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CHAPTER 2

BASIC TOOLS AND OPERATIONS OF


ANALYTICAL CHEMISTRY

Assoc. Prof. Dr. Salina Mat Radzi


Faculty of Science and Technology
Universiti Sains Islam Malaysia

Monday, September 19, 1


2016
Learning Objectives

• How to use reagent-grade


chemicals

• Volumetric glassware, how


to use and calibrate it

• How to prepare standard


base and standard acid

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2016
• Common lab apparatus for
handling and treating
samples

• How to filter and prepare


precipitate for gravimetric
analysis

• How to sample solids,


liquids and gases

• How to prepare solution for


analyte
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2016
Contents
2.1 Laboratory notebook
2.2 Laboratory materials and
reagents
2.3 The analytical balance
2.4 Volumetric glassware
2.5 Preparation of standard base
solutions
2.6 Preparation of standard acid
solutions

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2016
2.7 Handling and treating
samples.
2.8 Igniting precipitate –
gravimetric analysis
2.9 Obtaining the sample – it is
solid, liquid or gas?
2.10 Operations of drying and
preparing a solution of the
analyte
2.11 Laboratory safety.

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2016
2.1 Laboratory notebook
• All data must be recorded
permanently

• Advantages:
i. saving of time
ii. chances for a mistake are
reduced
iii. able to detect possible error
iv. data will not be lost
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2.2 Laboratory materials and
reagents

• Reagent-grade chemicals
are almost always used in
analyses.

• Primary standards are used


for preparing volumetric
standard solutions

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2016
Borosilicate glassware (Pyrex, Kimax) is normally
used because it is thermally stable.

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2016
2.3 The analytical balance
• The balance measurers
mass

• Weight – is the force


exerted on it by the
gravitational attraction

• Mass – is the quantity of


matter of which the object
is composed and is variant
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2016
Modern balances are electronic. They still compare one mass against
another since they are calibrated with a known mass. Common
balances are sensitive to 0.1 mg.

Electronic analytical balance


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2016
Mechanical balances operate as
first class levers. M1L1 = M2L2

Principle of analytical balance.

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2016
The single-pan balance is as
accurate as electronic balances,
and almost as fast.
But it can’t be interfaced to a
computer to collect and process
data.
And you have to read a scale
instead of a digital number.

Typical single-pan balance.

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2016
Weight in vacuum
• The most accurate
• No buoyancy
• In very careful work, a
correction should be made
• In most cases, correction is
not necessary
• Weighing must be made
using a same container

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2016
• Example: calibration of
glassware
• Buoyancy correction can
be neglected

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2016
Sources of error in weighing
• Zero point drift

• The weight

• Buoyancy

• Change in ambient
temperature

• Humidity
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2016
General rules of weighing

1. Protect the knife edges

2. Protect from dusk and


corrosion

3. Avoid contamination

4. Avoid draft errors

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2016
Weighing of solids
• Weighing bottle

• Replicate weighings are


carried out by difference

• Use bottle capped if the


sample is hygroscopic

• Direct weighing, a weighing


dish is used

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2016
Weighing bottles are used for drying samples.
Hygroscopic samples are weighed by difference,
keeping the bottle capped except when removing the
sample.

Weighing bottles.

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2016
Weighing of liquids
• Direct weighing

• Weighing vessel which is


capped

• Weighed by difference by
pipetting out an aliquot
from bottle

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2016
A weighing dish or boat is used for direct
weighing of samples.

Weighing dish

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2016
Types of weighing
Rough weighing Accurate weighing

• 2 or 3 significant • weight of sample to


figures be analyzed, dried
product (gravimetry)
• amount of substance or reagent being used
is only a few percent as a standard

• Top loading • 4 significant figures

• Ex: reagent to be • analytical balance


dissolved (0.1 mg)
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2016
2.4 Volumetric glassware

• Volumetric flasks
• Pipets
• Syringe pipets
• Burets

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2016
Volumetric flasks are
calibrated to contain an
accurate volume. See the
inside back cover of the
text for tolerances of
Class A volumetric
glassware.

Volumetric flask.
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2016
Volumetric pipets accurately deliver a fixed volume.
A small volume remains in the tip.

Transfer or volumetric pipets


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2016
Measuring pipets are straight-bore pipets marked at
different volumes.
They are less accurate than volumetric pipets.

