DEGREE IN CHEMISTRY

ANALYTICAL CHEMISTRY LABORATORY

LABORATORY MANUAL OF
GENERAL ANALYTICAL
CHEMISTRY
Laboratory Manual General Analytical Chemistry Degree of Chemistry-Universidade de Santiago de Compostela

INDEX
LABORATORY MANUAL OF GENERAL ANALYTICAL CHEMISTRY
1
INDEX .......................................................................................................................... 2
1. WORK AND SAFETY RULES IN THE LABORATORY . ................................... 3
1.1. General rules 3
1.2. General safety rules. 4
1.3. Safety pictograms 5
1.4. Waste disposal. 5
1.5. What to do in the event of an accident: First aid. 5
2. LABORATORY MATERIAL AND ITS USE ......................................................... 7
2.1. Cleaning of laboratory ware 8
3. BASIC OPERATIONS ............................................................................................. 9
3.1. Liquid measurement. 9
3.2. Weight. Mass measurement. 10
3.3. Solids transfer. 11
3.4. Liquid transfer. 11
3.5. Solution Preparation. 11
3.6. Filtration 12
3.7. Drying and ignition 13
4. LABORATORY NOTEBOOK ............................................................................... 14
EXPERIMENTS GENERAL ANALYTICAL CHEMISTRY 15
EXPERIMENT 1: GRAVIMETRIC DETERMINATION OF IRON ........................ 18
EXPERIMENT 2: DETERMINATION OF NICKEL IN STEEL.............................. 20
EXPERIMENT 3: DETERMINATION OF CHLORIDE IN WATER BY THE
MOHR METHOD.................................................................................................. 22
EXPERIMENT 4: DETERMINATION OF CARBONATE AND
BICARBONATE IN A WATER SAMPLE. INDIRECT METHOD ................... 24
EXPERIMENT 5: DETERMINATION OF CARBONATE AND
BICARBONATE IN A WATER SAMPLE. DIRECT METHOD........................ 26
EXPERIMENT 6: DETERMINATION OF Ca (II), Mg (II) AND HARDNESS
OF A WATER ....................................................................................................... 28
EXPERIMENT 7: DETERMINATION OF HYPOCHLORITE AND ACTIVE
CHLORINE CONTENT IN A BLEACH SAMPLE ............................................. 30
EXPERIMENT 8: DETERMINATION OF ORGANIC MATTER IN A FRESH
WATER SAMPLE ................................................................................................. 32
ANNEX 34
1.- Periodic table of elements ...................................................................................... 34
2.- Concentrations of commercial solutions of acids and bases .................................. 35
3.- Purity of the solid chemicals .................................................................................. 35
4.- Example of an experiment report in the laboratory notebook ................................ 36

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Laboratory Manual General Analytical Chemistry Degree of Chemistry-Universidade de Santiago de Compostela

1
1. WORK AND SAFETY RULES IN THE LABORATORY .

1.1. General rules

 Attendance at interactive classes: seminars, tutorials and laboratory is
compulsory for all students.
 Students must attend on the date, time and place they are cited, with the material
requested and with the experiment guideline read.
 The student will find his/her workplace clean and tidy, otherwise he/she must
inform the instructor. In addition, he/she will ensure that he/she have in his/her
table all the material needed, and that this material is in perfect condition.
 From the beginning to the end of the lab session the student will be responsible
for their workplace as well as the material present there.
 Before going to the laboratory, the student will carefully read the experiment
guideline to be performed. In general, before starting a experiment the student
will have to answer a series of questions about it, which the instructor will
correct and take into account for grading. In the experiments it will also be
necessary to bring to the laboratory the required calculations, indicated in the
experiment guidelines that appear in this manual.
 Materials, reagents and solutions that are shared and have a specific location
should only be taken at the time of use and should be returned to their original
place immediately. This applies to solid reagents placed near the balances,
indicator paper, indicators for titration, standard solutions, solutions prepared for
the student, etc., and especially those substances that require special conditions
for their conservation (anhydrous salts in desiccators).
 Before using a general use instrument (balances, vacuum pump, desiccators,
spectrometers, etc.) check that it is not being used by another student. If free,
you should make sure that it works correctly. Queues are frequent around these
sites. These should be avoided because safety regulations, therefore, the student
will remain at his/her table until the sites are free.
 Jokes or activities different to laboratory are NOT allowed.
 Students should never run in the laboratory, work alone, or carry out different
experiments to those proposed by the instructor.
 Inform the instructor if you want to leave the laboratory.
 Students should leave the lab whenever the instructor requests it or if it is
determined by any of the safety regulations.
 Before ending the experiment, the student should ask the instructor about the
quality of the results obtained.
 When the activity in the laboratory is finished in a normal way, all the used
material should be washed and left clean, and the workplace should be left in
order. The glassware will be placed on a sheet of clean filter paper

1
Some safety standards in the most complete practice laboratories can be found in chapter 1 of the book
by Martínez Grau (reference 2) or in the document on the website of the Risk Prevention Service of the
USC: (http://www.usc.es/estaticos/servizos/sprl/normalumlab.pdf)

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Laboratory Manual General Analytical Chemistry Degree of Chemistry-Universidade de Santiago de Compostela

IMPORTANT: Leave the laboratory material of your workplace perfectly clean

and in order. Notify the instructor of any breakage or deterioration suffered by the
material.
It is mandatory to request authorization before leaving the laboratory.

1.2. General safety rules.

It is absolutely forbidden to work in the laboratory without a lab coat or safety
glasses.
 Contact lenses are not allowed in the laboratory.
 In the laboratory, it is strictly forbidden to eat, drink and smoke.
 It is necessary to tie up long hair, have short nails and not use rings on hands.
Footwear will have to completely cover the feet. High heels are not allowed.
 Before working, familiarize yourself with safety devices of your laboratory.
 It is prohibited to take material or products out of the laboratory.
 Chemicals or solutions will not be flushed, unless they are inert, down the
laboratory drains, but into the appropriate waste containers.
 When using a chemical or performing any reaction that generates any toxic or
irritating gas, always work in an extraction hood in operation. The laboratory
atmosphere should be kept as clean as possible.
 Never return unused reagents to the original container.
 In case of an accident, notify the instructor immediately.
 The student should not forget to always read the label of any reagent before
using it.
Important: Avoid using glassware with cracks or breaks, contaminated or suspicious
solutions, etc.

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Laboratory Manual General Analytical Chemistry Degree of Chemistry-Universidade de Santiago de Compostela

1.3. Safety pictograms

1.4. Waste disposal.

The School of Chemistry, together with the Hazardous Waste Management Unit of the
USC, has a plan for the collection of waste that should not be discharged into the sewer
or deposited in the trash.
Broken glass material will be disposed into containers specially designed for this
purpose. The papers and other waste will be thrown in the trash.
Toxic chemicals will be discarded in special containers for this purpose.
Chemicals or solutions, unless they are inert, must not be flushed down the drains of the
laboratory.
Liquid substances or solutions that can be poured into the sink will be diluted
beforehand, especially in the case of acids and bases.

1.5. What to do in the event of an accident: First aid.

Important: In case of accident, notify the instructor immediately.
In case of an accident call 061, and if necessary, to the toxicological information
telephone 915 620 420. In any case, communicate the accident in writing to the
University's Occupational Risk Prevention Service (extension 33333).
Fire in the laboratory. Evacuate the laboratory, according to the indications of the
instructor and the existing signaling. If the fire is small and localized, extinguish it using
a suitable extinguisher, sand, or covering the fire with a container of adequate size to
extinguish it. Remove flammable chemicals that are near the fire. Never use water to
extinguish a fire caused by the inflammation of a solvent but dry ice.

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Laboratory Manual General Analytical Chemistry Degree of Chemistry-Universidade de Santiago de Compostela

Fire on a person. If student cloths are burning, he/she should shout immediately for
help. He/she should lie on the ground and roll on him/her-self to extinguish the flames.
Do not run or try to get to the safety shower if you are not very close. It is your
responsibility to help someone who is burning! If a student is burning, cover him with a
fireproof blanket, lead him to the safety shower, if he is nearby, or roll him on the floor.
Never use a fire extinguisher on a person. Once the fire has been extinguished, keep the
person lying down, taking care not to get cold and provide medical assistance.
Burns. Small burns produced by hot material, heaters or heating blankets, etc., will be
treated by washing the affected area with cold water for 10-15 minutes. The most
serious burns require immediate medical attention.
Cuts. Cuts produced by the breakage of glass material are a common risk in the
laboratory. These cuts have to be washed well, with plenty of running water, for at least
10 minutes. If they are small and stop bleeding in a short time, wash them with soap and
water, apply an antiseptic and cover them with a suitable bandage. If they are large and
do not stop bleeding, they require immediate medical assistance.
Spill of chemicals on the skin. Chemicals that have been spilled on the skin should be
washed immediately with plenty of running water for at least 15 minutes. Corrosive
products are especially dangerous, must act quickly and with energy, washing it
immediately with large amounts of cold water. The safety showers installed in the
laboratories will be used in those cases in which the affected area of the body is large
and washing in a sink is not enough. It is necessary to remove all contaminated clothing
as soon as possible while under the shower. It is necessary to remember that the speed
of washing is very important to reduce the severity and extension of the wound. It is
necessary to provide medical assistance to the affected person.
Action in case of corrosive chemicals in the eyes. In this case time is essential (less
than 10 seconds). The sooner the eye is washed, the less serious the damage will be.
Wash both eyes with plenty of running water for at least 15 minutes in an eye shower,
and, if not available, with a bottle to wash the eyes. It is necessary to keep the eyes open
with the help of the fingers to facilitate washing under the eyelids. It is necessary to
receive medical assistance.
Action in case of ingestion of chemicals. Before any specific action, ask for medical
assistance. If the patient is unconscious, lay him/her down, with his/her head on his/her
side. Cover it with a blanket so he/she is not cold. Do not leave him/her alone. Do not
allow him/her to drink liquids or cause vomiting.
Action in case of inhalation of chemicals. Immediately drive the affected person to a
place with fresh air. Requires medical assistance as soon as possible.

