2 Chemicals, Apparatus and Unit Operations of

Analytical Chemistry
2A Selecting and Handling Reagents and Other Chemicals
NIST (The National Institute of Standards and Technology)

2A-1 Classifying Chemicals

Reagent Grade
Reagent Chemical Committee of the American Chemical Society
The maximum limits of impurity allowed by the ACS specifications;
The actual assay for the various impurities.

Primary-Standard Grade
in addition to extraordinary purity and the assay is printed on the container label.
reference standards, complex substances that have been exhaustively analyzed.

Special-Purpose Reagent Chemicals

Solvents for spectrophotometry and high-performance liquid chromatography.

2A-2 Rules for Handling Reagents and Solutions

1. The best grade, the smallest bottle
2. Replace the top of every container immediately after removal of the reagent.
3. Hold the stoppers of reagent hollies between your fingers.
4. Never return any excess reagent to a bottle.
5. Never insert spatulas, spoons, or knives into a bottle.
6. Keep the reagent shelf and the laboratory balance clean and neat.
7. Observe local regulations (the disposal of surplus reagents and solution).

2B Cleaning and Marking Laboratory Ware

pencil.
baked permanently into the glaze by heating at a high temperature
saturated solution of iron(III) chloride

It is seldom necessary to dry the interior surface of glassware before use.

benzene or acetone, may be effective in removing grease films

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2C Evaporating Liquids
Fig. 2-1
Arrangement for the evaporation of a liquid

Bumping: sudden, often violent boiling that tends to spatter

solution out of its container.
Wet-ashing: Oxidation of the organic constituents of a sample
with oxidizing reagents such as HNO3, H2SO4,
H2O2, or aqueous Br2, or a combination.

2D Measuring Mass
2D-1 Types of Analytical Balances
Max. capacity Precision
at max. capacity
Analytical balance 1 g to few kg 1 part in 105~106
Macrobalance 160 to 200 g 0.1 mg
Semimicroanalytical balance 10 to 30 g 0.01 mg
Microanalytical balance 1 to 3 g 0.001 mg (1g)

2D-2 The Electronic Analytical Balance

Tare
Taring

2D-3 The Single-Pan Mechanical Analytical Balance

Precautions in Using an Analytical Balance
1. Center the load on the pan.
2. Protect the balance from corrosion.
3. Observe special precautions (Section 2E-6) for the weighing of liquids.
4. Consult the instructor if the balance appears to need adjustment.
5. Keep the balance and its case scrupulously clean.
6. Allow an object return to room temperature before weighing it.
7. Use longs or finger pads.

2D-4 Sources of Error in Weighing

Correction for Buoyancy

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buoyancy error : weighing error that develops when the object being weighed has a
significantly different density than the weights.

d d W1: the corrected mass of the object

W1 = W2 + W2 ( air air ) (2-1) W2: the mass of the standard weights
d obj d wts
dobj: the density of the object
dwts: the density of the weights
dair: the density of the air displaced
0.00 by them; 0.0012 g-cm-3

-0.10

Fig. 2-5 Effect of buoyancy on

-0.20
weighing data (density of weights =
8 gcm-3). Plot of relative error as a
-0.30
function of the density of the object
weighted.
0 2 4 6 8 10 12 14 16 18 20
Density of object, g/L

Ex. 2-1
A bottle weighed 7.6500 g empty and 9.9700 g after introduction of an organic
liquid with a density of 0.92 g-cm-3. The balance was equipped with stainless steel
weights (d = 8.0 g-cm-3). Correct the mass of the sample for the effects of
buoyancy.
mass of the liquid = 9.9700 - 7.6500 = 2.3200 g.
0.0012 0.0012
W1 = 2.3200 + 2.3200( ) = 2.3227 g
0.92 8.0

Temperature Effects
1. a buoyant effect on the pan and object
2. warm air trapped in a closed container weighs less than the same volume at a
lower temperature.
Both effects cause the apparent mass of the object to be low.
Allow heated objects to return to room temperature before being weighed.

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 Fig. 2-6
Effect of temperature on weighing data.
Absolute error in mass as a function of lime
after the object was removed from a 110C
drying oven. A: porcelain filtering crucible.
B: weighing bottle containing about 7.5 g of
KC1.

