Analytical Chemistry

Laboratory Experiments

Maridit C. Pedrosa and Kathleen C. Cedeño

Name: ________________________________________________________________

Course/ Section/Group No.________________________________________________

Semester &School Year __________________________________________________

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 Table of Contents

Experiment Title Pages

No.

1 Determination Of Weight Variation Using A Single Pan 19

Analytical Balance

2 Water Content Determination 24-25

3 Gravimetric Determination Of Iron As Fe 26-29

4 Analysis Of Acetic Acid In Vinegar 30-31

5 Analysis Of Soda Ash 32-33

Potentiometric Titration Of An Acetylsalicylic Acid In

6 34-38
Aspirin

7 Determination of Vitamin C in Fruit juice by iodometry 39-40

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 ANALYTICAL CHEMISTRY LABORATORY

Precision and accuracy in analytical chemistry depend largely on how efficiently the
students carry out the analysis in the laboratory. When strictly implemented, the following
guidelines will facilitate the work in the laboratory and minimize errors, which maybe incurred
during the course of the laboratory work.

1. Wearing of the laboratory gowns and safety glasses is strictly enforced in all
laboratories classes.

2. Each student should write all data directly to the laboratory journal, which is
provided and attached in the laboratory manual. All pertinent analytical data such as
weights of analytes and volumes of solutions are recorded in the journal.

3. Before coming to class, the student is required to write the following in the laboratory
journal: otherwise, he/she will not be allowed to work.

Experiment Number and Title

Objectives
Materials and Apparatus
Procedure (outline)

4. After the procedure, the students record all measurements taken under the heading
Data and Calculations. These are the written in ink, and may be tabulated.

5. The laboratory manual should kept neat and clean. If corrections are to be made, a
straight line is drawn across on the erroneous figures and the correct figures are written
adjacent to the cancelled ones.

6. All data and observations should be written in the laboratory journal: writing on loose
sheets are not allowed.

7. Towards the end of the laboratory period, the students should submit the laboratory
manuals to the laboratory instructor for checking/signature.

8. The laboratory report is to be submitted a week after as a requirement for each

experiment. This contains the following:

Date Performed and Date Submitted

Student’s Name, Subject and section, Group No.

Experiment Number and Title

Objectives of the Experiment

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 Principles Involved
Procedure (outline)

Materials and Apparatus

Data and Calculations

Discussion- This will contain a very brief description of what was done and what
was obtained/ observed. The past tense should be written in passive
voice.

Conclusions- This should relate results with the objectives set for the experiments.
Have the objectives been answered?

Answers to Guide Questions

3. In all laboratory work it is imperative that the scientist has a thorough understanding of
the theory behind each experiment, the techniques he will use, and the measurements
he must take before he begins experiments. Read the experiments carefully before
the laboratory period, and prepare a table in your notebook in which the data will be
entered.

SAFETY AND LABORATORY GUIDELINES

Accidents in the laboratory don’t just happen. They result from improper judgment,
incorrect techniques, or carelessness on the part of the victim or his neighbor. Accidents should
be reported immediately to the instructor to ensure that the proper attention may be given. The
following safely and laboratory guidelines must be observed at all the times.

1. EATING, DRINKING, SMOKING, AND HORSEPLAYING in the laboratory are

strictly prohibited.

2. NO littering or loitering is tolerated along corridors.

3. Students are required to wear the appropriate attire in the laboratory. Laboratory
gowns (white, knee length or longer with sleeves at least elbow length) and glasses /
goggles must be properly worn during the performance of the experiments. Dark
glasses in place of safety goggles/glasses are not allowed. Open-toed footwear is also
not allowed.

4. During the first laboratory period, students should familiarize themselves with the
safety features of the laboratory such as: location of safety showers, fire extinguishers,
sand, pails, medicine / first aid kit, fire escapes, and gas mains.

5. Students should perform only authorized experiments. Make-up classes/experiments

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 in the laboratory should be with instructor’s approval.

6. Students should always keep their work orderly. Bags, books, and other belongings are
to be placed in designated areas, not on the worktables.

7. Each group in the laboratory will be assigned as monitor in the experiments. This
monitor will be assigned for the preparation of reagents and borrowing of chemicals to
be used by the whole class and even purchased of chemicals if not available. (A group
that is not prepared in their assignment or failed to performed their duties will be given
0 in this area which constitute 30% of the laboratory grade)

8. REAGENTS

a. The label of the reagents bottles should be read carefully before anything is
taken from the bottle.

b. Reagents bottles should not be brought to your working area.

c. Only the required quantity of chemicals is to be taken from the reagent bottle.
Wasteful use of reagents, fuel gas and water should be avoided.

d. Contamination of reagents should be avoided. The spatulas, droppers and

pipettes assigned for each reagent should not be interchanged. Excess reagent
should never be poured back into reagent bottles.

e. Proper disposal of waste chemicals must be observed. Waste acid KMnO4 and
other solutions should be poured into their respective jars- never into the sink
(Bottles for waste disposal should be provided by the monitor)

f. Spilled chemicals should be wiped away immediately (per group should bring
their own detergents, tissue paper and rugs)

9. Cuts and Burns

a. All forms of injuries however minor should be reported immediately to the

instructor.

b. Cracked or broken glassware should be discarded immediately.

c. Hot glass tubing or a metal ring or stand should not be handled manually.

d. The burner should be lit only for the period of time in which it is actually
utilized.

e. Hair should be kept away from flame. Long hair should be fastened or clipped

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 so that it cannot fall forward into a flame.

10. Smelling and tasting of chemicals is prohibited unless students are specifically
directed to do so.

11. The pipette should not be used with the mouth. A rubber bulb aspirator should be
used to fill the pipette.

12. Acid should always be poured into water first. The heavier concentrated solution
should always be added to the lighter concentrated solution.

13. The hood should be used for experiments involving the use/production of
objectionable (i.e. poisonous, irritating) gases.

14. In using special pieces of equipment like Mettler balance, pH meter etc., the
appropriate and careful use should be maintained. The students should ensure that the
equipment is plugged into the right line voltage.

15. Insoluble refuse such as pieces of paper, wood, glass, cork, litmus paper, used
matchsticks, etc. should be placed in proper waste cans. NOT IN THE SINK.

16. Before leaving the laboratory room, the students shall see to it that

a. The gas and water outlets in the working are turned off.

b. All the equipment borrowed in the stockroom has been returned.

c. The working area or tables are cleaned and ready for the next students. (Points
will be deducted to the group with unclean working areas)

17. After each laboratory period, the student should always wash his/her hands.

18. At the end of the term, the students must secures a clearance from the laboratory
technician. In case breakages of glass wares/equipment was incurred, the laboratory
technician will not signed the clearance unless the students will replace the
broken/lost glass wares or materials

FIRST AID AND EMERGENCY MEAURES

Thermal Burns

Hold the burned area under cold water or in contact with ice for several minutes. Do not
apply ointment or bandages. If the burn is large and severe, call a physician at once.

Fires from burning reagents

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 Turn off all gas burners and cover the area of the mouth of the burning vessel with a
damp cloth to extinguish the fire. For larger fires, use dry sand or better still a fire extinguisher.

Fires from the burning cloth

Do not run or panic. Smother the fire with a wet laboratory gown or with water from the
safety shower, whichever seems most appropriate for the given situation.