Measuring pipets
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2016
Syringe pipets precisely deliver microliter volumes.
They are commonly used to introduce samples into a gas
chromatograph.

Hamilton microliter syringe

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2016
These syringe pipets can reproducibly deliver a selected
volume.
They come in fixed and variable volumes. The plastic tips
are disposable.

Single-channel and multichannel digital displacement


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pipets and microwell plates 27
2016
A 50-mL buret is marked in 0.1 mL increments.
You interpolate to 0.01 mL, good to about ±0.02 mL.
Two readings are taken for every volume measurement.

Typical buret.
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2016
Care and use of volumetric
glassware
• Cleanliness

• Rinse with the solution to


be measured

• Avoid parallax error in


reading

• Filled with distilled water


and stored with the stopper
inserted
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2016
General tips for accurate and
precise titrating
• Use stopcock
• Meniscus level
• Erlenmeyer flask with
magnetic stirrer and stirring
bar
• Permanent change in the
color at least 30 sec
• Triplicate

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2016
Position the black field just below the meniscus.
Avoid parallax error by reading at eye level.

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2016
Place the flask on a white background. Place the
buret tip in the neck of the flask while your swirl.

Proper technique for titration.


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Tolerances and precision of
glassware

• NIST has prescribed tolerances,


or absolute errors for glassware

• Class A glassware is accurate


enough for most analyses

• Glassware have certain


precision of reading depend to
the volume required

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2016
Techniques for calibrating
glassware

1. Volumetric flask
calibration

2. Pipet calibration

3. Buret calibration

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2016
2.5 Preparation of standard base
solutions
• NaOH usually used as titrant

• Na2CO3 is removed by
preparing a saturated
solution of NaOH

• Methyl orange and


phenolphtalein are normally
used as indicator

• NaOH usually standardized


by KHP
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2016
2.6 Preparation of standard
acid solutions
• HCI is the usual titrant
• Water should be boiled
• Primary standard NaCO3
• THAM, (HOCH2)CNH2
• Secondary standard NaOH
• Phenolptalein or
bromothylmol blue can be
used as indicator

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2016
2.7 Handling and treating
samples
Blood samplers
• Syringes are used to
collect blood samples

• Stainless steel or aluminum

• No contamination

• Vacutainers are used in


place of syringes
• Anticoagulating agent
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Desicators
• Is used to keep samples dry
before weight and for wet
sample
• Airtight container

• Maintain an atm of low humidity


• CaCI2 is used as desiccant
• Porcelain plate used to support
weighing bottles, crucibles and
etc
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2016
Use a desiccator to cool a dried or ignited sample.
Cool a red hot vessel before placing in the desiccator.
Do not stopper a hot weighing bottlle (creates a partial vacuum on
cooling).

Desiccator and desiccator plate


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CaCl2 is commonly used.
It needs periodic replacement when wet or caked.

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2016
Furnaces and Ovens
• Muffle furnace is used to
ignite sample to high T

• Temperature can up to
1200C

• Drying oven is used to dry


samples prior to weighing
• Ventilated for uniform
heating
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2016
Used to ignite samples at high temperatures, e.g., to dry ash
organic matter.

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2016
Used to dry samples before weighing.
Usually 110o C used.

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Drying oven. 43
2016
Hoods

• Fume hood is used when


chemicals or solutions are
to be evaporated

• Specially designed for


perchloric acid

• Dirties area

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2016
• Laminar-flow hoods
provide clean work area

• HEPA filter removes all


particles >0.3µm from the
air

• Vertical-flow hoods are


preferred when fumes are
generated.

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2016
A fume hood is “dirty” since it
draws in laboratory air.
A laminar-flow hood filters air
(0.3 mm HEPA filter) and flows it
out into the room.
Use it as a workstation for trace
analysis.

Laminar-flow workstation
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2016
Wash bottle
• To be used for quantitative
transfer of precipitates,
solutions and to wash
precipitates

• Variety of shapes and sizes

• Constructed by Florence
and glass tubing

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2016
Use these for quantitative transfer of precipitates and
solutions, and for washing precipitates.

Wash botltles: (a) polyethylene, squeeze type;


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(b) glass, blow type. 48
2016
Centrifuges
• Clinical laboratory
• Ex: separation of blood

Filters
• Filtering precipitates
• Types of crucibles:
i. Gooch
ii. Sintered glass
iii. Porcelain
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2016
Use for filtering non-gelatinous precipitates.

