MUKHANBETOVA NAZIRA

EXPERIMENTAL LABORATORY MANUAL

on discipline ANALYTICAL CHEMISTRY

CHEMICAL METHODS OF ANALYSIS:

TITRIMETRY and GRAVIMETRY
(part 1)

for the students of technical specialities

Nur-Sultan, 2019

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 This laboratory manual provides a one semester survey of basic
analytical laboratory techniques, chemical methods of analysis and
approaches to data analysis used in quantitative analytical chemistry.
The new edition of the lab manual emphasises chemical principles as
well as laboratory techniques. The manual helps students understand the
timing and situations for the various techniques. Each experiment is presented
with concise objectives, a comprehensive list of techniques, and detailed lab
intros and step-by-step procedures. This is done in the introductory section of
the manual, the individual lab introductions, and through extension questions
requiring research about traditional, more hazardous experimental methods.
Experimental laboratory manual is intended for students of specialty
5В072700 – «Food technology», 5В072800 – «Technology of processing
production», 5В070100 – «Biotechnology».

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 Content
page
1. INTRODUCTION 4
2. METHODICAL RECOMMENDATIONS ON THE 5
IMPLEMENTATION OF LABORATORY WORK
3. WORK SAFETY INSTRUCTIONS FOR PERSONS WORKING IN
CHEMICAL LABORATORY
3.1 General rules of safety 8
3.2 Chemical Safety 9
3.3 Workplace Hazardous Material Information System 9
3.4 Purity grades of chemicals and reagents 12
4. MEASUREMENT UNITS COMMONLY USED IN ANALYTICAL 14
WORK
LABORATORY WORK 1. BASIC LABORATORY GLASSWARE 19
AND APPARATUS
LABORATORY WORK 2. GRAVIMETRIC ANALYSIS 39
2.1 PRECIPITATION METHOD 41
2.2 VOLATILIZATION GRAVIMETRY 60
LABORATORY WORK 3. GRAVIMETRIC ANALYSIS OF WHEAT 70
FLOUR
LABORATORY WORK 4. THE ACID BASE TITRATION 76
LABORATORY WORK 5. THE ACID BASE TITRATION OF FOOD 97
LABORATORY WORK 6. PRECIPITATION TITRATION. 104
ARGENTOMETRY. MOHR’S METHOD
LABORATORY WORK 7. ARGENTOMETRY. VOLHARD’S 126
METHOD
LABORATORY WORK 8. COMPLEXOMETRIC TITRATION 132
LABORATORY WORK 9. REDOX TITRATION. 155
PERMANGANATOMETRY
LABORATORY WORK 10. IODOMETRY 175
Glossary of Analytical Terms 193

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 1. INTRODUCTION

Analytical chemistry – science field evolving and adapting methods,

devices and strategy for obtaining information about chemical composition,
structure and energy state of substances.
Goals of analytical chemistry: to detect chemical elements, which
compose particular substance - qualitative analysis; to determine the ratios of
different elements in investigative substance – quantitative analysis.
Various substances differ from each other by composition, structure,
physical and chemical properties. Most of properties can be used to learn about
qualities, which distinguish substance from others. These qualities are analytical
signals. Methods of analysis are based on obtaining analysis signals and
measurement of intensity of signals. According to action, which gives analytic
signal, methods of analysis are divided into physical and chemical
instrumental methods. They are employed in both in qualitative and quantitative
analysis.
Chemical methods of analysis – methods based on chemical interaction of
atoms, molecules and ions. These methods are employed to detect characterize
chemical properties of element or ion. Methods of chemical analysis can be
divided according the type of chemical reaction, rate of chemical reaction and
advisability (gravimetry, titrimetry, gas analysis, kinetic methods of analysis).
Physical methods are based on different parameters of substance
radioactivity, electromagnetic properties, radiation. Also there are biological
methods – based on use of biologically active substances and biological systems,
and biochemical methods – when substances of biological origin are investigated
with chemical methods.
Lately combined methods are used more often. Analysis of chemical
composition of substance proceeds by following steps: choosing a sample;
preparation of sample for analysis; extraction of component to investigate,
purification; choosing method and scheme of analysis; disruption or solving of
sample, separation and concentration; measurement of physical properties of
sample, chemical reagent or product of chemical reaction; calculation of analysis
data; estimation of results reliability.
This manual written to help first year students of food science and
biotechnology in analytical chemistry laboratory work. Practical work, described
in this book, includes classical, mostly used in practice, essential for VA
absolvent methods of chemical and instrumental analysis. Classical methods, for
example, gravimentry and titrimetry (volumetric) analysis, are presented, as well
as votalization, alkalimetry, complexometry, sedimetry, redoximentry. Issue also
contains method of qualitative macroanalysis, information on buffer and colloid
solutions. Theoretical background is given in each chapter. Main concepts,
questions, samples of tasks are also presented. Manual contains safety
instructions for chemical laboratory worker and list of chemical reagents with
chemical formulas.

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 2. METHODICAL RECOMMENDATIONS ON THE
IMPLEMENTATION OF LABORATORY WORK in LABORATORY
CLASS

With today's familiar cry by students for relevance in course work,

analytical chemistry stands out as one example of a practical and useful subject.
Chemical analysis is used in many fields of science, clinical, biochemist's,
physiologist's and the engineer's laboratory. It is an intrinsic tool in geology,
oceanography, air and water pollution. Rare is the chemist who does not rely
frequently upon analytical chemistry for the solution of problems.
The wide utility of analytical chemistry is sufficient reason alone for
treating it as an individual course. Another reason, nearly as important, is that
the analytical course is one of the few where the student learns careful and
quantitative laboratory skills and techniques. The skills are critically important
for the environmental technician, physician, dentist, pharmacist, forensic
scientist, quality control technician and for those in many other professions.
Analytical chemistry becomes a little more exciting when the student realizes
that an incorrect blood analysis may endanger a patient's life, or that an error in
quality control analysis may result in serious financial loss for manufacturer.
Objectives:
The major objective of this course is to provide a rigorous background in
analytical chemistry. The secondary goal is to develop in you the student an
appreciation of the difficult task of judging the accuracy and precision of
experimental data and to show how these judgments can be sharpened by the
application of statistical methods. The third aim is to introduce the student too
wide range of techniques of modern analytical chemistry. The final goal is to
teach the laboratory skills that will give students competence in their ability to
obtain high-quality analytical data.
Major Learner Outcomes:
At the completion of Analytical Chemistry, the students are expected to
develop the knowledge and comprehension of the core concepts of Analytical
Chemistry. The students will have developed a set of fundamental skills that can
be applied to various analytical situations. These skills will include the
following:
A. Problem-solving skills. Students that complete this course will be competent
problem-solvers. They will be able to identify the essential parts of a problem
and formulate a strategy for solving the problem. They will be able to estimate
the solution to a problem, apply appropriate techniques to arrive at a solution,
test the correctness of their solution, interpret their results and connect the
solution to related areas science.
B. Experiential learning skills (laboratory skills). The students that complete
this course will demonstrate that they are competent experimentalists. They will
be able to design and set up an experiment, collect and analyze data, identify
sources of error, interpret their results and connect it to related areas of science.

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C. Computer skills. The students will demonstrate they are competent users of
basic computer software, such as word processing, spreadsheet, data acquisition,
graphing programs and be able to perform internet searches.
D. Presentation skills. The students will express (orally and in writing) their
understanding of core principals, the results of experiential learning activities
(laboratory experiments, field work), and their analysis of problems.

LABORATORY INFORMATION
Chemistry is an experimental science. Therefore, laboratory sessions are a
extremely important and integral part of the Analytical Chemistry course. Class
attendance and laboratory work are required. Each student is automatically
registered for the laboratory section. Each section will meet once a week for 2
hours.
The laboratory exercises are designed and scheduled to help you correlate
and comprehend the material presented in discussion/lecture that week. In light
of this, the information gleaned from laboratory experimentation is fair material
for exams and quizzes. If you cannot attend a laboratory period, it is to your
advantage to get caught up as soon as possible.
Laboratory Reports: Reports which are late will be assessed a 10%
penalty for each period beyond the due date.
Reports: A report for each laboratory experiment will be due one week
after the scheduled completion date of the experiment. The title of the
experiment, what analyte was determined, the mean value of the analyte, the
standard deviation, calculated confidence limits (all the required information
may be found in a single spreadsheet and associated graphs). The original
observations from your laboratory notebook, any computer generated data tables,
graphs, and calculations will also be included as attachments.
Each laboratory period: I will assume that you have read the appropriate
material in the laboratory text prior to the laboratory discussion session. A very
brief discussion of the theory behind the experiment will be presented. Included
in the brief discussion of the individual experiment will be any modifications to
the procedure.
Initially we will design and generate MS Excel spreadsheets together, but
as the semester progresses, I will expect you to take on more of the responsibility
of the design and generation of your own MS Excel spreadsheets.
All experimental data must be entered in ink into your carbonless
laboratory notebook with numbered pages.
Laboratory reports are to be turned in to the front of the box labeled
CHEM 5, which is available in Room 2301, prior to the beginning of laboratory
on the due date. All reports submitted after the beginning of laboratory on a
scheduled due date will be considered late and will incur the late penalties.
Unauthorized Experiments are forbidden. Since you can endanger not
only yourself but others as well, any violation of this rule constitutes grounds for
immediate dismissal from the course. A laboratory schedule is included as an
addendum.

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 Assessment: The expected learning outcomes for the course will be
assessed through in class exams, take-home quizzes, home practice tasks and
problems, theoretical questions and worksheets, non-graded homework
assignments, polling the class and related non-graded quiz activities, and
discussions in class and at optional out of class review sessions. In addition,
students will be given an opportunity to take a standardized examination in
analytical chemistry at the conclusion of the course.
Extra Credit Options: Students always ask if there is some extra credit
that they can perform. The following extra credit option is available, but
remember the word extra implies extra work must be done to receive the credit.
As you can see from the laboratory schedule there are a significant
number of experiments that we will be performing this semester. However, if
you are exceptionally efficient during the semester there is sufficient time and
experiments available for you to do one or two extra experiments to obtain extra
credit.
Academic Honesty: You are expected to comply with the student
responsibility rules. Academic dishonesty of any sort will not be tolerated.
Students caught cheating or plagiarizing will be dealt with according to the
policies of the University. Students are strongly cautioned not to cheat in any
way, as their academic careers will be adversely affected. It is the students’
responsibility to familiarize themselves with the University’s academic policy.
Students with Disabilities: I encourage students with disabilities,
including “invisible” disabilities such as chronic diseases, learning, and
psychological disabilities, to explain their needs and appropriate
accommodations to me during my office hour. Please bring a verification of
your disability.
VERY IMPORTANT NOTE:
All students who enrolled in Analytical Chemistry have taken a positive
step to enroll. This to me means we have a contract between us, you will attend
class on time regularly and I will commence classes on time and will conduct a
class that is designed to help you understand the concepts presented in this
chemistry class.
If for any reason you want to break this contract, you (the student) must
make and take a positive step to remove yourself from the roll sheet prior to the
last day to drop the class. If you do not then the grade recorded on the final day
of the semester will be the grade for the semester.
Stated more bluntly:
Dropping Policy: Dropping this course is your responsibility. Do not
expect me to drop you from this course! If you quit showing up, I will keep
giving zero scores to your missed activities/quizzes, exams, and laboratory
reports that will ultimately result in an F. Please drop the course yourself.

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 3. WORK SAFETY INSTRUCTIONS FOR PERSONS WORKING
IN CHEMICAL LABORATORY

3.1 General rules of safety

1 Only persons that are introduced to safety rules and first aid methods
are allowed work in chemical laboratory. Students' knowledge is tested.
Person, introduced to safety rules must sign in safety rules instruction journal.
2 Student must obey established order in the work place, take care of
his or her health and of colleagues' health, perform requirements of this
instruction. Students can't use devices, which have defects and must report
lecturer about them.
3 Ill and intoxicated persons are not allowed to work.
4 All works in chemical laboratory must be performed only if gas and
electricity supply systems work correct, and fume hood is functional.
5 Fire prevention requirements:
✓ Avoid actions, which can lead to conditions, favourable to fire.
✓ Students must be introduced to main fire elimination measures,
coordinate their actions during fire danger.
✓ Smoke only in area, specially set on this purpose.
6 Requirement for electricity safety:
✓ Electrical devices can be exploited only according to their instructions,
given by manufacturer.
✓ Don't use defect sockets, plugs, switches and other defect equipment.
✓ Electrical devices must be grounded, if it is required by use rules.
✓ Switch off electrical device if current flow outside circuit is noticed.
✓ Don't connect to one socket several high power devices, if their
requirement of current may exceed permeability of installation cables.
✓ Electricity distribution boards must be locked. It is forbidden to fix
devices connected to the electrical circuit.
✓ Remember, voltage up to 36 volts is not dangerous to human.
7 Work carefully with laboratory equipment, glassware and devices and
start work with them only after learned how to use them. If equipment is
broken, report to laboratory worker immediately.
8 Connection of the devices must be checked by laboratory assistant
before use.
9 If gas, water supply, canalization, electricity system defect is noticed,
report to laboratory worker.
10 If gas flow is noticed, close gas valve and don't switch on any
devices, which can induce flame or sparks.
11 When leaving laboratory, check if all electrical and gas devices are
switched off and if no water or gas flow is present. Last leaving laboratory
person is directly responsible for this requirement.
12 Each laboratory must contain: first aid medicaments, sand box for
fire
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extinguish, woolen blanket, resin gloves and shoes, resin carpet for isolation,
safety glasses.
13 If accident took place, help injured person with first aid and call
emergency medical service if is needed, use telephone number 103.
14 Report accident to leader and don't change anything in accident
location, unless it causes danger to people. Necessary changes must be noted
in act.
15 Personal care:
✓ Work only with clean laboratory robes.
✓ Wash hands before and after work with warm water and soap, use
disinfection and neutralization measures.
✓ Don't keep food at the work place, eat only in special place.

3.2 Chemical Safety

1. The vapours of many organic solvents are flammable or combustible.
Do not expose electric sparks, open flames and heating elements to organic
solvent vapours. UNLESS OTHERWISE STATED, ASSUME ALL
ORGANIC SOLVENTS ARE FLAMMABLE.
2. Many chemicals (solid, liquid or vapour) are poisonous. Do not taste
chemicals. If it is necessary to smell a chemical, do so by fanning the vapours
towards your nose. Never inhale directly. Avoid inhaling dust or fine powders.
Use fume hoods and personal protective equipment when necessary.
3. Do not pipet with your mouth.
4. Be extremely careful when transferring, distilling or refluxing volatile
liquids.
5. Do not return used chemicals back to the stock container.
6. Do not tap flasks under vacuum.
7. Do not heat, measure or mix any chemicals in front of your face.
8. Never heat a closed system – it will act as a bomb!
9. Never pour water into concentrated acid. Pour acid slowly into water,
stirring constantly. Mixing acid with water is often exothermic.
10. Concentrated acids and bases are stored in the fume hood. Do not
carry them to your bench.
11. Make sure test tubes containing reactions are pointed away from
people, especially when they are being heated. Pressurized gas cylinders must
only be operated by the TA.

3.3 Workplace Hazardous Material Information System

WHMIS, is the name given to the legislation covering hazardous
materials used in Canadian workplaces, including educational institutions. In
basic terms, suppliers are required to adequately label their products and
provide accompanying Material Safety Data Sheets (MSDS), employers are
required to educate workers and ensure that the appropriate safety information
is available to the employees, and employees are required to learn the
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information on hazardous products before using them. In Chemistry
laboratories, you are the employee, and therefore, are required to know the
properties of the chemicals you will be handling before you enter the
laboratory.
Apart from requiring that MSDS be available to workers, one of the
other important aspects of WHMIS is the requirement for clear labels and
hazard symbols on hazardous products. The following eight hazard symbols
should be used as guides for the handling of chemical reagents:

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Emergency Procedures:
✓ Become familiar with the location of the safety showers, eyewash stations,
first aid kits and fire extinguishers. Remember, every sink with a hose can
act as an eyewash station.
✓ Know the route you are supposed to take in case of an evacuation.
✓ If your clothes catch on fire, STOP, DROP and ROLL.
✓ In a potentially life threatening emergency situation, notify your TA and
call 911.
✓ For non-life threatening security emergency situations, notify your TA
and call Campus Security.

First Aid
Burns represent the most common injury in the chemistry lab. They are
generally of either the thermal or chemical type. First aid for surface burns of
the thermal type involves immersing the burned part in cool water or applying
an ice pack to relieve pain and prevent swelling and blistering. The burn is
then covered with a clean, sterile, lint-free dressing. Do not apply lotions,
ointments or oily dressings. For more serious burns involving deeper layers of
skin and tissue, arrange for immediate medical aid.
To minimize injury due to chemical burns, the chemical must be
removed from the skin immediately. Flush liquid chemicals away with water;
continue to flush for 20 minutes. Continue first aid as for a thermal burn
(preceding paragraph). Medical attention should always be sought in the case
of chemical burns, especially as delayed reactions are not uncommon.
Chemicals Spilled on the Skin Over a Large Area. Quickly remove
all contaminated clothing while using the safety shower to flush the chemical
from the skin. Time is of the essence here and there is no place for modesty.
Continue to flush the affected area with water for at least 20 minutes. Do not
use chemical neutralizers. Treat any chemical burns as outlined in the Burns
section above.
Chemicals Spilled on the Skin Over a Limited Area. Immediately
flush the affected area with cold water. Once again, time is of the essence. Do
not use chemical neutralizers. Treat any chemical burns as outlined in the
Burns section above.
Chemicals Splashed into the Eyes. Immediately flood the eyes with
water so as to dilute and eliminate the chemical. Hold the eyelids open to
facilitate the process. Flush the eyes for at least 20 minutes. Apply clean
dressings over both eyes and arrange for immediate medical aid, regardless of
the severity of the injury.
Accidental Ingestion of Chemicals. Contact the Poison Control Centre.
Relay the following information: identity of the poison, the quantity taken, the
route of entry into the body and the time elapsed since the ingestion. Follow
the instructions given for treatment.

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 Medical Aid is available from Student Health Services. If medical aid
is required, do not try to go by yourself. The TA in charge of the lab will
make arrangements to have someone accompany you.

3.4 Purity grades of chemicals and reagents

Chemicals and reagents play a critical role in the manufacturing and
testing of pharmaceutical products, medical devices, biologics, cell- and
tissue-based products, and many other healthcare-related solutions.
Lab reagent should have: 1) Guaranteed quality parameters: specified
purity and specified impurities issued on CoA; 2) Proper package and label;
3) Defined shelf life/expiration date.
Most of us working in laboratories use different chemicals but lack
required clarity on their grades. Validated Methods specify the grade of
reagents to be used. It is important to use specified grades otherwise errors
can arise due to contamination from reagents themselves. On the other hand
you can incur additional cost in analysis if you use a superior grade of reagent
when your analysis does not have such high purity requirements.
Laboratory reagents are classified on the basis of purity and intended
use. The following list describes the seven most common grades for
chemicals and reagents, from highest to lowest grade/purity:
1. ACS grade meets or exceeds purity standards set by the American
Chemical Society (ACS). This grade is acceptable for food, drug, or
medicinal use and can be used for ACS applications or for general procedures
that require stringent quality specifications and a purity of ≥95%.
2. Reagent grade is generally equal to ACS grade (≥95%) and is
acceptable for food, drug, or medicinal use and is suitable for use in many
laboratory and analytical applications.
3. USP grade meets or exceeds requirements of the United States
Pharmacopeia (USP). This grade is acceptable for food, drug, or medicinal
use. It is also used for most laboratory purposes, but the USP being followed
should always be reviewed prior to beginning to ensure the grade is
appropriate for that methodology.
4. NF grade meets or exceeds requirements of the National
Formulary (NF). The USP and the NF (USP– NF) jointly publish a book of
public pharmacopeial standards for chemical and biological drug substances,
dosage forms, compounded preparations, excipients, medical devices, and
dietary supplements. The listings here should be reviewed to determine which
would be considered equivalent grades.
5. Laboratory grade is the most popular grade for use in educational
applications, but its exact levels of impurities are unknown. While excellent
for teaching and training, it is not pure enough to be offered for food, drug, or
medicinal use of any kind.

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 6. Purified grade, also called pure or practical grade, meets no official
standard; it is not pure enough to be offered for food, drug, or medicinal use
of any kind.
7. Technical grade is used for commercial and industrial purposes;
however, like many others, it is not pure enough to be offered for food, drug,
or medicinal use of any kind.
ACS, Reagent, and USP-NF grades are typically equivalent and
interchangeable but, even so, appropriateness should always be confirmed
before application. This can be done by reviewing the applicable regulatory
requirements.
Lab, purified, and technical grades have their own uses. For example,
lab-grade chemicals, because of their low cost and good chemical purity, are
used widely in educational applications, such as teaching laboratories at both
the secondary school and college levels; however, lab-grade chemicals would
not be appropriate for use in the quality control laboratory of a pharmaceutical
or medical device manufacturer. ACS-, USP-, or reagent-grade chemicals
should be applied in this setting, because they have fewer impurities that
could ultimately impact patients taking the drugs made with those chemicals.
With seven different and in equivalent types of chemical purity grades,
it is crucial to understand how they can impact products. Using a lower-purity
grade than a product’s intended use requires could be a costly mistake.
Similarly, using a higher-purity grade when not required could result in
unnecessary costs. Add in the increased regulatory scrutiny and it becomes
even more important to have a complete understanding of the components
that your process requires.
Table 1 lists the properties of commercial acids and bases commonly
used in environmental laboratories. To prepare a dilute solution, cautiously
add the required amount of concentrated acid/alkaline as received, and mix to
a designated volume of the proper type of distilled water. Dilute to 1 L and
mix thoroughly.
Table 1. Preparation of Acid and Alkaline Solutions

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 4. MEASUREMENT UNITS COMMONLY USED IN ANALYTICAL
WORK

As an analytical scientist your main concern would have been to report

your findings in terms of what is present in your sample and in what amount.
Most instruments convert input in other units to concentration or other
required units. You might be inclined to think that it is sufficient to have a
knowledge of concentration units and their interconversions. An
understanding of different units is bound to give you a better understanding
on how the systems function to give you the desired results.
All analytical measurements are based on the three basic fundamental
units of length, mass and time. The results are expressed in quantities derived
from these fundamental units. Let us now look into the different properties in
analytical work and their quantification units.
Length. The SI unit for length is meter which in absolute terms is the
length traversed by light in vacuum during a time interval of 1/229792458 of
a second. The old prototype of the meter is still preserved at the International
Bureau of Weights and Measures. The meter is too long a unit for expressing
molecular/ atomic dimensions and wavelengths of electromagnetic radiation.
These are expressed in subunits of the meter.
1 m = 10-6 m
1 nm = 10-9 m
1 cm-1 = 1/wavelength (nm)
Mass. The kilogram is equal to the mass of international prototype of
kilogram. A gram is 1/1000 of the weight of the kilogram. However, in most
analytical work even gram is considered to be too large quantity and masses
expressed in fractions of the gram.
1 Kg = 1000 g
1 mg = 10-3 g = 10-6 Kg
1 g = 10-6 g = 10-9 Kg
1 pg = 10-9 g = 10-12 Kg
Time. A second was originally defined as 1/86400 fraction of the mean
solar day. The definition has since been revised and the accepted definition
defines a second as the duration of 9192631770 periods of the radiation
corresponding to the transition between two hyperfine levels of the ground
state of Cs – 133 atoms.
Time measurements are important for reactions in kinetic studies,
chromatographic separations, radioactive measurements and fluorescence
studies. The units range several seconds to sub-fractions of a second.
1 ms = 10-3 s
1s = 10-6 s
1 ps = 10-9 s

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 Volume. Accurate measurement of volumes is necessary in titrimetry,
dilutions and quantitative reactions. Litre is too large a unit so fractions
commonly used in analytical work are:
1 ml = 10-3 L
1l = 10-6 L
The measurement of liquid volume can be performed using graduated
cylinders, volumetric flasks and measuring vessels. Unlike counting, which
can be exact, measurements are never exact but are always estimated
quantities. Obviously, some instruments make better estimates than others, so
more precise liquid volume is measured by calibrated measuring vessels:
• Pipette – vessel, used to suck, to drop and to measure liquid. Mohr
pipette measures only one, definite and marked on it volume. Graduated
pipettes allow measurement of any volume that would not exceed the volume
of pipette's graduated section. Such pipettes commonly are graduated with 0.1
ml scale and allow to measure volume in 0.005 ml precision.
Semimicropipettes and micropipettes can be graduated with 0.01 and 0.001
ml scale.
• Automatic micropipette – instrument, used to suck, to drop and to
measure liquid.
• Burette - glass tube (generally with 0.1 ml scale), used to drop and to
measure liquid volume. Semimicroburettes and microburettes can be
graduated with 0.01 or 0.001 ml scale.
• Measuring flasks – are used to measure various volumes and to
prepare various concentration solutions.
Volume of liquid, which is colorless and moistens surfaces, is measured
looking at the bottom of liquid's meniscus in the measuring vessels. Colorful
liquid’s volume, when we can't see the bottom of meniscus, is measured by
deducting according to a top of meniscus. Meniscus should be in a level of a
person who measures (Fig. 1).