Chemicals on skin

Wash the affected area immediately and thoroughly with plenty of water. If the chemical
is applied on you in quantities that cannot be easily flushed away by laboratory faucets, use the
safety shower. Wash the skin again with a reagent that is appropriate for the chemical spilled.

For acid — Wash with saturated sodium bicarbonate solution and again with water. Dry
and cover the skin with ointment.
For alkalis — Wash with saturated boric acid solution and again with water. Dry the skin
and apply ointment.
For organic chemicals - Wash with rubbing alcohol (75% isopropyl alcohol). Clean well
with soap and water.

Eye Accidents

Immediately flush the eyes with water for at least 15 minutes. Do not attempt to apply
any chemical neutralization to the eyes since deeper burns might results from the heat of
reaction. In all cases, take the patient to the student’s clinic.

Cuts

Allow minor cuts to bleed for a few seconds. Remove bits or fragments of substances
from the wounded area, and apply a disinfectant and bandage. For serious cuts, send for the
doctor at once. Meanwhile, check the bleeding by applying pressure with a sterile pad over the
wound.

Poisoning by swallowing

Dilute the poison as fast as possible by drinking plenty of water. Then neutralize the
poison: for acid, use milk of magnesia, and for alkalis, use vinegar. For other poisons, induce
vomiting by freely giving lukewarm water with two tablespoons of salt per glass until the
expelled liquid is clear.

Electrical Shock
Remove the source of shock as soon as possible. Use a dry towel when moving wires on
equipment. If the victim is not breathing administer artificial respiration.

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 BASIC LABORATORY OPERATIONS AND TECHNIQUES

Successful laboratory work depends on how well students learn to use the various
laboratory equipment correctly and with precision. Careless use of the pipette, burette, or balance
can ruin an entire experiment and results in the loss of many hour of work. Careless handling of
reagents can contaminate the contents of the bottle and spoil not only the student’s results but
also those of his classmates. Therefore, it is suggested that the student study carefully the proper
use of the different equipment, as well as observe the correct technique in analysis.

A. CHOOSING AND HANDLING CHEMICALS AND REAGENTS

1. Classification of Commercial Chemicals

TECHNICAL AND COMMERCIAL GRADE. Chemicals labeled technical or commercial

grade are of indeterminate quality and should be used only where high purity is not of paramount
importance. Thus, the potassium dichromate and sulfuric acid used in the preparation of cleaning
solution can be of this grade. In general, however, technical- or commercial grade chemicals are
not used in analytical work.

USP GRADE. USP Chemicals have been found to confirm to the tolerance levels established in
the Unites States Pharmacopoeia. The specifications are designed to limit contaminants that are
dangerous to health, thus, chemicals passing the USP tests may still be quite heavily
contaminated with impurities that are not physiological hazards.

REAGENT GRADE. Chemicals carrying this designation meet the minimum specifications of
the Reagent Chemical Committee of the American Chemical Society. This committee is charged
with establishing practical concentration limits for all the impurities normally associated with a
given reagent. Chemical suppliers label their products with either the actual results of
determinations for the various impurities or the maximum amount of each impurity allowed by
the specifications. Reagent grade chemicals are of high purity and are the most common grade of
chemicals used in quantitative analysis.

PRIMARY STANDARD GRADE. Primary standards are substances obtainable in

extraordinarily pure form. Primary standard-grade reagents, which are available commercially,
have been carefully analyzed, and the assay value is printed on the label.

SPECIAL PURPOSE REAGENTS. A number of manufacturers produce chemicals designed

for specific uses. Some examples include photometric solvents: HPLC solvents, products for
liquid scintillation counting, reagents for non-aqueous atomic spectroscopy, and reagent for
electron microscopy. Detailed information that is pertinent to their applications is provided for.
Thus, for spectrophotometric solvents, data are supplied as to absorbance at various wavelength,
UV cutoff wavelengths and assay value.

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 2. Handling of Reagents and Solutions

The availability of reagents and solutions with established purity is of prime importance for
successful analytical work. A freshly opened bottle of a reagent grade chemicals can be used
with confidence in most applications; whether the same confidence is justified when the bottle is
half full depends entirely upon how it is handled after being opened.

Perhaps the first rule to observe in handling reagents is to read the label, even before opening
the bottle. Make sure that you have selected the appropriate grade of chemical necessary for the
job at hand. Be sure to note any special warnings on the label, such as poison or flammable and
handle the chemical accordingly. Only conscientious adherence to the following rules will
prevent contamination of reagents.

a. Replace the top of every container immediately after removal of the reagent.

b. Hold stoppers between fingers: stoppers should never be set on the desk top.

c. Unless specifically directed to do the contrary, never return any excess reagent or
solution to the bottle. The minor saving that results from returning such excess is
likely to be futile in view of the risk of contaminating the entire bottle.

d. Again, unless specifically instructed otherwise, do not insert spoons, spatulas,

or knives into a bottle containing a reagent or chemical. Instead, shake the capped
bottle vigorously or hit the bottle sharply on the wooden table so as to dislodge the
contents. hen pour out the desired quantity. In some instances, these measures will
not loosen the contents and a clean porcelain or stainless steel spatula must be
used.

Despite one’s best efforts to the contrary, an occasional spill is going to occur. There is
little harm associated with most spills unless they are not cleaned up immediately. Enumerable
balances and bench tops have been pitted and marked by stray sodium hydroxide pellets left by
unthinking analysts. Consult your laboratory instructor on how to clean up and dispose of spilled
chemicals.

B. EQUIPMENT AND MANIPULATIONS ASSOCIATED WITH DRYING AND

WEIGHING.

Most solids absorb atmospheric moisture (are hygroscopic) and, as a consequence change
in composition. This effect assumes appreciable proportions when a large surface area is
exposed, as with a sample or a reagent chemical that has been ground to a fine powder. It is
ordinarily necessary to dry such solids before weighing to free the results from dependence upon
the humidity of the surrounding atmosphere.

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1. WEIGHING BOTTLES

A weighing bottle is a lightweight cylinder with a ground-glass stopper snugly fitting the
lid. Solids are conveniently dried and stored in weighing bottles.

Manipulation of weighing bottles. The moisture bound on the surface of many solid materials
can be removed by heating at 105 to 110°C for about an hour.

Weighing data can be significantly affected by moisture absorbed as a consequence of

handling a dried weighing bottle with one’s fingers. For this reason, the bottle should be
manipulated with tongs, chamois finger cots, clean cotton gloves, or strips of clean paper.

2. DESSICATOR, DESSICANTS

Oven drying is the most convenient method for removing absorbed moisture from a solid.
The technique, of course, is not appropriate for samples that undergo decomposition at the
temperature of the oven. Furthermore, with some solids, the temperature attainable in ordinary
drying ovens is insufficient to affect complete removal of the bound water.

While they cool, dried materials are stored in desiccators which help prevent the uptake
of moisture. The base section of a container contains a quantity of a chemical drying agent.
Samples are placed on a perforated plate that is supported by a constriction. A lightly
greased glass surface provides a tight seal between the base and the lid.

Several substances (desiccants) find use as a drying agent in desiccators. Among these
are anhydrous calcium chloride, calcium sulfate, anhydrous magnesium perchlorate and
phosphorous pentoxide.

Use of desiccators. Whether it is being replaced or removed, the lid of the desiccators is
properly moved by sliding rather than by lifting motion. An airtight seal is achieved by slight
rotation and direct downward pressure upon the positioned lid.

