EXPERIMENT 2

ANALYSIS OF AN UNKNOWN VINEGAR SAMPLE

Objectives
1. To prepare the sodium hydroxide solution.
2. To standardise the base against potassium hydrogen phthalate.
3. To analyse the unknown vinegar sample.
Introduction
In this experiment you will learn about primary standard, standardisation and
standard solution. By definition, standard solution is a solution whose solute
concentration is accurately known. A solute which can be obtained in a very
pure, stable, weighable form is called a primary standard. An accurately
weighted primary standard is dissolved in the desired solvent and diluted to an
accurately known final volume in volumetric flask. Then the volumetric flask is
inverted a few times to obtain homogeneous solution. This solution thus
prepared is known as the primary standard solution.
You will first prepare an approximate concentration of sodium hydroxide solution.
Sodium hydroxide is not a primary standard because it is hygroscopic; meaning
that it absorbs moisture rapidly when exposed to air. Thus its accurate
concentration can only be determined by standardizing the solution against a
very pure potassium hydrogen phthalate in a series of replicate titrations. This
process is called standardisation. Potassium hydrogen phthalate (KHP) is a
monoprotic acid with the formula KHC8H4O4. The standardised sodium hydroxide
solution is then used to determine the acetic acid content of a vinegar sample.
Sometimes, the primary standard form of the desired reagent cannot be
obtained. Thus a secondary standard solution can be used. An approximate
concentration of the solution of the reagent is first prepared, and then its true
concentration is determined by standardisation process. Standardisation can be
achieved by titrating the prepared solution against (a) a measured mass of a
suitable primary standard substance; (b) another reliably known secondary
standard solution; or (c) by direct analysis for the reagent of interest by some
suitable non-volumetric method such as spectroscopic analysis.
In this experiment, we shall use standardisation method (a) i.e. using potassium
hydrogen phthalate as the primary standard to prepare a secondary standard
solution of sodium hydroxide. The standardised solution of sodium hydroxide is
then used to analyse the content of acetic acid in a vinegar sample.
Procedure
A. Preparation of the sodium hydroxide solution
In this Part A of the experiment you will prepare 600 mL of approximately
0.25 M sodium hydroxide solution by diluting a laboratory prepared stock
solution of approximately 50% (w/w) NaOH. The density of the
commercially prepared stock solution of 50% (w/w) NaOH is 1.525 g/mL.

the density of the 50% (w/w) NaOH prepared in the laboratory may be
slightly different.
1. First, the rough density of the prepared 50% NaOH were determined by
measuring the mass of 1o mL solution. A dry and empty 50 mL beaker
were weighted. 10 mL of the NaOH solution were measured in a
cylinder and transfer it to the pre-weighted beaker. The beaker were
reweighted. The difference in weight gives the weight of 10 mL 50%
NaOH prepared in this laboratory. Using the density of the prepared
50% NaOH, calculate the volume of the stock solution required to
prepare 600 mL of approximately 0.25 M sodium hydroxide solution.
2. About 300 mL of distilled water were placed into a clean plastic bottle.
Using a dropper, measure into a graduated cylinder, the calculated
volume of the stock NaOH solution required. Then carefully pour the
contents of the cylinder into the partially filled plastic bottle. Rinse the
cylinder out a few times with fresh distilled water and add all rinses
into the contents of the plastic bottle. Screw the cap on the plastic
bottle and mix the contents thoroughly by carefully and vigorously
inverting the bottle and swirling it repeatedly. Finally add the remaining
volume of water in three 100 mL batches, mixing the contents in the
bottle thoroughly each time. The bottle should be shaken at least 20
times after the last addition.
B. Standardisation of the base against potassium hydrogen phthalate
Here you will standardise your just prepared sodium hydroxide solution
against the primary standard, potassium hydrogen phthalate. You will also
adopt a weighing technique called weighing by difference. First, weigh the
container containing the primary standard. Then remove some of the
solute and place it in a separate container. Reweigh the original container
and the residual content. The difference between the two values gives the
mass of the solute removed. If the weight of the solute removed has not
yet reached the desired weight, repeat the process. This technique is a
very important technique to learn and use because it eliminates
systematic errors from the balance. The technique of weighing by
difference is applicable to measuring mass of hygroscopic samples.
1. Accurately, weight about 1 g sample of dry primary-standard grade
potassium hydrogen phthalate (KHP) on to a weighing boat. The KHP
has been dried earlier, in an oven at 110c for 2 hours and stored in a
desiccator prior to use.
2. Use the appearance of the above 1 g sample as a guide to accurately
weigh two more such samples by difference. Quantitatively, transfer
each sample from the weighing boat into a 250 mL conical flask. Make
sure all the samples has been transferred by rinsing the boat with the
small amount of water from your wash bottle. Then add 35 mL of water
to each flask and swirl the flask until all the solids dissolve. Rinse any
drops of the sample solution on the side walls of the flask with distilled
water.
3. Rinse and fill a 50 mL burette with the NaOH solution you wish to
standardise. Be very careful with air bubbles especially at the tip of the
burette. Remove the air bubbles before adjusting the initial volume and

