is the molar concentrtion
of NH3 in this solution? (Ans. = 14.8)

• The maximum allowed concentration of chloride in drinking

water is 2.50 x 102 ppm Cl-. What is the concentration in
molarity? ( Ans = 7.05 x 10-3M)

36
 PREPARATION OF SOLUTION

Example: Describe the preparation of 250

mL of 0.100 M Na from reagent grade NaOH
[Known MW: NaOH = 40, Na= 23.00]
1. Calculate the weight (g) of NaOH that is
equivalent to the required moles of Na in
solution
Calculations ???
2. Weigh ??? g of solid (generally  0.1 mg, ie
up to 4 decimal places in grams)
3. Dissolve in water, transfer (quantitatively with
rinsings) to a 250 mL volumetric flask, and
dilute to the mark
 DILUTION OF SOLUTION

The moles solute in concentrated (1) solution

equals the moles in dilute (2) solution

 M1  V1 = M2  V2

Example: Describe the preparation of 50

mL of 0.100 M NaOH solution from a 0.5
molar solution
Calculations…
How to ???… 
Glassware requirement: ?? mL pipet and
?? mL volumetric flask