Figure 1. Measurement of volume by watching meniscus

15
 Concentration expresses the amount of substance present in the
sample. It is the most important unit for expression of your results.
Moles – amount of substance that contains as many elementary entities such
as atoms, molecules, ions as there are in 0.012 to Kg of C – 12.
Molarity (M) – number of gram moles of solute in 1 L of solution i.e number
of modular weight expressed in grams.
Molality (m) – not in common use. It is the number of moles of solute
dissolved in 1 kg of solvent.
Normality (N) – number of gram equivalent moles of solute in 1 L of
solution.
ppm or ppb – concentration expressed in parts per million or parts per
billion.
1 ppm = mg solute/liter=1μg/ml
1ppb= 1μg solute/ litter =1 nanogram solute/ml
Percentage by weight is weight of solute needed to give the desired
concentration.
Percentage by volume is volume of solute required to give the desired
concentration.
Pressure measurements are necessary in measurements involving gases
and liquids and when expressing barometric pressure readings. It is defined as
the ratio of force to area over which the force is applied. SI unit is Pascal
which is 1 N/ .

Temperature. Precise temperature control is necessary in reaction

studies, volumetric measurements and chromatographic separations.
Temperature is the degree of hotness or coldness of a body. It is
expressed in degrees Kelvin (0K) where Kelvin is a fraction 1/273.16 of the
thermodynamic temperature of triple point of water. 0K is also referred to
as 0 C. Pure water has freezing point of 0°C and boiling point of 100 0 C at
mean sea level.
Energy measurements. All chemical reactions involve changes in
energy mainly as heat energy and light energy. Even at spectroscopic level
transitions involve energy changes which lead to identification and
quantification of elements and molecule species.
Heat should not be confused with temperature. The SI unit of heat is
Joule whereas in most thermal analysis calorie or millicalorie is in common
use.
1 cal is equal to amount of heat required to raise temperature of 1 g of
water by 1°C.
Light energy is necessary for initiation of certain photochemical
reaction processes. The common unit is Candela which is the illumination in a

16
given direction of a light source that emits monochromatic radiation of
frequency 540 Hz and radiant intensity of 1/ 683 watt per steradian.
Electrical units. All analytical instruments give response in electrical
units which gets converted to desired units such as pH, temperature, humidity,
concentration, pressure, resistance, conductance, etc. The electrical units are
based on measurements of current and voltage.
1 ampere is equal to current maintained in straight parallel conductors
of infinite length of negligible circular cross-section and placed 1 m apart in a
vacuum that would produce a force between them of 2* per meter of
length.
1 ma = 10-3 amp
1 μa = 10-6 amp
One volt is potential difference between two parallel, infinite planes
spaced 1 m apart that create an electric field of 1 N per coulomb. It is also the
potential difference between two points of a conducting wire when an electric
current of one ampere dissipates 1 watt of power between.
1mV=
1 µV =
1 ohm is resistance offered to flow of current of 1 ampere between two
points at a potential difference of one volt.
1mho is unit used for conductance measurements and is reciprocal of
ohm.
The coulomb is a measure of the quantity of electricity. If a current of 1
amp flows for 1 second, then 1 coulomb of electricity has passed.
That means that you can work out how much electricity has passed in a
given time by multiplying the current in amps by the time in seconds.
Number of coulombs = current in amps x time in seconds
Q = I*t
The Faraday. Electricity is a flow of electrons. For calculation
purposes, we need to know how to relate the number of moles of electrons
which flow to the measured quantity of electricity.
The charge that each electron carries is 1.60 x 10-19 coulombs. If you
ever needed to use it in an exam, you would be given the value.
1 mole of electrons contains the Avogadro constant, L, electrons - that
is 6.02 x 1023 electrons. You would also be given that in an exam if you
needed to use it.
That means the 1 mole of electrons must carry
6.02 x 1023 x 1.60 x 10-19 coulombs = 96320 coulombs
This value is known as the Faraday constant.
Absorbance (A) plays a vital role in spectroscopic studies such as UV -
Vis, Infrared, Atomic Absorption spectroscopy, etc.
𝐼𝑡
𝐴 = 𝑙𝑜𝑔
𝐼°

17
where It is intensity of transmitted light of a particular wavelength after
passing through the sample and I0 is the intensity before reaching the
sample. Absorbance being a ratio does not have units but conventionally it is
expressed in terms of absorbance unit AU.
Liquid density is measured with an aerometer or pycnometer. The
density of liquid depends on the temperature. If it is required to estimate more
exact density, the liquid needs to be thermostated up to normal temperature or
to recalculate the density, which is estimated in any temperature value, into
the density of normal condition (273.15 K temperature, 101.325 Pa pressure).
If there is not an aerometer or pycnometer, liquid density can be
estimated in a 50 ml or 100 ml measuring flask: it is balanced empty and dry -
a g, the same flask with deionized water is weighted – b g, and eventually the
same flask filled up to its mark with ascertainable liquid is balanced – c g,
Liquid density is estimated using formula:

An attempt has been made to introduce to you the units and their
importance in analytical work. As you gain proficiency in inter-conversions
you will start appreciating what you are doing and feel greater involvement in
your work.
In order to have to use the same units, a common set of fundamental
units, called SI units are defined which are given in Table 1.2. Some more
derived units and their equivalent SI units are given in Table 1.3. It is
advisable to practice to use only these units so that the basic tool of numbers
will be on same scale and international comparison of results is easy.
Table 1.2 Fundamental SI units

Table 1.3 Other SI and Non-SI Units

18
 LABORATORY WORK 1
BASIC LABORATORY GLASSWARE AND APPARATUS

Learning Objectives
1) To learn some basic analytical chemistry definitions and techniques
2) Understand the general function of analytical instruments
3) Knowing the proper use will help ensure safe laboratory practices

Have you seen a laboratory in your school? It is a place where

experiments are carried out and analyses are performed to reach a conclusion.
Most laboratories are well-organized and clean places that have
provisions to control conditions such as temperature, pressure, humidity,
etc. A good chemistry laboratory is fully-equipped with the basic measuring
and analytical laboratory apparatus that allow a good study of all the branches
of chemistry.
A chemistry laboratory should be equipped with the following
facilities:
1. Working table: It is a place where a chemist works. It should consist of
gas taps, sink, reagent shelf, waste paper basket, a side shelf for keeping
glassware apparatus, a fume closet and a gas cylinder.
2. Reagent shelf: All the reagents and chemicals should be kept in a reagent
shelf with proper labels.
3. Exhaust fans: A laboratory should have exhaust fans on top of the walls
with a vent to expel poisonous gases and fumes.
4. Balance room: There should be a balance room with a number of balances
for weighing chemicals. It should be free of dust and smoke for accurate
measurements.

COMMON LABORATORY APPARATUS AND EQUIPMENT

I list below name and descriptions of common laboratory glassware and
apparatus. As a chemist, you should be familier with all of them. You will
learn about:
• Beakers
• Erlenmeyer flasks, AKA conical flasks
• Florence flasks, AKA boiling flasks
• Test tubes, tongs, and racks
• Watch glasses
• Crucibles
• Funnels
• Graduated cylinders
• Volumetric flasks
• Droppers
• Pipettes
• Burets
19
 • Ring stands, rings, and clamps
• Tongs and forceps
• Spatulas and scoopulas
• Balances
The basic tool in all quantitative analyses is the analytical balance, used
for the accurate weighing of samples and precipitates. For
usual analytical work the balance should be able to determine differences in
mass of 0.1 milligram (about 0.000004 ounce). In microanalyses the balance
must be about 1,000 times more sensitive, and, for special work, balances of
even higher sensitivity have been constructed.
Analytical balances are designed for great precision in quantitative
chemical analysis. They yield readability to four decimal places to the right of
the decimal point (up to .0001 g). They are extremely sensitive and, since air
currents can affect their measurement, must be covered by a draft shield. They
are used for samples up to about 320 g. Top-loading balances, which can
measure objects up to 200 g, are less expensive but less exacting than
analytical balances. They are considered semi-analytical balances, with a
readability of up to three decimal places to the right of the decimal point (up
to .001 g). Precision balances have a readability of 0.01 g. They produce
steady readings in a wider range of environmental conditions than analytical
balances, being less sensitive to temperature fluctuations. They can have a
capacity from 600 g to 34,000 g.
Microbalances and ultra-microbalances are used to weigh the smallest
samples. They offer a capacity of up to 6 g with readability up to seven
decimal places to the right of the decimal point (.0000001 g). Moisture
balances measure the moisture content in a material sample by using halogen
heating with precise weighing technology.
Electronic scales and balances can provide weights in more than a
dozen units, including grams, kilograms, pounds, newtons, grains, and
ounces, and often in several operating languages. Application modes can be
set for statistics, formulation, differential weighing, density determination,
pipette calibration, parts counting, animal weighing, check weighing, percent
weighing, filling, gross-net-tare weighing, and statistical quality control.
Hence, it’s important to choose a balance that can report the information
specified by the laboratory protocols and quality control systems.
Balance use in the chemistry laboratory
1. Preparing the balance for use
• Before weighing anything on the analytical balance you must make sure
that it is leveled and zeroed.
• To check the leveling on the balance, look at the leveling bubble on the
floor of the weighing chamber. If it is not centered, center it by turning the
leveling screws on the bottom toward the back of the balance.

20
 • Once the balance is leveled, close all the chamber doors and press the
control bar on the front of the balance. After a few seconds, a row of zeros
will appear. This indicates that the balance is zeroed and ready for use.
2. Weighing a liquid, powder, or granular substance
✓ These substances must always be weighed using an appropriate
weighing container.
✓ Place the weighing container on the balance pan and close the doors.
✓ Tare the container by briefly pressing the control bar. The readout will
read zero with the container sitting on the pan. This allows the mass of
your sample to be read directly.
✓ Add the substance to be weighed. Be careful not to spill chemicals on
the balance. If need be, you can remove the container from the
weighing chamber while you add the sample provided that noone
presses the control bar before you weigh your sample.
✓ With the sample and its container sitting on the pan, close the chamber
doors and read the display to find the mass of your sample.
3. Weighing a solid object directly on the balance
If the object you need to weigh is a solid object, you can weigh it directly on
the pan. Be sure the balance is zeroed. Open the chamber doors, carefully
place the object on the balance pan, close the doors, and read the mass of your
object.
4. Cleaning up and shutting down the balance
When you are done with the balance, make sure you have properly cleaned up
any chemicals that may have spilled on the balance. At the end of the day, the
balance can be turned off by lifting up gently on the control bar.

Figure 2. Analytical balance

21
 LABORATORY GLASSWARE AND APPARATUS

Erlenmeyer flask (conical flask)

Beaker
Used for titration or filtration of
Used for measuring liquid roughly
liquids and to prevent air
volume with low accuracy
contamination to sample during work

Weighing bottles
Weighing dish
They are used for drying samples.
Hygroscopic samples are weighed by A weighing dish or boat is used for
difference, keeping the bottle capped direct weighing of samples.
except when removing the sample.

Graduated cylinder Test tube holder

Used for measuring liquid with better Used for holding test tubes
accuracy than beaker

22
 Crucible Mortar and Pestle

Used for burn sample at high Used for graining materials which have
temperature large particle size to small

Round bottom flask Volumetric flask

Used for distillation or heating Used for measuring liquid with high
of liquid, allows uniform heating accuracy

Pipette
Separatory funnel
Used for transfer exact amount of
liquid Used for Liquid-Liquid extracts,
designed for increase separation
efficiency

23
 Measuring pipets are
straight-bore pipets
marked at different
volumes.
They are less accurate than
volumetric pipets.

Single-channel and multichannel

digital
displacement pipets and microwell
plates

These syringe pipets can

reproducibly deliver a selected
volume.
They come in fixed and variable
volumes. The plastic tips are
disposable.

Buchner funnel Watch glass

Used for vacuum filtration using Used for air drying or oven drying of
filter paper liquid

Glass rode

Used for stirring

of liquid for
several purposes
Bottle are used for store reagents or
samples

24
 Funnel
Desiccator
Used for liquid transfer. Also for
Used for store material and protect it simple filtration
from air contamination or humidity

Bruch
Wash bottle
Used for cleaning of all types of
Used for dispensing small amount of glassware
liquid like solvent of distilled water

Boss head
Bottle dropper
Used for holding clamp with stand rode
Used mainly for indicators or in the distillation system
reagents

25
 Thermometer
Distillation head
Used for measuring temperature
Used for connecting distillation flask
with condenser and thermometer in
the distillation system

Condenser
Receiving adapter
Used for condensing volatile liquid
Used to connect condenser with during distillation
receiving flask in the distillation
system

Stand
Used
commonly as
base for Clamp
holding
distillation Used for holding glassware along with
system and stand and boss head
burette along
with clamp
and boss head

26
 Ring with boss head

Used for holding separatory funnel or

funnel along with stand Pipette bulb

Used along with pipette to suck liquid

Wire gauze

Bunsen burner Used for spread the head of burner

homogeneously
Used and heat source

Forcep

Used for holding small objects like

Filter paper filter paper
Used for filtration, available with different
pore size

27
 Dropper

Used for transfer liquid drop by drop

Heat Mantle

Used as source of heat, mainly for

distillation system

Balance

Centrifuge Used for measuring mass of materials

and samples
Used for separation of precipitations
from supernatant

28
 Burette

Used for titration where titrant pored

inside

Meniscus illuminator

Position the black field just below the

meniscus.

Avoid parallax error by reading at eye

level.

Bottle top dispenser

Burette Clamp

Used along with stand to hold burette

Used for transfer accurate amount from

the bottle (mostly used for acids and
organic solvent)

29
 Muffle furnace
Drying oven

Used to ignite samples at high Used to dry samples before weighing.

temperatures, e.g., to dry ash organic Usually 110o C used.
matter

Kjeldahl flasks

Wash Bottles: (a) polyethylene,

squeeze type;
(b) glass, blow type.

Use these for quantitative transfer of Use these for acid digestions. They are
precipitates and solutions, and for tilted while heating to avoid losses from
washing precipitates. “bumping”.

30
 Crucible and cover supported on a
wire
triangle for charring off paper

Heat or ignite the crucible to a

constant weight (to 0.3-0.4 mg)
before adding the filtered
precipitate.
Fold the filter paper over the
precipitate.
Drive off moisture at low heat. Then
gradually increase heat till the paper
begins to char.
After the paper is gone, ignite the
precipitate.

Filtering crucibles: (a) Gooch

crucible;
(b) sintered-glass crucible; (c)
porcelain filter crucible
Use for filtering non-gelatinous
precipitates

Magnetic stirrer
pH meter
It is a device which provides mixing
and keeping the chemical solutions It is used to determine the pH of the
and mixtures at a certain time and solutions prior to experiments and to
temperature by the help of a monitor pH value during experiments
magnetic bar

31
 Water bath

It is a water filled temperature

adjustable equipment used for
maintaining solution and mixture
samples in containers such as glass
tubes, glass bottles, beakers, flasks,
etc. at constant temperature during
the experiments

Procedure for filtering a precipitate

Figure 3. Proper technique for transfer of a precipitate

32
 The precipitate is transferred to the filter in several steps.
The first step is to decant the majority of the supernatant through the
filter paper without transferring the precipitate (Figure 3). Decant the solution
by pouring down the stirring rod. This prevents the filter paper from clogging
at the beginning of the filtration process. The precipitate is rinsed while it
remains in its beaker, with the rinsing decanted through the filter paper.
Finally, the precipitate is transferred onto the filter paper using a stream
of rinse solution. After decanting the mother liquor, add wash water to the
precipitate and decant again, repeating 2-3 times.
Then wash the precipitate into the filter. Any precipitate clinging to the
walls of the beaker is transferred using a rubber policeman (a flexible rubber
spatula attached to the end of a glass stirring rod).
An alternative method for filtering a precipitate is a filtering crucible.
The most common is a fritted-glass crucible containing a porous glass disk
filter. Fritted-glass crucibles are classified by their porosity: coarse (retaining
particles larger than 40–60 μm), medium (retaining particles greater than 10–
15 μm), and fine (retaining particles greater than 4–5.5 μm). Another type of
filtering crucible is the Gooch crucible, which is a porcelain crucible with a
perforated bottom. A glass fiber mat is placed in the crucible to retain the
precipitate. For both types of crucibles, the precipitate is transferred in the
same manner described earlier for filter paper. Instead of using gravity, the
supernatant is drawn through the crucible with the assistance of suction from
a vacuum aspirator or pump (Figure 4).

Figure 4. Procedure for filtering a precipitate through a filtering crucible.

The trap prevents water from an aspirator from back-washing into the suction flask.

Volumetric Glassware
In quantitative chemistry, it is often necessary to make volume
measurements with an error on the order of 0.1%, one part per thousand. This
involves using glassware that can contain or deliver a volume known to a few
hundredths of a milliliter, or about 0.01 mL. One can then report quantities
greater than 10 mL to four significant figures.

33
 Glassware designed for this level of accuracy and precision is
expensive, and requires some care and skill to give best results. Four main
types of volumetric glassware are common: the graduated cylinder, the
volumetric flask, the burette and the pipette. These have specific uses and will
be discussed individually. There are some points that are common to all types,
however. These involve cleanliness and how to read volumes accurately.
Cleanliness is essential to good results. Chemically clean glass supports
a uniform film of water, with no hanging droplets visible. Rinse your
glassware thoroughly with deionized water when you are finished with it. If
you are suspicious at all, wash it before you use it as well. With some types of
glassware, one "conditions" the apparatus by rinsing with a few small portions
of the solution one will be measuring prior to conducting the actual work.
This prevents water droplets from diluting one's solution, and changing the
concentration. More detail on how to do this will be given in the discussion of
the individual pieces of glassware.
All volumetric glassware is calibrated with markings used to determine
a specific volume of liquid to varying degrees of accuracy. To read this
volume exactly, the bottom of the curved surface of the liquid, the meniscus,
should be located at the scribed line for the desired volume. It is often easier
to see the meniscus if you put a white paper or card behind the apparatus. If
your eye is above or below the level of the meniscus, your readings will be
inaccurate due to the phenomenon of parallax. View the meniscus at a level
perpendicular to your eye to avoid this as a source of error.
Some volumetric glassware bears the label "TC 20°C" which stands for
"to contain at 20°C." This means that at 20°C, that flask will have precisely
the volume listed inside it. If you were to pour out the liquid, you would need
to get every drop out of it to have that volume. Alternatively, some volumetric
glassware bears the label "TD 20°C" which stands for "to deliver at 20°C."
This means that at 20°C, precisely the volume listed will leave it when the
contents are allowed to drain out of the vessel. It is not necessary to get every
last drop and, in fact, it is inaccurate to blow the last bit out of a volumetric
pipette.

Laboratory Experiment 1. Calibration of Volumetric Glassware

An important trait of a good analyst is the ability to extract the best
possible data from his or her equipment. For this purpose, it is desirable to
calibrate your own volumetric glassware (burettes, pipettes, flasks, etc.) to
measure the exact volumes delivered or contained. Volumetric glassware can
be calibrated by measuring the mass of water they contain or deliver. Glass
transfer pipettes and plastic micropipettes can be calibrated by weighing the
water delivered from them. A volumetric flask can be calibrated by weighing
it empty and then weighing it filled to the mark with distilled water.
This experiment also promotes improved technique in handling
volumetric glassware.
34
 To calibrate the glass we need a good analytical balance, and distilled
(or DI) water of known temperature. To be sure measurements are correct it is
a good idea to keep water, balance and calibrated glassware in the same room
long enough to be sure everything have the same temperature. Room doesn't
have to be thermostated, although temperature should not change during the
calibration process. It also won't hurt to calibrate the glass in the temperature
similar to the temperature in which it will be used, to minimalize later effects
of the glass and water thermal expansion.
Mass of the water can be converted to the volume using equation:

where V is a volume, m is a mass of water and d is density of water in the

given temperature. Density of water is listed in the table below:
temperature density g mL-1
°C
15 0.99913
16 0.99897
17 0.99880
18 0.99862
19 0.99843
20 0.99823
21 0.99802
22 0.99780
23 0.99757
24 0.99733
25 0.99707
26 0.99681
*** (taken from the International Critical Tables of Numerical Data, Physics, Chemistry
and Technology, vol. III)

Calibration of volumetric flasks. Weigh empty, dry flask. Fill it with

distilled water to mark. Weigh again. Mass difference is the mass of water.
Repeat 3-4 times.

Volumetric flask — for preparing liquids with volumes of high

precision. It is a flask with an approximately pear-shaped body and a long
neck with a circumferential fill line.

35
Calibrating 25 mL pipette
Correct use of the pipette:
1. Make sure that the pipette filler is dry and that any solution previously used
does not contaminate your sample. Fit it to the pipette and check that it is
working properly i.e. it draws solution into the pipette and the pipette does not
leak when held vertically. Do not force the filler onto the pipette in trying to
stop a leak - the pipette is likely to break and cause an injury.
2. Rinse the pipette with the solution it is to contain.
3. Fill the pipette again, so that the solution is above the graduation mark and
has no bubbles in it.
4. Wipe the outside of the pipette with a tissue or paper towel.
5. Adjust the solution correctly to the mark allowing the bottom of the
meniscus to sit upon the graduation mark, with the pipette held vertically and
viewed with the eye in line with the mark.
6. Touch the pipette tip against the inside of the vessel from which the
solution was taken to remove any drop of solution remaining on the outside of
the tip.
7. Release air into the top of the pipette (with some pipette fillers it is
necessary to remove the filler from the pipette at this stage) and let the
solution drain naturally (by gravity only) into the collecting vessel.
8. Hold the pipette vertically for five seconds after the last drop.
9. Touch the tip against the inside of the vessel - this removes some of the
solution held in the tip. The final portion of solution remaining in the tip
should not be expelled, because the calibration of the pipette will have
allowed for it.
10. Wash the pipette so that solution does not dry in it.
Do not:
a) Blow down the pipette.
b) Hold it by the bulb (hand warmth will alter the volume).
c) Allow solution to dry out in the pipette tip.
Note that you cannot check the accuracy of the pipette unless you know
that the balance and the thermometer are accurate too. However, you can
estimate the precision with which you can measure 25 cm3 with the pipette. If
the balance is correctly calibrated and set-up properly, the random error due
to weighing will be very small compared with that due to pipetting.
Dissolved air in the water affects its density. De-gas the water - the
usual techniques are by oiling, using an ultrasonic tank or bubbling helium
through it - about 10 minutes for 1 liter.
Inspect the pipette and the pipette filler. Ensure that the pipette is not
chipped and that the filler is clean and dry, otherwise the volume
measurements will not be correct. Fill the pipette with water and allow it to
drain out. Check that the tip is not blocked and the water drains freely. If the
pipette is clean no droplets of water will be left on the sides of the pipette. If
the pipette is dirty or blocked, clean it or select another one that is clean.
36
 Calibration Procedure:
1. Ask the laboratory supervisor to make the checks normally done in the
laboratory to ensure that the balance is working satisfactorily.
2. Check and record the temperature of the water.
3. Make sure that the weighing bottle is clean and dry, put it on the scale pan
and tare the balance to zero. An alternative: tare the balance before weighing
the bottle, and weigh it.
4. Use the pipette in the recommended manner (see above) to transfer 25 cm3
of water from the conical flask to the weighing bottle.
5. Return the weighing bottle to the balance and note the weight.
6. Empty the water from the weighing bottle back into the conical flask, dry
the beaker with a paper towel.
7. Repeat the steps 3-6 to obtain 10 weightings.
8. Check and record the temperature of the water again.
9. Calculate the volumes of the 10 pipettes, their mean and standard deviation.