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Laboratory Manual General Analytical Chemistry Degree of Chemistry-Universidade de Santiago de Compostela

2. LABORATORY MATERIAL AND ITS USE

Most of the material used in a chemistry laboratory is made of glass; This is due to its
advantageous characteristics, such as easy cleaning, transparency, chemical inertness,
ability to withstand high temperatures. The drawback of this type of material is its
fragility, which requires careful care in handling.
The set of laboratory material can be classified into the following groups:

a) Laboratory material for measuring volumes. This type of volumetric material is

calibrated and should not be heated.

b) Other glass material. For the realization of basic operations such as filtration,
drying, etc., a wide variety of glass material is used.

c) Other laboratory material. In addition to glass, utensils made of materials such as

porcelain, wood, iron and plastic are used in the laboratory.

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Laboratory Manual General Analytical Chemistry Degree of Chemistry-Universidade de Santiago de Compostela

2.1. Cleaning of laboratory ware

For most laboratory manipulations it is very important that the material to be used is
CLEAN.
The cleaning of the material should be done immediately after each operation as it is
much easier and also the nature of the waste it contains is known.
To clean an object, first remove the waste (which is thrown in the right container).
Washing with water and soap of the whole piece is one of the best cleaning methods.
After that it is necessary to rinse with abundant water to remove soap and dirt. The last
washing operation consists of rinsing all the material with deionized or distilled water.
In the case of stains difficult to remove with soap and water, it would be necessary to
use other solvents (organic solvents, acids or bases, ...). If the dirt is very unruly,
solutions can be prepared, such as the chromic mixture (a saturated solution of
potassium dichromate in sulfuric or nitric acid) that gives excellent results, although
they are somewhat dangerous to handle because they are very corrosive and
carcinogenic.
Finally, if the material has to be dries, let it drain upside down in the sink. For a better
drying, the piece can be put in an oven (BE AWARE, never put glassware with plastic
or Teflon pieces, or with the two grinding pieces attached).
Important: Before proceeding with the cleaning of frosted glassware, and if it is
greased, the grease of the grinding must be completely eliminated with the help of a
paper (wrapped in tweezers) impregnated with hexane or acetone.
Never introduce volumetric or plastic material in the oven
At the end of the experiment, the material is kept clean

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Laboratory Manual General Analytical Chemistry Degree of Chemistry-Universidade de Santiago de Compostela

3. BASIC OPERATIONS
3.1. Liquid measurement.
Liquids can be measured by determining their volume. Four instruments are used to
measure liquid volumes: graduated cylinder, Pipette, Burette and Volumetric flask.
The graduated cylinder, pipette and burette measure the volume by delivering, while the
volumetric flask measures it by content. These instruments have marks on their surface
that indicate volumes of liquids. To measure the volume, the level of the liquid is
compared with the graduation marks indicated on the wall of the measuring instrument.
This level is read at the bottom of the meniscus that forms in the liquid.
To make a correct reading of a volume using a graduated cylinder, burette or
pipette, it is necessary that the eyes of the observer are at the same height as the
meniscus of the liquid. Otherwise the reading will be incorrect.
To take an approximate quantity of a liquid or a solution, a beaker or a graduated
cylinder of the volume closest to the quantity needed is used. In case of needing an
exact volume, a graduated pipette, a burette or graduated glass material will be used.
The difference between one instrument and another is not the volume it measures but
the accuracy and purpose.
Never introduce any material (including pipettes) into a reagent bottle to avoid
contamination of the entire product. To take a given volume of a reagent with a pipette,
a volume of liquid somewhat greater than the amount to be measured must be added to
a container (a beaker for example). Once the necessary amount of this container is
taken, the unused is discarded.
Burette: Used exclusively to measure the volume delivered accurately. Burettes, in
general, have the main markings indicated with numbers indicating milliliters, and
unnumbered subdivisions indicating 0.1 mL. They are provided with a valve to control
the flow of the liquid.
Before using a burette, make sure that it is clean and that the
valve does not allow liquid to escape when it is closed.
To fill the burette, make sure the valve is locked. Add 5 to 10
mL of titrant and carefully rotate the burette so that it
completely wet its interior. Then fill the burette above the zero
mark. Remove air bubbles from the tip, quickly opening the
valve and allowing small amounts of titrant to pass. Finally, fill
to zero.
During the titration, the valve should be handled with the left
hand while the reaction flask is shaken with the right 2. You
must ensure that the tip of the burette is inside the titration flask. Introduce the titrant
slowly while constantly stirring to ensure that the reagents are mixed well.
It is a very precise instrument so it should never contain and therefore add hot liquids.
Volumetric flask: Measures volumes by content with great precision. It only measures
a volume given by a capacity. Being a very precise instrument, it must be taken into
account that cannot be heated or hot liquids added to it.

2
Holler & Crouch, Skoog and Wert Fundamentals of Analytical Chemistry, 9th edition; Cengage, 2014.

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Laboratory Manual General Analytical Chemistry Degree of Chemistry-Universidade de Santiago de Compostela

To prepare a solution in a volumetric flask, the desired mass of the reagent is first
dissolved in a beaker with slightly less solvent than the final volume, by gentle stirring.
The solution is then transferred to the volumetric flask, and washed three times with
small volumes of solvent, adding the washings also to the volumetric flask. Finally, it is
filled to the upper line.
Pipettes: Pipettes are used to transfer volumes of liquid whose measurement requires
accuracy. There are several kinds, the ones that will be used to a greater extent are the
following: volumetric or transfer pipette, measuring pipette and micropipette.
The volumetric or transfer pipette is calibrated to deliver a
fixed volume. They are manufactured in different sizes
and can have one or two marks of piping (double piping
pipettes). If the pipette is filled to the piping line (ring
engraved on the top) and is completely discharged or up to
the next piping mark (double-pipette pipettes) the volume
indicated by the pipette is delivered.
The measuring pipette is calibrated to permit delivery of any variable volume up to a
maximum capacity.
In both the use of transfer and measuring pipettes, rubber bulb or other pipette suct
device are used to suction and deliver
liquids.
The micropipette transfers variable
volumes of a few milliliters or microliters
of liquid using disposable plastic tips. To
transfer a volume, the piston is pressed to
the first stop (A) and the tip is inserted in
the solution. Then the content previously
adjusted in the micropipette is aspirated.
Be careful not to generate bubbles (B). When delivering the aspirated volume, the
piston is pressed to the first stop (C) and pressed to the second stop to release the
volume completely (D). Finally, the tip is discarded (F).
NEVER insert a pipette or similar into a reagent bottle as it may contaminate it.
Transfer the necessary amount to a beaker or similar and take the solution from it.
Graduated cylinder: The volumes transferred with a graduated cylinder are less
accurate than those transferred with a pipette. Liquid is added until the meniscus
coincides with a certain level, the corresponding line number indicates the volume of
liquid contained. The accuracy of the measurements obtained decreases as their capacity
increases.
They are used only to measure. Solutions and mixtures should never be prepared in it.

3.2. Weight. Mass measurement.

Balances are normally used to weigh substances. There are several types of balances
that are characterized by their accuracy, sensitivity and maximum capacity. The most
used will be: analytical balance (macro balance) and the auxiliary balance.
The analytical balance (macrobalance) has a maximum load of 160 to 200 g, and an
accuracy of 0.1 mg.

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Laboratory Manual General Analytical Chemistry Degree of Chemistry-Universidade de Santiago de Compostela

The auxiliary balance has a sensitivity of between 0.1 and 0.01g, which is not very
accurate, but has a greater capacity of around 2500 g.
Weighing should never be done directly on the balance pan, but on a watch glass or on a
clean, dry glass container.
To carry out the weighing, first of all, the balance is tare to zero, e g. the watch glass or
beaker is weighed, and the tare button is pressed). Then, the substance to be weighed is
added with a spatula, if it is a solid, or with a pipette, if it is a liquid. Finally, the
weighing reading is carried out. The exact weight must be noted, indicating all the
decimal figures given by the balance used.
If more product has been added than necessary, remove some product and weigh again.
If there is still an excess product, withdraw more. The product after taking out of the
bottle should not be returned to it.
After weighing, the balance must be set to zero. The weighing chamber and the balance
pan must be left perfectly clean.