Filtering crucibles: (a) Gooch crucible;


(b) sintered-glass crucible; (c) porcelain filter crucible.
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2016
Techniques of filtration
• How do we increase the
rate of filtration?

i. Proper fitting of the filter


paper
ii. The suction supplied by
the weight of water in
the steam

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2016
• Let the precipitate settle
before filtering

• Wash the precipitate while it


is in the beaker

• Test for completeness of


washing

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2016
Mount the filtering crucible in a crucible holder and
connect the filtering flask to a water aspirator.

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2016
Crucible holders 53
These are ashless filter papers.
They are ignited away after collection of the
precipitate.
Use for gelatinous precipitates.

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2016
This provides a good seal and prevents air bubbles from being drawn
in.
Suction from the weight of the water in the stem increases the
filtration rate.
Let the precipitate settle in the beaker before beginning filtration.

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2016
Decant the solution by pouring down the stirring rod.
After decantiing the mother liquor, add wash water to the precipitate
and decant again, repeating 2-3 times.
Then wash the precipitate into the filter.

Proper technique for transfer of a precipitate


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2016
Use this to scrub the walls of the beaker and collect all the
precipitate (by washing).

Rubber policeman

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2016
2.8 Igniting precipitate –
gravimetric analysis

• Types of crucibles
- porcelain, platinium

• Ignition
- slowly
• Weighing
- constant weight

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2016
Heat or ignite the crucible to a constant weight (to 0.3-0.4 mg) before adding
the filtered precipitate.
Fold the filter paper over the precipitate.
Drive off moisture at low heat. Then gradually increase heat till the paper
begins to char.
After the paper is gone, ignite the precipitate.

Crucible and cover supported on a wire


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2.9 Obtaining the sample – it is
solid, liquid or gas?
• Most critical aspect of an
analysis

• Instructions for sampling


- ASTM - APHA
- AOAC

• Sample types
- gross sample
- lab sample
- analysis sample
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2016
Solids
• Problems
- inhomogeneity
- variation in size
- variation within the particles

• Take 1/50 to 1/100 for gross


sample

• Larger the particle size, larger


the gross sample

• Systematic sampling

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2016
Liquids
• Homogeneous

• Liquid mixing
- diffusion - shaken

• Timing is very important

• Sample to be analyzed

• Non-homogeneous liquid

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Gases
• Method involves
displacement of liquid

• Grab sample

• Concentration of analyte is
usually measured

• Temperature and pressure


are important in determining
the conc.

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2016
2.10 Operations of drying and preparing
a solution of the analyte
Drying the sample

• Inorganic sample will


generally be dried before
weighing

• Decomposition of side
reactions

• Plant and tissue samples


usually dried by heating
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2016
Sample dissolution

• Sample alteration is necessary to;


- get the analyte into
solution
- rid it of interfering organic
substances

• 2 types of sample prep:


i) totally destroy sample matrix
ii) partially destructive

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2016
Dissolving inorganic solids

• Strong mineral acids are


good solvents for many
inorganic
Ex: Nitric acid, Perchoric
acid and Hydrocloric acid

• Fusions are used when


acids do not dissolve
sample

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2016
Destruction of organic material for
inorganic analysis

Wet digestion
Dry ashing
• organic matter is
• organic matter
oxidized
is burned off
• perform in Kjeldah flask
• high T (400-700C)
• digestion mixtures
• atmosferic O2 serves
• biology samples
as the oxidant
• rapid, low level of T,
• elemental analysis
freedon from loss
• simple and freedom
• impurities from reagent
from positive error

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2016
2.11 Laboratory safety
• Familiarize with lab safety
rules and procedures

• ‘ Safety in Academic
Chemistry Laboratory’

• OSHA

• ‘ The Waste Management


Manual for Laboratory
Personnel’
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2016
CONCLUSION
• How to use reagent-grade
chemicals

• Volumetric glassware, how


to use and calibrate it

• How to prepare standard


base and standard acid

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2016
• Common lab apparatus for
handling and treating
samples

• How to sample solids,


liquids and gases

• How to prepare solution for


analyte

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2016
Recapitulation
1. Explain weighing by
difference.

2. List the general rules for the


use of balance

3. What are the advantages and


limitations of dry ashing and
wet digestion?

4. What are the 2 principles


means of dissolving inorganic
materials?
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