Appendix 3

The Measurement of Volume

General Considerations
The quantity of liquid used in an experiment is conveniently measured by the volume it occupies. How this volume is measured depends
upon how accurately the volume needs to be known and whether a fixed or variable quantity of liquid is needed. The most commonly used
units for volume are the liter (L), which equals 1 cubic decimeter by definition, and the related milliliter (mL), which is one-thousandth
(1/1000) of a liter. 1 mL = 1cm3 = 1 cc (cubic centimeter)

There are three general considerations to keep in mind when measuring the volume of a quantity of liquid. First, the glassware used must
be clean. Liquid droplets usually adhere to dirt or films on the glassware, so the amount of liquid delivered when the liquid is transferred
from the measuring container is too small. Second, in a piece of glassware with a narrow bore such as a buret or a pipet the surface of
the liquid will not be perfectly flat. If the intermolecular forces between the liquid molecules are less than those between the liquid
molecules and the glass, a concave meniscus will develop. This is the case for water and glass. By convention we measure the volume of the
liquid at the bottom of a concave meniscus us. If the intermolecular forces between the liquid molecules are greater than those between
the liquid molecules and the glass, a convex meniscus will develop. The volume at the top of the convex meniscus is read.

Third, the eye of the observer must be at the same level as the meniscus in order to avoid parallax error. Parallax is the apparent
displacement of a liquid level as an observer changes position. It occurs when the observer's line of vision is not perpendicular to the
surface of the calibrated scale being read and is a result of the refraction of light by the glass and the liquid.

Glassware
A. Beakers and graduated cylinders: When the volume of liquid used needs to be only approximately beakers or graduated cylinders
may be used. Liquid is poured into the glassware until the volume desired is reached as determined by using the scale imprinted on
the side of the glassware. The volumes obtained may be off by as much as 20% in the case of beakers, so only noncritical volumes
should be measured in this way.

B. Volumetric pipets: Volumetric pipets are used to deliver a fixed, accurately known volume of liquid into a container. They are
available in a variety of sizes between 0.5 and 200 m L, with larger pipets having the best relative accuracy.

Volumetric pipets are used with rubber bulbs according to the following procedure:
A small volume of liquid is drawn up into the pipet using a rubber bulb. The bulb is removed and the liquid is then used to thoroughly wet
the interior surface of the pipet. This liquid is drained out. The bulb is reattached and liquid drawn into the pipet until it is above the
pipet mark. Raise the pipet above the level of the liquid and wipe off any drops adhering to the outside. Replace the bulb with a moistened
forefinger. Slowly let the liquid drain back into its original container until the bottom of the meniscus is at the mark. Move the pipet to
the receiving container and let it drain. When liquid flow ceases touch the pipet tip to the inside wall of the container. Let the tip rest
there for at least 10 seconds. Remove the pipet from the container. Do not blow out the small remaining volume in its tip.

Volumetric pipets are used with suction bulbs by the same basic procedures, with the following changes:
In order to create suction the 'S" bead is squeezed simultaneously with the bulb. Release the bead first. Attach the bulb to the pipet.
Squeeze the "S" bead to suction liquid into the pipet. Squeeze the "E" bead to lower the liquid level in the pipet without removing the bulb.

Volumetric pipets are used with pipet pumps as follows:

Hold the pipet close to its upper end and insert it into the opening of the pump using slight pressure and a twisting motion. Submerge the
end of the pipet into the solution and turn the wheel with your thumb. Draw fluid up to the mark. To expel turn the wheel in the other
direction or push the plunger down.

Under no circumstances are you to pipet by mouth!

C. Burets are used when an accurately measured volume of either a quantity of liquid which is not known at the beginning of the
experiment or a known volume which does not correspond to any available volumetric pipet volume needs to be delivered to a container.
Buret volumes are measured by difference. A reading is made of the initial volume, followed by a reading of the final volume, and the
volume delivered found by subtraction. It is important to know that buret volumes are read to the nearest 0.01 Iii on typical 50 'mL
burets, and that the buret scale has 0.0 iii at the top and 50.0 mL at the bottom.