3.3. Solids transfer.

Small amounts of a granulated or powdered solid reagent are transferred from a bottle
into a container with a clean and dry spatula.
To introduce a solid into a narrow mouth container, a funnel of clean and dry solids can
be used.

3.4. Liquid transfer.

To avoid splashing when delivering a liquid from one container to
another, it rests on a glass rod on the tip of the container so that the liquid
flows through the rod and is collected in the other container. If the
container has a small mouth, a dry and clean glass funnel should be used
in which the liquid from the rod falls.

3.5. Solution Preparation.

Two types of solutions are prepared in the chemical laboratory,
depending on the accuracy of the material used: approximate concentration solutions
and exact concentration solutions. In both cases the solution can be prepared from a
solid reagent or from a liquid reagent or a solution.
The previous step to the preparation of any solution is the performance of some
previous calculations, which are different depending on the nature of the starting
compound.
In the case of approximate concentration solutions, the solution can be prepared in a
beaker or in a conical flask. For weighing an auxiliary balance is used and for the
measurement of volumes a graduated cylinder.
Exact concentration solutions are prepared in volumetric flasks. An analytical balance is
used (writing down all the decimal figures) for solids and a pipette for liquids.

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Laboratory Manual General Analytical Chemistry Degree of Chemistry-Universidade de Santiago de Compostela

3.6. Filtration
A normal problem in the laboratory is to separate a liquid from a solid. In filtration, a
liquid is percolated through a porous material that retains the solid particles.
Filtration of an analytical precipitate takes place in three stages:
 Decantation, which consists of passing through the filter
or porous plate as much supernatant liquid as possible,
keeping the solid precipitated in the beaker where it was
formed. A stirring rod is used to direct the flow of
decanted liquid.
 Transfer, which involves moving the solid from the
beaker to the filter paper or porous plate, using a rubber
policeman (which is a stirring rod with a piece of rubber
tube adapted at one end).
 Washing, which consists of adding the washing liquid over the precipitate and
letting it pass through the filter paper or porous plate to eliminate possible
interference.
Filtration can be done by gravity or vacuum.
Normal or gravity pressure, a glass funnel, usually
with a long shank and filter paper, of adequate porosity
consistent with the particle size of the precipitate is
used for gravity filtration. The filter paper is folded as
shown in the figure. Once placed inside the funnel, the
paper will be moistened with the washing liquid, so
that the outer surface of the paper adheres perfectly to
the inner wall of the funnel. The funnel with the filter
paper will be placed on a support, so that the rod is in
contact with the wall of the collection container of the
filtrate, and then the liquid will be poured into the
funnel, sliding it along the rod, proceeding as indicated
above. Care must be taken that in additions of product
to the filter, the solution never surpass the edge of the
paper because in that case liquid would pass through
the filter paper and drag, precipitate, to the filtrate.
This type of filtration is usually used in those cases where the precipitate is almost
colloidal, or when it is interesting to remove a small insoluble impurity, ensuring that
the solution passes completely transparent.

In vacuum, a Buechner funnel with a circular

filter paper of the same diameter as the funnel
or a filter plate, a kitasato flask and a vacuum
pump is used for vacuum filtration.
If a Buechner funnel is used, the filter paper is
placed on the inner plate of the Buechner
funnel, then moistening it with the washing
liquid until total adhesion.

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Laboratory Manual General Analytical Chemistry Degree of Chemistry-Universidade de Santiago de Compostela

The Buechner funnel or filter plate is attached to a Kitasato flask using a rubber cone
and the lateral tubing is connected to the vacuum system.
Care should be taken so the the kitasate flask is disconnected from the vacuum system
before closing it.
Vacuum is much faster than gravity filtration and is normally used to separate
precipitates from solutions containing them (mother liquor).

3.7. Drying and ignition

In an analytical laboratory two heating systems are normally used: ovens and muffles.
The main difference lies in the working temperatures and therefore in their applications.
Ovens: The maximum working temperature of an oven reaches 150 ºC. They are used
to dry reagents, precipitates and glassware at approximately 110 ° C. Everything that
goes into the oven must be marked. A watch glass or beaker must be used to introduce
reagents or precipitates into the oven.
Muffle furnace: Working temperatures are much higher, from 200 ° C to 1500 ° C.
They are used to ignite samples, reagents and precipitates. Due to the high temperatures
only refractory laboratory materials can be used.
To work with the heating systems, it is necessary to take care when introducing and
removing the material. Use gloves and long tweezers if necessary.
When removing the reagents or precipitates from the oven or muffle, they are usually
introduced into a desiccator to prevent them from absorbing moisture from the
atmosphere. A desiccator is a closed glass container, with a ground-glass surfaces,
which are lightly coated with grease to ensure a good seal when the top is in place. It
usually contains a chemical drying agent (silica gel, alumina, ...) so that the internal
atmosphere remains free of moisture. It is used to store objects and substances in a dry
atmosphere. After placing a hot object in the desiccator, the lid is left somewhat open
for a few minutes until the object has cooled slightly. To open a desiccator, slide the lid
horizontally, instead of trying to open it by pulling the lid up.

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Laboratory Manual General Analytical Chemistry Degree of Chemistry-Universidade de Santiago de Compostela

4. LABORATORY NOTEBOOK
A laboratory notebook is needed to record the measurements and observations concerning an
analysis. The laboratory notebook summarizes the work that has been done and the results
obtained. The notebook must be permanently bound. Most of the notebooks have enough space,
there is therefore no need to crowd entries.
Standards for a laboratory notebook:
1.- The laboratory notebook serves to immediately take note of all experimental observations,
briefly but concisely and clearly. You should not use a sheet of paper that may be lost, but a
notebook. Record all data and observations directly into the notebook. Neither quantitative nor
qualitative data should be omitted.
2.- Date each page of the notebook as it is used.
3.- Supply each entry or series of entries with a a title or heading.
4.- Never attempt to erase or obliterate an incorrect data; instead, cross it out with a single
horizontal line and locate the correct entry as nearby as possible.
5.- In the laboratory notebook each experiment must contain the following entries:
• The title of the experiment
• A brief statement of the principles on which the analysis is based (2-5 lines)
• The chemical equations of the main reactions of the analysis
• The calculations necessary for the preparation of solutions
• All weighing data, volume and / or instrumental measures necessary to calculate the
results
• A summary of the observations trying to interpret them
• The equations used to calculate the results
• The final result and the conclusions that can be drawn from it
• The answers to the questions included in the manual.

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Degree in Chemistry
2nd Year

GENERAL ANALYTICAL
CHEMISTRY

EXPERIMENTS
General Analytical Chemistry Degree in Chemistry-Universidad de Santiago de Compostela

GENERAL ANALYTICAL CHEMISTRY

Degree in Chemistry

2nd Year
STUDENT MATERIAL TO TAKE INTO THE LAB
Lab Coat
Safety glasses
Laboratory Notebook
WORKING RULES
Before the experiment sessions
The student must have read and understood the experiment description script and
performed the indicated calculations.
The student is also suggested to look for information on the experiment he is going to
do and try to answer the questions.
At the beginning of each experiment session
Before beginning each lab session, the instructor will verify that the student has read
and understood the corresponding experiment guideline and made the previous
calculations.
During the sessions
The experiments are performed in groups of two students, unless otherwise indicated.
Each group will be assigned a worktable with the necessary equipment.
Always work at the table, unless the gas hood is needed.
Always keep the worktable clean.
When finished
Clean the table and the material used.
Before leaving the laboratory, the instructor will verify that the student has finished the
experiment and understood the work done.
Notify the instructor before leaving the laboratory.

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General Analytical Chemistry Degree in Chemistry-Universidad de Santiago de Compostela

ANALYTICAL CHEMISTRY EXPERIMENT GUIDELINES

EXPERIMENT 1: Gravimetric determination of iron

EXPERIMENT 2: Determination of nickel in a steel
EXPERIMENT 3: Determination of chloride in water using the Mohr method
EXPERIMENT 4: Determination of carbonate and bicarbonate in a water sample.
Indirect method
EXPERIMENT 5: Determination of carbonate and bicarbonate in a water sample.
Direct method
EXPERIMENT 6: Determination of calcium, magnesium and hardness of a water
EXPERIMENT 7: Determination of hypochlorite and active chlorine content in a
bleach sample
EXPERIMENT 8: Determination of organic matter in a fresh water sample

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General Analytical Chemistry Degree in Chemistry-Universidad de Santiago de Compostela

EXPERIMENT 1: GRAVIMETRIC DETERMINATION OF IRON

OBJECTIVES
The objective of this experiment is to determine the percent of iron in an aqueous sample by gravimetric
analysis and to experiment the most relevant experimental procedures used in gravimetric methods. This
is a two-days experiment.