When a heated object is placed in a desiccators, the increased pressure of the enclosed air is often
sufficient enough to break the seal between the lid and the base. If heating has caused the grease
on the ground-glass surface to soften, there is further danger that the lid may slide off and break.
Upon cooling, the opposite effect is likely to occur, the interior of the desiccators now being a
partial vacuum. Both of these conditions can cause the contents of the desiccators to be
physically lost or contaminated. Although it defeats the purpose of the desiccators somewhat, it
is wise to leave the lid open just a bit for the first few minutes to allow some cooling to occur
before finally sealing the lid. It also helps to break the seal several times during cooling to
release any vacuum that develop. Finally, it is prudent to lock the lid in place with one’s thumb
while moving the desiccators to ensure against accident breakage.

Very hygroscopic materials should be stored in containers equipped with snugly fitting covers,
and covers should remain in place during storage in the desiccators. Other substances may be
stored without container covers.

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3. ANALYTICAL BALANCE

The analytical balance is the most basic tool in all laboratory work in analytical
chemistry. The most important specifications of a balance are its accuracy, precision, capacity,
sensitivity, and readability. The term “analytical balance” is used to describe a balance capable
of weighing objects with a very high degree of accuracy and precision. Capacity refers to the
maximum weight that the balance can measure. Macro analytical balances can weigh objects of
up to several hundred grams, while semi-micro analytical balance has a capacity of perhaps 100
to 160 grams. The term sensitivity and readability are somewhat confusing when examining
balance specifications. Sensitivity is generally taken as the smallest weight that will produce a
certain measurable response, typically 0.1 or 0.01 mg. Readability refers to the smallest
discernable scale division, which may or may not be the same as the sensitivity of the balance.

Analytical balances, which differ considerably in appearance design and performance

characteristics, are of two types, namely, singly-pan balance and the equal arm balance. In recent
years, the single pan balance has become very popular, as it is fast and easy to use.

Technique in Weighing. Objects are weighed either directly or by difference. In direct

weighing, the receiving vessel or a sheet of weighing paper is placed on the pan and weighed.
The sample is transferred, and the container plus sample is reweighed. Some balances can be set
to zero with the empty receiving vessel on the pan- a process called “taring”. Thus when the
sample is transferred, only its weight is displayed. In weighing by difference, the weight of the
weighing bottle and its contents (sample or reagent) is first obtained. The estimated amount or
material needed for the experiment is cautiously poured into a receiving beaker or flask. Gentle
tapping of the weighing bottle with its top provides adequate control over the process; slight
rotation of the bottle is also helpful. Finally, the bottle is weighed again. The difference between
the two weighs represents the weight of sample taken. This technique is especially useful when
weighing hygroscopic or volatile substances because the weighing container can be kept close
during the weighing process.

C. VOLUMETRIC GLASSWARES

Volumetric glass wares refer to glass containers that are designed to measure the volume
of liquids with high degree of accuracy. These such containers- the burette, the pipette, and
volumetric flask — are found in every introductory quantitative analysis laboratory. Volumetric
containers are marked by the manufacturer as to the manner of calibration and temperature at
which the calibration was made. Items marked TD are designed to deliver the specified volume
at the calibration temperature. Items marked TC and/or which have a frosted ring near the top are
designed to contain the specified volume at the calibration temperature.

Glass wares expand and contracts with the rising and falling of temperature. However an
object that has expanded on heating does not always return to the same volume on cooling- a
phenomena called hysteresis. For this reason, volumetric glassware should not be heated much
above its calibration temperature. It is especially inappropriate to dry such glassware in a
laboratory drying oven.

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CLEANING GLASSWARE

Glassware should be soaked and/or scrubbed with warm detergent, then rinsed, first with
large quantities of tap water to remove detergent and finally several small portions of distilled
water. Remember that impurities may not be visible to the eye. Water will wet clean glassware,
forming an unbroken, uniform film on the surface. Grease and other organic materials that
survive a vigorous cleaning with detergent can usually be removed with a cleaning solution
consisting of sodium dichromate dissolved in concentrated sulfuric acid. Cleaning solution can
be prepared by dissolving about 5 g of sodium dichromate in 5 mL water in a large Pyrex flask
and slowly adding about 100 mL of concentrated sulfuric acid with constant stirring. After
cooling, the solution is transferred to a labeled storage bottle. The solution may be rinse until it
acquires the green color indicative of chromic ion. The cleaning action may be slow at room
temperature but become quite rapid at 60 to 70 °C. Warm the cleaning solution in a beaker or
flask and transfer a small portion to the glassware being cleaned. If too large volume is used, it
may cause undesirable heating of the glassware. Dichromate cleaning solution should be handled
with extreme caution, especially when it is warm. It will attack skin and clothing with the same
vigor and speed at which it attacks grease on the walls of the glass container. Spills should be
diluted immediately with a large volume of water.

Glassware in which solution have been allowed to stand for long periods or have
evaporated to dryness may be especially hard to clean.

1. BURETTES

A burette consists of a long tube of highly uniform diameter marked with volume
graduations and fitted with a ground glass or Teflon stopcock and short delivery tip. A ground-
glass stopcock must be lightly greased so that it forms a liquid-tight seal. In applying the grease,
ensure that the stopcock is dry, and avoid the area immediately adjacent to the hole. Teflon
stopcocks do not require lubrication.

Rather than drying a burette to remove traces of water simply rinse it several times with a
few milliliters of the solution it will contain. Each portion of rinse solution should be expelled
through the stopcock to ensure that it and the tip are also rinsed. It is common practice to overfill
the burette and open the stopcock fully to dislodge any small air bubbles that may collect at the
junction of the stopcock and the tip. Once the entire burette is free of bubbles, the liquid is
drained slowly until the level reaches the graduations. Any solution clinging to the outside of the
burette tip is removed by touching the tip to the inside wall of the beaker. Wiping the tip is not
recommended because of the risk of some of the liquid “wicking out”.

Aqueous solution wets the wall of the burette, giving a shallow curve to the surface of the
liquid, which is called meniscus. The bottom of the meniscus is taken as the level of the solution.
In estimating the volume, the eye should be level with this point to avoid making a reading error,
called parallax. If the meniscus is above eye level, the opposite effect occurs. When the stopcock
is opened fully, the layer of liquid wetting the inside wall cannot drain as rapidly as can the main
body of liquid. Therefore, you should allow 20 to 30 seconds to elapse between the time the
stopcock is closed and the time the volume is measured.

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 As the end point of the titration is approached, it is often desirable to deliver less than one
drop of liquid at a time from the burette. A fraction of a drop is delivered by opening the
stopcock only slightly until a portion of a drop is clinging to the tip, closing the stopcock, and
rinsing the partial drop off the tip and into the receiving container with a stream of water from a
plastic wash bottle.

2. PIPETTES

Pipettes are devises used to accurately transfer volumes of liquid. They are available in a
variety of types of application. Pipettes marked with a frosted band at the top are calibrated to
deliver a specific volume when the last drop is blow out. The absence of a frosted band means
that an allowance has been made for the small amount of liquid remaining inside after the pipette
has drained freely. Volumetric or pipettes are designed to deliver a definite specific volume of
between 0.5 and 100 mL

Ostwald-FoIin pipettes (available in volumes from 0.5 to 10 ml) are similar to

volumetric pipettes except that they are calibrated to deliver a specific volume when the last drop
is blown out. Both measuring and serological pipettes are used to deliver a variable volume,
generally between 1 and 25 ml. The only difference between them is that serological pipettes are
calibrated to deliver their maximum volume when the last drop is blown out.