0 10 20
Time after removal from oven, min

2D-5 Auxiliary Balances

For weighings that do not require great accuracy.
Precision
Balances Max. capacity
at max. capacity
sensitive top-loading 150 to 200 g 1 mg
top-loading 25,000 g 0.05 g

2E Equipment and Manipulations Associated with Weighing

Drying or ignition to constant mass is a process in which a solid is cycled through
heating, cooling, and weighing steps until its mass becomes constant to
within 0.2 to 0.3 mg.
2E-1 Weighing Bottles
Fig. 2-7 Typical weighing bottles.

A
2E-2 Desiccators and Desiccants
Oven drying is the most common way.
Desiccatora device for drying substances or objects.

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 Fig. 2-8
Components of a typical desiccator. The
base contains a chemical drying agent.
Desiccator plate
Ground-glass
surfaces Desiccant: chemical drying agent, such
as anhydrous calcium chloride, calcium
sulfate (Drierile), anhydrous
magnesium perchlorate (Anhydrone
or Dehydrite), or phosphorus
pentoxide.
Desiccant

2E-3 Manipulating Weighing Bottles

Fig. 2-10
Fig. 2-9 Quantitative transfer of
Arrangement solid sample. Note the
for the drying use of tongs to hold the
of samples. weighing bottle and a
105 to 110C paper strip to hold the
heating cap to avoid contact
between glass and skin.

2E-4 Weighing by Difference

2E-5 Weighing Hygroscopic Solids
2E-6 Weighing Liquids

2F Filtration and Ignition of Solids

2F-1 Apparatus
1. simple Crucibles
Containers,
porcelain, aluminum oxide, silica, and platinum (constant mass)
Ni, Fe, Ag and gold for high temp fusion

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2. Filtering Crucibles
Containers + filters
Sintered-glass (frittled-glass) crucibles:
fine, medium, and coarse porosities
(marked f, m & c). (200C)

Gooch crucible: perforated bottom that

supports a fibrous mat.
Fig. 2-11
Glass mats can tolerate temp in excess
Adapters for
of 500C and are substantially less
filtering crucibles.
hygroscopic than asbestos.

3. Filter Paper
Ashless: (9- or 11-cm) leave a residue 0.1 mg
Table 2-1 Comparison of Filtering Media for Gravimetric analyses
Gooch
Glass Porcelain Al2O3
Characteristic Paper crucible,
crucible Crucible crucible
Glass Mat
Speed Slow Rapid Rapid Rapid Rapid
Convenience Troublesome, Convenient Convenient Convenient Convenient
and ease of inconvenient
preparation
Max. ignition None >500 200-500 1100 1450
temp. C
Chemical C (reducing Inert Inert Inert Inert
reactivity properties)
Porosity Many Several Several Several Several
available available available available available
Convenience Satisfactory Unsuitable; Unsuitable; Unsuitable; Unsuitable;
with gelatinous filter tends filter tends filter tends filter tends
precipitate to clog to clog to clog to clog
Cost Low Low High High High

4. Heating Equipment
Oven: max. temp ranges from 140 to 260C; for many ppts: 110C .
Microwave laboratory ovens: shorten drying cycles.

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2F-2 Filtering and Igniting Precipitates
Preparation of Crucibles
Filting and Washing Precipitates
decantation, washing, and transfer
Fig. 2-12 (a) Washing by
decantation. (b)
transferring the
precipitate.

Decantation: pouring a
liquid gently so as to not
disturb a solid in the
bottom of the container.

Creeping: a solid moves up

the side of a wetted
container or filter
paper.

Do not permit a gelatinous precipitate to dry until it has been washed completely.

2F-3 Directions for Filtering and Igniting Precipitates

Preparation of a Filter Paper
Transferring Paper and Precipitate to a Crucible
Ashing Filter Paper & Using Filtering Crucibles

Fig. 2-15 Ignition of a

precipitate.
Proper cruciblc
position for
preliminary charring.

Fig. 2-16 Train for vacuum filtration. The trap isolates the
filler flask from the source of vacuum.