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Burets are used as follows:
Between 5 and 10 mLs of the liquid that will fill the buret are placed in it. This liquid is swirled around inside the buret to rinse and coat
all surfaces, and then drained out the tip. Repeat this step. Fill the buret above the zero-mark using a funnel to avoid spillage. Drain liquid
through the tip to fill it and displace any air bubbles in the stopcock until the liquid level is at or just below the zero mark. Record this
initial volume. Move the receiving container under the buret tip. For dispensing a known volume of liquid open the stopcock until the desired
liquid volume is obtained. Record the final buret volume and be sure to use the volume actually delivered in your calculations. For titrations
add liquid to the container slowly to ensure that the endpoint is not overshot. Any liquid which splashes onto the sides of the container
may be rinsed down with solvent Partial drops from the buret may be added to the flask by letting a small amount of liquid hang from the
tip of the buret, touching the container wall to the tip, and then rinsing the wall with solvent. Record the buret reading at the endpoint
and find the volume used by difference.

D. Volumetric Flasks: In preparing solutions of known molarity the final volume of the solution must be known since molarity is
defined as moles of solute per liter of solution. Volumetric flasks are used for this purpose. They are only used to contain a known
volume and never to deliver liquid.

Volumetric flasks may be used according to the following procedure:

Fill the volumetric flask between one-half and two-thirds full with liquid. Quantitatively transfer the desired quantity of solid into it using
a powder funnel. Rinse the powder funnel with liquid to insure all of the solids went into the flask. Swirl the flask to aid in the dissolving
of the solid. After it is all dissolved fill the flask to the mark, using an eyedropper to add the last few drops. Be careful not to overshoot!
Stopper the flask and invert it several times to thoroughly mix the solution.

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 Appendix 4
Titration Technique

Burets are long, narrow, finely graduated tubes as shown in the figure.1. They are designed to deliver precise and variable volumes of
liquids into other containers. A stopcock or pinch clamp at the base of the buret provides for release of volumes between about 0.05
mL and the total volume of the buret. Burets are especially useful for adding solutions stepwise in small increments. Burets typically
have uncertainties of about + 0.1%. Thus, you might measure 21.33 + 0.02 mL using a buret.

The steps for using a buret are illustrated in the figure .2 provided. First secure the buret in a buret clam attached to a ring stand (1) .
If you have never used a buret or have only used it a few times, it is wise to practice manipulation of the stopcock or pinch clamp to
adjust the liquid flow using deionized water. Partially fill a clean buret with deionized water. Then adjust the stopcock or pinch clamp a
number of times until you have the feel of the degrees of turn or pressure required to release liquid one drop at a time or in a steady
flow. The stopcock should be handled with the thumb and two fingers (2) along with a slight inward pressure on the plug to prevent
leakage. The pinch clamp should be handled with the thumb and third finger. Do not use the buret for the actual experiment until you
are conformable carrying out these operations with relaxed muscles.

Fill a clean buret that has already been rinsed with your reagent solution with a few more milliliters of solution than you need for the
task at hand (3). Then open the stopcock or pinch clamp long enough to fill the buret tip (2). Since the volume of solution delivering by
the buret is always determined by taking the difference between an initial volume and the final volume, it is not necessary or even worth
the effort to adjust the initial reading to the zero-calibration mark. Therefore, record the initial volume whenever it is by observing
the position on the graduated scale of the lowest portion of the meniscus (4). Make certain that your eye is at the same level as the
meniscus (5). A dark background placed behind the buret and at or just below the meniscus makes it easier to read (6).

Place the receiving flask under the buret and over the white paper that enhances visibility at the end point. Make certain that you have
added the required drops of an indicator solution if you are performing an acid-base titration or an oxidation-reduction titration. Open
the stopcock or pinch clamp carefully to adjust the liquid flow from dropwise to a rapid flow as desired (7). When as much solution as is
needed has been delivered, close the stopcock or pinch clamp, and touch the inner wall of the receiving container to the buret tip to
remove any hanging drop (8). If you are using the buret for titration to an endpoint, then rinse the wall of the receiving flask with
deionized water (9), and record the final volume by observing the new position of the meniscus. If you are using the buret not for
titration to an endpoint, but simply to deliver a carefully measured volume of a liquid, do not rinse the wall of the receiving vessel with
deionized water before observing and recording the final volume.

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