Calibrating a 50-mL Burette

This procedure tells how to construct a graph such as Figure 1 in the
textbook to convert the measured volume delivered by a burette to the true
volume delivered at 20°C.
1. Fill the burette with distilled water and force any air bubbles out the tip.
See whether the burette drains without leaving drops on its walls. If drops are
left, clean the burette with soap and water or soak it with cleaning solution.
Adjust the meniscus to be at 0.00 mL, and touch the burette tip to a beaker to
remove the suspended drop of water. Allow the burette to stand for 2-5 min
while you weigh a weighing bottle flask fitted with a cup. If the level of the
liquid in the burette has changed, tighten the stopcock and repeat the
procedure.
2. Drain 10 mL of water slowly into the weighing bottle, and cap it tightly to
prevent evaporation. Allow 30 s for the film of liquid on the walls to descend
before you read the burette. Estimate all readings to the nearest 0.01 mL.
Weigh the weighing bottle again to determine the mass of water delivered.
3. Repeat the procedure for 20, 30, 40, and 50 mL. Then do the entire
procedure (10, 20, 30, 40, 50 mL) a second time.
4. Use the table in the textbook to convert the mass of water to the volume
delivered. Repeat any set of duplicate burette corrections that do not agree to
within 0.05 mL. Prepare a calibration graph like Figure 3-2 in the textbook,
showing the correction factor at each 10-mL interval.

SELF-CHEKING CONTROL QUESTIONS:

1. Your weight of water is converted to the true volume using data from
Table 27-3 of SHW. What are the three corrections that are embodied
in those values?

37
 2. Explain why it is not necessary to weigh the water samples on the
analytical balance.
3. When the glass of a burette expands due to an increase in temperature
does the diameter of the bore increase or decrease?
4. Most volumetric glassware is calibrated at what temperature?
5. What do the letters T.D. and T.C. that are found on various types of
volumetric glassware, signify?
6. What is an experiment?
7. What is a laboratory? Give characteristics of a good chemistry
laboratory.
8. What is apparatus?
9. How is a round-bottom flask different from a flat-bottom flask?
10.What is the difference between glass tube and glass rod?
11.How is a pipette different from a burette?
12.What is Bunsen burner? What is it used for?
13.Why is an analytical balance kept inside a transparent enclosure with
doors?
14.How is an experiment recorded?
15.List a few safety rules that you should follow while working in a
chemistry laboratory
16.Fill in the blanks.
a) __________ and __________ are used to crush, grind and mix solid
substances.
b) __________ is used for collecting gas during experiments.
c) A (spatula/dropper) is used to take _____ quantities of ____chemicals.
d) A glass rod is also known as __________ tube.
e) ____________ are used for stirring, mixing and heating liquids.
f) ____________ flasks allow more uniform heating and/or boiling of liquids.
g) An apparatus with a long narrow tube having a nozzle at one end and a
bulb in the middle is called ____________.
h) ____________ is also known as Erlenmeyer flask.
i) Solids are kept in ____________ while being weighed.
17. State whether the following statements are True or False. Correct the
false statements.
1. _____A china dish is used to evaporate liquids by heating.
2. _____A burette is also called a graduated cylinder.
3. _____A tripod stand is used for supporting apparatus while heating.
4. _____A dropper is used to take small quantities of solid chemicals.
5. ______A flat-bottom flask is used for heating liquids.
18. Choose the correct answer for each of the following.
1. Which of the following apparatus are made of glass?
a) Wire gauze and test tube
b) Test tube holder and beaker
c) Beaker and test tube
38
d) Round-bottom flask and test tube stand
2. Funnel is used for __________ chemicals.
a) heating b) storing c) stirring liquid d) pouring liquid
3. Given below are some apparatus and their use. Which of these is incorrect?
Apparatus Use
a) China dish Evaporating chemical solution by heating
b) Round-bottom flask Storing chemicals
c) Pestle and mortar To grind, crush and mix solid chemicals
d) Glass rod Stirring liquid chemicals
4. Which of these is used to evaporate a liquid, to hold solids while being
weighed or as a cover for a beaker?
a) Spatula b) Pestle and mortar c) Watch glass d) China dish
5. Which of the following apparatus is used for supporting glassware during
heating?
a) Test tube holder b) Wire gauze c) Beehive shelf d) Iron stand
6. Which of the following apparatus is used for heating liquids and titration
experiments?
a) Conical flask b) Pipette c) Measuring cylinder d) Burette

Reference
1. Chemistry Education Dept. (2010). Laboratory Work Manual ‘General
Chemistry Laboratory I’, Faculty of Mathematics and Science Education,
Yogyakarta State University.
2. Baker, R.W. et al. 2008. Chemistry 1 Laboratory Handbook. Sydney:
School of Chemistry, The University of Sydney.
3. Sienko, M.J., Plane, R.A and Marcus, S.T. (1984), Experimental
Chemistry, 6nd edition, Japan: Kosaido Co
4. Heasley, V.L., Christensen, V.J. and Haesley, E. 1997. Chemistry and Life
in the Laboratory, 4th edition. New York: Prentice Hall Inc.
5. Holum, J.R and Denison, D.C.1978. Laboratory Manual Fundamental of
General, Organic, and Biological Chemistry. 2nd edition, New York: John
Willey & Sons.

LABORATORY WORK 2
GRAVIMETRIC ANALYSIS

Objective:
• Mention the main steps of gravimetric analysis.
• Let's try to illustrate typical techniques used in gravimetric analysis.
• To perform and develop skills in Precipitation Gravimetric method of
qualitative analysis.

39
 Gravimetric analysis (GA) is a part of quantitative analysis and is
defines as the process of weighing an element or a definite compound of the
element in as pure form as possible. The determination of GA is depends on
transformation of the element into a pure stable compound which can be
readily converted into a form suitable for weighing. It involves the separation
of the constituents to be estimated in the form of an insoluble compound of
known composition. The insoluble compound is washed to make it free from
impurities, dried and weighed. From the weight of the compound,
composition and amount of constituent is calculated. Depending on the nature
of the sample, results are expressed in terms of percentage weight by weight
(w/w) or weight by volume (w/v).
Compare to volumetric analysis, GA is slow, time consuming and
tedious. However, result obtained by GA is very accurate. It is performed by
precipitation, filtration, washing, ignite on or drying method. GA is generally
applicable for analysis of standard which are used for calibration of different
instruments. For example determination of aluminium from alum or
determination of zinc as zinc oxide from zinc sulphate is done by gravimetric
methods. GA is quite complicated and gives less precision so pharmacopoeia
generally avoids AG when equally accurate methods are available.
Advantages of GA:
✓ Precise and accurate
✓ Errors are readily checked
✓ Absolute method
✓ Inexpensive apparatus
Disadvantages of GA:
✓ Time consuming
✓ Slow method
✓ Tedious
Application of Gravimetric Analysis:
✓ Analyze standard that are used for testing or calibration of instruments.
✓ Analyze the compound with high accuracy.
✓ Applicable only for those substances which form metallic compounds
on ignition and which do not contain volatile matter.
Gravimetric analysis is based on the quantitative isolation of the
desired constituent – the analyte of interest – from the sample in highly pure
form or in some combined form and weighing the isolated constituent. The
desired constituent is usually isolated or separated by precipitation. From the
weights of sample and precipitate, the percentage of the constituent in the
original sample can be calculated.
In a gravimetric analysis, isolation of an analyte may be carried out by:
1. precipitating it in an insoluble form,
2. depositing it as a pure metal by electrolysis,
3. converting it to a gas which is absorbed in a suitable reagent.

40
 Types of Gravimetric Methods
The four examples in the previous section illustrate different ways in
which the measurement of mass may serve as an analytical signal. When the
signal is the mass of a precipitate, we call the method precipitation
gravimetry. The indirect determination of PO33– by precipitating Hg2Cl2 is an
example, as is the direct determination of Cl– by precipitating AgCl.
In electrogravimetry, we deposit the analyte as a solid film an electrode
in an electrochemical cell. The deposition as PbO2 at a Pt anode is one
example of electrogravimetry. The reduction of Cu2+ to Cu at a Pt cathode is
another example of electrogravimetry.
When we use thermal or chemical energy to remove a volatile species,
we call the method volatilization gravimetry. Volatilization
gravimetry involves separating components of our mixture by heating or
chemically decomposing the sample. The heating or chemical decomposition
separates out any volatile compounds, which results in a change in mass that
we can measure. In determining the moisture content of bread, for example,
we use thermal energy to vaporize the water in the sample. To determine the
amount of carbon in an organic compound, we use the chemical energy of
combustion to convert it to CO2.
Finally, in particulate gravimetry we determine the analyte by
separating it from the sample’s matrix using a filtration or an extraction. The
determination of total suspended solids is one example of particulate
gravimetry.

2.1 PRECIPITATION METHOD

Precipitation method is a process of weighing an element in form of
precipitates which is separated by filtration from solution.
Factors affecting on precipitation method:
• Precipitates must be free from soluble impurities.
• Precipitates must be insoluble in solution.
• Precipitates must be readily separated from the solution by filtration.
• Precipitates must be convertible into a pure compound by ignition or by
simple evaporation.
Gravimetric precipitation analysis relies on the formation and collection
of a precipitate. This procedure involves a number of possible sources of
error. These are summarized below, along with their effect on the calculated
percentage oh the substance being analyzed.
Table 2. Sources of error in gravimetric analysis
Source of error Effect of error on the Minimising the error
calculated result
No substance is Less precipitate, Choose a substance of
completely insoluble. A therefore very low solubility as
small amount of underestimates. the precipitate. Use a
substance remains in minimum amount of
41
solution. solvent for dissolving
and rinsing.
Small amounts of Less precipitate, Handle the precipitate
precipitate are lost therefore carefully.
during transfers. underestimates.
Incomplete precipitation Less precipitate, Check filtrate for traces
occurs. therefore of substance by adding
underestimates. precipitating reagent
until no further
precipitate forms.
Incomplete rising of More precipitate, Rinse the precipitate
precipitate leaves therefore overestimates. carefully.
absorbed ions.
Incomplete drying of More precipitate, Dry to constant mass.
precipitate occurs. therefore overestimates.
Precipitate decomposes Less precipitate, Choose a stable
during drying. therefore precipitate.
underestimates.
More than one More precipitate, Select the precipitating
substance precipitates. therefore overestimates. reagent carefully.

Precipitation is effected by inorganic or organic precipitating agents.

Two common inorganic precipitating agents are silver nitrate, which is used
to precipitate halide ions such as chloride, and barium chloride, which is used
to precipitate sulfate ion. Potassium, ammonium, rubidium, and cesium ions
can be precipitated by sodium tetraphenylborate. In all of these precipitation
reactions, the product is a salt because it is formed by reactions between
cations and anions. Thus the bonding is ionic or electrovalent.
Organic precipitating reagents contain functional groups that combine
with inorganic ions to form insoluble salts. The organic reagent may contain
groups such as carboxyl or hydroxyl that ionize to form anions that combine
with cations to form insoluble salts. In this reaction, the bonding is also
electrovalent.
Some organic reagents contain nitrogen or oxygen that can combine
with metal ions by forming covalent or coordinate bonds.
Other organic reagents may contain two or more functional groups that
can combine with a single cation to form a ring structure. Such a reagent
would be called a bidentate ligand if it contained two functional groups, a
tridentate ligand if it contained three, and so forth. The product formed
between a cation and some multidentate ligand to form a ring structure is
called a chelate.
The factors which determine a successful analysis by precipitation are:
1) The reagent will react only with the analyte of interest to form a
precipitate,
42
 2) It forms one and only one product with the analyte and
3) That the analyte precipitates quantitatively from solution, that is,
>99.99%.
4) Precipitate must be formed quantitatively.
5) Precipitate must be formed within a reasonable time.
6) Its solubility should be low enough for quantitative separation. It
should be so slightly soluble, that its amount left behind in the solution
should not exceed 10-6 mol.
7) Weighed form of the precipitate must be in the form of a stoichiometric
compound of known composition. Failing this, it must be possible to
convert the precipitate to a stoichiometric weighable form (usually by
ignition).
8) Particle of the precipitate must be of such size that they do not pass
through the filtering medium and is unaffected by the washing process.
9) It should be easily and quickly filterable and it should be possible to
remove the soluble contaminations by washing the precipitate.
10) The precipitate must be free of impurities.
Operations used in Precipitation Gravimetric Analysis:
• Precipitation
• Filtration
• Washing
• Drying or ignition
• Weighing
• Calculation
Example: Gravimetric analysis of a sulphate or halides
Na2SO4 + BaCl2 → BaSO4 + NaCl
NaCl + AgNO3 → AgCl + NaNO3

1 SAMPLE PRETREATMENT. The first step in performing

gravimetric analysis is to dissolve the given sample and to prepare the
solution. Some form of preliminary separation may be necessary to eliminate
interfering materials. Also, adjustment of the solution conditions is necessary
to maintain low solubility of the precipitate and to obtain it in a form suitable
for filtration.
2 PRECIPITATION. Precipitation is an ionic reaction in which the
positive ion of one substance in solution combines with the negative ion of
another substance, also in a solution, to form a sparingly soluble substance.
Most of the precipitates encountered in analytical chemistry are sparingly
soluble salts which behave like strong electrolytes i.e. salt which are almost
completely ionized. The primary condition for precipitation of a substance to
take place from a solution is that the product of the ionic molar concentrations
of the substance should exceed the solubility product of the substance.
Typically, an analysis is carried out by causing the analyte to
precipitate from an aqueous solution. The precipitate is then filtered, washed
43
free of impurities, and converted to a product of known composition by
suitable heat treatment. This product is then weighed (this precipitate form is
called weighable). The amount of analyte originally present is then
determined using appropriate stoichiometric ratios.
Precipitation mechanism is an important step and the completeness of
precipitation of the desired constituent is determined by the solubility of the
constituent at equilibrium. Therefore, the precision of the analytical result
depends on the factors that affect the solubility of a precipitate namely the
choice of precipitant, the amount of precipitant added, the conditions of
precipitation, etc. which make the analytical results incorrect unless the
proper steps are taken.
Factors Affecting Precipitation:
1. Choice of precipitant: The precipitant should be such that it
produces a precipitate which is completely insoluble i.e. solubility product
should not exceed 10-6 mol. The structure of the precipitate formed should be
such so as to allow rapid filtration and washing. Organic reagents have a
special place in inorganic analysis (generally termed as organic precipitants)
because of the following advantages offered by them.
a) Many of the chelate compounds are very insoluble in water, so that metal
ions may be quantitatively precipitated.
b) The organic precipitant often has a high molecular weight. Thus a small
amount of metal may yield a large weight of precipitate, minimizing
weighing errors.
c) Some of the organic reagents are fairly selective, yielding precipitates
with only a limited number of cations. By controlling factors such as pH
and the concentration of masking agents, the selectivity of an organic
reagent can often be greatly enhanced.
d) The precipitates obtained with organic reagents are often coarse and bulky
and hence can be easily handled.
e) Further, metal chelates are mostly anhydrous. Hence, the precipitates dry
quickly. This can be accelerated by washing the precipitate with alcohol.
2. Amount of precipitant: The amount of precipitant added is also of
great importance. If a large excess of precipitant is added, the precipitate
formed redissolves as it raises the solubility of the precipitate and if just
enough amount is added then complete precipitation might not take place as
some amount is required to reach the solubility product value. Hence, in
precipitating a substance, a reasonable, excess of precipitant is invariably
added to ensure completeness of precipitation. The excess precipitant
provides excess of common ions and the solubility of precipitate is decreased.
For analogous reasons, the precipitate is washed with a solution containing
common ions.
3. Effect of temperature: The solubility product of a substance is
constant only when its temperature is unaltered. Usually the solubility
increases with the increase in temperature. When the precipitation is carried
44
out at higher temperature, the precipitate formed is of high purity due to better
crystal structure. Hence, wherever possible, precipitation which is carried out
at higher temperature is most advantageous but then it should be cooled
before filtration.
4. Effect of pH: The solubility of the precipitate with the change in pH
of the solution is inevitable. The effect depends on the type of precipitate.
Generally, the precipitate of metal hydroxides and those of sparingly soluble
salts of weak acids are precipitated only in alkaline or neutral pH ranges.
Smaller the dissolution constant for the acid, higher is the pH required for
practically complete precipitation of its salt. The selectivity of organic
reagents can always be improved by the control of pH.
5. Effect of complex formation: In the presence of certain ions, the
desired component is likely to form complex ions having higher dissociation
constants and this will lead to incomplete precipitation. So the unwanted ions
should be prevented from getting precipitated out by masking them. Masking
is the procedure of forming soluble complexes with the unwanted ions and
thus keeping them in solution.

Types of precipitate
Precipitates are classified into
• crystalline,
• and amorphous like curdy or gelatinous precipitates.
Crystalline precipitates are relatively pure and consist of easily
filterable particles. Curdy precipitates are agglomerates of colloidal particles
and are of filterable size. However, they are more easily contaminated than
crystalline precipitates and hence must be washed with an electrolyte solution.
Gelatinous precipitates are flocculated colloids. The particle size is smaller
than that of curdy precipitates and hence is difficult to filter. They must also
be washed with an electrolyte solution to prevent peptization.
Generally, the primary precipitate obtained from a hot dilute solution is
in the form of crystals of nearly perfect lattice structure. However, those
obtained from concentrated solutions are generally very small crystals of
imperfect structure. There is considerable variation in particle size for any
given primary precipitate. Such a primary precipitate is subjected to digestion
or ageing. This is done by allowing the primary precipitate to remain in
contact with the solution from which it is formed, normally at higher
temperature. The smaller particles exhibit higher solubility and dissolve. As a
result, the solution becomes supersaturated with respect to the larger particles.
This results in the deposition of the dissolved particles on the larger particles
and increase in the average particle size. This is known as digestion, ageing
or Ostwald ripening of the precipitate.
Under suitable conditions, the process of ageing also improves the
perfection of the crystal lattice structure to some extent. For various reasons
most of the precipitates carry with them impurities from the solution. During
45
digestion these impurities, to some extent, return to the solution when smaller
particles dissolve.
3 FILTRATION. Filtration is a process of separating precipitates from
the mother liquor. The media employed for filtration are:
· Filter paper.
· Gooch crucible.
· Porous fritted plates of resistance glace (Pyrex sintered crucible).
· Vitreosil filtering crucibles (Silica).
· Porcelain filtering crucibles (Porcelain).
The choice of filtering medium depends on nature of the precipitates
and by cost factor.
Properties of filter paper:
· It should be ash-less.
· Size and diameter of filter paper should be according to the bulk of the
precipitates.
· Pores of filter must be smaller than the size of the particle of the precipitates.
Example: Bulky precipitates like aluminium hydroxide need a larger
filter paper than dense precipitates like barium sulphate.

Figure 5. Preparing a filter paper cone. The filter paper circle in (a) is folded in half (b),
and folded in half again (c). The folded filter paper is parted (d) and a small corner is torn
off (e). The filter paper is opened up into a cone and placed in the funnel (f ).

The precipitate is transferred to the filter in several steps. The first step
is to decant the majority of the supernatant through the filter paper without
transferring the precipitate (Figure 6). This prevents the filter paper from
clogging at the beginning of the filtration process. The precipitate is rinsed
while it remains in its beaker, with the rinsings decanted through the filter
paper. Finally, the precipitate is transferred onto the filter paper using a
stream of rinse solution. Any precipitate clinging to the walls of the beaker is
transferred using a rubber policeman (a flexible rubber spatula attached to the
end of a glass stirring rod).

46
 Figure 6. Proper procedure for transferring the supernatant to the filter paper cone.

An alternative method for filtering a precipitate is a filtering crucible.

The most common is a fritted-glass crucible containing a porous glass disk
filter. Fritted-glass crucibles are classified by their porosity: coarse (retaining
particles larger than 40–60 μm), medium (retaining particles greater than 10 –
15 μm), and fine (retaining particles greater than 4–5.5 μm). Another type of
filtering crucible is the Gooch crucible, which is a porcelain crucible with a
perforated bottom. A glass fiber mat is placed in the crucible to retain the
precipitate. For both types of crucibles, the precipitate is transferred in the
same manner described earlier for filter paper. Instead of using gravity, the
supernatant is drawn through the crucible with the assistance of suction from
a vacuum aspirator or pump (Figure 7).

Figure 7. Procedure for filtering a precipitate through a filtering crucible. The trap
prevents water from an aspirator from back-washing into the suction flask.

4 WASHING. Precipitates must be washed with liquid to remove all

soluble impurities sticking with the precipitates.
47
 Properties of Ideal washing liquids:
· Having no solvent action on precipitates but must removes all foreign
impurities.
· Should not form any volatile product with precipitates.
· Should easily volatile on ignition.
· Should have no dispersive action on the precipitates.
· Should not interfere with precipitates.
If precipitates get colloid during filtration the solution used for washing
must contain electrolytes e. g. ammonium nitrate solution is used for washing
iron (III) hydroxide.
If precipitates tends to oxidize during filtration, then solution used for
washing must reconvert the oxidize form to its original one e. g. acidified
hydrogen sulphide water for copper sulphide.
If precipitates settles rapidly or is gelatinous by nature, then washing is
done by decantation. Gelatinous precipitates require more washing than
crystalline ones e. g. aluminium hydroxide requires more washing than
calcium oxalate.
5 DRYING OR IGNITION. After washing, precipitates are dried or
ignited depending on the nature of precipitates and on the filtering medium.
Precipitates that are dried (below 250°C) or ignited (above 250°C)
should be collected on filter paper, porcelain filtering crucibles or silica
filtering crucibles.
Placing the precipitate in a laboratory oven and heating to a temperature
of 110 o C is sufficient when removing water and other easily volatilized
impurities. Higher temperatures require a muffle furnace, a Bunsen burner, or
a Meker burner, and are necessary if we need to thermally decompose the
precipitate before weighing.
The temperature at which precipitates are dried or ignited can be
determined by a study of thermogravimetry. Thermogravimetry is a technique
in which a change in the weight of a substance is recorded as a function of
temperature or time. It is used in conjunction with other techniques like
differential thermal analysis (DTA), gas chromatography and mass
spectrometry.
Crystalline precipitates absorb water or solvent can be easily removed
by heating the precipitates e. g. cuprous thiocyanate.
6 WEIGHING. Ignited sample is cooled for a few minutes and then
kept in a desicator to avoid moisture adsorption and then weighed on a
chemical balance.
7 CALCULATION. The results of a gravimetric analysis are generally
computed from two experimental measurements: the weight of sample and the
weight of a known composition precipitate.
The precipitate we weigh is usually in a different form than the analyte
whose weight we wish to find . The principles of converting the weight of one
substance to that of another depend on using the stoichiometric mole
48
relationships. We introduced the gravimetric factor (GF), which represents
the weight of analyte per unit weight of precipitate. It is obtained from the
ratio of the formula weight of the analyte to that of the precipitate, multiplied
by the moles of analyte per mole of precipitate obtained from each mole of
analyte, that is,
𝑔
𝑀𝑜𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑎𝑛𝑎𝑙𝑦𝑡𝑒( ) ∙ 𝑛(𝑚𝑜𝑙𝑒 𝑎𝑛𝑎𝑙𝑦𝑡𝑒 𝑖𝑛 1 𝑚𝑜𝑙𝑒 𝑜𝑓 𝑝𝑝𝑡)
𝐺𝐹 = 𝑚𝑜𝑙𝑒
𝑔
𝑀𝑜𝑙𝑎𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑝𝑟𝑒𝑐𝑖𝑝𝑖𝑡𝑎𝑡𝑒 ( )
𝑚𝑜𝑙𝑒

Example: Calculate GF for P in Ag3PO4 ppt:

𝐴𝑟(𝑃) ∙ 𝑛(𝑃) 31 ∙ 1
𝐺𝐹𝑃/𝐴𝑔3𝑃𝑂4 = = = 0.074
𝑀𝑟𝐴𝑔3𝑃𝑂4 419

Table 3. Selected precipitation gravimetric methods for inorganic

cations and anions (arranged by precipitant)
Analyte Precipitant Precipitate Formed Precipitate Weighed
Ba2+ (NH4)2CrO4 BaCrO4 BaCrO4
Pb2+ K2CrO4 PbCrO4 PbCrO4
Ag+ HCl AgCl AgCl
Hg22+ HCl Hg2Cl2 Hg2Cl2
Al3+ NH3 Al(OH)3 Al2O3
Be2+ NH3 Be(OH)2 BeO
Fe3+ NH3 Fe(OH)3 Fe2O3
Ca2+ (NH4)2C2O4 CaC2O4 CaCO3 or CaO
Sb3+ H2S Sb2S3 Sb2S3
As3+ H2S As2S3 As2S3
Hg2+ H2S HgS HgS
Ba2+ H2SO4 BaSO4 BaSO4
Pb2+ H2SO4 PbSO4 PbSO4
Sr2+ H2SO4 SrSO4 SrSO4
Be3+ (NH4)2HPO4 NH4BePO4 Be2P2O7
Mg2+ (NH4)2HPO4 NH4MgPO4 Mg2P2O7
Zn2+ (NH4)2HPO4 NH4ZnPO4 Zn2P2O7
Sr2+ KH2PO4 SrHPO4 Sr2P2O7
CN– AgNO3 AgCN AgCN
I– AgNO3 AgI AgI
Br– AgNO3 AgBr AgBr
49
 Cl– AgNO3 AgCl AgCl
ClO3– FeSO4/ AgNO3 AgCl AgCl
SCN– SO2/ CuSO4 CuSCN CuSCN
SO42– BaCl2 BaSO4 BaSO4

In gravimetric analysis, we are generally interested in the percent

composition by weight of the analyte in the sample, that is,
𝒎𝒑𝒑𝒕
𝑾%𝒂𝒏𝒂𝒍𝒚𝒕𝒆 = ∙ 𝑮𝑭𝒂𝒏𝒂𝒍𝒚𝒕𝒆/𝒑𝒑𝒕 ∗ 𝟏𝟎𝟎%
𝒎𝒔𝒂𝒎𝒑𝒍𝒆

1st Example. Calculate the amount of sulphate as barium sulphate from

sodium sulphate.
Solution of sodium sulphate (Na2SO4) is treated with solution of barium
chloride (BaCl2) to get precipitates of barium sulphate (BaSO4). The
precipitates are then washed, dried and ignited to get free from impurities and
then weighed.
Na2SO4 + BaCl2 → BaSO4 + 2 NaCl
white ppt
Mol. Weight of BaSO4 = 233.42 gm
Mol. Weight of SO4- = 96.06 gm

Suppose obtained weight of BaSO4 precipitates = X · gm

233.42 gm of BaSO4 = 96.06 gm of SO4-2 ions
X · gm of BaSO4 = ?
BaSO4 = 96.06 · X / 233.32 = 0.411X gm of SO4-2 ions

Suppose 25 ml solution is consumed, then

25 ml solution contains = 0.411X gm of SO4-2 ions
1000 ml solution conatins - ?
1000 ml solution conatins = 0.411X · 1000 / 25 = 16.44X gm of SO4-2 ions

2nd Example. Calculate the amount of zinc oxide from zinc sulphate.
A solution of zinc sulphate is boiled to convert it into zinc carbonate by
adding solution of sodium carbonate. Sodium carbonate is added to
precipitate zinc completely as zinc carbonate. Precipitates of zinc carbonate is
boiled for few minutes to convert it into zinc oxide and collected in a tarred
Gooch crucible. Precipitates are washed with hot water until it gets free from
alkali and then dried, ignited and weighed to a constant weight.
ZnSO4 + Na2CO3 → ZnCO3 + Na2SO4
ZnCO3 → ZnO + CO2
ZnSO4 = ZnCO3 = ZnO
ZnSO4 = ZnO

50
Mol. Weight of ZnSO4 = 168 gm
Mol. Weight of ZnO = 81.38 gm

81.38 gm of ZnO = 168 gm of ZnSO4

1 gm of ZnO = 168 · 1 / 81.38 = 1.984 gm

3rd Example: Calculate the amount of Boric acid from Borax.