Syringe pipettes are available that can deliver either fixed or variable volumes in the
range of 1 to 100 uL. They employ a disposable polypropylene tip into which the liquid is drown
by action of a spring- operated piston. The liquid is dispensed by simply reversing the action of
the piston.

Before filling a pipette, it should be rinsed two to three times with small portions of the
liquid to be transferred into it. This is done by drawing in the liquid through the tip, rotating the
pipette while holding it in a horizontal position to ensure that the rinse solution contacts the
entire inside surface and draining it through either the tip or the top opening. Pipettes are filled
by drawing liquid in through the tip by the sucking action of an evacuated rubber bulb held over
the top opening. Liquid is drawn in above the top graduation and the bulb is replaced quickly
with the index finger. At this point, the tip is wiped to remove any droplets of liquid clinging to
the outside and the pipette is allowed to drain slowly until the level reaches the graduation mark.
This is best accomplished by reducing the pressure of the index finger and rotating the pipette
back and forth between the thumb and middle finger. The tip of the pipette should be touch to the
side of the waste container to remove any partial drops that may have formed and are clinging to
the outside. Finally, the index finger is removed and the pipette is allowed to drain freely, usually
onto the side of the receiving vessel to minimize splashing and possible sample loss. Pipettes
should never be filled by using the mouth instead of a rubber bulb. Because they are difficult to
clean, it is good practice to rinse pipettes with distilled water immediately after use.

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 3. VOLUMETRIC FLASK

Volumetric flasks are calibrated to contain a particular volume of liquid at 20°C. A

careful examination of the writing on the flask will reveal the letters TC (” to contain’), as
opposed to the letters TD (‘to deliver”), that are found on burettes and many pipettes. These
flasks are available with capacities ranging from 1 to 2000 mL.

Volumetric flasks are used to prepare solutions of known concentration. A weighed

sample is delivered in a minimum volume of solvent, transferred to the appropriate size flask and
diluted to the mark with solvent. If the sample is not dissolved prior to being transferred to the
flask, it should be allowed to dissolve completely before filling the volumetric flask with solvent.
This permits easy mixing by swirling. Once full, mixing is more difficult and is accomplished by
holding the stopper firmly in place while repeated inverting the flask. The large air bubble rising
through the solution cause mixing. It is very easy to overfill a volumetric flask while trying to
make the final volume adjustment. This problem can be avoided by using a disposable dropping
pipette or medicine dropper to add the last mL or so of solvent.

Volumetric flask should not be used as storage bottle. Once the flask has been filled and
its contents mixed, the solution should be transferred to an ordinary bottle for long term storage,
and the flask should be rinsed and cleaned.

4. SAMPLE PREPARATION

Most solid absorb atmospheric moisture to some extent, thereby undergoing a change in
composition. The extent of absorption depends not only on the chemical nature of the substance
but also on the amount of exposed surface area and the atmospheric humidity. In such instances,
it is usually necessary to dry the solid in an oven before weighing. In order to achieve a uniform
and reproducible composition. Generally, a temperature of about 110°C for 1 to 2 hours is
sufficient for small quantities of samples. The material to be dried is placed in an open weighing
bottle, which, in turn, is place inside a small beaker covered with watch glass supported by glass
hooks on the edge of thee beaker.

When the samples are removed from the oven, the weighing bottle and its top must be
cooled to room temperature (about 30 minutes) in a low-humidity environment to prevent
reabsorption of moisture. The devise used to accomplish this is a desiccators (refer to previous
discussion).

On those few occasions when samples must be weighed in their hydrated form, the
desiccators can be converted into a high-humidity chamber by using a shallow tray of water in
place of desiccant. Samples stored in such an environment will tend to hydrate fully and reach a
uniform, reproducible composition.

5. DISSOLUTION AND DECOMPOSITION

Although many samples may arrive at the laboratory in solid form, analysis procedures
usually involve measurements or manipulation of the analyte in aqueous solution. The process of

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dissolving a sample often is far from simple or routine and may even represent the majority of
the total analysis time. Ordinarily, the entire sample must be dissolved. Attempts to dissolved
just the analyte often result in incomplete separation from the undissolved residue. Since the
decomposition-dissolution• process involves the addition of other chemicals, the analyst must
keep in mind the limitation of the method chosen and be certain that no reagent are added that
would interfere in latter steps. In addition extra care must be taken to avoid the loss of analyte
through the formation of volatile compounds.

Concentrated Acids

Strong inorganic acids are simple to use, relatively safe, and can dissolved a wide variety
of materials. Because the vapors are very corrosive, acid solutions should be heated under a well-
ventilated fume hood.

HYDROCHLORIC ACID

Although normally referred to as a non-oxidizing acid, This reagent does oxidized and
dissolves metals that lie below hydrogen on the activity scale, such as magnesium, iron, and zinc.
Aqueous hydrochloric acid is an excellent solvent for metal oxide. The concentrated reagent is
about 37% HCI by weight or about 12M. At this concentration, it is fairly volatile and the vapors
can give a severe stinging sensation in the eyes and nose. Hydrogen chloride gas is easily
volatilized from, aqueous solution by heating until a constant-boiling 6M solution is formed.

NITRIC ACID

With the exception of aluminum and chromium, all common metals will dissolve in hot,
concentrated nitric acid. Much of the acid’s dissolving power is derived from the ability of the
nitrate ion to act as an oxidizing agent. Concentrated nitric acid is about 70% HNO 3 by weight or
16M. Concentrated acid that has stood for a long time may decompose slightly, forming yellow-
brown nitrogen dioxide. There is no reason to discard such a solution, however, since nitrogen
dioxide is a normal reduction product formed whenever metals are dissolved in nitric acid.

SULFURIC ACID

Unlike concentrated nitric acid and hydrochloric acids, concentrated sulfuric acid
contains very little water (98% H2SO4 or 18M) and has a high boiling point (340°C). As a result,
hot sulfuric acid is a very effective oxidizing agent for many metals and for organic compounds
as well. Concentrated sulfuric acid has a very strong affinity for water and generates a great deal
of heat when it hydrates. Extreme care should be used in diluting sulfuric acid solutions.

AQUA REGIA
A mixture of three parts concentrated HCI to one part concentrated HNO3 (by volume) is
an extremely powerful oxidizing agent known as aqua regia or “royal water”. The name was
chosen for its ability to dissolve noble metals such as platinum and gold, which are insoluble in
either acid or alone. When mixed, the two acids react to yield elemental chlorine and nitrosyl
chloride.

15
 3HCI + HNO3------------- Cl + NOCI(g) + 2H2
The dissolving power of the mixture is derived mainly from the ability of chlorine and
nitrosyl chloride to convert the metals to metal chlorides, which are then transformed to stable
complex anions through reaction with chloride ion. The overall reaction for gold is
Au(s) + 4HCI + HNO3-------- HAuCl + NO(g) + 2H2

HYDROFLUORIC ACID

Many ores and minerals contain appreciable quantities of metal silicates which will not
dissolve completely in oxidizing acids. Aqueous hydrofluoric acid has been found to be a
particularly effective solvent for such substances, due to its availability to form volatile silicon
tetrafluoride. Since fluoride ion is such an effective complexing agent, excess hydrofluoric acid
often must be removed completely after the dissolution process. Usually, this is done by repeated
addition of concentrated sulfuric acid followed by evaporation to near dryness. The silicon
tetrafluonde and hydrochloric acid are volatilized during the evaporation steps. HF reacts slowly
with silica in glass and given sufficient time, it will produce a frosted surface. Whenever
possible, HF solutions should be kept in plastic containers. When glass must be used, the
solutions should not be allowed to remain in the container any longer than is absolutely
necessary.
Concentrated HF is about 49% HF by weight or 29M. It can cause painful burns and
serious injuries if allowed to come in contact with the skin. Unfortunately, there may be no
discomfort or indication of a burn for several hours after the exposure. For these reasons, this
acid demands great t care during handling. Many chemists choose never to handle this reagent
without the use of protective gloves.

