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CALIBRATION OF VOLUMETRIC
GLASSWARE

DISCUSSION: For very accurate volumetric analysis, it is advisable to calibrate the

volumetric glassware. Though a volumetric pipet may be labeled 25 mL,
it will not deliver exactly that volume. There are allowed tolerances in
manufacture. For example, a 100 mL volumetric flask is manufactured
to a tolerance of ±0.08 mL, and since liquids and glass expand or
contract as temperature rises and falls, the tolerance applies at the
temperature indicated on the flask, usually 20°C. The tolerance values
established for volumetric glassware by the National Institute of
Standards and Technology (NIST) are listed below in Table I. It should
be noted that glassware meeting these specifications is termed "class-A"
glassware, and it is adequate for all but the most exacting work, for
which calibrated glassware is a necessity.

TABLE I Tolerances for Volumetric Glassware

Volume Capacity Volumetric Transfer Burets
mL Flasks Pipets
1 ± 0.02 mL
2 ± 0.02 mL ± 0.006 mL
5 ± 0.02 mL ± 0.01 mL ± 0.01 mL
10 ± 0.02 mL ± 0.02 mL ± 0.02 mL
25 ± 0.03 mL ± 0.03 mL ± 0.03 mL
50 ± 0.05 mL ± 0.05 mL ± 0.05 mL
100 ± 0.08 mL ± 0.08 mL ± 0.10 mL
200 ± 0.10 mL ± 0.10 mL
250 ± 0.12 mL
500 ± 0.20 mL
1000 ± 0.30 mL

Volumetric glassware that commonly require calibration if very

exact work is to be done would be the volumetric flask, the volumet-
ric pipet and the buret. These three items are described further in
the following paragraphs.
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Volumetric Flask: A volumetric flask is calibrated to contain (TC)

the indicated volume of water at 20oC when the bottom of the
meniscus is adjusted to just rest on the center of the line marked on
the neck of the flask. Most flasks bear the label "TC 20oC" indicating
that the flask is calibrated to contain the indicated volume at 20oC.
Other types of glassware, such as pipets and burets, may be cali-
brated to deliver (TD) the indicated volume. Volumetric flasks are
normally manufactured with capacities from 5 mL to 5 L. They are
used in the preparation of standard solutions and in the dilution of
solutions to fixed volumes prior to taking aliquots (with a transfer
pipet) in an analysis.

Though temperature must be considered when dealing with the

accurate measurement of volumes, modern laboratory glassware
made of Pyrex® or other low expansion borosilicate glass can be
safely heated without fear of breakage in an oven to at least 320oC
without harm. Glassware is normally dried at 110-150oC.

Burets: Burets are used to deliver accurately known, but variable,

volumes up to its maximum capacity. The precision attainable with
a buret is substantially greater than with a pipet. A buret equipped
with a glass stopcock valve requires a layer of lubricant between the
ground-glass surfaces of the stopcock for a liquid-tight seal. Because
this lubricant can get into the tip and on the inner wall of the buret,
thorough cleaning is needed after use. Silicone lubricants are
especially difficult to remove, and often require hot alkali solutions,
which can also attack glass. For this reason, Teflon® is used to form
the rotating part of a stopcock. It is resistant to chemical attack, acts
as its own lubricant and is soft enough to form a liquid-tight seal.

Pipets: Pipets permit the transfer of accurately known volumes from

one container to another. Common types of pipets are shown in
Figure 1, (in the hard copy manual) and their characteristics are
listed in Table II.

Volumetric pipets are typically available between 0.5 and 200 mL.
Because an attraction exists between most liquids and glass, a small
amount of liquid tends to remain in the tip of the pipet after the pipet
is emptied. This residual liquid is never blown out of a volumetric
pipet; but with other pipet types it is proper to blow out the last drop,
as indicated in Table II.
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Table II Characteristics of Pipets

Type of Type of Usual Available Type of
Pipet Calibration Function Capacity, mL Delivery
Volumetric TD to deliver fixed volume 1 to 200 mL free flow

Mohr TD to deliver variable volume 1 to 25 mL to lower

calibration line

Serological TD to deliver variable volume 0.1 to 10 mL blow out last drop

Ostwald-Fohn TD to deliver fixed volume 0.5 to 10 mL blow out last drop

Lambda TD to deliver fixed volume 0.001 to 2 mL blow out last drop

Lambda TC to contain fixed volume 0.001 to 2 mL wash out with

suitable solvent

Syringe TD to deliver variable volume 0.001 to 1 mL tip emptied

by syringe

CLEANING Clean glassware is imperative for accurate and precise volumetric

GLASSWARE: applications. It is therefore necessary to thoroughly clean all glassware
before use. A brief soaking in a warm detergent solution is usually
sufficient to remove the grease and dirt responsible for water breaks. If
detergent is ineffective, treatment with cleaning solution usually helps.
The following solutions are commonly used.