Borax is an alkaline substance, and reacts with conc. HCl to form Boric
acid. Boric acid is freely soluble in boiling water and precipitated out in cold
water. To get high grade of Boric acid, Borax is treated with conc. HCl as it is
volatile in nature and won’t left any residual traces on crystal surface of Boric
acid.
Weight and dissolve 5 gm of Borax in 15 ml of distilled water. Add 7
ml of conc. HCl, mix thoroughly with glass rod and mark the original volume
with glass rod.
Evaporate the solution till the volume reduces to half of the original
volume. Allow to cool at room temperature. Keep it aside for few min and
add ice water. Filter the residue under suction and dry it in air. Weight the
compound preparation.
Na2B4O7.10H2O → 4H3BO3 + 5H2O + 2NaCl
Mol wt of Borax = 381.37gm
Mol wt of Boric acid = 61.83gm
Practical yield: X gm

381.37 gm of Borax = 4 × 61.83 gm of Boric acid

X gm of Borax = X · 4 · 61.83 / 381.37 = 0.674X gm of Boric acid

4th Example. An ore is analyzed for the manganese content by

converting the manganese to Mn3O4 and weighing it. If a 1.52g sample yields
Mn3O4 weighing 0.126g, what would be the percent Mn3O3 in the sample?
The percent of Mn is?

51
1st EXPERIMENT. Gravimetric analysis by quantitatively determining the
amount of chloride in an unknown.
Equipment: Analytical balance, 6 pieces of 250-mL beaker, Bunsen
burner, 3 funnels, funnel support, plastic wash bottle, 10-mL graduated
cylinder, 100-mL graduated cylinder, ring stand, iron ring, wire gauze, 3
stirring rods, 3 rubber policemen, 3 pieces of #1 Whatman filter paper, 3
watch glasses, weighing paper
Chemicals: unknown chloride sample (sample #1), 0.5 M AgNO3, 6 M
HNO3, acetone, distilled water

In this experiment, silver chloride will be produced from an unknown

chloride compound. The percent chloride will then be determined based on
the amount of silver chloride recovered from the precipitation reaction. In
order to recover the precipitate, the following steps must be made. References
to Figure 8 will be made in the Procedure:

This experiment also illustrates the concept of stoichiometry.

Stoichiometry is the determination of the proportions in which chemical
elements combine and the mass relations in any chemical reaction.
In aqueous solution silver ion undergoes the following reaction with
chloride:
Ag+ (aq) + Cl- (aq) = AgCl (s)
52
 Silver chloride is a relatively insoluble compound with a solubility
product Ksp = [Ag+][Cl-] = 1.8 10-10.
An excess of silver ion is added so that the chloride concentration at
equilibrium will be negligible. If enough silver nitrate solution is not used, the
precipitation will be incomplete, resulting in a substantial error and a low
value for the % Cl in the sample.
Silver chloride slowly photodecomposes by the following reaction:
2AgCl(s) + 2hυ → 2Ag(s) + Cl2(g)
Since chloride is lost as chlorine gas, the above reaction causes the
results to be low. The silver metal produced during photodecomposition is
responsible for the violet color that develops in the precipitate.
If photodecomposition occurs in the presence of excess silver ion, the
following reaction occurs:
3Cl2(aq) + 3H2O + 5Ag+ → 5AgCl(s) + ClO3- + 6H+
This causes the analytical results to be too high.
Dry silver chloride is virtually unaffected by exposure to light. As the
analysis is performed, it is almost impossible to prevent photodecomposition
of the wet silver chloride precipitate. Generally, the effect is small and can be
ignored provided that exposure to direct sunlight, or extended exposure to
fluorescent lights, is avoided. The simplest way to minimize photo-
decomposition is to store the silver chloride in a dark space (desk drawer).
The silver chloride precipitate initially forms as a colloid, which is
coagulated with heat. Nitric acid and a small excess of silver nitrate aid
coagulation by providing a relatively high electrolyte concentration. The
solution is kept slightly acidic during the precipitation step to eliminate
possible interference from anions of weak acids (for example, CO3-2). These
anions form slightly soluble silver salts in neutral solution. Nitric acid is
added to the wash liquid to maintain a high electrolyte concentration and to
prevent peptization during the washing step. (Peptization is the formation of
a colloid by dispersion of a precipitate. Colloids pass through filter crucibles
while precipitates don’t.) The excess acid is volatized during the subsequent
heat treatment. Finally, the precipitate is collected in a previously weighed
filtering crucible, washed, and brought to constant mass at 105C.

PROCEDURE:
I. Preparation of Filter Crucibles
1. Clean and dry three porcelain filter crucibles (see note below). Make sure
crucibles are marked so they can be distinguished from one another. Use a
permanent marker, not a paper or tape label.
2. Dry crucibles in the oven at 100-110°C for one hour or overnight. The
crucibles should be put in a labeled beaker and covered with a watch glass
when in the oven. 3. Cool the crucibles in a desiccator for 20 minutes and
weigh.
4. Repeat Steps 2 and 3, this time oven-drying for only 20 minutes.
53
5. Repeat this procedure until the mass of each crucible agrees to within 0.3
mg between weighings.

II. Preparation of the Chloride Unknown Samples

1. Dry the sample in an oven at 110 °C for 1-2 hours or overnight.
2. Weigh out accurately, by difference, three portions of the dried sample of
about 0.3 to 0.5 g each to within +0.1 mg.
NOTE: NEVER transfer chemicals inside the balance.
3. Dissolve each portion in a clean, separate, labeled 400 mL beaker, using
150 mL of distilled water to which about 1 mL of concentrated nitric acid has
been added.
4. Place a watch glass cover on each beaker.

III. Precipitation of Chloride with Silver Ion

1. Heat the chloride solutions to gentle simmering on a hotplate and keep each
one hot until the AgCl is fully precipitated. Precipitate the chloride from one
unknown solution at a time.
2. Go to the hood containing the stock silver nitrate solution and carefully
pour about 80 mL of the solution into a 100 mL graduated cylinder. [Each
unknown will require about 50-70 mL to precipitate the Cl- completely. DO
NOT FILL ANY CONTAINER LARGER THAN 100 mL with the stock silver
nitrate solution. Owing to severe wastage of very expensive silver nitrate in
the past, any student caught filling a larger container with the stock solution
will be penalized severely.
3. Stirring constantly with a glass stirring rod (do NOT use a magnetic stirrer
and stir bar), add the silver nitrate from the graduated cylinder in
approximately 5 mL increments to your first unknown solution until the
precipitation of the silver chloride is complete. To check for complete
precipitation, silver nitrate must be added in small quantities and vigorously
stirred. Allow the precipitate to settle a bit and add some more silver nitrate
solution (no stirring yet). If the solution becomes cloudy, keep adding. If the
solution remains clear, then add a total of about 5% more silver nitrate
solution than you have added to that point.
4. Now place the beaker (covered) in your locker for at least one hour to
“digest” before filtering. This minimizes exposure of the AgCl to light and
consequent decomposition.
5. Repeat this precipitation and digestion for your other unknown solutions,
one at a time. If you have used a graduated cylinder to monitor the volume of
silver nitrate solution used for your first unknown solution, then you can then
estimate about how much you need to add to the remaining samples. Simply
ratio the volume to be used based on the masses of the two unknown samples
that you weighed out.

54
IV. Filtration and Final Weighing
This procedure should be done separately for each sample in turn.
1. After the solution has digested for a minimum of 1 hour, filter the
supernatant liquid through a labeled, weighed filter crucible with suction,
keeping most of the precipitate in the beaker.
NOTE: Always break the suction on the flask before turning off the
water flow on the aspirator.
2. Test the filtrate in the suction flask for complete precipitation by again
adding a few drops of silver nitrate solution. If your filtrate remains clear,
dispose of the filtrate in the appropriate waste container.
3. Wash the precipitate with three 25-mL portions of 0.01 M nitric acid (2
drops of concentrated HNO3 per 100 mL of water) using your washing bottle.
[A standard-sized washing bottle will hold about 500 mL.] The washings are
poured through the filter crucible and the precipitate is left in the beaker. If
any of the precipitate has dried on the sides of the beaker or the glass stirring
rod, scrape them down with a rubber policeman and rinse with small amounts
of the wash solution during this process to ensure that 100% of the precipitate
will be filtered off into the filter crucible.
4. Stir the bulk of the precipitate up in a small volume of 0.01 M HNO3 and
quantitatively transfer the precipitate to the crucible.
5. After filtering, place the crucibles in a large beaker covered with a watch
glass and dry at 120-140°C for 2 hours. You can leave the crucibles
overnight, if you return the next day and put them in your desiccator.
6. Cool in a desiccator and weigh.

7. Return them to the oven for 20 minutes. Then cool in the desiccator for 20
minutes and reweigh. Repeat this step until the mass of a crucible with the
precipitate agrees to within 0.4 mg.

RESULTS
1. Mass of original chloride sample: msample =
2. Determine the approximate volume (mL) of silver nitrate solution
needed by calculating the volume of silver nitrate required if the
unknown was pure sodium chloride: 𝑉𝐴𝑔𝑁𝑂3 =
3. Mass of silver chloride ppt produced: mAgCl ppt =

55
CALCULATIONS
Calculate the % chloride in the sample.
The gravimetric factor of Chlorine is given by
𝐴𝑟(𝐶𝑙) ∙ 𝑛(𝐶𝑙) 35.5𝑔 𝐶𝑙 − 𝑚𝑜𝑙𝑒 −1 ∙ 1
𝐺𝐹𝐶𝑙/𝐴𝑔𝐶𝑙 = =
𝑀𝑟𝐴𝑔𝐶𝑙 143.321𝑔 𝐴𝑔𝐶𝑙 𝑚𝑜𝑙𝑒 −1
= 0.247368𝑔 𝐶𝑙 − /𝑔 𝐴𝑔𝐶𝑙
where m = the mass in grams.
The mass of chlorine in each sample is therefore:
𝑚(𝐶𝑙− ) = 𝑚𝐴𝑔𝐶𝑙𝑝𝑝𝑡 ∙ 𝐺𝐹𝐶𝑙/𝐴𝑔𝐶𝑙 = 𝑚𝐴𝑔𝐶𝑙𝑝𝑝𝑡 ∙ 0.247368
Finally, the percent Cl- in each sample is:
𝑚𝐴𝑔𝐶𝑙𝑝𝑝𝑡
𝑊𝐶𝑙 % = ∙ 𝐺𝐹𝐶𝑙/𝐴𝑔𝐶𝑙 ∙ 100%
𝑚𝑠𝑎𝑚𝑝𝑙𝑒

2nd EXPERIMENT. Determination the concentration of sulfate ion in the

solid sample using gravimetric analysis
Aim: You will be given a solid powder, which has been dried to constant
mass. The sample is water soluble. The purpose of this experiment is to
determine the concentration of sulfate in your solid sample using gravimetric
analysis.
Safety Precautions:
• Goggles and apron must be worn at all times in the lab.
• Hydrochloric acid is corrosive to skin and clothing.
• Barium compounds are toxic. Wash thoroughly with soap and water
before leaving the lab.
Apparatus: analytical balance (0.0001 g), porcelain crucibles (2), 250 mL
beaker (for water bath), watch glasses (2), funnel, ashless filter paper,
hotplate, Muffle furnace , desiccator, centrifuge, wash bottle
Reagents: unknown sulfate solution, Na2SO4, 25.0 mL of 6.0 M HCl, 100.0
mL of 0.10 M BaCl2, iron nitrate (ready)

Sulfate is quite common in nature and may be present in natural water

in concentrations ranging from a few to several thousand milligrams/liter.
Sulfates are of considerable concern because they are indirectly responsible
for two serious problems associated with the handling and treatment of
wastewater. Odor and sewer corrosion problems result from the reduction of
sulfates to hydrogen sulfide under anaerobic conditions.
In an aqueous solution, sulfate ion undergoes the following reaction
with barium:
2+ 2−
𝐵𝑎(𝑎𝑞) + 𝑆𝑂4(𝑎𝑞) = 𝐵𝑎𝑆𝑂4 ↓
𝐾𝑠𝑝 = [𝐵𝑎2+ ] ∙ [𝑆𝑂42− ] = 1.1 ∙ 10−10 𝑎𝑡 25°
Barium sulfate which forms as a crystalline precipitate, is collected on a
suitable filter, washed with water, then ignited and weighed. From the mass of
BaSO4, the amount of sulfate present in the original sample is calculated.
56
 In this experiment, the analysis of sulfate is performed using
barium chloride as a reagent to precipitate sulfate from the dissolved sample.
The mass of sulfate in the sample can be calculated by simple stoichiometry
from the mass of the weighing form of the sulfate precipitate.
In order to ensure maximum filterability and minimum contamination,
the sulfate is precipitated under conditions that maximize the particle size.
These conditions include: (a) avoiding excessively high concentrations of
precipitating reagent; (b) slow addition of reagent to a hot solution, with
vigorous stirring; (c) avoiding a great excess of reagent. The digestion of the
precipitant after the reaction minimizes errors due to co-precipitation.
For accurate measurements, we must be sure that the composition of
the weighing form is known exactly. You must be very careful in your mass
measurements throughout this experiment – for example, do not handle your
weighing bottle with your bare hands, to avoid leaving fingerprints that would
increase the mass of the bottle. Of course, the recovery of the sulfate
precipitate must be quantitative, and the final weighing form must be pure.

PROCEDURE:
I. Preparation of Crucibles
1) Each crucible should be cleaned and rinsed thoroughly with distilled water.
2) Make sure that the crucibles are marked properly so they can be
distinguished from one another. Use a permanent marker, not a paper or tape
label. You can mark the sides of crucibles with a solution of iron nitrate.
3) For drying, place the cleaned crucibles in the furnace. Remove the
crucibles with tongs (never touch crucibles with your hands or with paper for
the duration of the experiment) and allow them to cool for 5 minutes before
placing them in a desiccator for cooling to room temperature. Cooling will
take about 10 min in the desiccator.
4) Weigh crucibles to the nearest 0.0001 g. Return them to the oven for 1 hour
and repeat the weighing process which should be carried out until two
consecutive masses agree to within  0.0010 g. It is extremely important that
the crucibles should be treated exactly in the same way during this process
and later on when they contain the precipitate.
Note: You need to use the same balance throughout the course of this experiment.
Use of different balances, when weighing the crucibles, will introduce an error into your
calculations (a common cause for not being able to bring the crucibles to constant mass).

II. Preparation of the Sulfate sample solution

1. Dry the sample (Na2SO4) in an oven at 110°C for 1-2 hours or overnight.
2. Weigh out accurately, by difference, three portions of the dried sample of
about 0.3 to 0.5 g each to within +0.1 mg.
NOTE: NEVER transfer chemicals inside the balance.
3. Record the combined mass of the beaker plus sample on your lab report:
m1 beaker =
𝑚2 𝑏𝑒𝑎𝑘𝑒𝑟+ 𝑁𝑎2𝑆𝑂4 =
57
4. Add 50 mL of distilled water, followed by 20 drops of 6M HCl (aq), to the
sample in the beaker. Stir the contents of the beaker until the sample has
entirely dissolved. Leave the stirring rod in the beaker.
5. Place a watch glass cover on each beaker.

III. Precipitation of the Unknown Samples

Treat each unknown solution separately.
1) After adding of 6.0 M HCl solution, cover the beaker with watch glass and
heat the solution nearly to boiling in a water bath.
• Solubility of BaSO4 at room temperature is around 0.3 – 0.4 mg per
100 g of water. Its solubility increases when excessive amount of
mineral acid is present. On the other hand, precipitation should be done
in acidic medium. Because in neutral and basic solutions Ba2+ ions
precipitate with PO43-, CO32- or OH- ions which are present in the
solution. Therefore, precipitation is carried out in weakly acidic
medium and addition of excess acid is avoided. Precipitation in a
weakly acidic medium provides precipitate to occur in the form of large
particles.
2) For each sample, heat 50.0 mL of 0.10 M BaCl2 solution in a beaker nearly
to boiling.
3) Add this solution quickly with vigorous stirring to the hot sample solution.
• Use a separate stirring rod for each sample and leave it in the solution
throughout the experiment.
4) Rinse the beaker walls with distilled water and then cover with a watch
glass. Digest the precipitated BaSO4 at just below the boiling point for 2 hours
in the water bath.
5) Decant the hot supernatant through a fine ashless filter paper placed on a
filtering funnel. Make sure the filter paper is well-seated as shown in Figs. 8
and 9 (Prepare a piece of medium ashless paper by folding the paper in half
and then in quarters. Tear off a corner of the outside fold as shown in Fig. 8,
so it catches all of the precipitate.) Initially, filter as much of the supernatant
liquid as possible (solid accumulating on the filter paper drastically slows the
rate of filtration). A glass rod over the top of the beaker and extending into the
funnel will minimize spilling (ask your assistant for a demonstration). Rinse
the glass rod and the beaker with distilled water to recover the final pieces of
precipitate. Wash the precipitate twice by using about 10.0 mL portions of
distilled water for each wash.

58
 Figure 8. Folding filter paper Figure 9. Proper filtering technique

6) Place paper and its contents into a porcelain crucible that has been brought
to a constant mass previously. Gently char off the paper on a Bunsen burner:
• Place the crucible vertically on a triangle supported by a ring stand and
adjust the ring so that the bottom of the crucible is positioned 10 to 15
cm above a flame which is 1 to 2 cm in height as shown in Fig. 10.
Place the lid on the crucible but displace it to one side so that steam can
escape through a slit of ~2 mm in width. Apply heat slowly and gently
so that violent boiling of the water and bursting of the package avoided.
• When drying is complete, fully cover the crucible and char the paper by
increasing the heat applied to the crucible. Escaping gases should not
burst into the flame. Occasionally lift the lid and check the progress of
the charring operation, by observing the blackening of the paper and
the disappearance of white areas.

Figure 10. Igniting a precipitate

• Because of difficulty of drying and weighing a precipitate on a filter

paper, it is burned away, leaving behind only the precipitate.
• At high temperatures, BaSO4 may be reduced to BaS by the reaction
with C of the filter paper.
BaSO4 (s) + 4C (s) → BaS (s) + 4CO (g)
This reaction can be prevented by burning the filter paper at rather low
temperatures.
59
7) Ignite the crucible to a constant mass at 800C in an electric furnace, for 1
hour. Cool and weigh. Repeat heating, cooling and weighing until the mass of
the crucible is constant within ±0.0010 g. Once a constant mass is reached,
discard the solid in the waste container provided.
• The term ignition means “to heat to a high temperature” not “to set to
fire to” If ignition is done at very high temperature BaSO4 may
decompose as follows.
BaSO4 (s) → BaO(s) + SO3 (g)
• Clean the crucibles by rinsing each thoroughly with distilled water and
return them to the technician.

RESULTS
1. Mass of original sodium sulfate (Na2SO4) sample:
m1 beaker =
𝑚2 𝑏𝑒𝑎𝑘𝑒𝑟+ 𝑁𝑎2𝑆𝑂4 =
m sample = m2 – m1 =
2. Determine the approximate volume (mL) of barium chloride solution
needed by calculating. The volume of barium chloride required if the
unknown was pure sodium sulfate: 𝑉𝐵𝑎𝐶𝑙2 =
3. Mass of barium sulfate ppt produced: 𝑚𝐵𝑎𝑆𝑂4(𝑠) =

CALCULATIONS
Calculate the % sulfate ions in the sample.
The gravimetric factor of Sulfate ion is given by
𝑀𝑟(𝑆𝑂42− ) ∙ 𝑛(𝑆𝑂42− ) 96 ∙ 1
𝐺𝐹𝑆𝑂42−/𝐵𝑎𝑆𝑂4 = = = 0.4120𝑔 𝑆𝑂42− /𝑔 𝐵𝑎𝑆𝑂4
𝑀𝑟𝐵𝑎𝑆𝑂4 233
The mass of sulfate ions in each sample is therefore:
𝑚(𝑆𝑂42− ) = 𝑚𝐵𝑎𝑆𝑂4 𝑝𝑝𝑡 ∙ 𝐺𝐹𝑆𝑂42−/𝐵𝑎𝑆𝑂4 = 𝑚𝐵𝑎𝑆𝑂4 𝑝𝑝𝑡 ∙ 0.4120
Finally, the percent sulfate ions in each sample is:
𝑚𝐵𝑎𝑆𝑂4 𝑝𝑝𝑡
𝑊𝑆𝑂42− % = ∙ 𝐺𝐹𝑆𝑂42− /𝐵𝑎𝑆𝑂4 ∙ 100%
𝑚𝑠𝑎𝑚𝑝𝑙𝑒

2.2 VOLATILIZATION GRAVIMETRY

The volatilization is the process of converting a chemical substance

from a liquid or solid state to a gaseous or vapor state. Other terms used to
describe the same process are vaporization, distillation or sublimation.
One substance can often be separated from another by volatilization
and can then be recovered by the condensation of the vapor.
Volatilization Gravimetry involves separating components of mixture
by heating or chemically decomposing the sample at a suitable temperature.
The volatile product is then collected and weighed, or, alternatively, the mass
of the product is determined indirectly from the loss in mass of the sample. In
60
other words, thermal or chemical energy is used to precipitate a volatile
species. For example, to determine the water content of a compound by
vaporizing the water using thermal energy (heat). Heat can also be used, if
oxygen is present, for combustion to isolate the suspect species and obtain the
desired results.