INTRODUCTION
The iron contained in a sample can be analyzed by precipitating it as hydrated oxide (reddish-brown
color; Kps = 4 10-38), from a basic solution following by ignition to produce Fe2O3.
Precipitation starts around pH = 2. Hydrated oxide is gelatinous, has a weak basic character and may have
occluded impurities, due to the large surface area it presents. When the presence of impurities is
suspected, the initial precipitate is dissolved in acid and precipitated again. Thus, occlusion contamination
decreases.
The use of Fe2O3 (s) as a weight form requires all iron being in oxidation state +3.

2Fe3+ + 6 NH3 + 3H2O → Fe2O3 (s) . xH2O + 6 NH4+

Fe2O3 (s) . xH2O → Fe2O3 (s) + xH2O↑ 900ºC

EXPERIMENTAL PROCEDURE

FIRST DAY
Prepare the crucible
Mark 2 porcelain crucibles. Bring them to constant mass, heating them to redness in a muffle
furnace for 30 minutes (use tweezers and gloves). Then cool them in a desiccator for 30 minutes and
weigh each crucible on an analytical balance. Repeat the above process: 30 minutes of heating to redness,
30 minutes of cooling in a desiccator and weighing. Your two weighings should agree to within 0.5 mg. If
not, you should repeat the process one more time.

Sample preparation
Transfer two 5 mL aliquots of the unknown sample to a 250 mL beaker each. In a fume hood,
add 15 mL of water and 1 mL of concentrated nitric acid and boil for a few minutes. Be careful not to boil
away all the water. Dilute the sample to 200 mL with distilled water.

Precipitation
Add, to the hot solution, ammonia (1:1) with constant stirring to produce a faint odor of
ammonia in the vapors over the solution. Cover the glass with a watch glass (leave the rod inside the
glass) and boil for 5 minutes (digestion of the precipitate). Check vapors for ammonia. Remove the glass
from the stove, wash the back of the watch glass with hot water, collect the washes in the beaker; cool
long enough (30 minutes).

Filtering and washing the precipitate

Decant the supernatant liquid on an ashless filter paper (Albet 1238 or similar), ensuring that all the
precipitate remains in the beaker, where it is washed by decantation with 50 mL portions of hot NH4NO3
solution. (Do not pour liquid higher than 1 cm from the top of the funnel). Repeatedly wash the
precipitate with hot ammonium nitrate until no Cl- is detected in the filtered supernatant (Cl- is detected
by acidifying a few milliliters of the filtrate with a drop of concentrated nitric acid and adding a few drops
of the silver nitrate solution). Finally, transfer any remaining solid from the beaker to the filter with the
aid of a rubber policeman and more hot ammonium nitrate. Cover each of the funnels with a ribbed watch
glass and let the filter paper drain with the precipitate for a while. Carefully lift the paper out of the
funnel, fold it and transfer it to one of your accurately weighed crucibles. Fold up the filter papers as
much as possible.

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General Analytical Chemistry Degree in Chemistry-Universidad de Santiago de Compostela

SECOND DAY
Ignition and weighing of the precipitates
Carefully, dry each crucible with a small flame. The flame should be directed at the top of the
container. Avoid spattering. After it is dry, char the filter paper by increasing the flame temperature. The
air must reach the crucible freely to avoid the reduction of iron by carbon from the filter paper and the
flame gases. Any carbon left on the crucible should be burned away by directing the burner flame at it.
Finally ignite the product for 15 minutes with the full heat of the burner (gloves and tweezers should be
used to handle the crucible). Cool each crucible briefly in air and then in a desiccator for 30 minutes (the
desiccator should be taken to the furnace where the crucibles are located), weigh the crucible and bring to
constant mass with repeated heatings in the muffle furnace (variations not greater than 0.5 mg). You are
required to do a maximum of three weighings for each crucible.

PREVIOUS CALCULATIONS
Explain how a 2% (w / v) solution of ammonium nitrate (100 mL) would be prepared

MATERIAL
2 porcelain crucibles, 2 x 250 mL beakers, 2 watch glasses, rubber policeman, funnels, ashless filter
paper, stove, butane gas bottle, desiccator, muffle furnace, tweezers, gloves, analytical balance

CHEMICALS
1.- Supplied:
- HNO3 (c).
- NH3 (c).
- AgNO3 (0.1 M).
- NH4NO3 (Solid).
- HCl (c).
- Iron solution.

2.- Prepare:
- NH4NO3 (2%, p/v), 300 mL
- Diluted Ammonia (1:1), 100 mL

LITERATURE
D.C. HARRIS, Quantitative Chemical Analysis, Ninth Edition.; W.H. Freeman, 2016.

FINAL CALCULATIONS
Calculate, for each sample, the percentage of iron (w / v) in the problem solution and also indicate the
average percentage of iron in the problem solution.

QUESTIONS
1.- What are the reactions in which Fe (III) is involved until obtaining anhydrous Fe2O3?
2.- What is meant by precipitation form and weighing form of a precipitate? Indicate, in this procedure
what is the form of precipitation and the form of weighing.
3.- In the sample preparation stage, nitric acid is added. What happens? Write the reaction that takes
place.
4.- Why is the sample diluted to 200 mL before proceeding to precipitation?
5.- What reaction takes place between chloride ion and silver nitrate?
6.- Why do you have to remove chloride ions from the precipitate?
7.- The precipitate is washed with ammonium nitrate. Why? Could it be washed with water?
8.- What does it mean to bring a crucible at a constant mass?

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General Analytical Chemistry Degree in Chemistry-Universidad de Santiago de Compostela

EXPERIMENT 2: DETERMINATION OF NICKEL IN STEEL

OBJECTIVES
The objective of this experiment is to perform the determination of nickel in steel using a gravimetric
analysis technique. The most relevant experimental procedures used in gravimetric methods are
implemented. This is a two-day experiment.

INTRODUCTION
Nickel present in a steel sample can be precipitated from a slightly alkaline medium with an alcohol
solution of dimethylglioxime (DMGH). Interference from Iron (III) is eliminated by masking with tartaric
acid. The precipitate is freed of moisture by drying at 110 ° C.

2DMGH + Ni +2  Ni(DMG)2 + 2 H+

The bulky character of the precipitate limits the mass of nickel that can be accommodated
conveniently and thus the sample mass. Care must be taken to control the excess of precipitating reagent
(dimethylglyxime alcoholic solution). If the alcohol concentration is too high, it can dissolve appreciable
amounts of nickel dimethylglyoxate, which leads to low results. If the alcohol concentration is too low,
some of the reagents may precipitate and cause a positive error

EXPERIMENTAL PROCEDURE

FIRST DAY
Prepare the crucible
Clean and mark 2 medium porosity sintered-glass crucibles. Bring the crucibles to constant mass
by proceeding as follows: insert the crucibles (marked) in an oven at 110 ° C for at least half an hour.
With the help of tweezers transfer the hot crucibles to a desiccator, cool for 30 to 40 minutes and weigh
accurately. Repeat the heating half an hour, cool and weigh. Continue until constant mass is obtained (±
0.0005 g).

Sample solution
Weigh 2 samples of about 0.2 g of steel and transfer them to individual 500 mL beakers. Use
separate rods for each glass. In the hume hood, dissolve each sample in about 50 mL of 6M HCl by gentle
warming. Once the steel has dissolved, carefully add approximately 15 mL of 6 M HNO3 and boil gently
to expel nitrous vapors (nitrogen oxides, which may have been produced). Dilute to about 200 mL with
distilled water and heat to boiling.

Precipitation
Introduce about 50 mL of 20% tartaric acid and sufficient 1:1 NH3 to adjust the pH of the solution
between 6 and 7, (acidify with 1: 1 HCl if the solution has a higher pH when adjusting the pH to 7). Heat
at 60-80 ° C, and add about 20 mL of the 1% dimethylglioxime solution. With good stirring add 6 M NH3
to produce a faint odor of ammonia in the vapors over the solutions, then add another 1 to 2 mL of NH3.
Digest the precipitate (sand bath) for 30 to 60 minutes, cool for at least one hour.

SECOND DAY
Filtration and washing of the precipitate
Filter the precipitate through the crucibles (previously brought at constant mass) using vacuum.
To do this, decant the supernatant liquid through the crucible, trying to decant as much liquid as possible
before passing the precipitate to the filter, which is then done by adding warm water and using the rubber
policeman. Wash the solid with water until the washing solution is free of chloride (See Note 1).
Bring the crucibles and their contents to constant mass by heating at 110 ° C.

Note 1.- Test the washing solution for chloride by collecting a small portion in a watch glass,
acidifying with nitric acid and adding a drop or two of 0.1 M silver nitrate. Washing is judged complete
when little or no turbidity develops.