GRAVIMETRIC TECHNIQUES

WEIGHING

All gravimetric procedures rely on the difference in weight of a container with and
without the precipitate. The empty container is heated to the same temperature at which the
precipitate will be heated, cooled to room temperature in desiccators and weighed. This process
is repeated until a constant weight (within a few tenths of a mg) is achieved. Ultimately, the
container with the precipitate is treated similarly.

FILTERS

Precipitates are collected on paper, sintered glass, or unglazed porcelain filters.

Collecting on paper is slower and more tedious but is necessary with gelatinous and very finely
divided crystalline precipitate because they tend to clog the tiny pores of other filters.

Sintered glass filters consist of a porous disk of small glass particles sintered (particularly
melted) together and set into the bottom of glass crucible. The crucible is labeled CM. or F for
course, medium and fine, depending on how porous the sintered glass disk is. Because the glass
particles can soften and fuse together, thereby changing the porosity, these filters should not be

16
heated above 200oC. Unglazed porcelain is similar in principle to sintered glass but has the
advantage of tolerating much higher temperatures.

Paper filters are circular in shape and available in several degrees of porosity. As might
be expected fine porosity paper passes liquid more slowly and clogs more easily than coarse-
porosity paper. Because it is quite hygroscopic paper cannot be dried to a constant weight and
must be burned away after filtering. As a result, it can be used only to filter precipitates that can
tolerate the high temperature encountered during burning. High quality filter paper is
manufactured in such a way that it produces a negligible amount of ash on ignition.

HEATING EQUIPMENT

Some precipitate can be weighed after drying at 110°C, while others must be ignited to
temperatures as high as 1000°C. Temperatures to about 300 oC can be achieved in a simple
electric oven. Sometimes the efficiency of the drying process in such ovens is improved by
forcing the precipitate through pre-dried air or by maintaining a partial vacuum in the heating
chamber.
Ordinarily heat lamps are used in numerous applications in drying precipitates. They are
capable of producing temperatures of several hundred degrees which is sufficient enough to char
filter paper.
Laboratory burners, such as the Meker burner, and heavily insulated ovens called muffle
furnaces, are used when precipitates must be heated above 300 oC. Burners are inexpensive and
simple but provide little control over the exact temperature to which the material is heated.
Muffle furnaces are expensive but can reach temperatures above l000oC that can be controlled to
within a few percent of the set value.

FILTERING TECHNIQUES

The actual filtering process is essentially the same with both filter crucibles and paper
although the physical setup is a little different. Filter crucibles are set into a rubber adapter
mounted on a filter flask which is connected to a water aspirator through a trap. The purpose of
the trap is to isolate the filter flask from an accidental backup of water through aspirator. Filter
paper is supported in a narrow stem funnel. The circular paper is folded in half twice and one
corner is torn off. Then it is opened to form a cone pressed into the bottom of the filter funnel,
and wetted with water. All air bubbles between the paper and the funnel are worked out gently
by pressing with the fingers. The removal of one corner of the folded paper allows a better seal
of the opened paper to the glass funnel, thereby preventing air from channeling between the
paper and the glass which can slow the filtering process considerably.

The first step of filtration is to decant gently the bulk of the liquid onto the filter.
Allowing the liquid to flow down a glass rod onto the filter prevents splashing and allows the
analyst to direct the flow. Depending on the nature of the precipitate, it may be desirable to wash
it with successive portions of a wash liquid, decanting each portion onto the filter. Finally, a
stream of water from a plastic wash bottle is used to transfer the bulk of the precipitate to the
filter. The precipitate is transferred last to minimize clogging of the pores of the filter which can
slow the filtering process considerably. In some cases it may be necessary to use a rubber

17
policeman (a small rubber squeegee fitted on the end of a glass rod) to loosen particles of
precipitate that stick to the walls of the container.

When all the precipitate has been transferred to the filter, it is washed from five to six
times with small portions of an appropriate wash liquid. Each portion of liquid should be directed
onto the upper portion of the filter medium so that it tends to wash the precipitate toward the
bottom, where it is less likely to be lost during handling. Each portion of the liquid should be
directed onto the upper portion of the filter medium so that it tends to wash the precipitate
towards the bottom, where it is less likely to be lost during handling. Each portion of the liquid
should be drained or drawn through completely before the next portion is added.

18
 Experiment # 1

DETERMINATION OF WEIGHT VARIATION USING A SINGLE PAN ANALYTICAL

BALANCE

The balance is basic equipment in any quantities analysis. An inadequate type of balance could
affect the accuracy of the results to a large extent. In the succeeding experiments, a single pan
analytical balance will be used. This type of balance meets the stringent requirements for the
various weights of materials is needed in terms of sensitivity, accuracy and precision.

This experiment will introduce the student to the single pan analytical balance and its proper use.
Some basic statistical measurement will also be performed to gauge the significance of the
results obtained.

Procedure:

Check the balance for level each time it is to be used. If the level bubble is not exactly centered
in the circle inscribed on the glass, adjust the leveling screws on the base until the level bubble is
exactly centered in the circle. Check the zero point each time the balance is to be used. Make
sure that the lever is in the arrest position before placing anything into or removing anything
from the pan.

Determine the weight of ten 25-centavo coins on the analytical Balance. Record the weight of
each coin in the space provided. After weighing, make sure that the lever is in the arrest position
and all the weight control knobs are returned to zero. Calculate the mean, average deviation,
standard deviation and range.

19
 Experiment # 2

WATER CONTENT DETERMINATION

This test is performed to determine the water (moisture) content of soils. The water content is
the ratio, expressed as a percentage, of the mass of “pore” or “free” water in a given mass of soil
to the mass of the dry soil solids.

For many soils, the water content may be an extremely important index used for establishing the
relationship between the way a soil behaves and its properties. The consistency of a fine-grained
soil largely depends on its water content. The water content is also used in expressing the phase
relationships of air, water, and solids in a given volume of soil.

Materials:

Drying oven,
Pan Balance,
3 pcs Moisture can,
Gloves,
Spatula.

Procedure:

1. Record the 3 moisture can and lid number. Determine and record the mass of empty, clean,
and dry moisture can with its lid (MC).
2. Place a representative sample of the moist soil in the moisture can and secure the lid.
Determine and record the mass of the moisture can (now containing the moist soil) with the
lid (MCMS).
3. Preheat oven for 30 min at 100-105 degrees centigrade.
4. After weighing the wet sample + cup, remove the lid—it is usual practice to place it on the
bottom of the cup-- and place the sample in the oven that is set at 105 °C. Leave it in the oven
overnight.
5. Remove the moisture can. Carefully but securely, replace the lid on the moisture can using
gloves or tongs, and allow it to cool in a desiccator.
6. Allow the desiccator to be ajar while the moisture can with the sample is still hot. Cover the
desiccator when the sample is ready for weighing.
7. Weigh the sample and place in the desiccator again after weighing. Record the weight and the
difference in weight.
8. Heat for another 30 mins and repeat the cooling and weighing process until constant weight
is obtained. If constant weight is obtained, Determine and record the mass of the moisture can
and lid (containing the dry soil) (Mcds) and calculate the % moisture in the sample.
9. Empty the moisture can and clean the can and lid.