Figure 11. Apparatus for determining the sodium hydrogen carbonate content of antacid
tablets by a gravimetric volatilization procedure
Volatilization methods can be either direct or indirect. For example for
water:
• DIRECT METHOD: Water vapor is collected on any of several solid
desiccants, and its mass is determined from the mass gain of desiccants.
• INDIRECT METHOD: Amount of water is determined by the loss of
mass of the sample during heating, is less satisfactory because it must
assumed that the water is the only component volatilized.
Water eliminated in a quantitative manner from many inorganic
substances by ignition is an example of a direct determination. It is collected
on a solid desiccant and its mass determined by the gain in mass of the
desiccant.
Another direct volatilization method involves carbonates which
generally decompose to release carbon dioxide when acids are used. Because
carbon dioxide is easily evolved when heat is applied, its mass is directly
established by the measured increase in the mass of the absorbent solid used.
Determination of the amount of water by measuring the loss in mass of
the sample during heating is an example of an indirect method. It is well
known that changes in mass occur due to decomposition of many substances
when heat is applied, regardless of the presence or absence of water. Because
one must make the assumption that water was the only component lost, this
method is less satisfactory than direct methods.
This often fault and misleading assumption has proven to be wrong on
more than a few occasions. There are many substances other than water loss
that can lead to loss of mass with the addition of heat, as well as a number of
other factors that may contribute to it. The widened margin of error created by

61
this all-too-often false assumption is not one to be lightly disregarded as the
consequences could be far-reaching.
Nevertheless, the indirect method, although less reliable than direct, is
still widely used in commerce. For example, it's used to measure the moisture
content of cereals, where a number of imprecise and inaccurate instruments
are available for this purpose.
Depending on the method of analysis,
the equipment for volatilization gravimetry
may be simple or complex. In the simplest
experimental design, we place the sample in a
crucible and
decompose it at a
fixed temperature
using a Bunsen
burner, a Meker
burner, a laboratory oven, or a muffle furnace.
The sample’s mass and the mass of the residue
are measured using an analytical balance.

Figure 12. The scheme of votalization procedure

1st EXPERIMENT. Determination of percentage of water of

crystallisation in a salt using votalization method.
The aim of this experiment is to determine the percentage of water of
crystallisation in of a sample of hydrated Barium Chloride
62
 Equipment: crucible and cover, triangle, crucible tongs, Bunsen
burner, ring stand, ceramic tile(s), iron ring, stainless steel spatula or scoop
Reagents: unknown hydrate.

Some salts, when crystallised from aqueous solution, incorporate water

molecules into the structure. This is known as “water of crystallization”, and
the 'hydrated' form of the compound. A hydrate salt is composed of anions
(negative ions) and cations (positive ions) which are surrounded by and
weakly bonded water molecules. Each hydrate salt has a fixed number of
water molecules associated with it, called waters of hydration or water of
crystallization. When a salt holds waters of hydration, we call it a hydrated
salt or a hydrate (hydrate from hydor, the Greek word for water).
Barium chloride dihydrate, BaCl2  2H2O, has two waters of
crystallization, or two waters of hydration. Other hydrates have waters of
hydration ranging from one to twelve. Upon heating, a hydrate decomposes
and produces an anhydrous salt and water (in the form of steam).
∆
𝐵𝑎𝐶𝑙2 ∙ 2𝐻2 𝑂(𝑠) → 𝐵𝑎𝐶𝑙2(𝑠) + 2𝐻2 𝑂 ↑

You will use techniques of quantitative analysis to determine the

percent by mass of water in a solid.
The accurate determination of the composition of substances is
essential in modern technology and important in our everyday life. Typical
problems in which analytical chemistry plays a role are determining the
compositions of lunar and other extraterrestrial samples, monitoring harmful
levels of pollutants in the atmosphere above our cities and in our water
supplies, maintaining quality control over drug and food products, detecting
trace impurities in ultra pure semi-conductor materials (transistors, diodes,
etc.), and making clinical investigations which determine the nature and
concentration of materials in biological fluids.
As can be seen from the examples given, analytical determinations may
be either qualitative or quantitative in nature. A qualitative analysis is aimed
at determining the identity of a substance (what is present); a quantitative
analysis determines the amounts of known substances present in a particular
sample (how much is present).
This experiment will introduce you to precision weighing and
quantitative analysis techniques. You will determine the percent by mass of
water in a sample of solid. The solid contains one or more hydrates – salts that
crystallize with a definite number of water molecules in each formula unit.
For instance, barium chloride dihydrate, BaCl2·2H2O, is a hydrate containing
two molecules of water (water of crystallization) for each BaCl 2 unit. You
will heat the solid to drive off the water of crystallization, and from the loss in
mass, calculate the percent of water that was present.

63
Part1. Theoretical Percentage
Calculate the theoretical percentage of water in barium chloride
dihydrate.
𝑀(𝐻2 𝑂) ∙ 𝑛(𝐻2 𝑂)
𝑊𝐻2 𝑂 % = ∙ 100%
𝑀𝐵𝑎𝐶𝑙2 ∙2𝐻2 𝑂

Part 2. Experimental percentage

The experimental percentage of water in a hydrate is found by
comparing the mass of water driven off to the total mass of the compound,
expressed as a percentage.
1. Obtain a porcelain crucible from the stockroom, rinse with water, and heat
on a clay triangle for five minutes over a direct flame to remove any
surface moisture. Use crucible tongs when handling hot crucibles.
2. Weigh the cool, dry crucible and lid. Record the weight (m1) on the data
sheet.
3. Place between 1.0 and 1.5 g of BaCl2 2H2O in the crucible and reweigh
the crucible (m2), lid and contents. Record the mass on the data sheet.
Calculate the weight of the hydrate (m3). Record the mass of the hydrate
on the data sheet.
4. Place the crucible back on the clay triangle with the lid almost covering
the crucible. Heat gently at first, then with a hot flame for 10 minutes.

Figure 13. Experimental Set Up

5. Allow the crucible to cool until it is cool to the touch. Weigh the crucible
and lid and record the mass on the data sheet. This procedure is called
heating to constant weight. Consider the last weighing to be your final
weight.
6. Complete the calculations to determine the percent water in the
compound. Show the calculations on the data sheet.

64
7. Dispose of the BaCl2 2H2O. Repeat the procedure as Trial 2 on the data
sheet.
8. Cleanup. Soak the crucible in tap water to remove the residue. Use dilute
hydrochloric acid, if necessary, to remove any residue that remains. Rinse
the cleaned crucible with distilled water before setting it to dry beside the
sink. Clean your lab area before being signed out by your lab assistant.

RESULTS:
𝑀𝐵𝑎𝐶𝑙2 ∙2𝐻2 𝑂 =
Mass of empty crucible and lid (g): m1 =
Mass of crucible with lid and sample solid before heating (g): m2 =
Mass of crucible with lid and sample solid (m3, g):
after 1st heating 𝑚13 =
after 2nd heating 𝑚23 =
after 3rd heating 𝑚33 =

CALCULATION:
Mass of solid sample (g): m4 = m2 – m1 =
Mass of water in solid (g): 𝑚𝐻2 𝑂 = m2 – m3 =
Percent water % by mass can be found by using the equation:
𝑚𝐻2 𝑂
𝑊𝐻2 𝑂 % = ∙ 100%
𝑚4

CONTROL OF MASTERING THE TOPIC

Typical calculation tasks
Task 1. A 10.00 mL solution containing Cl- was treated with excess AgNO3
to precipitate 0.4368 g of AgCl. What was the molarity of Cl - in the
unknown?
Task 2. Phosphate is precipitated from its solution with ammonium
molybdate, as (NH4)3[PMo12O40xH2O]. Since the precipitate does not have a
constant composition with regard to water content, it is dissolved in ammonia
and the molybdate is precipitated with Pb(NO3)2, as PbMoO4.
a) What is the value of the gravimetric factor for the calculation of %P?
b) If the final precipitate weighs 0.100 g, what is the weight of P in the initial
sample?
Task 3. A 0.2025 g sample consisting of only BaCl2 and KCl required 20.25
mL of 0.1200M AgNO3 solution for the quantitative precipitation of chloride.
Calculate the %Ba and %K in the sample.
Task 4. A 0.4994 g sample of a hydrate of CuSO4 • xH2O, is heated to a
constant weight of 0.3184 g (total loss of water). Calculate the value of x.
Task 5. In the gravimetric determination of sulfate in a 0.2841 g sample of
pure Na2SO4, a BaSO4 precipitate weighing 0.4604 g was obtained. The
weight of the precipitate was smaller than the theoretical one, since some
BaSO4 was converted to BaS during the heating process.
65
a) Calculate the per cent of BaS in the precipitate (Hint: best to solve
algebraically).
b) The per cent error of the analysis (Hint: compare calculated with weight
stated in problem).
Task 6. Consider a 1.0000 g sample containing 75% potassium sulfate (FW
174.25) and 25% MSO4. The sample is dissolved and the sulfate is precipated
as BaSO4 (FW 233.39). If the BaSO4 ppt weighs 1.4900, what is the atomic
weight of M2+ in MSO4?
Task 7. A mixture of mercurous chloride (FW 472.09) and mercurous
bromide (FW 560.99) weighs 2.00 g. The mixture is quantitatively reduced to
mercury metal (At wt 200.59) which weighs 1.50 g. Calculate the %
mercurous chloride and mercurous bromide in the original mixture.
Task 8. In the gravimetric analysis of iron, hydroxide may be added to a
solution containing Fe3+ to precipitate a gelatinous mess which is ignited to
form Fe2O3. If 0.2864 grams of Fe2O3 were formed from the ignition of the
precipitated mess, how many grams of FeCO3 were contained in the original
sample analyzed?
Task 9. A sample of ore containing manganese weighed 1.2354 grams. This
sample was heated in a solution of nitric acid, which dissolved the manganese
ion producing manganese(III) nitrate (Mn(NO3)3). The acidity of the solution
was adjusted, and Hydrogen sulfide gas was bubbled into the solution
producing 0.2876 grams of manganese(III) sulfide (Mn2S3). What is the
percentage of manganese in the original sample?
Task 10. A certain barium halide exists as the hydrated salt BaX22H2O,
where X is the halogen. The barium content of the salt can be determined by
gravimetric methods. A sample of the halide (0.2650 g) was dissolved in
water (200 cm3) and excess sulfuric acid added. The mixture was then heated
and held at boiling for 45 minutes. The precipitate (barium sulfate) was
filtered off, washed and dried. Mass of precipitate obtained = 0.2533 g.
Determine the identity of X.
Task 11. Suppose that a 0.2045g unknown sample is analyzed using the
procedure for this lab experiment. If the initial crucible weight is 3.0531g and
the final crucible weight is 3.5016g, what is the %Cl by mass of the unknown
sample?
Soy sauce weighing 74.6 g was heated in an oven to constant mass. The final
mass was 14.2 g. What percentage of water did the sauce contain?
Task 12. Soy sauce weighing 74.6 g was heated in an oven to constant mass.
The final mass was 14.2 g. What percentage of water did the sauce contain?
Task 13. An unknown hydrate is weighed out, heated, and reweighed after
drying. If the original hydrate weighed 1.725 g, but after heating it weighed
0.941 g, what is the percentage of water in the unknown compound?
Task 14. Gypsum is a naturally occurring hydrate of CaSO4. If it a sample is
dehydrated and it is found to contain 21.0% water, what is the chemical
formula for gypsum?
66
15. Determine the percentage composition of the following compounds:
a) lead (IV) oxide (PbO2) b) sodium carbonate (Na2CO3)
16. Find the empirical formula of:
a) a compound that contains 65.2% scandium and 34.8% oxygen by mass
b) an oxide of copper that contains 89% copper by mass
17. Explain the meaning of the following terms:
a) precipitate b) gravimetric analysis c) weighable form of ppt
18. A student is given solutions of lead(II) nitrate, copper(II) chloride and
barium hydroxide.
a) Name the precipitates that could be made by mixing together pairs of
solutions.
b) Write full and ionic equations for each of the reactions.
19. Design a flowchart to show how the salt content of a savoury spread could
be determined by gravimetric analysis.

QUESTIONS FOR TEST SELF-CHECK

(with multiple responses «correct-incorrect»)
1. Write the advantages and drawbacks of gravimetric analysis.
2. What are the properties of an ideal precipitating reagent?
3. What type of particles is preferred as precipitates? Why?
4. Write the experimental variables to control the size of the particle in a
precipitation reaction.
5. What can be the types of impurities present in precipitates? Name at least
three of them.
6. Describe the preparation of 25.0 mL of 6.0 M HCl from the concentrated
HCl solution.*
7. Describe the preparation of 50.0 mL of 0.10 M BaCl2 from solid
BaCl22H2O. *
* Density and mass percent values for the concentrated HCl solution are written outside
the bottle present in the hood. These values are also listed in the web page.
8. What is the importance of digestion step during precipitation?
9. What is the importance of making the sulfate solution slightly acidic before
the addition of BaCl22H2O solution?
10. What is the importance of ignition at proper temperature?
11. Suppose that a small portion of the sulfate precipitated as lead sulfate
rather than as barium sulfate. How this would change the result of the
analysis?
12. From the following list, identify the interfering species in the sulfate
determination method used in this experiment: Pb2+, Na+, NO3–, CO3 2-, PO43- .
13. In gravimetric analysis, which of the following steps has to be carried out
after “drying” of the precipitate?
a) Ignition and incineration b) Digestion c) Filtration d) Washing
14. In gravimetric analysis, how is the solubility of the precipitate reduced?
a) by adding excess of precipitating reagent
b) by adding minimum precipitating reagent
67
c) by increasing the concentration of analyte
d) be decreasing the concentration of analyte
15. What is the temperature range for ignition during gravimetric analysis?
a) 250 – 1200 b) 250 – 1000 c) 150 – 500 d) 100 – 350
16. If Q: concentration of the substance momentarily produced in the solution
by mixing the reagents and S: equilibrium solubility, then what is the correct
representation for “relative supersaturation”?
𝑄−𝑆
a) Relative supersaturation =
𝑆
𝑄+𝑆
b) Relative supersaturation =
𝑆
𝑄∗𝑆
c) Relative supersaturation =
𝑆
𝑄
a) Relative supersaturation = [ ] ∗ 𝑆
𝑆
17. At 298K, the solubility of silver chloride is 1.1*10 -10. What is the
solubility of silver chloride in water?
a) 1.05*10-5 (mol/L) b) 1.03*10-6 (mol/L)
c) 1.10*10-7 (mol/L) d) 1.02*10-5 (mol/L)
18. Complete the following reaction, which summarizes the gravimetric
estimation of iron: Fe3+ + 3OH- → Fe(OH)3 (s)
2Fe(OH)3 (s) → ?
a) Fe2O3 (s) + 3H2O b) Fe3O4 (s) + 2H2O
c) Fe2O3 (s) + 2H2O d) FeO (s) + 3H2O
19. Which of the following sources of error could account for a higher mass
of product than is expected?
a) The precipitate was completed dried, with some loss of product
b) Most of the supposed product is dissolved in aqueous solution
c) The precipitate was not completely dried
d) None of the above
20. Which of the following statements correctly describes the importance of
the dissolved analyte in gravimetric analysis, with regards to its reaction with
the solution?
a) It forms a soluble product
b) Its reaction with the solution forms an insoluble product, which can be used
to determine the identity of an unknown species
c) It increases the solubility of the solution
d) Reacting with the solution decreases the solubility of the overall system
21. Gravimetric analysis measures the ______ of a material formed in the
reaction of the analyte with the reagent.
a) Mass b) Density c) Volume d) Concentration
22_____________is a type of co-precipitation in which impurities are trapped
within the growing crystal.
a) Nucleation b) Occlusion c) Crystallization d) Filtration

68
23. Sometimes a precipitate standing in contact with the mother liquor
becomes contaminated by the precipitation of an impurity on top of the
desired precipitate. This phenomenon is called________
a) Co-precipitation b) Post precipitation c) Digestion
24. A colloid is solid made up of particles having diameters less than ____cm
a) 10-7 b) 10-4 c) 10-22
25. ______is a process in which a minimum no. of atoms, ions or molecules
join together to give a stable solid
a) Nucleation b) Occlusion c) Adsorption
26. _________is a process where the precipitate is re-dissolved and
precipitated out of a cleaner environment.
a) Digestion b) Dissociation c) Filtering
d) Crystallization e) None of these
27. Digestion can help reduce the amount of ____________
a) Post-precipitation b) Co-precipitation c) Precipitation d) Nucleation
28. The mass of substance is measured as a function of temperature in _____.
a) Precipitative gravimetry b) Particulate Gravimetry
c) Thermogravimetry d) Electrogravimetry
29. _________is the incorporation of trace element into mineral structure
during solid solution formation and recrystallization of minerals.
a) Adsorption b) Post precipitation
c) Nucleation d) Co-precipitation
30. ________is a term used to describe the effect on a solution of two
dissolved solutes that contain the same ion or ionsю
a) Common ion effect b) Salt effect d) Adsorption e) Phase effect
31. Ion product _______________Ksp, thus a precipitate will form
a) Greater than b) Equal to c) Less than d) Zero

Reference
1. D. A. Skoog, D. M. West, F. J. Holler, and S. R. Crouch, Analytical
Chemistry: An Introduction, 7th ed., Chapter 8, pp. 179-201.
2. Gary D. Christian, Analytical Chemistry, sixth edition, University of
Washington, 2004, chapter ten, pages 313 to 338.
3. Analytical Chemistry for Technicians, John Kenkel, 3rd edition, page 130,
142.
4. Analytical Chemistry Handbook, Pradyot Patnaik, 2nd edition, page 297.
5. Sawyer, C. N., McCarty, P. L., and Parkin, G. F. 2000. Chemistry for
Environmental Engineering. Fourth Edition, McGraw-Hill, Inc., New
York.

69
 LABORATORY WORK 3
GRAVIMETRIC ANALYSIS OF WHEAT FLOUR

Objectives:
1) Study the main methods of Gravimetry Analysis and the basic
operations such as filtration, precipitation, drying, heating
2) Learn about the components, characteristics and best uses for the
most common varieties of flour.
3) Determination of moisture of wheat flour based on air-oven method
4) Determination of alcoholic acidity of wheat flour based on acid-base
titrimetry method

Gravimetry based on measurement of weight of an analysed species or

a compound containing the analysed species. Measuring mass is the most
fundamental of all analytical measurements, and gravimetry is unquestionably
the oldest analytical technique.
Using Mass as a Signal:
There are two ways to use mass as an analytical signal. We can, of
course, measure an analyte’s mass directly by placing it on a balance and
recording its mass. For example, determination of the total suspended solids
in water released from a sewage-treatment facility. Suspended solids are just
that; solid matter that has yet to settle out of its solution matrix. The analysis
is easy. A sample collects and passes it through a preweighed filter that
retains the suspended solids. After drying to remove any residual moisture,
the filter weighs. The difference between the filter’s original mass and final
mass gives the mass of suspended solids. It is a direct analysis because the
analyte itself is the object being weighed.
If the signal is the mass of a precipitate, the method calls precipitation
gravimetry.
Sometimes it is easier to remove the analyte and use a change in mass
as the analytical signal. If thermal or chemical energy is used to remove a
volatile species, the method calls volatilization gravimetry. For example,
determine a food’s moisture content by a direct analysis. One possibility is to
heat a sample of the food to a temperature at which the water in the sample
vaporizes. If we capture the vapor in a preweighed absorbent trap, then the
change in the absorbent’s mass provides a direct determination of the amount
of water in the sample. An easier approach, however, is to weigh the sample
of food before and after heating, using the change in its mass as an indication
of the amount of water originally present. This technique calls an indirect
analysis since we determine the analyte by a signal representing its
disappearance.
Volatilization gravimetry involves separating components of our
mixture by heating or chemically decomposing the sample. The heating or

70
chemical decomposition separates out any volatile compounds, which results
in a change in mass that we can measure.
Whether an analysis is direct or indirect, volatilization gravimetry
usually requires that we know the products of the decomposition reaction.
This is rarely a problem for organic compounds, which typically decompose
to form simple gases such as CO2, H2O, and N2. For an inorganic compound,
however, the products often depend on the decomposition temperature.
Depending on the method of analysis, the equipment for volatilization
gravimetry may be simple or complex. In the simplest experimental design,
we place the sample in a crucible and decompose it at a fixed temperature
using a Bunsen burner, a Meker burner, a laboratory oven, or a muffle
furnace. The sample’s mass and the mass of the residue are measured using an
analytical balance.
Flour is the powdery substance created when a dry grain is pulverized.
This is referred to as the milling process. The most common varieties of flour
are made from wheat although any grain can be made into flour, including
rice, oats, corn or barley.
All-purpose flour is made from the endosperm of wheat. This flour is
often bleached to give it a clean, white appearance and enriched to include
nutrients that are lost due to the removal of the germ and bran. All-purpose
flour has a medium balance of starch and protein so that it can be used in a
wide variety of products without being too heavy or too delicate.
The production of uniform bakery products require control over the raw
materials used in their formation. Flour is a biological material and when
obtained from different sources can vary considerably in its protein quality,
protein quantity, ash, moisture, enzymatic activity, color, and physical
properties. It is essential for the baker to be aware of any variations in these
characteristics from one flour shipment to the next. The purpose of flour
testing is to measure specific properties or characteristics of flour. For
example,
Table 4. Requirements for refined wheat Flour for General Purpose

71
 Ideally the results of these tests can be related to the flour’s
performance in the bakery.
The American Association of Cereal Chemists (AACC) publishes
approved methods for determining various properties of flour and bakery
products.
The routine analysis of flour may include the determination of
moisture, ash, added chalk, SO2, oil, protein, acidity, iron, thiamine and
nicotinic acid, an examination for improves and bleaching agents and a
microscopic examination.
Industrially, certain other types of analysis are of some importance,
etc., examination of the gluten, physical tests on the dough produced from the
flour, determination of the particle size, maltose, color and grade figures.

1st EXPERIMENT. Moisture Content of Wheat Flour

Materials: Pre-dried dish (glass or aliminium), desicator, oven, balance,
spatula.

The simple air-oven method is sufficiently accurate for the routine

analysis of flour moisture at the flour mill or bakery. The procedure involves
heating a small sample of flour (~2g) for 1 hr at 266˚F (130˚C + 1˚C) and
taking the loss in weight as the moisture content.
The moisture content of the flour is important for two reasons. First, the
higher the moisture content, the lower the amount of dry solids in the flour.
Flour specifications usually limit the flour moisture to 14% or less. It is in the
miller’s interest to hold the moisture as close to 14% as possible. Secondly,
flour with greater than 14% moisture is not stable at room temperature.
Organisms naturally present in the flour will start to grow at high moistures,
producing off odors and flavors.
PROCEDURE:
1. A small sample of flour or ground wheat (approximately 5 grams) is weighed and
placed in a moisture dish:
M1dish =
M2dish + flour =
M3 flour = M2 – M1 =
2. The sample is heated at 130 degrees Celsius in an air oven for 1 hour.
3. The sample is cooled to room temperature and the residue is weighed:
4
M dish + flour =
M5 flour = M4 – M1 =
RESULTS:
Moisture content is determined by heating a flour or ground wheat sample in an air oven
and comparing the weight of the sample before and after heating
M3 −M5
W H 2O % = 100%
M3

72
where M1 – weight of dried dish before drying
M2 – weight of flour with dish before drying
M3 – weight of flour in dish before drying
M4 – weight of flour with dish after drying
M5 – weight of flour in dish after drying
M3 – M5 – weight of moisture

2nd EXPERIMENT. Alcoholic Acidity of Wheat Flour

Material: Conical flask, water bath, clear filtrate, pipette,
phenolphthalein, balance
Reagents: 90% ethyl alcohol, standard 0.05N NaOH solution, 1%
phenolphthalein in alcohol

Flour when stored for long, undergoes types of deterioration, which in

turn gives high values for alcoholic acidity, hence, alcoholic acidity is an
index of deterioration of flour during storage.
Alcoholic acidity therefore refers to the combined acidity as we, get by
1) hydrolysis of fats by lipases into free fatty acids, 2) hydrolysis of proteins
into amino acids by proteolytic enzymes, 3) acidity due to the presence of
certain acids salts etc.
Alcoholic acidity is defined as mg of H2SO4 required for 100 g of the
sample to have the same alcohol soluble acids.
Limits: AA (alcoholic acidity) = 0.062 – 0.18% max
PROCEDURE:
1. Weigh 5 g of the flour sample into 100 mL conical stoppered flask.
Mflour =
2. Add 50 ml of 90% neutral ethyl alcohol.
3. Stopper the flask, shake the contents of the flask for 1 hour.
4. Filter the alcoholic extract (through an ordinary dry filter paper).
5. Titrate 10 ml of alcoholic extract against standard 0.05N NaOH
solution using phenolphthalein as indicator:
NNaOH = 0.05N
VNaOH =
6. Calculate the percentage alcoholic acidity as sulphuric acid.
7. Calculate the alcoholic acidity of the sample using the following
formula:
24.52  N NaOH V NaOH
AA(as H 2 SO4 ) =
M
where M – weight of flour
NNaOH – normality of standard alkali solution
VNaOH – volume in ml of the standard sodium hydroxide solution
used in titration

73
 3rd EXPERIMENT. Determination of Ash in Wheat Flour
Materials: Bunsen burner, porcelain cruse, desicator, flour, oven,
balance.