Dilute Nitric Acid: Films which adhere to the inside of flasks and bottles
may often be removed by wetting the surface with dilute nitric acid,
followed by multiple rinses with distilled water.

Dichromate-Sulfuric Acid Cleaning Solution:

This solution must be prepared and handled with ex-

treme care. Eye protection must be worn at all times
during use and avoid contact with clothing or skin.

Dissolve 92 g sodium dichromate in 458 mL water, and cautiously add,

with stirring, 800 mL concentrated sulfuric acid. After the glassware has
been cleaned with a detergent and rinsed carefully, pour a small quantity
of the chromate solution into the glassware, allowing it to flow down all
parts of the glass surface. Pour the solution back into its stock bottle.
Rinse the glassware well. The cleaning solution may be reused until it
acquires the green color of the chromium(III) ion. Once this happens, it
should be discarded.

Aqua Regia Cleaning solution:

Aqua Regia must be prepared and handled with extreme

care. Wear eye protection at all times during use and
avoid contact with clothing or skin.
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Aqua regia is made up of three parts of concentrated HCl and one

part of concentrated HNO3. This is a very powerful, and extremely
dangerous and corrosive, cleaning solution. Use in a hood with
extreme care. Contact your instructor if you have any questions.

Ultrasonic Cleaners: Ultrasonic glass cleaners are very good for

cleaning pipets and burets. The glassware is soaked in a warm
detergent solution through which is passed acoustic energy of
frequency at or above 40 kHz. The ultrasonic vibrations dislodge
dirt and grease quickly from glass surfaces, in a most case in a matter
of 5 to 10 minutes. The detergents are designed to rinse easily from
glass, leaving a very clean surface. Ultrasonic cleaners provide a
rapid and safe method for cleaning glassware on a day to day basis,
and it is the method of choice for cleaning volumetric glassware.

METHODS OF There are three general methods commonly employed to calibrate

CALIBRATION: glassware. These are as follows:
1. Direct, absolute calibration
2. Indirect, absolute calibration
3. Relative calibration
Direct calibration: A volume of water delivered by a buret or pipet,
or contained in a volumetric flask, is obtained directly from the
weight of the water and its density. The data in Table III are the
volumes of 1.0000 g of water at several temperatures, and what the
volume would be when corrected to 20°C. For example, if at 25°C,
a 20.00 mL pipet delivered 19.970 g of water. The volume delivered
at 25°C would be 19.970 g x 1.0040 mL/g = 20.05 mL. At 20°C, the
volume would be 19.970 g x 1.0037 mL/g = 20.04 mL.

Table III
Volume Occupied by 1.0000 g of Water
Weighed in Air Against Stainless Steel Weights
Temperature, °C volume of volume in mL
T 1.0000 g H2O at T corrected to 20°C
16 1.0021 mL/g 1.0022 mL/g
17 1.0022 mL/g 1.0023 mL/g
18 1.0024 mL/g 1.0025 mL/g
19 1.0026 mL/g 1.0026 mL/g
20 1.0028 mL/g 1.0028 mL/g
21 1.0030 mL/g 1.0030 mL/g
22 1.0033 mL/g 1.0032 mL/g
23 1.0035 mL/g 1.0034 mL/g
24 1.0037 mL/g 1.0036 mL/g
25 1.0040 mL/g 1.0037 mL/g
26 1.0043 mL/g 1.0041 mL/g
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27 1.0045 mL/g 1.0043 mL/g

28 1.0048 mL/g 1.0046 mL/g

Indirect calibration: Volumetric glassware can be calibrated by

comparison of the mass of water it contains or delivers at a particular
temperature with that of another vessel which had been calibrated
directly. The volumes are directly related to the masses of water.
This method is convenient if many pieces of glassware are to be
calibrated.

Relative calibration: It is often necessary to know only the volumet-

ric relationship between two items of glassware without knowing the
absolute volume of either. This situation arises, for example, in
taking an aliquot portion of a solution. Suppose that it is desired to
titrate one-fifth of an unknown sample. The unknown might be
dissolved and diluted to volume in a 250 mL volumetric flask. A 50
mL pipet would then be used to with draw an aliquot for titration.
For the calculation in this analysis, it would not be necessary to
know the exact volume of the flask or the pipet, but it would be
required that the pipet deliver exactly one-fifth of the contents of the
flask. The method used for the relative calibration in this case
would be to discharge the pipet five times into the flask and marking
the level of the meniscus on the flask.