20
Data Analysis:

(1) Determine the mass of dry soil.

M S = CDS-MSC

(2) Determine the mass of pore water.

MW = CMS-MCD

(3) Determine the % water content.

Mw
w = −−−− x 100
Ms

21
 Experiment # 3

GRAVIMETRIC DETERMINATION OF IRON AS Fe

(Adapted from Harris’s Quantitative Chemical Analysis)

A sample containing iron can be analyzed by precipitation of the hydrated hydroxide from basic
solution, followed by ignition to produce Fe2O3:

Fe 3+ (aq) + 3 OH-(aq) + x H2O(l) ------------→ Fe(OH)3H20 (s)

900 deg C

Fe(OH)3H20 (s) ---------------→ Fe2O3(s)

You will use this gravimetric technique to determine the weight percent of Fe in an iron ore
sample. You will make three replicate measurements, which will allow you to determine both an
average and a 95% confidence interval for your data.

Procedure:

General Comments: (a) This is a two-week experiment. (b) You and your lab partner(s) should
be strategic about dividing up the tasks for this experiment. Specifically, you should be doing
Steps 1 and 2 at the same time. (c) Never insert a pipet into any common reagent bottle. Instead,
pour out some for yourself in a beaker. (d) Each lab team should have two gas jets to speed up
the crucible heating.

1. Bring three porcelain crucibles and caps to constant mass by heating over a Bunsen burner
(Figure 1). (Each group will have two gas jets, so you should be heating two of your crucibles at
the same time.) Increase the amount of air being mixed with the fuel until you see an inner light
blue cone in the flame—this is the hottest part of the flame. Adjust the height of the metal ring to
expose the crucible to that light blue cone.

Figure 1. Positioning a crucible above a burner.

Note that the tilt is important! You want to maximize the exposure of the crucible to the flame.

22
The crucibles should be heated to redness for 15 min. (Be sure that all oxidizable substances on
the entire surface of each crucible have burned off.) Then cool each crucible for 30 min in a
desiccator (to minimize the adsorption of water vapor onto the crucible) and weigh each crucible
on an analytical balance. Avoid touching the crucibles with your bare fingers; the weight of your
fingerprints will register on the balance! Then repeat the above process: 15 min of heating to
redness, 30 min of cooling in a desiccator, and weighing on an analytical balance. Your two
weightings’ should agree to within 1 mg. If not, you should repeat the process once more.
(Usually the last weight is the most accurate.) When you are done weighing your crucibles, store
them in a desiccator and put them away in your cabinet for use next week.

2. Meanwhile, accurately weigh three samples from one of the unknown vials. Each sample
should be around 0.5~0.3 g. Put each sample in a 400-mL beaker, and fit all three beakers onto a
large hot plate in a fume hood. Wearing acid gloves, dissolve each sample in 10 mL of
concentrated (~12 M) HCl. Heat gently with stirring. (Keep the rubber policemen out of the
solution—we don’t want bits of rubber in our samples!) More acid may be necessary to
completely dissolve the samples. Make sure that you do not boil off all the water! It is easy to
completely cook your samples, which means you will have to start over. If there are insoluble
impurities, filter through qualitative filter paper and wash the filter very well with distilled water.
(This will usually not be necessary.)

3. Add 5 mL of 6 M HNO3 to each sample, and boil for a few minutes to ensure that all iron is
oxidized to Fe (III). Again, be careful not to boil away all the water!

4. Dilute the sample to 200 mL with distilled water and add 3 M ammonia with constant stirring
until the solution is slightly basic (as determined with litmus paper or pH indicator paper).
Digest the precipitate by boiling for 5 min and allow the precipitate to settle. (Alternatively, if
the sample never comes to a boil, it is sufficient for the solution to have been heated vigorously
for 25 min.)

5. Set up a filter rack and fit three long-necked funnels with coarse, ashless filter paper ( ( (
Whatman 41, 110-mm diameter). Wet paper so that it will stick to the funnel. For each sample,
decant the supernatant liquid (that is, the liquid above the precipitate) through one of the filters.
Follow the procedure shown in Figure 2:

23
Do not pour liquid higher than 1 cm from the top of the funnel. Transfer any remaining solid
from the 400-mL beaker to the filter paper with the aid of a rubber policeman. Wash the
precipitate with hotter 1% NH4NO3 (you will need to heat your own).Test for Cl - in each
precipitate by transferring a small volume of filtrate from each receiving beaker to a well (on a
well plate), and then adding a few drops of 0.1 M AgNO. If you see a milky white color,
indicating the formation of AgCl(s), you still have a significant amount of Cl- in your precipitate.
Clean out the receiving beaker for that precipitate, and wash the precipitate with hot 1%
NH4NO3. Repeat until the white color is non-existent or faint.

6. Cover each of the funnels with a ribbed watch glass. This will both protect each precipitate
from dust and allow it to dry during the week. If you are done with your crucible weighings
(Step 1), you are done for the week!

WASTE DISPOSAL FOR WEEK 1: The well plate solutions, which contain Ag must go into
waste bottles. Everything else can go down the drain with lots of water.

7. (Week 2) Don’t be surprised at how much volume has been lost from your hydrated iron
samples! Carefully lift the paper out of the funnel, fold it (Figure 3), and transfer it to one of
your accurately weighed crucibles. Fold up the filter papers as much as possible. Do not let the
paper stick out over the top edge of the crucible.

Figure 3. Folding filter paper and placing it

inside a crucible for ignition.
Continue folding paper so entire
package fits at the bottom of the
crucible. Be careful not to puncture the
paper.

8. Dry each crucible cautiously with a small flame, as shown in Figure 1. The flame should be
directed at the top of the container. Avoid spattering. After it is dry, char (or blacken) the filter
paper by increasing the flame temperature. (However, take the flame away if the paper starts to
inflame.) Once the paper is charred, you can be even more aggressive and aim the flame directly
at the paper. Any carbon left on the crucible should be burned away by directing the burner
flame at it. To make your job easier, try to avoid spreading out charred residue over a lot of the
inner surface of the crucible. Use tongs to manipulate the crucible. Finally, ignite the product for
15 min with the full heat of the burner. Again, to maximize efficiency, have two burners going
simultaneously.

24
 9. Cool each crucible briefly in air and then in a desiccator for 30 min. weigh the crucible,
reignite, and bring to constant mass (within 1 mg) with repeated heating. However, like last
week, you are required to do a maximum of (only) three weighings for each crucible.

WASTE DISPOSAL FOR WEEK 2: All iron waste can go into the trash.

DATA ANALYSIS:

Calculate the weight percent of iron in each sample, and the average, the standard deviation, and
the 95% confidence interval for the set of three weight percent values. You should use the last
weight obtained for each crucible in your calculations. Note that the uncertainty will be
determined solely by the variation in the weight percent of iron in your three trials--do not
propagate uncertainties in the weights of the crucibles. Discuss the possible sources of both
systematic and random error in the experiment, and judge what the dominant sources may be.
Identify the sign of each systematic error, and try to estimate its magnitude.