Ash content is determined by high temperature incineration in an

electric muffle furnace.
• When a sample is incinerated in an ash oven, the high temperature
drives out the moisture and burns away all the organic materials (starch,
protein, and oil), leaving only the ash. The residue (ash) is composed of the
noncombustible, inorganic minerals that are concentrated in the bran layer.
• Ash content results for wheat or flour ash are expressed as a
percentage of the initial sample weight. Wheat or flour ash is usually
expressed on a common moisture basis of 14 percent.
The ash content in wheat and flour has significance for milling. Millers
need to know the overall mineral content of the wheat to achieve desired or
specified ash levels in flour. Since ash is primarily concentrated in the bran,
ash content in flour is an indication of the yield that can be expected during
milling. Ash content also indicates milling performance by indirectly
revealing the amount of bran contamination in flour. Ash in flour can affect
color, imparting a darker color to finished products. Some specialty products
requiring particularly white flour call for low ash content while other
products, such as whole wheat flour, have a high ash content. Acid insoluble
ash indicates silica contamination. Limits: Ash – max 1%; AIA (acid
insoluble ash) – max 0.10%.
PROCEDURE:
First of all 2gr of flour was weighed into well-dried porcelain, and then
was heated onto a Bunsen burner until 350 – 400oC, then it was transferred
into oven. After two hours ash was transferred to desicator. After cooling it
was weighed. Finally total ash was calculated as a percentage of samples.

CONTROL OF MASTERING THE TOPIC

Typical calculation tasks
1) A 2.00 g sample of limestone was dissolved in hydrochloric acid and
all the calcium present in the sample was converted to Ca 2+(aq). Excess
ammonium oxalate solution, (NH4)2C2O4(aq), was added to the solution to
precipitate the calcium ions as calcium oxalate, CaC2O4(s). The precipitate was
filtered, dried and weighed to a constant mass of 2.43 g. Determine the
percentage by mass of calcium in the limestone sample.
2) A particular water soluble fertilizer contains phosphorus in the form
of phosphate ion, PO43-. A student used the following procedure to determine
the percentage of phosphorus in a sample of soluble fertilizer. 5.17g of
fertilizer was added to 250.0 mL volumetric flask and water was added to
make it up to the mark. 20.00 mL of this solution was pipetted into a conical
flask. A slight excess of precipitating agent was added to precipitate the
74
phosphate ions as Mg(NH4)PO4. The precipitate was filtered, washed with
water and then converted by heating into Mg 2P2O7. The mass of Mg2P2O7 was
0.0321g. Calculate the percentage by mass (%) of phosphate in the fertilizer.
3) A 3.46 g sample of limestone (CaCO3) was dissolved in 0.1M (HCl)
solution according to the following equation:
CO3 (s) + 2HCl (aq) => Ca2+(aq) + 2Cl -(aq) + CO2(g) + H2O (l)
Excess 0.1M (NH4)2C2O4 (aq), was added to the resulting solution to
precipitate the calcium ions as calcium oxalate, CaC2O4(s). The precipitate
was filtered, dried and weighed at 2.03 g. Determine the percentage by mass
of calcium in the limestone sample.
4) As a result of the mishap, we have 0.7209 g of a mysterious mixture
containing MgCl2 and NaNO3. We would like to know the relative amount of
each compound in our mixture, which is fully dissolved in water. We add an
excess of our precipitating agent silver (I) nitrate, AgNO3(aq), and observe the
formation of a precipitate, AgCl (s). Once the precipitate is filtered and dried,
we find that the mass of the solid is 1.0320 g. What are the mass percent
of MgCl2 and NaNO3 in the original mixture?
5) In impure sample of Na3PO4 weighting 0.1392g was dissolved in
25ml of water. A solution containing 50 mL of 3% w/v mercury (II) chloride,
20 mL of 10% w/v sodium acetate and 5 ml of glacial acetic acid was then
prepared. The solution containing the phosphate was added dropwise to the
second solution, oxidizing PO33- to PO43- and precipitating Hg2Cl2. After
digesting, filtering, and rinsing, the precipitated Hg2Cl2 was found to weigh
0.4320 g. Report the purity of the original sample as w/w Na3PO4.
7) A 0.6113 g sample of Dow metal, containing aluminum, magnesium,
and other metals, was dissolved and treated to prevent interferences by the
other metals. The aluminum and magnesium were precipitated with 8-
hydroxyquinoline. After filtering and drying, the mixture of Al(C 9H6NO)3 and
Mg(C9H6NO)2 was found to weigh 7.8154 g. The mixture of dried precipitates
was then ignited, converting the precipitate to a mixture of Al2O3 and MgO.
The weight of this mixed solid was found to be 1.0022 g. Calculate the %w/w
Al and %w/w Mg in the alloy.
8) An ore containing magnetite, Fe3O4, was analyzed by dissolving a
1.5419 g sample in concentrated HCl, giving a mixture of Fe2+ and Fe3+. After
adding HNO3 to oxidize any Fe2+ to Fe3+, the resulting solution was diluted
with water and the Fe3+ precipitated as Fe(OH)3 by adding NH3. After
filtering and rinsing, the residue was ignited, giving 0.8525 g of pure Fe 2O3.
Calculate the w/w Fe3O4 in the original sample.
9) A 26.23 mg sample of MgC2O4*H2O and inert materials is heated to
constant weight at 1200C, leaving a residue weighing 20.98 mg. A sample of
pure MgC2O4*H2O, when treated in the same fashion, undergoes a 69.08%
change in its mass. Determine the %w/w MgC2O4*H2O in the sample.
10) A sample of slag form a blast furnace is analyzed for SiO2 by
decomposing a 0.5003 g sample with HCl, leaving a residue with a mass of
75
0.1414 g. After treating with HF and H2SO4 and evaporating the volate SiF4, a
residue with a mass of 0.0183 g remains. Determine the %w/w SiO 2 in the
sample.
11) A 101.3 mg sample of an organic compound known to contain Cl is
burned in pure O2 and the combustion gases collected in absorbent tube. The
tube used to trap CO2 increases in mass by 167.6 mg, ant the tube for trapping
H2O shows a 13.7 mg increases. A second sample of 121.8 mg is treated with
concentrated HNO3 producing Cl2, which subsequently reacts with Ag+,
forming 262.7 mg AgCl. Determine the compounds composition, as well as
its empirical formula.
12) The thermogram below shows the change in mass for a sample of
calcium oxalate monohydrate, CaC2O4*H2O. The original sample weighted
24.60 mg and was heated from room temperature to 1000C at a rate of 5C
min. The following changes in mass
corresponding temperature ranges
were observed:
Loss of 3.03 mg from 100 – 250C
Loss of 4.72 mg from 400 – 500C
Loss of 7.41 mg from 700 – 850C

Determine the identities of the votalization products and the solid

residue at each step of the thermal decomposition.

LABORATORY WORK 4
TITRIMETRIC ANALYSIS
ACID-BASE TITRATION

Objective: To determine the amount of substance in a solution of

unknown concentration using various titrimetric methods.
At the end of this unit the student is expected to be able to:
1. Answer questions such as: What is volumetric analysis, titration,
equivalent point, end point, primary standard, titrant and what is
Standardization?
2. Calculate the volume of titrant at the equivalent point.
3. Understand the methods that are used for the detection of the equivalent
point.
4. Know the requirements for a reaction to be applied in volumetric analysis.
5. Answer the questions: what is titration curve? Why it is important? How it
can be derived?
6. Calculate the concentrations of all species participating in the titration
reaction at any point during titration.
7. Do all sorts of volumetric calculations.
76
 Titrimetric (volumetric) analysis is a method of quantitative analysis
used to determine unknown concentration of known substance. A generic
chemical reaction for titrimetric analysis is:

where a moles of analyte A contained in the sample reacts with t moles of the
titrant T in the titrant solution.
The definite volume of the analyte (i.e.; the substance to be determined)
is allowed to react with a suitable reagent (titrant) whose standard solution
can be prepared and the volume of the solution consumed for complete
reaction is used to find out the concentration of analyte solution.
At this point, it is necessary to know definitions of some useful terms.
In titrimetric analyses, the solution of accurately known concentration
i.e.; standard solution is called the Titrant and the substance to be determined
is called Analyte.
The volume of the titrant added is measured with a special type
of glassware called a burette which is graduated and has a stopcock at one
extreme end to control the flow of titrant.

Figure 14. Apparatus needed for titration

In Titrimetric analysis, we often talk about standard

solutions. Standard solution is the one whose concentration is known. The
chemicals which are used to prepare these standard solutions are of two
kinds: Primary Standard and Secondary Standard.
A Primary Standard is a compound of sufficient purity from which a
standard solution can be prepared by direct weighing of a quantity of it
followed by dissolution in a defined volume of a solvent. The solution
obtained is thus a primary standard solution. A compound should satisfy
following criterion to act as a primary standard:
1) It should be pure. In case slight impurities are present then the
impurity level should not be too high and its percentage should be known
2) It should be stable up to moderate temperatures required for drying
and it should be stable indefinitely at room temperature i.e., it should not be
77
altered in air during weighing. This means it should not be hygroscopic,
oxidized by air or affected by CO2. Its composition should be unchanged
during storage.
3) The substance should be capable of being analysed for impurities by
known reactions.
4) It should have a high relative molecular mass so that weighing errors
are minimum or negligible.
5) The substance should be readily soluble under the conditions in
which it is employed.
6) The reaction with the standard solution should be stoichiometric and
instantaneous. The titration error should be negligible.
A solution prepared from a primary standard substance whose
concentration is known from the weight of the substance in a known volume
of the solution is called primary standard solution.

Figure 15. A standard solution prepared from a primary standard substance whose
concentration is known from the weight of that substance in a known volume (or weight) of
the solution.

A Secondary standard substance is a substance whose actual active

content is found by comparison against a primary standard through chemical
reactions.
Thus a Secondary standard solution is one in which the concentration
of the dissolved solute has not been found from the weight of the compound
dissolved but by reaction (titration) of a volume of the solution against
measured volume of a primary standard solution i.e. its concentration or titre
has been obtained by standardization, or which has been prepared from a
known weight of a secondary standard substance.
Standardization. The process of finding the concentration or the
reacting strength of a solution by titrating with a known amount of the
substance which is pure or has a known reaction value.
Titre ([T] = g/ml).The reacting strength of a standard solution, usually
expressed as the weight of titrated substance equivalent to 1 ml of the
standard solution. One should not confuse it with total volume of the titrant
used.
78
 You must know definition of some useful terms:
• Titrant or Standard solution – a solution of accurately known
concentration.
• Titration – the process of determining unknown concentration by
adding the small increments of standard solution until the reaction is
just complete.
• Burette – kind of laboratory glass for exact measurement of volume of
solution used. Burette is graduated and has a burette tap or stopcock at
one extreme end to control the flow of titrant.
Equivalence point (synonymous Stoichiometric Point or Theoretical
Point). The point in a titration at which the amount of titrant added is
chemically equivalent to the amount of substance titrated.
End point. The point at which the completion of a reaction is
practically observed. When using an indicator, the end point occurs when
enough titrant has been added to change the color of the indicator.
Indicator – a molecule whose conjugate acid or conjugate base has a
different color.
Standard substance – a substance used for standardizations primary
titrant solution. A compound has satisfied following criterions to act as a
standard substance:
• It should be pure.
• It should be stable up to moderate temperatures required for drying and
it should be stable indefinitely at room temperature. This means its
composition should be unchanged during storage.
• It should have a high molecular mass so that weighing errors
are minimum.
• The substance should be readily soluble.
• The reaction with the standard solution should be stoichiometric and
instantaneous. The titration error should be negligible.
Titration. The word titration comes from the Latin word "titulus",
which means inscription or title. The French word title means rank. Therefore,
Titration means the determination of concentration or rank of a solution with
respect to water with a pH of 7.
The standard solution is usually added from a graduated vessel called a
burette. The process of adding standard solution until the reaction is just
complete is termed as titration and the substance to be determined is said to be
titrated.
All chemical reactions cannot be considered as titrations. A reaction
can serve as a basis of a titration procedure only if the following conditions
are satisfied:
• The reaction must be a fast one.
• It must proceed stoichiometrically.
• The change in free energy (ΔG) during the reaction must be sufficiently
large for spontaneity of the reaction.
79
 • There should be a way to detect the completion of the reaction.
End point and Equivalent point. For a reaction, a stage which shows
the completion of a particular reaction is known as end point. Equivalence
point is a stage in which the amount of reagent added is exactly and
stoichiometrically equivalent to the amount of the reacting substance in the
titrated solution. The end point is detected by some physical change produced
by the solution, by itself or more usually by the addition of an auxiliary
reagent known as an 'indicator'. The end point and the equivalence point may
not be identical. End point is usually detected only after adding a slight excess
of the titrant. In many cases, the difference between these two will fall within
the experimental error.
Indicator. It is a chemical reagent used to recognize the attainment of
end point in a titration. After the reaction between the substance and the
standard solution is complete, the indicator should give a clear colour change.
When a titration is carried out, the free energy change for the reaction is
always negative. That is, during the initial stages of the reaction between A &
B, when the titrant A is added to B the following reaction takes place.

Equilibrium constant,
a = activity co-efficient.
Large values of the equilibrium constant K implies that the equilibrium
concentration of A and B are very small at the equivalence point. It also
indicates that the reverse reaction is negligible and the product C & D are
very much more stable than the reactants A & B. Greater the value of K the
larger the magnitude of the negative free energy change for the reaction
between A & B. Since, Free Energy Change = ∆G = – RT lnK
where, R = Universal gas Constant = 8.314 JK-1mol-1, T = Absolute
Temperature (K).
The reaction of the concentration of A & B leads to the reduction of the
total free energy change. If the concentrations of A & B are too low the
magnitude of the total free energy change becomes so small and the use of the
reaction for titration will not be feasible.
Expressions of Concentration of Solutions. A solution is a
homogeneous mixture of two or more components, the composition of which
may be changed. The substance which is present in smaller proportion is
called the solute, while the substance present in large proportion is called the
solvent.
The concentration or strength of solution means the amount of solute
present in a given amount of the solution. The concentration may be
expressed in physical or chemical units.
Normality (N): It is defined as number of gram equivalents of the
solute present in 1 litre (1000mL.) of the solution. If W g of solute of
80
equivalent weight E is present in V mL of the solution, the normality of the
solution is given by:

Molarity (M): It is defined as the number of moles of the solute

present in 1 litre (or 1000 mL) of the solution. A one molar solution contains
1 mole of the solute dissolved in 1 litre of the solution.

Molality (m): It is defined as the number of moles of solute dissolved

in 1000 g of the solvent. One molal solution contains one mole of the solute
dissolved in 1000 g of the solvent.
Normal solution: A solution containing one gram equivalent weight
of the solute dissolved per litre is called a normal solution; e.g. when 40 g of
NaOH are present in one litre of NaOH solution, the solution is known as
normal (N) solution of NaOH. Similarly, a solution containing a fraction of
gram equivalent weight of the solute dissolved per litre is known as
subnormal solution. For example, a solution of NaOH containing 20 g (1/2 of
g eq. wt.) of NaOH dissolved per litre is a sub-normal solution. It is written as
N/2 or 0.5 N solution.
• Formulae used in solving numerical problems on volumetric analysis;
• Strength of solution = Amount of substance in g litre-1.
• Strength of solution = Amount of substance in g moles litre-1.
• Strength of solution = Normality × Eq. wt. of the solute = molarity ×
Mol. wt. of solute.
• Molarity = Moles of solute/Volume in litre.
• Number of moles = Wt.in g/Mol. wt = M × V (initial) = Volume in
litres/22.4 at NTP (only for gases).
• Number of milli moles = Wt. in g × 1000/mol. wt. = Molarity ×
Volume in mL.
• Number of equivalents = Wt. in g/Eq. wt = x × No. of moles ×
Normality × Volume in litre (Where x = Mol. wt/Eq. wt).
• Number of mill equivalents (meq.) = Wt. in g × 1000 / Eq. wt =
normality × volume in mL.
• Normality = x × No. of mill moles (Where x = valency or change in
oxidation number).
• From the total volume of known solution (titrant) needed to react the
end point, the concentration of the unknown solution (analyte) can be
calculated using formula N1V1=N2V2 =>
𝑽𝟏 ∙ 𝑵𝟏
𝒂𝒏𝒅 𝑵𝟐 =
𝑽𝟐
𝑵𝟐 ∙ 𝑬𝒒(𝒂𝒏𝒂𝒍𝒚𝒕𝒆)
𝒕𝒉𝒆𝒏 𝑻𝒂𝒏𝒂𝒍𝒚𝒕𝒆 =
𝟏𝟎𝟎𝟎
81
 𝒎𝒂𝒏𝒂𝒍𝒚𝒕𝒆 = 𝑻 ∙ 𝑽𝒕𝒐𝒕𝒂𝒍 𝒔𝒍𝒏
𝒎𝒂𝒏𝒂𝒍𝒚𝒕𝒆
𝑾𝒂𝒏𝒂𝒍𝒚𝒕𝒆 , % = ∙ 𝟏𝟎𝟎%
𝒎𝒔𝒂𝒎𝒑𝒍𝒆
where N1, N2 → Normality of titrant and titrate respectively, V1, V2 →
Volume of titrant and titrate respectively.

Titration curves
The most important characteristics of titration methods are the titration
curves. The graphic show the dependence of the concentration of the
participants of the reaction occurring at titration (or the concentration
logarithm, or some solution property or characteristics) on the volume of the
added titrant (or the titration degree). For example, for the reactions of acid-
base interaction such characteristic is its pH.

The experimental titration curves result from measuring some system

characteristic in the process of titration (optical density, strength of diffusion
current, etc.) which changes depending on the volume of the added titrant and
then we draw the corresponding diagram. We mark the amount of the added
reagent on X-axis and on Y-axis (in case of liner curves) we mark the values
of the quantities which change linearly with the concentration change of one
of the reagents (electrical conductivity, optical density, etc.). When drawing
the logarithmic curves we mark on Y-axis the values of the quantities linearly
connected to the concentration logarithms of reagents (e. g. pH).

VOLUMETRIC ANALYSIS

It involves the estimation of a substance in solution by neutralization,

precipitation, oxidation or reduction by means of another solution of
accurately known strength. This solution is known as standard solution.
Volumetric analysis depends on measurements of the volumes of
solutions of the interacting substances. A measured volume of the solution of
a substance A is allowed to react completely with the solution of definite
82
strength of another substance B. The volume of B is noted. Thus we know the
volume of the solutions A and B used in the reaction and the strength of
solution B; so the strength of the other solution A is obtained. The amount (or
concentration) of the dissolved substance in volumetric analysis is usually
expressed in terms of normality. The weight in grams of the substance per
litre of the solution is related to normality of the solution as,
Weight of the substance (g per litre) = Normality × gram equivalent
weight of the substance.

Conditions of Volumetric Analysis:

a) The reaction between the titrant and titrate must be expressed.
b) The reaction should be practically instantaneous.
c) There must be a marked change in some physical or chemical property
of the solution at the end point.
d) An indicator should be available which should sharply define the end
point.
Different methods to determine the endpoint include:
pH indicator. A pH indicator is a substance that it changes its colour in
response to a chemical change. An acid-base indicator changes its colour
depending on the pH (e.g., phenolphthalein). Redox indicators are also
frequently used. A drop of indicator solution is added to the titration at the
start; at the endpoint has been reached the colour changes.
Potentiometer. It is an instrument that measures the electrode potential
of the solution. These are used for titrations based on a redox reaction; the
potential of the working electrode will suddenly change as the endpoint is
reached.
pH meter. It is a potentiometer that uses an electrode whose potential
depends on the amount of H+ ion present in the solution. (It is an example of
an ion-selective electrode.) This allows the pH of the solution to be measured
throughout the titration. At the endpoint, there will be a sudden change in the
measured pH. This method is more accurate than the indicator method and is
very easily automated.
Conductance. The conductivity of a solution depends on the ions
present in it. During many titrations, the conductivity changes significantly.
(i.e., during an acid-base titration, the H+ and OH- ions react to form neutral
H2O, this changes the conductivity of the solution.) The total conductance of
the solution also depends on the other ions present in the solution, such as
counter ions. This also depends on the mobility of each ion and on the total
concentration of ions that is the ionic strength.
Colour change that can be detect by naked eye. In some reactions, the
solution changes colour without any added indicator. This is often seen in
redox titrations, for instance, when the different oxidation states of the
product and reactant produce different colours.

83
 Precipitation. In this type of titration the strength of a solution is
determined by its complete precipitation with a standard solution of another
substance.
eg: AgNO3 + NaCl = AgCl + NaNO3
titrant analyte white ppt
AgNO3 + K2CrO4 = Ag2CrO4 + 2KNO3
titrant indicator brown-red ppt

Titration Methods. Titrations can be classified by the type of reaction.

Different types of titration reaction include:
Titration Technique Titrant Indicators to
Method be used
Neutralisation Alkalimetry MeOH pH indicator
(acid-basic Acidimetry HAn
titration) Halometry HAn, MeOH
Nonaqueous HClO4 in acetic
titration acid or nitrometane
NaOH or CH3ONa
in methanol
Redoximety Permanganatometry KMnO4 natural color
(reducing- Iodometry I2, KI and Na2S2O3 change or
oxidising) Bromatometry KBrO3 redox
Cerimetry Ce(SO4)2 indicator
Vanadatometry NH4VO3
Titanometry Ti2(SO4)3
Nitritimetry NaNO2
Precipitation Argentometry AgNO3 precipitating
titration Mercurometry Hg2(NO3)2 reagent or
Rhodanometry KSCN conductivity
Complexometry Mercurimetry Hg(NO3)2 metal ion
(complex Fluorimetry NaF indicator
compounds Complexonometry EDTA
formation)

Titration Techniques. In almost all cases, a burette is used to meter

out the titrant B volume ( mlB ). When a titrant reacts directly with an analyte
A, the procedure is termed a direct titration. The alternative technique is
called a back titration. Here, an intermediate reactant E is added in excess of
that required to exhaust the analyte A, then the exact degree of excess is
determined by subsequent titration of the unreacted intermediate E with the
titrant B. Another technique is called replacement titration as we will see
shortly.

84
 Direct Titration: In this method as mentioned earlier the titrant reacts
directly with the analyte usually in the conical flask in the presence of an
indicator.
Back titration is used when the analyte A either does not react with the
standard solution T or reacts too slowly. In this event, a previously known
excess of another standard solution E is added to the analyte, and the residue
of E after the reaction with the analyte A is complete is titrated with the
standard solution T:
A + Eexcess = Product + Eexcess
Eexcess + T = Product
Replacement (Substitution) Titration: Titration by substitution is used
when direct titration of the analyte is difficult, as is the case when no suitable
titrant or essential indicator is available. In this event, a reaction with an
undetermined excess of a suitable reagent E is used to convert the analyte A
into another compound D:
A + Eexcess → D
The produced D is titrated by the standard solution T: D + T →Product
Using the second reaction we can calculate the produced D and from the first
reaction we calculate the amount of A.

ACID BASE TITRATION

Acid-base titrations are based on the neutralization reaction between

the analyte and an acidic or basic titrant. These most commonly use a pH
meter, or a conductance meter to determine the endpoint. In our experiments
we will use a pH indicator to detect the endpoint of the reaction.
Neutralization is a chemical reaction, also called a water forming reaction, in
which an acid and a base or alkali (soluble base) react and produce a salt and
water:
acid + base →salt + water
For example, the reaction between hydrochloric acid and sodium hydroxide
solutions:
hydrochlorid acid + sodium hydroxide → sodium chloride + water
HCl + NaOH → NaCl + H2O
In acid-base titrations, solutions of alkali are titrated against standard
acid solutions. The estimation of an alkali solution using a standard acid
solution is called acidimetry. Similarly, the estimation of an acid solution
using a standard alkali solution is called alkalimetry.

The Theory of Acid–Base Indicators:

Ostwald, developed a theory of acid base indicators which gives an
explanation for the colour change with change in pH. According to this
theory, a hydrogen ion indicator is a weak organic acid or base. The

85
undissociated molecule will has one colour and the ion formed by its
dissociation will have a different colour.
Let the indicator be a weak organic acid of formulae HIn. It has
dissociated into H+ and In- . The unionized molecule has one colour, say
colour (1), while the ion, In- has a different colour, say colour (2).