2G Measuring Volume
2G-1 Units of Volume
liter (L), milliliter (mL)
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2G-2 The Effect of Temperature on Volume Measurements
The coefficient of expansion: 0.025%/C, standard temp: 20C
Ex. 2-2 A 40.00-mL sample is taken from an aqueous solution at 5C. What
volume does it occupy at 20C?
0.025%
V20o = V5o + (20 5)(40.00) = 40.00 + 0.15 = 40.15mL
100%

2G-3 Apparatus for Precisely Measuring Volume

pipets, buret, and volumetric flask Tolerances, Class A Transfer Pipets
Capacity, mL Tolerances, mL
Pipets
0.5 0.006
Volumetric, or transfer, pipet: 1 0.006
(Fig.2-17a) delivers a single, fixed 2 0.006
volume between 0.5 and 200 mL. 5 0.01
10 0.02
Measuring pipets (Fig.2-17b, c): max. 20 0.03
capacity ranging from 0.1 to 25 mL. 25 0.03
50 0.05
100 0.08
Table 2-2 Characteristics of Pipets
Type of Available
Name Function Type of Drainage
Calibration* Capacity, mL
Volumetric TD fixed vol. 1-200 Free
Mohr TD variable vol. 1-25 To lower calibration line
Serological TD variable vol. 0.1-10 Blow out last drop
Serological TD variable vol. 0.1-10 To lower calibration line
Ostwald-Folin TD fixed vol. 0.5-10 Blow out last drop
Lambda TC fixed vol. 0.001-2 Wash out with suitable
(to contain) solvent
Lambda TD fixed vol. 0.001-2 Blow out last drop
Eppendorf TD variable or 0.001-1 Tip emptied by air
(to deliver) fixed vol. displacement
Burets
Burets, like measuring pipets, enable the analyst to deliver any volume
Volumetric Flasks: 5 mL to 5 L
1. preparation of standard solutions
2. dilution of samples to a fixed volume

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 Fig. 2-19
Burets:
(a) glass-bead valve,
(b) Teflon valve

Fig. 2-20 Typical

volumetric flasks.

2G-4 Using Volumetric Equipment

Cleaning
soaking in a warm detergent solution, tap water, distilled water
It is seldom necessary to dry volumetric ware.
Avoiding Parallax
Parallax is the apparent displacement of a liquid level or of a pointer as an
observer changes position. Parallax occurs when an object is viewed from a
position that is not at a right angle to the object.

A meniscus is the curved surface of a liquid at its interface with the

atmosphere.
Fig. 2-21 Method for reading a buret.
1
The eye should be level with the
Correct eye meniscus. The reading shown is 34.37
level for
reading mL. If viewed from position 1, the
reading appears < 34.37 mL, from
2 position 2, it appears larger.

2G-5 Directions for Using a Pipet

Never use your mouth to draw liquid into a pipet because of the possibility of
accidentally ingesting the liquid being pipetted.
Cleaning
Measuring an Aliquot
The small volume remaining inside the tip of a volumetric pipet should not be blown
or rinsed into the receiving vessel.

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2G-6 Directions for Using a Buret

1. Cleaning
2. Lubrication of a Glass Stopcock
3. Filling
4. Titration
Buret readings should be estimated to the nearest 0.01
mL.

Fig. 2-23 Recommended method for manipulating a

buret stopcock.

2G-7 Directions for Using a Volumetric Flask

2H Calibrating Volumetric Classware

Table 2-3 Volume occupied by 1.000 g of water weighed in air against stainless steel
weights.
T, Volume, mL T, Volume, mL T, Volume, mL T, Volume, mL
C At T 20 C C At T 20 C C At T 20 C C At T 20 C
10 1.0013 1.0016 16 1.0021 1.0022 21 1.0030 1.0030 26 1.0043 1.0041
11 1.0014 1.0016 17 1.0022 1.0023 22 1.0033 1.0032 27 1.0045 1.0043
12 0.0015 1.0017 18 1.0024 1.0025 23 1.0035 1.0034 28 1.0048 1.0046
13 1.0016 1.0018 19 1.0026 1.0026 24 1.0037 1.0036 29 1.0051 1.0048
14 1.0018 1.0019 20 1.0028 1.0028 25 1.0040 1.0037 30 1.0054 1.0052
15 1.0019 1.0020

Ex 2-3 A 25-mL pipet delivers 24.076 g of water weighed against stainless steel
mass at 25 C. Calculate the volume delivered by this pipet at 25 C and 20C.

At 25 C: V = 24.976 g 1.0040 mL/g = 25.08 mL

At 20 C: V = 24.976 g 1.0037 mL/g = 25.07 mL

2I The Laboratory Notebook

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