25
 Experiment # 4

ANALYSIS OF ACETIC ACID IN VINEGAR

The active component in vinegar is acetic acid in which the concentration ranges from 4 to 6%
CH3COOH. The acid is classified as a weak monobasic or monoequivalent acid. The
equivalence point for the titration of the acid in vinegar with standard sodium hydroxide will be
in the basic range. Phenolphthalein will be an appropriate indicator for this titration.

Standardization:

KHC8H4O4(aq) + NaOH H2O(l) + NaKC8H4O4(aq)

( potassium acid phthalate)

Titration of Unknown:

HC2H3O2(aq) + NaOH(aq) Pb H2O(l) + NaC2H3O2(aq)

A. Preparation of 0.1 N Solution of Sodium hydroxide

Boil approximately 1L of distilled water. Be sure to protect the water from the atmosphere as it
cools. Dissolve about 4g of sodium hydroxide in the boiled water. Stir the solution well and
pour into a rubber stoppered bottle and label the bottle.

B. Standardization of 0.1N NaOH Using KHP

Pour from a weighing bottle into 250-mL beakers, or flasks, triplicate samples of between 0.3
and 0.7 g each of pure, dry potassium acid phthalate (potassium biphthalate, KHC 8H4O4),
accurately weighed to four significant figures.

Record these weight and subsequent data in the data space provided in the manual. Label the
beakers in order to distinguish between them. Add to each sample about 100 mL of distilled
water. Add 2-3 drops of phenolphthalein to each beaker.

Fill the burette with the prepared NaOH solution, using the customary precautions to guard
against dilution. Run out enough NaOH from the bottom to remove any air bubbles from the tip
of the buret. Refill the burette and record the initial readings onto the data table.

Titrate the potassium acid phthalate with the NaOH to the first appearance of a faint permanent
pink color. In order to avoid spattering, be sure to have the tip of the burette near the surface of
the solution being titrated. Add the hydroxide slowly but steadily, at the same time, gently stir

26
the solution in the beaker. Avoid splashing drops upon the sides of the beaker. If a flask is used
, gently swirl the contents of the flask during titration. Near the end of the titration, rinse the
sides of the beaker or flask with water from the wash bottle. Complete the titration with NaOH
to the point whose one drop of the alkali changes the color of the solution from colorless to faint
pink. Repeat the titration with the other two samples, recording all data in your lab manual.

C. Determination of Acetic Acid Content of Vinegar

Pipet 25 mL of vinegar into a 250 mL volumetric flask, dilute to the mark, and mix thoroughly.
Pipet a 50 mL aliquot of this solution into an Erlenmeyer and add 50 mL of water and 2 drops of
phenolphthalein indicator. Titrate with standard base to the first permanent pink color. Repeat
with titration on two additional aliquots.

What is the percentage of acetic acid by weight in the vinegar? Average your results in the usual
manner.

Notes:

1. Do not handle the solid NaOH with the fingers. This substance is corrosive.
2. Never use a glass-stoppered bottle to store the prepared NaOH solution.
3. Store the remaining standard NaOH solution for succeeding experiments.
4. Dry KHP in the oven at 105-110oC for 2 hours or more.

27
 Experiment # 5

ANALYSIS OF SODA ASH

Soda ash is crude sodium carbonate being a technical grade of anhydrous sodium carbonate. It
usually contains impurities like the chloride and hydroxide from small to about moderate
amounts. Some of the impurities, especially the hydroxide, react with the standard acid titrant
and contributes to the total alkaline strength of the soda ash. The titration with the standard acid
to the methyl orange endpoint completely neutralizes the carbonate ions at about pH 4. This
titration analysis does not necessarily give the amount of Na 2CO3 but only expresses total
alkalinity in terms of percent Na2CO3 or Na2O.

Since the sample is frequently homogeneous, the method of aliquot portions is employed. Either
methyl red or methyl orange can be employed as the indicator.

Standardization:

HCl(aq) + NaOH(aq) PH H2O(l) + NaCl(aq)

Titration of Unknown:

Na2CO3(aq) + 2HCl(aq) MO H2O(l) + CO2 + 2NaCl(aq)

A. Preparation of 0.1 N HCl

Measure into a clean glass-stoppered bottle approximately 1 liter of distilled water. With a
graduated cylinder or measuring pipette, add to the water about 8.5 mL of concentrated
hydrochloric acid. Stopper the bottle, mix the solution well by inversion and shaking and label
the bottle.

B. Standardization of 0.1 N HCl using 0.1 N NaOH

Rinse a previously cleaned 50-mL burette at least 4 times with proportions of the prepared HCl.
Then fill the burette with the acid solution and place the burette in burette holder. In all these
steps, pour directly from the bottle to the burette; do not use the beaker or other vessel as an
intermediary.

Using the prepared NaOH solution, carry the same procedure with a second previously cleaned
burette.

Run 20-25 mL of the base from the burette into 250-mL Erlenmeyer flask. Add 2-3 drops of
methyl orange to give a faint but distinct color to the solution. Cautiously run in HCl from the
other burette until the color is an orange shade, intermediate between pink and yellow. In
reaching this point, any hanging drops from the burette should have been transferred to the
solution by means of the stirring rod or by coming into contact with the inside of the flask. Wait

28
half a minute for the liquids in the side of the burette to drain, and then take the final reading.
Record the values in the data space provided in the manual.

Refill the burettes and do 2 more titration.

Obtain the ratio of the volume of the HCl solution to that of sodium hydroxide solution, and the
ratio of the volume of alkali to that of the acid. Results of the two titrations should not vary by
more than two parts in one thousand. If the variation in the results is greater than this, repeat the
titration until satisfactory values are obtained. Inaccurate values (as indicated by the final
outcome of the titrations) should not be erased. They should merely be marked “incorrect” and
not used in establishing the final mean value.
C. Determination of Total Alkalinity of Soda Ash

Weigh accurately in a cleaned 250-mL Erlenmeyer flask a sample of the dried unknown of
appropriate size. The instructor will specify the size of the sample required. Dissolved the
sample in about 125 mL distilled water. Place a clean funnel in a 250-mL volumetric flask and
transfer the solution from the beaker to the flask. Rinse the beaker, add the rinsing to the flask,
and finally dilute to the mark. Mix the contents of the flask thoroughly by inversion and
shaking. Pipet a 50-mL aliquot into an Erlenmeyer flask and add 2 drops of methyl orange.
Titrate with standard acid. Repeat the titration with two other 50-mL aliquots. At the end of the
titrations, be sure to empty and thoroughly rinse the volumetric flask for a substantial period of
time.

Report the percentage of sodium.

Report the percentage of sodium carbonate in the sample. A precision of 3 to 5 parts per
thousand is not unusual for the titration.

NOTE: Store the remaining standard HCl solution for the succeeding experiments.

29
 Experiment # 6

POTENTIOMETRIC TITRATION OF AN ACETYLSALICYLIC ACID IN ASPIRIN

Many Acid-Base titrations are difficult to accomplish using a visual indicator for one of
several reasons. Perhaps the analyst is color-blind to a particular indicator color change; there
may not be a suitable color change available for a particular type of titration or the solutions
themselves may be colored, opaque or turbid. It may be desired to automate a series of replicate
determinations. In such situations, an acid-base titration may be conducted potentiometrially,
using a glass hydronium ion selective electrode, a suitable reference electrode and a sensitive
potentiometer (a pH meter) may be advantageous.