Since HIn and In- have different colours, the actual colour of the
indicator will dependent upon the hydrogen ion concentration [H +]. When the
solution is acidic, that is the H+ ions present in excess, the indicator will show
predominantly colour (1).
On other hand, when the solution is alkaline, that is, when OH - ions
present in excess, the H+ ions furnished by the indicator will be taken out to
form undissociated water. Therefore there will be larger concentration of the
ions, In-. Thus the indicator will show predominantly colour (2).
Some indicators can be used to determine pH because of their colour
changes somewhere along the change in pH range. Some common indicators
and their respective colour changes are given below:
Indicator Colour on Acidic Range of Colour Colour on Basic
Side Change Side
Methyl Violet Yellow 0.0 - 1.6 Violet
Bromophenol Yellow 3.0 - 4.6 Blue
Blue
Methyl Orange Red 3.1 - 4.4 Yellow
Methyl Red Red 4.4 - 6.2 Yellow
Litmus Red 5.0 - 8.0 Blue
Bromothymol Yellow 6.0 - 7.6 Blue
Blue
Phenolphthalein Colourless 8.3 - 10.0 Pink
Alizarin Yellow Yellow 10.1 - 12.0 Red

i.e., at pH value below 5, litmus is red; above 8 it is blue. Between these

values, it is a mixture of two colours.
Indicators Used for Various Titrations:
The choice of a suitable indicator for a particular acid-base titration
depends on the nature of the acid and the base involved in the titration. We
may have the titration of:
1) a strong acid with a strong base
2) a weak acid with a strong base
3) a strong acid with a weak base
4) a weak acid with weak base
Which indicator is suitable for a given titration, can be found by
examining the titration curve of that titration. We have already discussed that
86
a suitable indicator is one which has a small pH range that falls wholly on the
upright portion of the titration curve.

1. Strong Acid against a Strong Base.

Let us consider the titration of HCl and NaOH. The pH values of
different stages of titration shows that, at first the pH changes very slowly and
rise to only about 4. Further addition of such a small amount as 0.01 mL of
the alkali raises the pH value by about 3 units to pH 7. Now the acid is
completely neutralized. Further of about 0.01 mL of 0.1 M NaOH will
amount to adding hydrogen ions and the pH value will jump to about 9. Thus,
near the end point, there is a rapid increase of pH from about 4 to 9.
An indicator is suitable only if it undergoes a change of colour at the
pH near the end point. Thus the indicators like methyl orange, methyl red and
phenolphthalein can show the colour change in the pH range of 4 - 10. Thus,
in strong acid- strong base titrations, any one of the above indicators can be
used.
But, the next diagram shows the pH curve for adding a strong acid to a
strong base. Superimposed on it are the pH ranges for methyl orange and
phenolphthalein.

You can see that neither indicator changes colour at the equivalence
point. However, the graph is so steep at that point that there will be virtually
no difference in the volume of acid added whichever indicator you choose.
However, it would make sense to titrate to the best possible colour with each
indicator.
If you use phenolphthalein, you would titrate until it just becomes
colourless (at pH 8.3) because that is as close as you can get to the
equivalence point.
On the other hand, using methyl orange, you would titrate until there is
the very first trace of orange in the solution. If the solution becomes red, you
are getting further from the equivalence point.

87
2. Weak Acid against Strong Base.
Let us consider the titration of acetic acid against NaOH. The titration
shows the end point lies between pH 8 and 10. This is due to the hydrolysis of
sodium acetate formed. Hence phenolphthalein is a suitable indicator as its
pH range is 8 - 9.8. However, methyl orange is not suitable as its pH range is
3.1 to 4.5.
The second diagram shows the pH curve for adding a strong base to a
weak acid.

This time, the methyl orange is hopeless! However, the

phenolphthalein changes colour exactly where you want it to.

3. Strong Acid against Weak Base.

Let us consider the titration ammonium hydroxide against HCl. Due to
the hydrolysis of the salt, NH4Cl, formed during the reaction, the pH lies in
the acid range. Thus, the pH at end point lies in the range of 6 to 4.
Thus methyl orange is a suitable indicator while phenolphthalein is not
suitable.
The third diagram shows the pH curve for adding a strong acid to a
weak abase.

88
 This time it is obvious that phenolphthalein would be completely
useless. However, methyl orange starts to change from yellow towards orange
very close to the equivalence point.
You have to choose an indicator which changes colour on the steep bit
of the curve.
Table 5. The types of titrants in acid-base titration
Strong Strong Weak Acids Weak Bases
Acids Bases
HCl NaOH Acetic acid Ammonia
HNO3 KOH Hydrocyanic acid Magnesium hydroxide
HBr etc HF Pyridine
H2SO4 Oxalic acid Sodium carbonate
HI Ethanoic acid Potassium carbonate
HClO4 etc etc

1st EXPERIMENT. Standardization of titrant NaOH solution against a

primary standard.
Apparatus: volumetric flask 250 mL, filter funnel, Erlenmeyer flask,
beaker 250 mL, burette 25 mL, pipette 10 mL.
Chemicals: 0.1N oxalic acid dihydrate, H2C2O4 ⋅ 2H2O solution, 0.1 N
solution of sodium hydroxide NaOH, Phenolphthalein indicator.

Standard solutions of strong acids and alkali can’t be prepared

immediately using the exact weight or volume of a more concentrated
solution. That’s why at first we prepare the solutions of approximate
concentration and then we standardize them.
As primary standards for acid solutions we use sodium borate
Na2B4O7·10H2O (borax), sodium carbonate Na2CO3 or its decahydrate
Na2CO3·10H2O.
The following reactions lay the foundation of acid standardization:
Na2B4O7 + 2HCl + 5H2O = 4H3BO3 + 2NaCl
Na2CO3 + 2HCl = 2NaCl + H2O + CO2↑.
During both titrations we use methyl orange as an indicator because in
the equivalence point a saline solution of a weak acid (the medium is
subacidic) is obtained.
The standardization of alkali solutions is conducted on oxalic acid
dihydrate H2C2O4 · 2H2O; they are titrated in the presence of phenolphthalein
as the medium is alkalescent in the equivalence point:
H2C2O4 + 2NaOH = Na2C2O4 + 2H2O
Using the results of the titration we calculate the normality of the
prepared process solution.
If there are any fixanals containing 0.1 mole of NaOH, HCl, H2SO4
then the titrants are prepared from them. There are also fixanals of the

89
primary standards mentioned above, the use of which greatly increases the
analysis fulfilment.
In this experiment, the primary standard is oxalic acid dihydrate,
H2C2O4 ⋅ 2H2O. It will be used to standardize a solution of sodium hydroxide.
Sodium hydroxide solutions pick up carbon dioxide from the air. This
contamination can affect the strength of the base solution and can spoil the
sharpness of the end point in the titration. The procedure below is designed to
prepare and standardize carbonate-free NaOH.
2 NaOH (aq) + H2C2O4 ⋅ 2H2O(s) = Na2C2O4 (aq) + 4 H2O (l)

PROCEDURE:
1) Reagent preparation
There are several ways to prepare free carbonate NaOH or KOH
solution.
To prepare 0.1 mol- eq/l NaOH or KOH solution the easiest way is to:
• Take a new bottle of NaOH or KOH pellets and quickly weigh 4.00 g of
NaOH or 5.60 g of KOH (NaOH has a molecular weight of 40 g/mol and
KOH 56 g/mol)
• Using a conical flask, dissolve the pellets in 200 ml of hot (40°C approx.)
freshly boiled distilled water, cover the flask with plastic film and leave to
cool to room temperature.
• Using a volumetric flask, quickly complete to 1000 ml with the same
freshly boiled distilled water.
• For long storage, use a polythene flask.

2) Standard preparation
To calibrate NaOH solution, use dihydrate oxalic acid H2C2O4*2H2O as
standard (molecular weight 126.0 g/mol). As in aqueous media, the 2 acid
functions are titrated together; a 0.1 mol-eq/l oxalic solution contains 0.05
mol/l (or 1/20 mol/l) of oxalic acid.
To prepare 1000 ml of 0.1 eq/l of standard. Weigh exactly 6.3000 g
(126.0/20) of oxalic acid. Using a volumetric flask, dissolve to 1000 ml with
freshly boiled distilled water.
3) Preparation of buret:
1. Firstly, a burette, pipette and flasks wash by distilled water.
2. Obtain about 100 mL of the sodium hydroxide solution in a clean
beaker. This should be enough for the initial cleaning of your burette
and for your first 3 trials.
3. Clean your burette: Add about 5 mL of the base solution from the
beaker to the burette (use a funnel to pour). Move the funnel around
while adding to ensure the sides of the burette are coated with base.
Alternatively, you can remove the burette with the 5 mL of
titrant from the burette stand and carefully tilt and rotate to coat all
interior surfaces with the titrant. Drain the solution through the
90
 stopcock into a waste beaker. Repeat this rinse with a second 5 mL
portion of base.
4. In a burette fill by a working solution NaOH: Pour more of the sodium
hydroxide solution into the burette until it is near the 0.00 mL mark.
Open the stopcock to allow several drops to rinse through the tip of the
burette. This should eliminate any air bubbles in the burette tip. Record
your initial buret reading on the data sheet for trial 1 (the volume does
not need to be exactly 0.00 mL).

4) Titration procedure:
• By means of the pipette, remove 10 mL of oxalic acid solution to each
of the three Erlenmeyer flasks. Remember that before removal of acid,
the pipette must be washed with acid solution.
• Add 1-3 drops of phenolophtaleine into each of the Erlenmeyer flasks.
• Fill up the burette with 0.10 M of NaOH solution up to the zero mark
(bottom menisque).
• Add 0.10 M NaOH solution drop-wise from the burette while stirring
slowly till the solution in the flask becomes a faint pink.
• When the solution becomes pink you must finish the titration process
and read the total volume of 0.10 M NaOH solution. It is an equivalent
point of acid-base titration.
• The experiment must be repeated three times (for 3 flask).
• Therefore the burette must be filled up with 0.10N NaOH solution up to
the zero mark. Repeat the procedure for flasks 2 and 3.
• Calculate the average volume of 0.10M NaOH solution from the three
measurements.
• Calculate the normality concentration of NaOH solution.

Figure 16. Titration of oxalic acid with sodium hydroxide

Setup of the apparatus during the titration.

91
5) Results of titration:
• Volume of standard solution for titration: Voxalic acid = 10 mL
• Normality of standard solution for titration: Noxalic acid = 0,1N
• Equivalent weight of oxalic acid: Eq( H 2C2O4  2H 2O) =
• Volume of titrant consumed for the 1st titration: V1NaOH =
• Volume of titrant consumed for the 2nd titration: V2NaOH =
• Volume of titrant consumed for the 3rd titration: V3NaOH =
• Average amount of titrant consumed for titration:
1 2 3
∗
𝑉𝑁𝑎𝑂𝐻 + 𝑉𝑁𝑎𝑂𝐻 + 𝑉𝑁𝑎𝑂𝐻
𝑉𝑁𝑎𝑂𝐻 =
3

6) Calculation:
The result is expressed as mol-eq/l concentration and based on the
following formula:
V NaOH ( ml ) N oxalic acid
=
Voxalic acid ( ml ) N NaOH =>
Voxalic acid ( ml )  N oxalic acid
N NaOH =
V * NaOH ( ml )
N NaOH  Eq( oxalic acid )
TNaOH =
1000

The calibration result can be accepted if 3 determinations give a result

with a relative standard deviation of less than 0.5%

2nd EXPERIMENT. Standardization of titrant HCl solution with

Na2B4O7*10H2O primary standard.
Apparatus: volumetric flask 250 mL, filter funnel, Erlenmeyer flask,
beaker 250 mL, burette 25 mL, pipette 10 mL.
Chemicals: 0.1N Na2B4O7*10H2O primary standard solution, 0.1N
solution of hydrochloric acid, methyl orange indicator.

For standardization of working HCl solution use by a method (a

measured volume of another primary standard solution) as the primary
standard sodium tetraborate or borax (Na2B4O710H2O) which reacts with
acid on the equation:
Na2B4O7 + 2HCl + 5H2O = 2NaCl + 4H3BO3
B4O72- + 2H3O+ = 3H2O + 4H3BO3
Borax or sodium tetraborate (Na2B4O7 10H2O) can be used as
a primary standard since it does not decompose under normal storage, it is
readily obtained in a very pure form (99.999% purity), it reacts with a known
stoichiometry and can be weighed and used directly.
92
 In water, the salt dissociates:
Na2B4O710H2O → 2Na+ + B4O72- + 10H2O
and the anion is hydrolysed: B4O72- + 7H2O → 4H3BO3 + 2OH-
The liberated hydroxide ions can be titrated with a strong acid and at
the point of their neutralization, the solution in the flask will contain the very
weak acid H3BO3, which will dissociate according to:
H3BO3 + H2O → H2BO3- + H3O+ Ka = 5.8 x 10-10
Thus at the neutralization point (or equivalence point: the point when
all the liberated OH- have been converted to H2O) the solution will be slightly
acidic (pH ~ 4.8; the actual pH depending on volumes and amounts used).
The indicator used to identify the strong base-strong acid equivalence point
must therefore change colour over the pH range 4.8 ± 1.
Safety Note: During this experiment you will be working with a weak base and a
strong acid. You must wear eye protection at all times. In the event that any reagent used
in this investigation comes in contact with your skin or eyes, wash the affected area
immediately with lots of water. Notify your instructor.

PROCEDURE:
I. Preparation of a primary standard sodium tetraborate solution.
To count weight of sodium tetraborate shot, which is necessary for
preparation 200 mL of 0.1 mol-eq/L solution.
The necessary quantity of sodium tetraborate (exact shot) is weighed in
glass or porcelain crucible, is transferred through the funnel
into volumetric flask (200 mL spaciousness). Then a crucible with the rests of
sodium tetraborate is weighed again. Shot in a volumetric flask is dissolved in
hot water, washing off the rests of salt from funnel into a volumetric flask.
After full dissolution of shot the solution is cooled and the liquid’s top surface
is curved into a meniscus, close a stopper and carefully mix.
Count molarity, normality and titer of primary standard solution of
sodium tetraborate using next formulas:
𝒎𝒔𝒐𝒍𝒖𝒕𝒆 𝒎𝒔𝒐𝒍𝒖𝒕𝒆 𝒎𝒔𝒐𝒍𝒖𝒕𝒆
𝑪𝑴 = ; 𝑵= ; 𝑻=
𝑴 ∙ 𝑽𝒔𝒍𝒏 𝑬𝒒 ∙ 𝑽𝒔𝒍𝒏 𝑽𝒔𝒍𝒏
II. Preparation of HCl solution.
The concentration of the concentrated solution of HCl was known as
10.170M. This is determined by the assay provided on the container of the
HCl. 4.916ml of the stock solution was measured and poured into 500 ml
volumetric flask filled with distilled water to the mark for which it
concentration is known to be 0.1M.
III Preparation of burette:
5. Firstly, a burette, pipette and flasks wash by distilled water.
6. Obtain about 100 mL of the hydrochloric acid solution in a clean
beaker. This should be enough for the initial cleaning of your burette
and for your first 3 trials.
7. Clean your burette: Add about 5 mL of the acid solution from the
beaker to the burette (use a funnel to pour). Move the funnel around
93
 while adding to ensure the sides of the burette are coated with base.
Alternatively, you can remove the burette with the 5 mL of
titrant from the burette stand and carefully tilt and rotate to coat all
interior surfaces with the titrant. Drain the solution through the
stopcock into a waste beaker. Repeat this rinse with a second 5 mL
portion of base.
8. In a burette fill by a working solution HCl: Pour more of the acid
solution into the burette until it is near the 0.00 mL mark. Open the
stopcock to allow several drops to rinse through the tip of the burette.
This should eliminate any air bubbles in the burette tip. Record your
initial burette reading on the data sheet for trial 1 (the volume does not
need to be exactly 0.00 mL).
IV. Titration procedure:
• By means of the pipette, remove 10 mL of borax solution to each of the
three Erlenmeyer flasks. Remember that before removal of acid, the
pipette must be washed with borax solution.
• Add 1-3 drops of methyl orange into each of the Erlenmeyer flasks.
Solution turns into yellow colour.
• Fill up the burette with 0.10 M of HCl solution up to the zero mark
(bottom menisque).
• Add 0.10 M HCl solution drop-wise from the burette while stirring
slowly till the solution in the flask becomes a pink.
• When the solution becomes pink you must finish the titration process
and read the total volume of 0.10 M HCl solution. It is an equivalent
point of acid-base titration.
• The experiment must be repeated three times (for 3 flask).
• Therefore the burette must be filled up with 0.10N HCl solution up to
the zero mark. Repeat the procedure for flasks 2 and 3.
• Calculate the average volume of 0.10M HCl solution from the three
measurements.
• Calculate the normality concentration of HCl solution.

Results of titration:
• Volume of standard solution for titration: Vborax = 10 mL
• Normality of standard solution for titration: Nborax = 0,1N
• Equivalent weight of borax: 𝐸𝑞𝑁𝑎2𝐵4𝑂7∙10𝐻2 𝑂 =
• Volume of titrant consumed for the 1st titration: V1HCl =
• Volume of titrant consumed for the 2nd titration: V2HCl =
• Volume of titrant consumed for the 3rd titration: V3HCl =
• Average amount of titrant consumed for titration:
1 2 3
∗
𝑉𝐻𝐶𝑙 + 𝑉𝐻𝐶𝑙 + 𝑉𝐻𝐶𝑙
𝑉𝐻𝐶𝑙 =
3

94
Calculation:
The result is expressed as mol-eq/l concentration and based on the
following formula:
𝑉𝑏𝑜𝑟𝑎𝑥 𝑁𝐻𝐶𝑙 𝑉𝑏𝑜𝑟𝑎𝑥 ∙ 𝑁𝑏𝑜𝑟𝑎𝑥
∗ = => 𝑁𝐻𝐶𝑙 = ∗
𝑉𝐻𝐶𝑙 𝑁𝑏𝑜𝑟𝑎𝑥 𝑉𝐻𝐶𝑙

𝑁𝐻𝐶𝑙 ∙𝐸𝑞𝐻𝐶𝑙
𝑇𝐻𝐶𝑙 =
1000

𝑁𝐻𝐶𝑙 ∙𝐸𝑞𝑁𝑎2 𝐵2𝑂7∙10𝐻2𝑂

𝑇𝐻𝐶𝑙/𝑁𝑎2𝐵4 𝑂7∙10𝐻2 𝑂 =
1000

The calibration result can be accepted if 3 determinations give a result

with a relative standard deviation of less than 0.5%

CONTROL OF MASTERING THE TOPIC

Typical calculation tasks
Task 1. How many grams of KOH should be taken to prepare 500 mL 0.05 M
of alkali solution.
Task 2. What volume of hydrochloric acid with the mass fraction of HCl
equal to 20 % (density 1.10 g/mL) should be taken to prepare 500 mL of 0.1
M of HCl solution.
Task 3. How many grams of Na2B4O7·10H2O should be taken to prepare 250
mL of its 0.1N solution (feq =1/2, M(Na2B4O7 · 10H2O) = 381 g/mol)?
Task 4. What mass of oxalic acid dihydrate should be taken in order to use 20
mL of 0.1 M of NaOH solution (M(H2C2O4 · 2H2O) = 126 g/mol)?
Task 5. Calculate the content of hydrochloric acid and general acidity of
human gastric juice sample (in mol/L) if to titrate 10.0 mL of the juice with
methyl orange we used 3.10 mL of 0.098 M of NaOH solution and with
phenolphthalein – 6.0 mL of the alkali.
Task 6. 9.7770 g of concentrated solution of HNO3 were diluted by water to
get 1 litre of the solution in the volumetric flask. To titrate 25.0 mL of the
obtained solution we used 23.40 mL of 0.1040 M of NaOH solution.
Determine the mass fraction of nitric acid in its concentrated solution.
Task 7. To titrate 5.0 mL of sulphuric acid solution we used 4.12 mL of 0.102
M of NaOH solution. Calculate the normality of the acid solution.
Task 8. To titrate 0.286 g of Na2CO3·10H2O in the presence of methyl orange
we used 24.10 mL of HCl solution. Calculate the molarity of HCl solution.
Task 9. A 1.05 g sample of limestone was reacted with a 50.00 mL aliquot of
0.500 M hydrochloric acid. After the reaction had ceased, the excess acid was
back titrated with 0.500 M NaOH(aq) solution to the bluish bromothymol
blue endpoint. A titre of 23.40 mL was obtained. What was the % w/w
CaCO3 in the limestone?
Task 10. What is the concentration and titer of 10.00 mL of HBr if it
takes16.73mL of a 0.253M LiOH solution to neutralize it?
95
Task 11. A sodium carbonate (Na2CO3) primary standard solution is prepared
by dissolving 10.587 g of the substance in enough distilled water, then
transferring it quantitatively to a 250 mL volumetric flask and finally making
up to the mark with distilled water. To titrate 20.0 mL of the obtained solution
we used 21.15 mL of HCl solution. Determine the normality and titer of
hydrochloric acid solution.
Task 12. 10.00 mL of a dilute acetic acid solution are titrated with a sodium
hydroxide (NaOH) solution of molar concentration 0.1078 M. At the
equivalence point, it is found that 13.42 mL of NaOH have been added. What
is the molarity of the unknown acetic acid solution?
Task 13 Write out a balanced reaction for the neutralization of sulfuric acid
(H2SO4) with sodium hydroxide. What volume of 0.541M NaOH is necessary
to react completely 20.0 mL of sulfuric acid whose molarity is 1.26 M?

QUESTIONS FOR TEST SELF-CHECK

(with multiple responses «correct-incorrect»)
1. In the method of acid-base titration the standard solutions are the
following:
a) NH4OH; b) H2SO4; c) H3BO3; d) NaOH.
2. As primary standards in the method of acid-base titration we use the
following substances:
a) H2C2O4 · 2H2O; b) Na2CO3 · 10H2O;
c) Na2B4O7 · 10H2O; d) Na2SO4 · 10H2O.
3. Four aqueous solutions with the volume of 1 liter have been prepared from
the substance weights (or gas volume) indicated below. What are the cases
when the molar concentration of the equivalent of the obtained solution is
equal to 0,1 mol/L?
a) 4.0 g NaOH; b) 2.24 L HCl (norm. cond.);
c) 4.9 g H2SO4 (feqv = 1/2); d) 5.6 g KOH.
4. The concentration of solutions or the amount of which substances in the
mixture can be determined by the method of acid-base titration?
a) NaCl; b) Na2CO3; c) Na2Cr2O7; d) HCl.
5. Which factors determine the choice of the indicator at acid-base titration?
a) interval of colour transition of the indicator;
b) area of pH leap on the titration curve;
c) pH in the equivalence point;
d) volume of the titrated solution.
6. Which indicators can be used to titrate ammonia solution by a standard
HNO3 solution?
a) bromphenol blue, ∆pH = 3.0…4.6;
b) neutral red, ∆pH = 6.8…8.0;
c) methyl orange, ∆pH = 3.1…4.4;
d) phenolphthalein, ∆pH = 8.2…10.0.
7. In aqueous solutions of which salts litmus (pT=7) will become blue?
96
a) CaCl2; b) Al2(SO4)3; c) NaNO3; d) Na2CO3.
8. To titrate 10,0 mL of NaOH solution we used 12,0 mL of 0,10 M of HCl
solution. Which of the following figures corresponds to the composition of
the analyzed alkali solution?
a) 0.00480 g/mol; b) 7.2·1022 NaOH molecules/L;
c) 0.12 mol/L; d) 12 g/L.
9. To titrate 10,0 mL of H3PO4 solution in the presence of methyl orange we
used 5,0 mL 0,2 M of NaOH solution. What are the mass and the amount of
H3PO4 in 1litre of the analyzed solution?
a) 4.9 g; b) 9.8 g; c) 0.05 mol; d) 0.1 mol.
10. In 1 liter of water 22.4 mL of a gaseous HCl (norm. cond.) were
dissolved. What are the pH and pOH of the obtained solution?
a) pH = 3; b) pH = 1; c) pOH = 11; d) pOH = 13.

Reference
1 Tan,Y.T., Ashy Kumren. (2011) Chemistry for Matriculation. Selangor,
Malaysia: Oxford Fajar.
2 Tan,Y.T., Loh,W.L., Kathirasan Muniandy. (2010) Ace ahead chemistry
volume 1 and 2. Selangor, Malaysia: Oxford Fajar.
3 Retrived from www.chemguide.co.uk/physical/acidbaseeqia/theories.html
4 Analytical Chemistry for Technicians, John Kenkel, 3rd edition, page 130,
142.

LABORATORY WORK 5
THE ACID BASE TITRATION OF FOOD

Objective: to determine total acidity of milk, juice, vinegar and oil acid
value via acid-base titration, making use of the reaction of weak acid with a
strong base, sodium hydroxide.
At the end of the laboratory session you should be able to:
✓ use an analytical balance,
✓ use a pipette filler and a pipette,
✓ use a volumetric flask to make up a solution of a given concentration
accurately,
✓ use a burette to carry out a titration.
Other outcomes: You will develop an understanding of how an acid-
base indicator can be used to establish the end-point of a titration.