PREVIOUS CALCULATIONS
Explain how a solution of 20% (w / v) tartaric acid in water (100 mL), and 6 M HCl (100 mL) and 6 M
HNO3 (30 mL) would be prepared

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General Analytical Chemistry Degree in Chemistry-Universidad de Santiago de Compostela

MATERIAL
2 medium porosity sintered-glass crucibles, 2 x 500 mL beakers, stir rods, rubber policemans, clamps,
oven, desiccator, sand bath, vacuum pump, analytical balance

CHEMICALS
1.- Supplied:
- Dimethylglioxime, 1% (w / v) in ethanol. (Already prepared)
- HNO3 (c).
- HCl (c).
- NH3 (c)
- Tartaric acid (solid)
- 0.1 M silver nitrate (already prepared)

2.- Prepare:
- 20% (w / v) tartaric acid in water, 100 mL
- HCl (6 M), 100 mL,
- HNO3 (6 M), 30 mL

LITERATURE
Holler & Crouch, Skoog and Wert Fundamentals of Analytical Chemistry, 9th edition; Cengage, 2014.

FINAL CALCULATIONS
Calculate the percentage (w/w) of nickel in the steel sample. MW Ni (C4H7O2N2) 2 = 288.93 g / mol

QUESTIONS
1.- Suppose that the nickel content (AW = 58.71) in a steel is approximately 5% and you would need to
analyze a sample of 2.00 g of metal. Which volume of dimethylglioxime solution (MW = 116.12) at 1%
(w / w) in alcohol should be used to precipitate all nickel, taking into account that we must have an excess
of 30% dimethylglyxime in the solution in which the analysis is performed (Density of the alcoholic
solution = 0.97 g / mL)?
2.- What does it mean to carry a crucible at a constant mass?
3.-What would happen in the gravimetric determination if tartaric acid was not added to the solution?
4.- The acidic medium is necessary to dissolve the steel according to the oxidation-reduction reaction:
Fe + 2H + ↔ Fe2 + + H2
Why is it necessary to add nitric acid next? Why are nitrous vapors generated by adding nitric acid?
5.- Why is it necessary to remove chloride from the precipitate?
6.- What is meant by precipitation form and weighing form of a precipitate? What are the forms of
precipitation and weighing in this gravimetry?
7.- Why is the sample diluted to 200 mL before proceeding to precipitation?
8.- The precipitate is washed with warm water. Why? Could it be washed with cold water?

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General Analytical Chemistry Degree in Chemistry-Universidad de Santiago de Compostela

EXPERIMENT 3: DETERMINATION OF CHLORIDE IN WATER BY THE

MOHR METHOD

OBJECTIVES
The objective of this experiment is to determine the content of chloride in a sample of tap water by means
of a precipitation titration. The most relevant experimental procedures used in precipitation titrations are
implemented; In this case, the Mohr method is used.

INTRODUCTION
Chloride ion is one of the major inorganic anions in water and wastewater. The chloride’s concentration
in water is variable and is mainly due to the nature of the land. Usually, the chloride ion concentration in
natural waters is less than 50 mg/L.

Titration of chlorides is based on the precipitation reaction with the silver ion, forming a white precipitate
of silver chloride:
KpsAgCl=1.8 10-10

At the end point the excess of silver ion forms the precipitate of silver chromate (red brick color) (MOHR
METHOD).
KpsAg2CrO4=1.1 10-12

EXPERIMENTAL PROCEDURE

Standardization of the 0.01 M silver nitrate standard solution

1.- Prepare a solution of approximately 0.01 M silver nitrate (250 mL).
2.- Prepare 100 mL of a 0.015 M sodium chloride solution (primary standard).
3.- Transfer 10 mL aliquots of the previous solution in a conical flask, add 100 mL of distilled water and
1 mL of the 5% chromate indicator solution. Titrate it with the silver nitrate solution, which is added from
a 50 mL burette. A white precipitate of silver chloride is observed first, and finally a red precipitate of
silver chromate appears. Repeat the standardization procedure at least three times.
4.- Calculate de molarity of the silver nitrate solution
OBSERVATIONS: It is convenient to keep the silver solutions in topaz containers, due to the ease of
reducing silver salts to metallic silver

Chloride titration
Transfer 100 mL of the water sample in a conical flask. If necessary, add sodium hydrogen
carbonate to ensure that the pH is around 8. Then add 1 mL of the potassium chromate indicator solution.
Titrate the solution with the standardized silver nitrate solution until a red brick precipitate of silver
chromate is formed. The flask should be kept on a white background (e.g. filter paper).
Repeat the procedure for at least three times.

PREVIOUS CALCULATIONS
Calculate the mass of solute for the preparation of the 0.01 M solution of silver nitrate (250 mL) and the
standard solution of 0.015 M sodium chloride (100 mL).

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General Analytical Chemistry Degree in Chemistry-Universidad de Santiago de Compostela

CHEMICALS
1.- Supplied:
- Silver nitrate, AgNO3 (169.96 g / mol).
- Sodium chloride, NaCl (58.43 g / mol). Dry the reagent at 105-110 ° C in an oven for one hour, allow to
cool and keep in a desiccator.
- Sodium hydrogen carbonate, NaHCO3 (84.01 g / mol)
- Indicator solution of 5% chromate (w/v): prepared by weighing 5 g of potassium chromate in 100 mL of
deionized water
- Deionized water
2.- Prepare:
- Silver nitrate solution of 0.01M
- 0.015M sodium chloride solution
CAUTION:
- Check on the label of the containers the water content of the reagents
- Silver and chromium compounds are toxic. Silver solutions can cause burns and skin blemishes.

MATERIAL
250 mL Conical flasks, 250 and 100 mL volumetric flasks, 250 mL beakers, 50 mL burette, 1 and 10 mL
pipettes, watch glasses, stirring rod, analytical balance

LITERATURE
Holler & Crouch, Skoog and Wert Fundamentals of Analytical Chemistry, 9th edition; Cengage, 2014.

FINAL CALCULATIONS
Determine the exact concentration of chloride contained in the sample, expressed as mg/L

QUESTIONS
1.- Why is it necessary to adjust the reaction pH to 8?
2.- What are the possible interferences in this method?
3.- Briefly describe the basis of the other volumetric precipitation methods used to determine halides
4.- Could the determination of chloride in water be carried out using a gravimetric method?

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General Analytical Chemistry Degree in Chemistry-Universidad de Santiago de Compostela

EXPERIMENT 4: DETERMINATION OF CARBONATE AND BICARBONATE

IN A WATER SAMPLE. INDIRECT METHOD

OBJECTIVES
The objective of this experiment is to carry out the determination of carbonate and bicarbonate in an
aqueous sample by means of an indirect titration method. The most relevant experimental procedures
used in acid base titrations are implemented; in this case, from the total alkalinity and the bicarbonate
concentration, the initial carbonate concentration is calculated.

INTRODUCTION
In this experiment, two titrations will be carried out. In the first one, total alkalinity (due to bicarbonate
and carbonate) is determined by titration of the sample with a standardized solution of HCl, of exactly
known concentration, to the end point of methyl orange.

Another aliquot of the sample is treated with an excess of NaOH to convert bicarbonate to carbonate.
Then, all the carbonate is precipitated with barium chloride. The excess of NaOH (not used to transform
bicarbonate to carbonate), is immediately titrated with the standardized solution of HCl and
phenolphthalein as indicator, and thus the amount of bicarbonate present can be determined.

From the total alkalinity and the bicarbonate concentration, the initial carbonate concentration is
calculated.

Note: HCl is not a primary standard type substance and therefore its solution should be standardized
against a primary type standard before proceeding with the titration of the sample (the procedure is
indicated below). NaOH is also not a primary standard type substance. As a standardized solution of
NaOH must be used to carry out the titration, it will be supplied by the instructor.

EXPERIMENTAL PROCEDURE

HCl Standardization
1.- Prepare a solution of approximately 0.1 N HCl from concentrated HCl.
2.- Dry the primary standard sodium carbonate for about 1 hour at 110 ° C and cool in a desiccator. This
operation has already been done previously by the instructor (take the dried sample directly from the
desiccator). Prepare a 0.0800 N solution of sodium carbonate.
3.- Pipette 10 mL of the previous solution into a 250 mL conical flask, add 3 or 4 drops of indicator
(methyl orange) and 50 mL of distilled water. Titrate with 0.1 N HCl until the solution just changes from
orange to pink. Repeat the titration to get at least two concordant readings.
4.- Calculate the average normality of HCl.

Test sample analysis

Aliquot 1. Pipette 10 mL of the sample into a 250 mL conical flask, add 3-5 drops of methyl orange and
titrate with the standardized 0.1 N HCl solution to the end point (from orange to pink). Record the final
volume.
Perform two additional titrations on the same sample.
Aliquot 2. Pipette 10 mL of the sample into a 250 mL conical flask, add 20 mL of the 0.1 N NaOH
solution (of exactly known concentration and supplied by the instructor). Stir and add 10 mL of 10%
BaCl2 (w/v) using a graduated cylinder. Stir again to precipitate barium carbonate, add 3-5 drops of
phenolphthalein indicator and immediately titrate with the standardized 0.1 N HCl solution to the end
point (when the pink color disappears). Record the final volume.
Do two additional titrations on the same sample.