Two electrodes, after calibration [to relate potential in millivolts (mV) to a pH value] are
+
immersed in a solution of the analyte. One is an indicator electrode, selective for H3O and the
other a stable reference electrode, normally the standard calomel electrode (SCE), with an
invariant potential. Nowadays, combination electrodes are widely used, were both indicating
and reference electrodes are combined in one compartment. The potential difference, which
after calibration is pH, is measured after the successive addition of known increments of acid or
base titrant.

When a potentiometric titration is being performed, interest is focused upon changes in

the emf of an electrolytic cell as a titrant of known concentration is added to a solution of
unknown. The method can be applied to all titrimetric reactions provided that the concentration
of at least one of the substances involved can be followed by means of a suitable indicator
electrode. The critical problem in a titration is to recognize the point at which the quantities of
reacting species are present in equivalent amounts. The titration curve can be followed point by
point, plotting as ordinate, successive values of the cell emf (pH) vs the corresponding volume of
titrant added. A typical titration curve is presented in Fig. 1.

The equivalence point in the titration is determined by plotting the potential or pH against
the volume of the titrant added. A sharp break in the titration curve is observed at the vicinity of
the equivalence point. The equivalence point in the titration curve can be determined by
extending a straight line along the lower and upper curve that comes before and after the sharp
rise or inflection curve. Two parallel lines are drawn along the Y axis before and after the
inflection curve starting from a point from the extended line
( A or D) until the point where it intersects at the lower or upper curve (B or C).

30
Figure 1. Curve for the titration of 25.00mL of 0.100M HCl with 0.100M NaOH
The midpoints ( E and F) of two lines parallel to the Y axis are then connected. The
equivalence point is the point where the line intersects at the inflection curve (G) and
corresponding volume is the equivalence point volume.

For titration that involves a weak monoprotic acid, the ionization constant (pka)
corresponds to the pH at half the equivalence point volume. When the analyte is a diprotic acid
or dibasic the graph will have two inflection curves. The first and second ionization constants
are then determined in the same manner as in the monoprotic substance.

The Reference Electrode

Most commonly, the reference electrode is the silver/silver chloride electrode. The
potential is based on the following equilibrium:
-
AgCl(s) + e ------------Ag(s) + Cl (aq)
The half cell is:
Ag[(AgCl(Sat'd),KCl(xM)]

NOTE: Electrodes respond to the activity of the electroactive species in solution. However, as a
practical matter it is more convenient experimentally to use concentration. For this reason the discussion
in this laboratory experiment will be made in terms of concentration rather than the more correct activities.

The practical version of this electrode is a silver wire dipping into a saturated solution of
KCl; when fabricated this way its electrode potential is 0.199V (vs. Normal Hydrogen Electrode,
o
NHE) @ 25 C. The potential is a function of temperature and the concentration of KCl in the
solution. Such an electrode is comparatively rugged, reliable, and inexpensive.

31
The Indicator Electrode

The heart of the glass electrode is a thin glass membrane, specially fabricated to preferentially
+
exchange H3O . The outside of the membrane is in contact with the analyte solution containing
+
the unknown [H3O ]. The inside of the membrane contacts a hydrochloric acid solution of fixed
concentration. A silver wire, coated with AgCl dips into this solution; the other end of the wire is
connected to the measuring device.

The Mechanism of the Response

A change in hydronium ion concentration causes a change in composition of the glass membrane
due to an ion exchange process involving the solution and the membrane. A corresponding
change in membrane potential, proportional to pH, is what is measured. All other potentials are
constant. In effect the membrane potential (variable) is measured against two fixed potentials,
the external reference and the internal reference, both Ag/AgCl reference electrodes. Potential
difference is measured using a high impedance potentiometer. This high resistance dictates a
very small current flow.

Each glass electrode is different, due to the difficulty of reproducing the glass membrane;
it is, therefore, necessary to standardize the meter and electrode against at least two solutions of
accurately known pH. Such standard buffer solutions are available from many different
manufacturers.

A.) DETERMINATION OF THE % ACETYLSALICYLIC ACID IN ASPIRIN

Procedure:

Accurately weigh the aspirin tablet in a 150 mL beaker. Drop onto the tablet two drops of
deionized water and wait a few minutes. The tablet should crumble. To the tablet in the beaker
now add 15 mL of 95% ethanol and stir the tablet with a glass rod until it dissolves. The white
solid that dissolves slowly is starch and it may not dissolve completely. The change in pH will be
monitored with the pH meter throughout the titration. The equivalence point volume in the
titration will be determined graphically from the titration curve and by the first derivative
methods. From these results the concentration of acetylsalicylic acid in the tablet will be
determined.

Operation and Calibration of pH meter (pH600-Pocket sized)

Operation:

• Do not be alarmed if white crystals appear around the cap. This is normal with pH
electrodes and they dissolve when rinsed with water.
• Remove the protective cap and turn the pH600 on.
• Immerse it into solution up to the maximum immersion level.

32
 • Stir gently and wait until the display stabilizes.
• After use, rinse the electrode with water to minimize contamination.
• Store the electrode with a few drops of storage solution or pH 7 buffer solution in the
protective cap.
• Always replace the protective cap after use.

Caution: Do not use distilled or ionized water for storage purposes.

Calibration:

The calibration procedure is very simple and fast.

• Immerse the tester up to the maximum level in pH 7 buffer.

• Allow the reading to stabilize and using a small screwdriver turn the pH 7 Calibration
Trimmer to read 7.0.
• Calibration is now complete.

Caution: always use fresh buffers for calibration and never reuse them.

Making a pH measurement.

1. After standardization wash and dry the pH electrode using DI water

2. Dilute to the mark the acid solution using a 250-mL volumetric flask. Use
distilled water only. Mix the solution thoroughly.
3. Pipet a 50-mL aliquot portion and transfer this into a 100-mL beaker. Add 2-3 drops
phenolphthalein. Measure the initial pH reading of the solution.

4. Add 1.0 mL of the standard titrant ( contained in a buret). Stir the solution and allow
enough time to obtain a constant reading. Record the pH reading.

5. Repeat Step 4 until a large increase in pH reading is observed. At this point, add two more
1.0mL portions of the standardized titrant, recording the pH after each 1.0 mL addition.

6. Rinse the electrode with distilled water.

7. Repeat steps 2,3,4 and 5. However, this time add the titrant in 0.5 mL increments (for
Trial 2 and Trial 3)

a. Report the concentration of the unknown acid in equivalence per liter of solution.

b. Prepare a potentiometric titration curve by plotting pH or E against volume of

base titrant. Determine the equivalence point. If the acid is a weak acid,
determine the Ka value.

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 8. Once the pH exceeds 5.0 make an accurate volume reading and then use the
following sequence.
a. Add four drops of titrant to the beaker; record the pH but not the volume.
b. Repeat step (a) until the pH increases to a value above 10.5.
c. Record the volume which corresponds to the last four drop increment.
Continue the titration using 1.0 mL increments until the pH change
corresponding to each addition is less than 0.1 pH unit.
9. Do trials 2 and 3 following the same procedure.

CALCULATION OF RESULTS

Calculate the % acetylsalicylic acid in each sample, the average value, the absolute deviation,
and the relative average deviation in ppt and the confidence interval at a suitable confidence
level. Assuming the value supplied on the label is the true value, calculate the absolute and
relative error of your determination.

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