EXPERIMENTAL In this lab you will be calibrating a 50 mL pipet and a 50 mL

buret.
PROCEDURE: The method you will use will be the direct method.
I. Calibration of a 50 mL Volumetric Pipet
Ensure the pipet you desire to calibrate is clean. If small droplets of
water adhere to the inner surface of the pipet after delivering
deionized water, the pipet is dirty and must be cleaned before
proceeding further. Select a stoppered container to receive the
50 mL volume delivered from the pipet. Determine the mass of the
empty, stoppered receiver to the nearest milligram. With the pipet
at the same temperature as the water, transfer a 50 mL portion of
temperature-equilibrated water to the receiving container with the
pipet. Weigh the stoppered receiver and its contents and calculate
the mass of water delivered by difference. From the delivered mass
of water, calculate the volume delivered using the appropriate data
from Table III. Repeat the calibration three times and calculate the
mean volume delivered and the standard deviation. Report your
results on the Report Sheet.
II. Calibration of a 50 mL Buret
Ensure the buret you desire to calibrate is clean. If small droplets of
water adhere to the inner surface of the buret after delivering
deionized water, the buret is dirty and must be cleaned before
proceeding further. Fill the buret completely full with temperature-
equilibrated water and make sure that air bubbles are not trapped in
the stopcock or tip. Draining water from the buret very slowly,
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lower the liquid level until the bottom of the meniscus just rests on
the 0.00 mL mark. Touch the tip to the wall of a beaker to remove
any adhering drop. Wait 10 min and recheck the volume. If the
stopcock is tight, there should be no perceptible change in the
meniscus. During this interval, weigh (to the nearest milligram) a
125 mL Erlenmeyer flask fitted with a rubber stopper, recording its
mass on the Report sheet.

Once tightness of the stopcock has been established, slowly transfer

(at a rate of about 10 mL/min) approximately 10 mL of water to the
flask. Touch the tip to the wall of the flask and stopper it. Wait one
minute, then record the apparent volume delivered from the buret to
the second place after the decimal. Refill the buret again to the 0.00
mL mark. Weigh the stoppered flask and its contents to the nearest
milligram. Determine the mass of water delivered by difference. Use
the data in Table III to convert this mass to the true volume deliv-
ered. Subtract the apparent volume from the true volume. This
difference is the correction that should be applied to the apparent
volume to give the true volume. Repeat the 10 mL calibration until
agreement between subsequent true values is within ±0.02 mL.

Starting again from the zero mark, repeat the calibration, this time
delivering about 20 mL to the receiver following the procedure given
above. Calibrate the buret delivering approximately 30, 40 and 50
mL, recording the data on the Report Sheet.

Prepare a plot of the correction factors (vertical axis) which are to be

applied to convert apparent to true volume versus the apparent
volume (horizontal axis) of water delivered. The correction factors
which must be applied to any apparent volume can then be read
from this graph.
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REPORT SHEET: CALIBRATION OF VOLUMETRIC

GLASSWARE

Name ____________________________________________ Date: _____________

Please print; last name first

Temperature of the water: _____________

I. Calibration of a 50 mL Volumetric Pipet

Trial: 1 2 3
mass of flask (with sample), g:

mass of flask (empty), g:

mass of water, g:

true volume, mL (corrected):

Mean Volume ± s.d. (mL): ____________________

II. Calibration of a 50 mL buret

A. The 10 mL Volume:

Trial: 1 2 3

mass of flask (with sample):

mass of flask (empty):

mass of water:

apparent volume (from buret):

true volume (corrected):

volume difference:
(true ! apparent)

mean difference: _______________ mean true volume ± s.d.: ____________________

(Continues on the following page.)

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Name ____________________________________________ Date: _____________
Please print; last name first

B. The 20 mL Volume:

Trial: 1 2 3

mass of flask (with sample):

mass of flask (empty):

mass of water:

apparent volume (from buret):

true volume (corrected):

volume difference:
(true ! apparent)

mean difference: _______________ mean true volume ± s.d.: ____________________

C. The 30 mL Volume:

Trial: 1 2 3

mass of flask (with sample):

mass of flask (empty):

mass of water:

apparent volume (from buret):

true volume (corrected):

volume difference:
(true ! apparent)

mean difference: _______________ mean true volume ± s.d.: ____________________

(Continues on the following page.)

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Name ____________________________________________ Date: _____________

Please print; last name first

D. The 40 mL Volume:

Trial: 1 2 3
mass of flask (with sample):

mass of flask (empty):

mass of water:

apparent volume (from buret):

true volume (corrected):

volume difference:
(true ! apparent)

mean difference: _______________ mean true volume ± s.d.: ____________________

E. The 50 mL Volume:

Trial: 1 2 3

mass of flask (with sample):

mass of flask (empty):

mass of water:

apparent volume (from buret):

true volume (corrected):

volume difference:
(true ! apparent)

mean difference: _______________ mean true volume ± s.d.: ____________________

Attach the graph of correction factors versus apparent volumes to the Report Sheets.