From aliquot 1, calculate the total alkalinity. From the results of aliquot 2, calculate the bicarbonate
concentration. Finally, calculate the carbonate concentration in the sample.

PREVIOUS CALCULATIONS
Calculate the amount of each chemical needed for the preparation of the 0.1 N solution of HCl (250 mL),
the standard solution of 0.0800 N sodium carbonate (100 mL) and 10% barium chloride (w/v) (50 mL)

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General Analytical Chemistry Degree in Chemistry-Universidad de Santiago de Compostela

MATERIAL
250 mL Conical flasks, 50, 100 and 250 mL volumetric flasks, 250 mL beakers, 50 mL burette, 10, 25
mL graduated pipettes, graduated cylinder, watch glasses, rods, analytical balance

CHEMICALS
1.- Supplied:
- HCl (c)
- Barium Chloride (solid)
- Sodium hydroxide of exact concentration.
- Sodium carbonate (solid)
- Indicators: methyl orange; phenophthalein
- Test sample

2.-Prepare:
- HCl approx. 0.1 N. 250 mL
- Barium chloride 10% (w/v) 50 mL
- Standard solution of 0.0800 N sodium carbonate. 100 mL

BIBLIOGRAPHY
D.C. HARRIS, Quantitative Chemical Analysis, Ninth Edition.; W.H. Freeman, 2016.
Holler & Crouch, Skoog and Wert Fundamentals of Analytical Chemistry, 9th edition; Cengage, 2014.

FINAL CALCULATIONS
Calculate the concentration of carbonate and bicarbonate in the sample. Express the results in carbonate
and bicarbonate molarity.

QUESTIONS
1.- What happens to the carbonate and bicarbonate ion when HCl is added?
2.- Why is it necessary to precipitate all the carbonate with barium ion?
3.- Which reaction takes place between carbonate and barium chloride?
4.- Which reaction takes place between bicarbonate and NaOH?
5.- During the process of standardization of the HCl solution, will the same analytical error be recorded if
phenolphthalein is used as an indicator instead of methyl orange?
6.- In aliquot 1, methyl orange is used as an indicator to determine total alkalinity. Could phenolphthalein
be used? Justify the answer
7.- When evaluating aliquot 2, phenolphthalein is used as an indicator, could methyl orange be used?
Justify the answer.
8.- In step 3 of the HCl standardization, do the 50 mL of water added have to be exact? Justify the
answer.
9.- Sodium hydroxide is not a primary standard, how could the NaOH solution be standardized?

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General Analytical Chemistry Degree in Chemistry-Universidad de Santiago de Compostela

EXPERIMENT 5: DETERMINATION OF CARBONATE AND BICARBONATE

IN A WATER SAMPLE. DIRECT METHOD
OBJECTIVES
The objective of this experiment is to determine the content of carbonate and bicarbonate in a water
sample. The most relevant experimental procedures used in acid base titrations are implemented in a
direct titration method.

INTRODUCTION
In the first stage of this experiment a hydrochloric acid solution is standardized. Sodium carbonate is
used, which is an excellent primary standard, following the reaction:

Na2CO3 + 2 HCl →CO2↑ + H2O + 2 NaCl

i.e.:
1) Na2CO3 + HCl → NaHCO3 + NaCl

2) NaHCO3 + HCl → CO2 + H2O + NaCl

Subsequently, the carbonate/bicarbonate present in the sample react with HCl as follows:
a) Na2CO3 + HCl -----> NaCl + Na HCO3
b) Na H CO3 + HCl -----> NaCl + CO2 + H2O
b’) Na H CO3 +HCl -----> NaCl + CO2 + H2O

This method uses 2 indicators:

a) PHENOLFTALEIN that turns at the first point of equivalence of the carbonate titration curve at pH =
8 from pink to colorless.
b) METHYL ORANGE that shows the end point of the titration at pH = 4 and turns from orange to pink.

EXPERIMENTAL PROCEDURE

HCl Standardization
1.- Prepare a solution of approximately 0.1 N HCl from concentrated HCl.
2.- Dry the primary standard sodium carbonate for 1 hour at 110 ° C and cool in a desiccator. This
operation has already been done previously by the instructor (take the dried sample directly from the
desiccator). Prepare a solution of 0.1000 N sodium carbonate.
3.- Pipette 20 mL of the previous solution, add 3 or 4 drops of the methyl orange indicator and 50 mL of
distilled water. Titrate with the 0.1 N HCl until the solution turns from orange to pink. Repeat the titration
to get at least 2 concordant reading.
4.- Calculate the average normality of HCl.

Determination of the content of sodium carbonate and bicarbonate in a sample

Pipette 20 mL of the sample into a conical flask and dilute with distilled water to approximately 100 mL.
Add 2-4 drops of phenolphthalein solution, titrate with the standardized 0.1 N HCl solution until the pink
color disappears. The titrant value is recorder as phenolphthalein end point.
Then add 2-4 drops of methyl orange indicator to the same solution and the titration is continued until a
pink colored end point is obtained. The titrant value from the beginning of the titration is recorded as the
methyl orange end point.
Repeat the titration to get at least two concordant readings.

PREVIOUS CALCULATIONS
Calculate the mass of reagents for the preparation of the standard solution of 0.1000 N sodium carbonate
(250 mL), and that of approximately 0.1 N HCl (500 mL).

MATERIAL
250 mL Conical flasks, 250- and 500-mL volumetric flasks, 250 mL beakers, 50 mL burette, 10- and 25-
mL graduated pipettes, graduated cylinder, watch glasses, rod, analytical balance

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General Analytical Chemistry Degree in Chemistry-Universidad de Santiago de Compostela

CHEMICALS
1.-Supplied :
- Na2CO3 (s)
- HCl (c)
- Solution of methyl orange (heliantine)
- Solution of phenolphthalein.
- Test sample

2.-Prepare:
- HCl solution approximately 0.1 N, 500mL.
- Solution of Na2CO3 0.1000 N, 250mL.

LITERATURE
D.C. HARRIS, Quantitative Chemical Analysis, Ninth Edition.; W.H. Freeman, 2016.
Holler & Crouch, Skoog and Wert Fundamentals of Analytical Chemistry, 9th edition; Cengage, 2014.

FINAL CALCULATIONS
Determine the concentration of carbonate and bicarbonate in the sample, express both results in g/L and
ppm.

QUESTIONS
1.- What is the equivalent weight of sodium carbonate?
2.- What is the acid-base indicator used in the titration of the hydrochloric acid solution? Why does its
color change?
3.- Why are two indicators used during sample titration? How important is the pH on indicators
performance?

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General Analytical Chemistry Degree in Chemistry-Universidad de Santiago de Compostela

EXPERIMENT 6: DETERMINATION OF Ca (II), Mg (II) AND HARDNESS OF

A WATER
OBJECTIVES
The objective of this experiment is to determine the concentration of calcium and magnesium and the
hardness of a water by a complexometric titration. The most relevant experimental procedures used in the
titrations with EDTA and metal ion indicators are implemented.

INTRODUCTION
Hardness is defined as calcium and magnesium ion content and is usually reported as mg of CaCO3 per
liter (ppm). Water hardness can be readily determined by titration with the chelating agent EDTA.
In this experiment, the total concentration of metal ions that can react with the EDTA (hardness) is first
determined. Ca2 + is then determined separately, after magnesium precipitation as Mg (OH)2 with a strong
base.

a) In hardness determination, the indicator eriochrome black T is used, which forms a very stable wine-
red complex, MgIn–, with the magnesium ion. As EDTA is added, it will complex free Ca2+ and Mg2+
ions, leaving the MgIn– complex alone until essentially all of the calcium and magnesium have been
converted to chelates. At this point EDTA concentration will increase sufficiently to displace Mg2+ from
the indicator complex; the indicator reverts to its uncombined form, which is sky blue, establishing the
end point of the titration.

Ca2++ H2Y2-  CaY2-+ 2H

+
Titration:

Mg + H2Y2-  MgY2-+ 2H
2+ +

Ca2++ Mg Y2-  Ca Y2- + Mg (The calcium complex is more stable,

2+

therefore as long as there is no complexed calcium, calcium can displace magnesium; When all calcium
has been complexed, magnesium is complexed by adding more EDTA).
Mg + HIn2- 
2+ +
End point: MgIn- + H (With EDTA defect)
MgIn- + H2 Y2-  Mg Y2- + HIn2- + H +

Wine red Colorless Colorless Blue

* Since the indicator requires traces of Mg2+ to operate properly, the addition of a known amount of
magnesium to waters poor in this ion is recommended.
b) The calcium in the sample is titrated at pH 12 and using murexide as an indicator. Calcium
forms a fairly stable pink complex with murexide; but less than the one that is formed with the EDTA.
The reaction that occurs at the end point of the titration:
4- 2-
Ca2+- Murexide + Y <-------> CaY + Murexide + H+
Pink Violet
Therefore, the equivalence point is detected by the color change of the solution from pink to violet;
However, this turn is not very clear, so murexide and green of naphthol B mixture can be used as an
indicator, which turns from green to blue, a color change that is much more noticeable.