doing the titration process. Turn the stopcock quickly 360 a few times
until all bubbles are removed. Then adjust the initial volume. You do not
have to start at the zero mark. Instead place the meniscus at your eye
level. Read and record the actual starting volume to the nearest 0.02
mL. wipe any adhering solution at the sides and the tip of the burette
with the laboratory tissue before you begin the titration.
4. Put three drops of phenolphthalein indicator into the first conical flask.
Place the flask under the burette and lower the burette tip well into it.
It is always advisable to have a *titration thief*for your first trial. Place
a piece of a white tile under the flask, hold the flask with your right
hand if you are right handed (and the other way around, if you are left
handed), control the stopcock of the burette with your left hand and
start titration by carefully turning the stopcock to let a gentle and
steady stream of the titrant flow (without splashing) into the acid
solution. Gently, swirl the solution in the flask. The base can be added
rapidly fast, but concentrate on the colour change. Initially the pink
colour disappears as soon as it is formed but with time, this colour
begins to linger as you swirl the flask. At this point, reduce the flow
rate of the titrant from the burette. The first permanent faint pink
colour that persists for at least 20 seconds is the end point.
C. Analysis of the unknown vinegar sample
1. First, the density of the vinegar sample were determined. Pipette 10 mL
vinegar into a dry pre-weighted 50 mL beaker. Reweigh the beaker. The
difference will give the weight for 10 mL vinegar sample. Take more
vinegar sample into 50 mL beaker for titration.
2. Pipette 10 mL vinegar sample from the beaker into a clean 250 mL
conical flask. Prepare two more such samples. Wash down the sides of
each flask with 25 mL water from your wash bottle.
3. Add 3 drops of phenolphthalein indicator into one of the titration
vessels and titrate the contents to end point with the standardised
NaOH solution from B. you may want to adopt the titration thief still,
at least for the first titration. Repeat the process for the other two
samples. Ideally, the titration volumes should be reproducible.
Answers
1. Weighing by difference can reduce, but not eliminate, systemic errors in
an experiment because systemic errors do not arise simply from errors in
measurement, but from a variety of sources. Weighing by differences is
still advised whenever possible. So that, while made to be as acurate as
possible, typical scales have error systematically as a part of their
measurements. If you place an object directly on the scale, it will be
effected by this error (keeping you from obtaining an accurate result).
Instead, measure the weight of object A, then add object B. You are able to
calculate the difference and obtain an exact measurement since both
objects are subject to the same error.
2. The titration equivalence point occurs when the acid present in the sample
has been exactly neutralized by the volume of base added. Additional

water added to the reaction vessel has no effect on the volume of base
added.

Discussion
Vinegar is a solution of acetic acid in water. Acetic acid, CH 3COOH, is a weak
monoprotic acid with a molar mass of 60.05 g/mole. The percent by mass of
acetic acid in vinegar can be determined by titrating a known amount of vinegar
with a standardized solution of sodium hydroxide solution of accurately known
concentration. Acetic acid and sodium hydroxide react as shown below:
CH3COOH (aq) + NaOH (aq) CH3COONa (aq) + H2O (l)
Sodium hydroxide is a hygroscopic solid which means it absorbs water from the
air. A weighed quantity of sodium hydroxide therefore contains an unknown mass
of water. Therefore, a solution of known molarity cannot be made by dissolving a
known mass of solid sodium hydroxide in water. The concentration of a sodium
hydroxide solution must be determined experimentally. This is done by titrating
the sodium hydroxide solution against a primary standard. A primary standard is
a substance from which a solution of known concentration can be prepared. The
primary standard used in this experiment is potassium hydrogen phthalate,
KHC8H4O4, which is referred to by the shorthand notation of "KHP". KHP has
several advantages such as it does not absorb moisture readily, it is easily dried,
it can be accurately weighed, it can be obtained in very pure form, it has a high
molar mass of 204.23 g/mole and it is very soluble in water. KHP is an acid, which
reacts in aqueous solution to neutralize the base, sodium hydroxide, as shown
below:
KHC8H4O4 (aq) + NaOH (aq) KHC8H4O4Na (aq) + H2O (l)

In this experiment, we use the average molarity of NaOH which is 1.92x10 -1 M to

calculate the weight percent of the acetic acid in the unknown vinegar solution.
At the end, we get 2.06%.
Conclusion

1. At the end of this experiment, we are able to prepare the sodium

hydroxide solution which give us the molarity 1.92x10 -1 M.
2. We also get to standardise the base against potassium hydrogen phthalate
by titrating with sodium hydroxide solution.
3. Lastly, we success to analyse the unknown vinegar sample by calculating
the weight percent of the acetic acid in the unknown vinegar solution that
give us 2.06 %.