EXPERIMENTAL PROCEDURE
Standardization of the EDTA solution
1.- Prepare 100 mL of the 0.005 M CaCl2 standard solution from CaCO3 as follows: Accurately weigh the
necessary amount of calcium carbonate. Then, add 1:1 HCl dropwise onto the solid, until the
effervescence ceases and the solution is clear. Dilute to the necessary volume in a volumetric flask.
2.- Prepare a solution of approximate 0.005 M EDTA
2.-Pipette 10 mL of the calcium chloride solution in to a 250 mL conical flask, add 5 mL of the pH 10
buffer solution, 0.5 mL of Mg-EDTA solution and a small amount of solid eriochrome black T indicator.
3.- Titrate with the 0.005 M EDTA solution to the end point when the color changes from wine red to
blue. Record the volume.
4.- Repeat the titration to get at least two concordant readings.
5.- Calculate the molarity of EDTA

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General Analytical Chemistry Degree in Chemistry-Universidad de Santiago de Compostela

Determination of the hardness of a water sample

Determination of the hardness. Transfer 200 mL of the sample into a 500 mL conical flask and add 6
mL of the pH 10 buffer solution and a small amount of solid eriochrome black T indicator. Titrate with
the standardized EDTA solution until color change (wine red to blue). Record the volume.
Repeat the titration to get at least two concordant readings.

Determination of calcium. Transfer 200 mL of the sample into a 500 mL conical flask. Add 4 mL of 2M
NaOH and stir for 2 minutes to precipitate Mg (OH)2 (which may be imperceptible). Add 0.5 mL of a
0.005M Mg-EDTA solution, a small amount of murexide and a small amount of naphthol green B, the
solution should be green. Titrate with the standardized EDTA solution until the end point, blue color.
Record the volume. The quantity of indicators is essential to get the right mix. If after several attempts,
the turn is not observed, murexide can be used alone, with a turn from pink to violet.
Repeat the titration to get at least two concordant readings.

PREVIOUS CALCULATIONS
Calculate the amount of reagent to prepare an approximately 2 M 50 mL NaOH solution, an approximate
0.005 M 250 mL EDTA solution from Na2H2Y.2H2O and a 0.005 M 100 mL solution of calcium chloride
from calcium carbonate.

MATERIAL
500 mL Conical flasks, 50, 100 and 250 volumetric flasks, 250 mL beakers, 50 mL burette, 10- and 25-
mL graduated pipettes, watch glasses, rods, auxiliary balance, analytical balance

CHEMICALS
1.-Supplied:
- NH3 (commercial solution) - Hydrochloric acid (c)
- Sodium hydroxide (solid) - EDTA (solid, disodium salt)
- Indic .: Eriochrome black T, murexide, Naphthol green - Calcium carbonate (solid)
- 0.005 M Mg-EDTA solution (solution already prepared by adding stoichiometric amounts of 0.01 M
EDTA and 0.01 M MgCl2).
- pH 10 buffer solution (100 mL): 57 mL of aqueous NH3 are added to 7 g of NH4Cl and diluted to 100
mL with distilled water.

2.-Prepare:
- NaOH solution, approximately 2 M. Prepare 50 mL.
- Solution of approximate EDTA. 0.005 M from Na2H2Yx2H2O. Prepare 250 mL.
- Standard solution of calcium chloride 0.005 M from calcium carbonate. Prepare 100 mL

LITERATURE
D.C. HARRIS, Quantitative Chemical Analysis, Ninth Edition.; W.H. Freeman, 2016.
Holler & Crouch, Skoog and Wert Fundamentals of Analytical Chemistry, 9th edition; Cengage, 2014.

FINAL CALCULATIONS
Calculate the total concentration of Ca2 + and Mg2 + in the test sample, as well as the individual
concentrations of each ion, expressed in molarity and in parts per million (ppm)

QUESTIONS
1.- In the titration of Ca2 + and Mg2 +, EDTA is present as H2Y2- while in the titration of calcium it is
present as Y4-. What is the reason for that?
2.- What is the mechanism of operation of metal ion indicators?
3.- What solutions, of those used in this experiment could be measured with a graduated cylinder? Justify
the answer

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General Analytical Chemistry Degree in Chemistry-Universidad de Santiago de Compostela

EXPERIMENT 7: DETERMINATION OF HYPOCHLORITE AND ACTIVE

CHLORINE CONTENT IN A BLEACH SAMPLE
OBJECTIVES
The objective of this experiment is to determine the content of hypochlorite and active chlorine in a
bleach sample using an indirect two-step procedure. The most relevant experimental procedures used in
redox titrations are implemented; In addition, the concept of normality is reviewed.

INTRODUCTION
In the first part of this experiment a solution of sodium thiosulfate (Na2S2O3) is standardized, which is
subsequently used as a titrating agent. Standardization consists in performing a IODOMETRY first (I2 is
released) and then a IODIMETRY (I2 is consumed). The reactions that take place are the following:
Cr2O72- + 6 I- + 14 H+ -----> 2 Cr3+ + 3 I2 + 7 H2O

3 ( I2 + 2 S2O32- -----> 2 I- + S4O62- )

Potassium dichromate is a primary standard and reacts with iodide in an acid medium, releasing iodine,
which will titrate with thiosulfate.

In the second part of the experiment, the content of hypochlorite and active chlorine in the bleach sample
is determined. This titration takes place as follows:

ClO- + 2 I- + 2 H+ -----> Cl- + I2 + H2O

I2 + 2 S2O32- -----> 2 I- + S4O62-

Hypochlorite first reacts under acidic conditions with an excess of iodide ion. The appearance of a
reddish-brown color due to the production of iodine is a sign that the reaction has occurred. Then, iodine
is titrated with a thiosulfate solution. The end point is when the last trace of yellow color disappears.
Because this change from pale yellow to colorless is not very distinct, a small quantity of starch solution
is added near the endpoint. Any iodine still present combines with starch to form a deep blue complex, so
the end point will be more clearly signaled by the disappearance of the blue color.
The concentration of bleach is normally reported as percent of mass or as ACTIVE CHLORINE, i.e. the
grams of Cl2 released when acidifying with HCl 100 g of bleach; that is, % chlorine equivalent to the
iodine released when treating hypochlorite in acidic medium in the presence of potassium iodide:

ClO- + Cl- + 2 H+ -----> Cl2 + H2O

(ClONa + 2ClH -----> Cl2 + H2O + ClNa)

EXPERIMENTAL PROCEDURE

Standardization of a solution of sodium thiosulfate (Na2S2O3 )

1.- Prepare 500 mL of sodium thiosulfate solution 0.1 N.
2.- Prepare 250 mL of potassium dichromate solution 0.1000 N,
3.- Pipette 25 mL of the 0.1000 N potassium dichromate solution into a 500 mL conical flask with frosted
neck and glass stopper, add 5 mL of concentrated HCl, distilled water up to approximately 200 mL.
4.- Add a small amount of solid potassium iodide, plug the conical flask quickly, shake and immediately
titrate with the 0.1N thiosulfate solution until the brown color of the solution due to iodine becomes pale
yellow.
5.- Add 1 drop of the starch solution, which will form a dark blue complex in the solution. Continue
titrating with thiosulfate solution, until the blue complex is not formed by adding starch solution, until a
green blue color appears.
6.- Repeat the titration to get at least two concordant readings.
7.- Calculate the normality of thiosulfate solution

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General Analytical Chemistry Degree in Chemistry-Universidad de Santiago de Compostela

Determination of hypochlorite and active chlorine content in the bleach sample

Pipette 2 mL of bleach into one of the conical flasks with frosted neck. Add 5 mL of acetic acid, 200 mL
of distilled water and a small amount of potassium iodide. Cover quickly and titrate with the standardized
thiosulfate solution.
When the color is pale yellow, add 2 drops of the starch solution and continue titrating, very carefully
(drop by drop), until the solution discolors.
Repeat the titration to get at least two concordant readings.

CALCULATIONS
Calculate the mass of sodium thiosulfate necessary to prepare 500 mL of the 0.1 N solution and the mass
of potassium dichromate to prepare 250 mL of a 0.1000 N solution.

MATERIAL
500 mL Conical flasks with cap, 250 and 500 mL volumetric flasks, 250 mL beakers, 50 mL burette, 2
mL and 10 mL graduated pipettes, watch glasses, graduated cylinder, rods, auxiliary balance, analytical
balance

CHEMICALS
1.-Supplied:
- Na2S2O3. 5H2O solid
- Solid potassium dichromate
- Solid potassium iodide.
- Concentrated HCl.
- Starch solution,
- Concentrated acetic acid
- Commercial hypochlorite sample (bleach).
CAUTION: Potassium dichromate should be handled with care, it is a recognized carcinogen

2.-Prepare:
- Solution of S2O32- approximately 0.1 N, 500 mL
- Standard solution of potassium dichromate 0.1000 N, 250 mL

LITERATURE
Holler & Crouch, Skoog and Wert Fundamentals of Analytical Chemistry, 9th edition; Cengage, 2014.

FINAL CALCULATIONS
Calculate the % of NaClO in the sample. Calculate the amount of active chlorine.

QUESTIONS
1.- Adjust the equations of the redox semireactions. What is the normality of thiosulfate?
2.- What is the equivalent weight of dichromate and thiosulfate in the reactions that take place?
3.- Why is a potassium iodide spatula tip added instead of weighing an exact amount of this reagent?
4.- Why is it necessary to cover the frosted flasks, after adding the reagents?
5.- What is the role of starch in this titration?
6.- In the case of the titration of the bleach sample, Why a colorless and not a bluish green solution is
obtained at the end point?

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General Analytical Chemistry Degree in Chemistry-Universidad de Santiago de Compostela

EXPERIMENT 8: DETERMINATION OF ORGANIC MATTER IN A FRESH

WATER SAMPLE
OBJECTIVES
The objective of this experiment is to determine the concentration of organic matter in a fresh water
sample using a redox titration. The most relevant experimental procedures used in redox titrations are
implemented; In addition, the concept of normality is reviewed.

INTRODUCTION
The most typical method to determine the amount of oxygen needed to oxidize the organic matter of a
water sample consists in the chemical digestion of it with potassium permanganate and is fundamentally
an index of easily oxidable carbonated matter by potassium permanganate.
The method uses potassium permanganate in acidic (sulfuric) medium as an oxidant. However, we must
previously standardize KMnO4 against a primary standard, in this case, oxalic acid. In an acid medium,
KMnO4 oxidizes the oxalate ion to carbon dioxide and water, following the reaction:
-
MnO4 + C2O4 + H
2- +
 Mn
2+
+ CO2↑ + H2O (Adjust the whole reaction)

This reaction proceeds slowly at room temperature, unless it is catalyzed with Mn (II) ions. Therefore, at
the beginning of the titration (perform with a warm solution), it takes a few seconds for oxalic acid to
discolor permanganate. When the concentration of Mn (II) ions in solution is already appreciable,
decolorization of KMnO4 occurs rapidly by autocatalysis.

For the determination of the organic matter, first the organic matter is oxidized with permanganate. The
amount of permanganate consumed is proportional to the organic matter in the sample. The excess of
permanganate not consumed by the sample is reduced with an excess of oxalic acid (or oxalate) and this
excess is back-titrated with the previously standardized solution of permanganate.

As the results are expressed as amount of oxygen consumed (mg/L units), this determination is also
designated as Chemical Oxygen Demand (COD). Values between 3-4 mg of oxygen/L correspond to non-
potable water, values greater than 4 mg/L to contaminated water.

EXPERIMENTAL PROCEDURE
Standardization of the permanganate solution
1.- Prepare 250 mL of 0.01 N permanganate solution
2.- Prepare 250 mL of 0.01 N of oxalic acid or sodium oxalate
3.- In a 250 mL conical flask add approximately 100 mL of distilled water and 5 mL of sulfuric acid (1:
3). To remove the organic matter that the flask and distilled water might have, add a few "milliliters
(drops) of the permanganate solution to a persistent pink color and boil the mixture 10 minutes with glass
beads (or porous dish). Now add a few drops of oxalic acid (or oxalate) until complete discoloration of
the conical flask content, and again, a few drops of permanganate until pale pink coloration. At this point,
the organic matter, that the water or the flask might have had, has been eliminated.
4.- Pipette 10 mL of the 0.01 N solution of oxalic acid (or oxalate) into the conical flask and titrate with
potassium permanganate (from the burette) to pale pink color proceeding as follows: add approximately
80% (7-8 mL) of the necessary permanganate, while the solution is stirred slowly and let stand until it
fades. Then heat up to 50-60 ° C and continue the titration. Persistence of the pale pink color for about 30
seconds indicates the end point of the titration.
4.- Repeat the titration to get at least to concordant readings.
5.- Calculate the normality of permanganate solution

Titration of a sample
Discard the contents of the flask from the previous titration, let it drain and, without washing it, add in it
100 mL of the water sample; add 5 mL of 1: 3 sulfuric acid and glass beads or porous dish. Heat and,
when it starts to boil, add 10 mL of the standardized potassium permanganate solution and let it boil for
exactly 10 minutes. Add 10 mL of oxalic acid (or more if 10 mL of acid has not been enough to discolor
the solution). Titrate the excess of oxalic acid with the standardized 0.01 N permanganate solution.

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General Analytical Chemistry Degree in Chemistry-Universidad de Santiago de Compostela

Determination of the organic matter content in a water sample

In water analysis, the amount of organic matter is expressed by the number of mL of 0.01 N
permanganate that reduces a liter of water, or by the amount by weight of permanganate that has been
employed. However, it is often expressed as the amount of oxygen (usually in mg) released by
permanganate per a liter of water. To make this last , take into account the following equivalences:
1 mL KMnO4 0.01 N =0.000316 g KMnO4
1mL KMnO4 0.01 N= 0.00008 g oxygen

PREVIOUS CALCULATIONS
Perform the calculations to prepare 250 mL of 0.01N permanganate solution and 250 mL of 0.01 N oxalic
acid solution.

MATERIAL
250 mL Conical flasks with cap, 250 mL volumetric flasks, 250 mL beakers, 50 mL burette, pipettes,
watch glasses, graduated cylinder, rod, glass beads, cooker, granatario, analytical balance

CHEMICALS
1. Supplied:
- Potassium permanganate (solid)
- Oxalic acid (solid)
- HCl (c).
- H2SO4 (c)
2.-Prepare:
- Solution of permanganate 0.01 N (store in amber bottle). Prepare 250 mL.
- Solution of 0.01 N oxalic acid or sodium oxalate 0.01 N. Prepare 250 mL.
- Diluted sulfuric acid 1: 3 (3 water). Prepare 160 mL

LITERATURE
Holler & Crouch, Skoog and Wert Fundamentals of Analytical Chemistry, 9th edition; Cengage, 2014.

FINAL CALCULATIONS
Calculate the organic matter content in the water. Express the results in mg of O2 / liter of water

QUESTIONS
1.- Write the redox semireactions and the global reactions that take place.
2.- Establish the equivalent weight of permanganate and oxalic.
3.- Oxalate is an anion of a weak acid. If it is in a strong acidic medium, does it remain as such ion or will
it be protonated?
4.- Why should the permanganate solution be stored in a dark jar? Why is it not possible to consider it as
a primary standard?
5.- Why is sulfuric acid added? What would happen during the titration if the medium is not acidic
enough?
6.- What is the primary standard used in this titration?
7.- What is the indicator used in this titration?

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General Analytical Chemistry Degree in Chemistry-Universidad de Santiago de Compostela

ANNEX
1.- Periodic table of elements

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General Analytical Chemistry Degree in Chemistry-Universidad de Santiago de Compostela

2.- Concentrations of commercial solutions of acids and bases

Acid/Base % (w/v) Density (g/mL)

HNO3 65 1,395

HCl 37 1,19

H2SO4 96 1,84

Acetic Acid 100 1,052

NH3 25 0,905

3.- Purity of the solid chemicals

Chemical Purity (%) Chemical Purity (%)

NH4NO3 98 BaCl2.2H2O 100

Ba(NO3)2 100 KI 100

CaCO3 100 K2Cr2O7 100

AgNO3 100 Na2S2O3.5H2O 100

NaHCO3 100 Na2CO3 100

NaCl 100 NaOH 100

Tartaric acid 100 Oxalic acid.2H2O 100

EDTA- KMnO4
100 98
Na2x2H2O

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General Analytical Chemistry Degree in Chemistry-Universidad de Santiago de Compostela

4.- Example of an experiment report in the laboratory notebook

Title of the experiment
1. Principle (including reaction equations)
2. Preparation of solutions
a. Previous calculations
b. Weights and concentration calculations (only for the primary standard)
3. Standardization of the titrant agent:
a. Data
Solution in the conical flask:
Solution in the burette:
Indicator:
Nº Volume of primary Burette reading
standard (mL) (mL)
1
2
3
Concordant readings average

b. Calculation of the concentration of the given solution

4. Sample analysis
a. Data
Solution in the conical flask:
Solution in the burette:
Indicator:
Nº Volume of primary Burette reading
standard (mL) (mL)
1
2
3
Concordant readings average

b. Calculation of the concentration of the given solution

5. Results
6. Answer to questions

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