Equipment Required: 25 mL or 50 mL burette , 10 mL volumetric

pipette, 1000 mL and 100 mL volumetric flasks, 250 mL conical Erlenmeyer
flasks (3), 100 mL beakers and graduated cylinder, stand, funnel, balance
Reagent: 0.1N sodium hydroxide (standardised) solution,
phenolphthalein indicator (1% ethanolic), CO2-free distilled/deionised water.

97
 Titrimetry is a chemical method for determining the concentration of
the solution using another solution of known concentration, called standard
solution or titrant.
Titration is the slow addition of one solution of a known concentration
to a known volume of another solution of unknown concentration until the
reaction reaches completion.
Acid-Base titration involves neutralization reaction between an acid
and a base. Its basis is the equivalence point, wherein the amount of the titrant
added is stoichiometrically equivalent to the amount of analyte, thus, the
concentration of the unknown can be calculated.
The type of acid-base titration where titrant is strong base solution is
called Alkalimetry.
Sodium hydroxide is the titrant wide used in titrating various foods and
drinks to determine its acidity.
Food acids are usually organic acids, with citric, malic, lactic, tartaric,
and acetic acids being the most common.
The organic acids present in foods influence the:
1. flavor (i.e., tartness),
2. color (though their impact on anthocyanin and other pH-influenced
pigments),
3. microbial stability (via inherent pH-sensitive characteristics of organisms),
4. and keeping quality (arising from varying chemical sensitivities of food
components to pH).
Organic acids may present:
• Naturally,
• By Fermentation,
• Added as part of a specific food formulation.
The importance of determining food acidity:
1) To determine the degree of maturity of fruits and vegetables and crop
(The titratable acidity of fruits is used, along with sugar content, as an
indicator of maturity, generally the higher the maturity, the lower the acid
content. e.g. in the ripening process).
2) To determine the freshness of foods (for example in milk, the more the
lactic acid levels, means that milk is rotten.
3) Acidity indicators reflect the quality of food (the amount of organic acids
in food directly affects the food flavor, color, stability, and the level of
quality.
4) Determination of acid on the microbial fermentation process (such as:
fermentation products in soy sauce, vinegar and other acids is an
important indicator of quality).
There are two ways to express food acidity:
Total Acidity or Titratable Acidity (TA) refers to the total
concentration of free protons [H+] and undissociated acids in a solution that
can react with a strong base and be neutralized.
98
 Active Acidity (AA) is the concentration only of free the H+ protons that
are present in the solution. The measure of the active acidity is the pH of the
solution. AA is only part of the total acidity and can not be greater than it.
A Titratable Acidity titration will generally use the strong base, NaOH,
and either a chemical indicator or pH meter to signal when equivalent
amounts of base have been metered into the sample. The concentration of
sodium hydroxide used is typically 0.1 N.
Principle is alkalimetry i.e. neutralization with sodium hydroxide
solution of known normality using a suitable indicator, such as methyl orange,
phenolphthalein indicator, etc. The choice of the indicator depends on the pH
when the colour changes and which acid is titrated. For the titration of weak
acids by strong base we choose indicator with colour rearrangement at higher
pH (6, 8 to 10) i.e. phenolphthalein indicator.

1st EXPERIMENT. Determination of milk acidity

As the acidity has a major influence on the taste of the product, this
parameter is used to test the quality of milk. As the acidity of milk increases
with the storage time, this parameter is also a means of checking storage
conditions. The acidity of milk is of two kinds.
• Natural acidity which is due to citrates and phosphates present in the
milk and dissolved CO2 during the process of milking and thereafter.
• Developed acidity which is due to lactic acid produced by the action of
bacteria on lactose in milk.
Expression of titratable acidity:
1) Soxhlet Henkel degree (°SH): – the volume (ml) of 0.25N NaOH used
per 100 ml of sample
2) Thorner degree (°Th): – the volume (ml) of 0.1N NaOH used per 100
ml of sample
3) Domic degree (°D): – the volume (ml) of 0.1N NaOH used per 100 ml
of the sample
Usually, acidity of milk is expressed as percentage of lactic acid. In this
case the acidity of cow milk ranges from 0.10 to 0.26 %.
Generally the acidity of milk means the total acidity (Natural +
developed) or titrable acidity. Fresh, freshly baked milk has the total acidity
of 16 – 18°T, but after two hours (if the milk has not cooled) the acidity rises.
Milk allowed for sale has an acidity of less than 21°T.

PROCEDURE:
1. Mix the milk sample thoroughly by avoiding incorporation of air.
2. Transfer 10 ml milk to the 150 mL conical flask or beaker.
3. Add 20 mL of distilled water (ambient water that has been just boiled).
4. Add 3-4 drops of phenolphthalein indicator and stir.

99
5. Rapidly titrate the contents with 0.1 M NaOH solution, continue to add
alkali drop by the drop and stirring the content till first definite change to faint
pink color, which lasts for 5 sec
6. Note down the final burette reading: VNaOH =
NNaOH =
7. Calculate Total Acidity using formula: TA = VNaOH * 10 (T)
8. Calculate percentage of lactic acid:
VNaOH  0.009
Wlactic acid % =  100%
Vmilk
1 ml of 0.1N NaOH alkali is equivalent to 0.009 g of lactic acid.

2nd EXPERIMENT. Determination of total acidity for fruit juice

The acidity of fruit juice may be determined by simple direct titration
with 0.1M sodium hydroxide, using phenolphthalein as an indicator.
The acidity of natural fruit juices is the result mainly of their content of
organic acids. For example, most fruits contain the tricarboxylic acid (citric
acid) whereas grapes are rich in tartaric acid and peaches, apricots and
plums in malic acids.
Both tartaric & malic acids are dicaroxylicacids.

PROCEDURE:
1. Weight approximately 10 gm juice in conical flask: mjuice =
2. Add 25 ml of distilled water.
3. Add 2 – 3 drops of phenolphthalein indicator and stir.
4. Titrate with standardized NaOH solution, continue to add alkali drop by the
drop and stirring the content till first definite change to faint pink color, which
lasts for 5 sec
5. Note down the final burette reading: VNaOH =
NNaOH =
6. Calculate percent acidity of fruit juice (example, citric acid):
192.43
Wcitric acid % = V NaOH (in L)  N NaOH 
3
Normal range for citric acid = 0.39 – 1.1 %
192.43 g/mol is the molecular weight of citric acid
Why we divide by 3 when we calculate the weight of citric acid?

7. Calculate total acidity of fruit juice:

VNaOH  N NaOH  M eq acid
TA, % =  100%
m juice  1000

100
Table 6. Standard Acids of Some Foods and milliequivalent weight (Meq):
Fruit Organic Milliequivalent Fruit Organic Milliequivalent
acid weight of acid acid weight of acid
Apple Malic 67 Orange Citric 64
Apricot Malic 67 Peach Malic 67
Banana Malic 67 Pear Malic 67
Blueberry Citric 64 Pineapple Citric 64
Cherry Malic 67 Plum Malic 67
Cranberry Citric 64 Raspberry Citric 64
Grapefruit Citric 64 Strawberry Citric 64
Grape Tartaric 75 Tomato Citric 64
Lemon Citric 64 Wine Tartaric 75
Lime Citric 64

3rd EXPERIMENT. Determination of total acidity of the vinegars and the

marinades.
Vinegar is an aqueous solution of an organic acid, the acetic acid.
The total acidity of vinegars is derived both from the original
fermentation process & from acidic salts present in the original used for
fermentation. It may be determined titrimetrically with 0.1M sodium
hydroxide, using phenolphthalein as an indicator.
CH3COOH(aq) + NaOH(aq) -> CH3COONa(aq) + H2O(l)
The natural acidity of vinegar is mainly due to the presence of acetic
acid (CH3COOH), which is volatile.
The purpose of this work is to determine the percentage of acetic acid
in marinades and pickles. Marinades are foods that are preserved with acetic
acid. Pasteurized or sterilized canned vegetables should contain 0.4 to
0.7% acetic acid and, in some cases, up to 1.0%.

PROCEDURE:
1. Weight 5 gm vinegar (marinade) in conical flask: m sample =
2. Add 50 ml of distilled water.
3. Add 2 – 3 drops of phenolphthalein indicator and stir.
4. Titrate with standardized NaOH solution, continue to add alkali drop by the
drop and stirring the content till first definite change to faint pink color, which
lasts for 5 sec
5. Note down the final burette reading: VNaOH =
NNaOH = 0,1 N
6. Calculate percent acidity as acetic acid (MW = 60.05g/mole):

Weight of acetic acid = (0.1M NaOH* volume of NaOH (in liter) * MW).
VNaOH  N NaOH  M eq ( acetic acid
)
TA, % =  100%
msample  1000

101
4th EXPERIMENT. Determination of oil acid value for oils and butter
Reagent: potassium hydroxide (KOH), about 0.1 mol/l solution in
ethanol (the exact concentration should be known), phenolphthalein indicator
(1% ethanolic), solvent mixture 1/1 (V/V) of 95 per cent (V/V) ethanol and
diethyl ether.

Rancidity may occur in oils, fats and butters samples upon storage
especially when they contains high content of fatty acid or fatty oils. The
decomposed components such as free fatty acids, peroxides, low molecular
weight aldehydes and low molecular weight of ketones are produced. This
would result in distinctive smell and affect the quality of the oils, fats and
butters samples.
This work describes method for the determination of the free fatty acid
content of animal and vegetable oils and fats. This content can be expressed
as an acid value, or as acidity.
The acid value is the number of mg of potassium hydroxide required to
neutralize the free fatty acids in 1 g of the fat. Sodium hydroxide may also be
used.
The acid value is determined by directly titrating the oil/fat in an
alcoholic medium against standard potassium hydroxide/sodium hydroxide
solution.
The acidity is an expression of the content (in %, m/m; percentage) of
free fatty acids as content of dominant or chosen fatty acid. According to the
nature of the fat it can be expressed as in Table 7.
Table 7. The nature of the fats food
Nature of fat Expressed as Molecular weight
Coconut, palm kernel and similar Lauric acid 200
oils
Palm oil Palmitic acid 256
All other oils Oleic acid 282

PROCEDURE:
1. Weigh accurately a quantity (2 - 3 g) of the fatty oil into a 250-mL conical
flask: m sample =
2. Add 50 mL of ethanol-ether solution. Shake it well. If necessary, reflux the
mixture gently until the substance is completely dissolved.
3. Titrate the solution with potassium hydroxide titrant until pink colouration
can be observed which persists for 30 sec.
4. Note down the final burette reading: VKOH =
5. Calculate the acid value according to the following equation:
VKOH  N KOH  k  56,11 
Acid Value =
msample
56.11 – it is a titer of 1L 0.1N KOH solution
k – Correction factor («titer») without unit
102
Acid value of sunflower oil is not more than 6.
When the acid value is less than 10, it is suggested that a 10-mL semi-
micro burette may be used for the titration.
6. The acid value is also expressed as per cent of free fatty acids (FFA)
calculated as oleic acid:
VKOH  N KOH  282
FFA, % =
msample
282 - Molecular weight of oleic acid in g/mol
Free fatty acids (FFA) calculated as oleic acid is 15.9%.

QUESTIONS FOR TEST SELF-CHECK

(with multiple responses «correct-incorrect»)
1) Define the following terms: titration, equivalence point, end point, titration
curve, primary standard solution and secondary titrant solution
2) A 60 mL HCl solution is titrated with 25 mL of a 0.60M KOH solution.
What is the concentration of the HCl solution?
A) 0.25 mol/L B) 1.56 mol/L C) 0.65 mol/L D) 2.5 mol/L
3) In a titration of a weak acid with a strong base, what is the pH of the
solution at the equivalence point?
Choose 1 answer:
A) > 7 is greater than, 7
B) < 7 is less than, 7
C) is equal 7
D) is equal 0
4) Which of the following describes the equivalence point on a graph of pH
versus the amount of titrant added to a solution?
A) The point where the magnitude of the slope of the curve is least
B) The point on the curve with the lowest pH
C) The point where the magnitude of the slope of the curve is greatest
D) The point on the curve with highest pH
5) Titration curves exhibit an asymptote at very large volumes of added
titrant. Which of the following experimental parameters determines the
location of this asymptote?
A) The pH of the initial solution
B) The Ka of the initial solution
C) The slope of the curve on the titration curve
D) The pH of the titrant
6) Which of the following pH indicator ranges would be the most useful for
the titration of a weak base with a strong acid?
A) 5-8 B) 8-10 C) 4-6 D) 7-8
6) Solve the neutralization problems below using the equation NaVa = NbVb.
Show all work:
1. If it takes 54 mL of 0.1 M NaOH to neutralize 125 mL of an HCl
solution, what is the concentration (normality and titer) of the HCl?
103
 2. If it takes 25 mL of 0.05 M HCl to neutralize 345 mL of NaOH
solution, what is the concentration (normality and titer) of the NaOH
solution?
3. If it takes 50 mL of 0.5 M Ca(OH)2 solution to completely neutralize
125 mL of sulfuric acid solution (H2SO4), what is the concentration
(normality and titer) of the H2SO4 solution?
4. How many milliliters of 0.360 M H2SO4 are required to neutralize 25.0
mL of 0.100 M Ba(OH)2?
5. What is the molarity of a 30.0 mL hydrochloric acid solution (HCl)
which is just neutralized by 48.0 mL of 0.100 M sodium hydroxide
(NaOH)?
6. 25.0 mL of aqueous sodium hydroxide solution of unknown
concentration was placed in the conical flask. The burette was filled to
the 50 mL mark with 0.10 mol*L-1 aqueous hydrochloric acid
solution. The sodium hydroxide solution was neutralised when 20.0 mL
of hydrochloric acid had been added. Determine the concentration
(normality and titer) of the sodium hydroxide solution.

Reference
1 Nielsen S. Food Analysis. Springer Science & Business Media, 2014.
2 Skoog D. A.; West D. M.; Holler F. J. Fundamentals of Analytical
Chemistry, 7th Edition, Thomson Learning, Inc, USA, 1996.

LABORATORY WORK 6
PRECIPITATION TITRATION
ARGENTOMETRY
MOHRS METHODS

Objective: Determination of chloride ions content in solid and liquid samples

by the Mohr Method
Learning Outcome:
• Students understand the terms volumetric analysis, morarity, molality
normality and redox titration.
• Students acquire the skill to prepare standard solutions of silver nitrate
and sodium chloride.
• Students understand the apparatus used for a titration.
• Students acquire the skill to perform the precipitation-titration in the
real lab after understanding the different steps.

Titration is a process by which the concentration of an unknown

substance in solution is determined by adding measured amounts of a
standard solution that reacts with the unknown. Then the concentration of the

104
unknown can be calculated using the stoichiometry of the reaction and the
number of moles of standard solution needed to reach the so called end point.
Precipitation titrations are based upon reactions that yield ionic
compounds of limited solubility.
Classification of methods precipitation titration (on titrant):
1. Argentometry
2. Thiocyanatometry
3. Mercurometry
4. Sulphatometry
5. Hexacianoferratometry
Characteristics of Precipitation Titration:
✓ They are fast and the stoichiometry is known and reproducible, (no
secondary reactions of interference).
✓ They are complete or can be quantified depending on the amount of
solubility product (in general a precipitation titration is considered complete
when Ksp< 10-8)
✓ An indicator can be used to find the equivalence point or titration end
point which, for this type of titration, corresponds to when precipitation of the
analyte under analysis is complete.

THE SOLUBILITY AND SOLUBILITY PRODUCT CONSTANT

When an ionic compound is dissolved in water, it usually goes into
solution as the ions. When an express of the ionic compound is mixed with
water, equilibrium occurs between the solid compound and the ions in the
saturated solution:
KxAy = xK+ + yA-
ppt
The equilibrium constant for this solubility process can be written:
[𝐾 + ]𝑥 ∙ [𝐴− ]𝑦
𝐾𝑒𝑞 =
[𝐾𝑥 𝐴𝑦 ]
However, because the concentration of the solid remains constant (in
heterogeneous systems), we normally combine its concentration with K eq to
give the equilibrium constant Ks, which is called the solubility product
constant:
𝐾𝑠 = 𝐾𝑒𝑞 ∙ [𝐾𝑥 𝐴𝑦 ] = [𝐾 + ]𝑥 ∙ [𝐴− ]𝑦
In general, the solubility product constant, Ks, is the equilibrium
constant for the solubility equilibrium of slightly soluble (or nearly insoluble)
ionic compounds. It equals the product of the equilibrium concentrations of
the ions in the compound, each concentration raised to a power equal to the
number of such ions in the formula of the compound.
At equilibrium in saturated solution of slightly soluble compound at
given temperature and pressure the value of Ks is constant and not depend on
ions concentration. The solubility product constant is thermodynamic
constant and depends on temperature and ions activity (ionic strength).
105
 The reaction quotient, Q, is an expression that has the same form as the
equilibrium constant expression Ks, but whole concentration values are not
necessarily those at equilibrium. Though the concentrations of the products
are starting values: 𝑄 = [𝐾 + ]𝑥 ∙ [𝐴− ]𝑦
Here Q for a solubility reaction is often called the ion product, because
it is product of ion concentrations in a solution, each concentration raised to a
power equal to the number of ions in the formula of the ionic compound.
• Precipitation is expressed to occur if the ion product Q for a solubility
reaction is greater than Ks: Q > Ks.
• If the ion product Q is less than Ks, precipitation will not occur (the
solution is unsaturated with respect to the ionic compound): Q < Ks.
• If the ion product Q equal Ks, the reaction is at equilibrium (the
solution is saturated with the ionic compound): Q = Ks.

Calculation of solubility
Solubility (S) it is the quantity of solute that dissolves in a given
quantity of solvent at a particular temperature. Solubility is often
expressed as the mass of solute per volume (g/L) or mass of solute per mass
of solvent (g/g), or as the moles of solute per volume (mol/L: molar
solubility). Even for very soluble substances, however, there is usually a limit
to how much solute can dissolve in a given quantity of solvent. In general, the
solubility of a substance depends on the temperature, the nature of solute or
solvent, and the pH.
Solubility, SM (mole/L), is the molar concentration of compound in
saturated solution.
𝑥+𝑦 𝐾𝑠
I. Saturated solution of slightly soluble ionic compound: 𝑆 = √𝑥 𝑥∙𝑦𝑦
II. Saturated solution of good soluble ionic compound.
This type of solutions not used in analytical practice. Such solutions are
very concentrated and have large ionic strength. Components of these
solutions (ion, molecules) can associate and form various polymers and
colloids.
III. Saturated solution of slightly soluble compound with very small
solubility:
• the substance have limited solubility but create ion pairs and various
molecular forms. The ionic strength of this solution is high and
solubility depends on common concentration of all molecular and ionic
forms;
• slightly soluble compound takes part in protolytic reaction with water
with the pH change.
The solubility is affected by pH. If the anion is the conjugate base of a
weak acid, it reacts with H+ ion. Therefore, the solubility slightly soluble
compound to be more in acid solution (low pH) than it is in pure water.

106
 In sour environment solubility of slightly soluble compounds is more
than more is its Ks and more is the hydrogen ion concentration:
𝐾𝑠 [𝐻+ ]
𝑆𝐾𝑥𝐴𝑦 = [𝐾 + ] √
= − = 𝐾𝑠 ∙ ( + 1)
[𝐴 ] 𝐾𝑎
when [𝐻+ ] = 𝐾𝑎 , 𝑆𝐾𝑥𝐴𝑦 = √2𝐾𝑆

Factors which influence to solubility:

1. Temperature.Solubility for most of substances is endothermic
process. Increase temperature occurs decrease solubility. But crystal
compounds at various temperature form hydrates another structure
(composition). Hydrates formation may be exothermic reaction.
2. Ionic strength of solution. Increasing of ionic strength causes
decreasing of ions activity and, accordingly, Ks will increase. Because,
solubility will increase. An example of it is salting effect.
Salting effect is increase the solubility of slightly soluble compounds in
presence of strong electrolytes, which not have common ions with precipitate
and not react with precipitate ions.
3. Common-ion electrolytes. Completeness of precipitation.
The importance of the solubility product constant becomes apparent
when we consider the solubility of one salt in the solution of another having
the same cation or anion. The effect of the common ion is to make slightly
soluble salt less soluble than it would be in pure water. This decrease in
solubility can be explained in terms of Le-Chatelier’s principle. It is example
of the common-ion effect.
Decrease of solubility of slightly soluble compounds in presence of
electrolyte with common ions called common-ion effect.
But solubility of slightly soluble compounds decrease to moment when
ionic strength of solution will begin to influence to solubility.
The ion is completely precipitated when its residual concentration (C min)
is less than 1×10-6 M (Cmin < 1×10-6 M). Amount of precipitant must be more
at 20-50 % it is necessary to stoichiometry equation.
If in solution are ions, which form slightly soluble compounds with
precipitant, the sequence of its precipitation determines (depends on)
Ks value.
Fractional precipitation is the technique of separating two or more ions
from a solution by adding a reactant that precipitates first one ion, than
another, and so forth.
4. The pH value (see above).
5. Complex compound formation. Solubility increases with increasing
concentration of ligand, complex compound stability and Ks value.
6. Redox process. Redox reaction shift on equilibrium in heterogeneous
system and change solubility of slightly soluble compounds.

107
 ARGENTOMETRY

The most important precipitating reagent is silver nitrate (AgNO3).

Titrimetric methods based upon silver nitrate as titrant are sometimes termed
argentometric methods. Potassium chromate can serve as an end point
indicator for the argentometric determination of chloride, bromide and
cyanide ions by reacting with silver ions to form a brick-red silver chromate
precipitate in the equivalence point region.
Fields of argentometry application:
• The determination of the anions Cl-, I-, Br- and Ag+ is also common.
• Environment: Determination of chloride in water.
• Food and beverage: Determination of chloride in finished products
(cooked meats, preserves). Determination of chloride in dairy products.
• Precious metals: Determination of silver in various alloys (for
jewellery).
• Pharmaceuticals: Titration of halides.
The reaction rates for the silver salt precipitation is rapid. The reaction
ratio is 1:1 and silver salts formed are generally quite insoluble. Table below
gives the solubility product, Ksp, for the silver salts that are involved in
precipitation titrations.
Table 8. Solubility products for silver salts
Anion Ksp Solubility (g/100mL)
-10
Cl- 1.8 x 10
Br- 5.2 x 10-13
I- 8.3 x 10-17
SCN- 1.1 x 10-12 0.00002
2- -12
CrO4 2.6 x 10 0.0025

Endpoint detection for argentometric titration. Another requirement

of titrimetric analysis is that there must be some method of determining when
the titration reaction has reached its equivalence point. In this experiment, you
will compare two methods of endpoint detection, one using a chemical
indicator and another using potentiometric detection. We will now describe
the common methods of endpoint detection for argentometric titrations.
Chemical Indicators. There are three common chemical indicators that
are associated with argentometric titrations:
1. The chromate ion, CrO42- (the Mohr method);
2. The ferric ion, Fe3+ (the Volhard method);
3. Adsorption indicators such as fluorescein (the Fajans method).
Titration Curves. Titration curves for precipitation reactions are
derived in a completely analogous way to the methods described for titrations
involving strong acids and strong bases. p-functions are derived for the pre-
equivalence point region, the poste-quivalence point region, and the
equivalence point for a typical precipitation titraton.
108
 Most indicators for argentometric titrations respond to changes in the
concentration of silver ions. As a consequence, titration curves for
precipitation reactions usually consist of a plot of pX or pT versus volume of
AgNO3.
It is convenient to define a general p-function as pT = -log[T], or where
X is a halide ion, pX = - log [X]. This is analogous to pH, which you of
course already know as pH = -lg[H+].
The curve for the titration of 50 cm3 of 0.0125 M KCl with 0.025 M
AgNO3 is shown in Fig.17.

Figure 17. Titration curve for 50mL of 0.0125M KCl versus 0.025M AgNO3

You may note here that the titration curve is quite similar to the one for
the titration between a strong base and a strong acid. According to this curve
there is a sharp increase in the concentration of silver ions immediately after
the equivalence point. This is indicated by a sharp decrease in the value of
pCl-(-ln(Cl-)). Such a sharp increase in the concentration of chloride ions can
be detected in different ways and accordingly there are three different
methods of detecting the end point of the titration.
According to end point detection method, three main procedures are
widely used depending on the type of application. These are:
1. Mohr’s Method
2. Volhard’s Method
3. Fajan’s Method
Table 9. Comparison of silver titration methods
Method Advantages Disadvantages
Mohr Simple Weak alkaline or neutral solution only,
Not suitable for iodide,
Requires a blank,
Some problems with specific cations
Volhard Capable of direct silver and Must be 1M nitric acid solution,
indirect halides analyses Some problems with specific anions
Fajans Capability for different pH Difficulty with dilute solutions,
ranges and selectivity with Should not be a high background ionic
specific indicators level.

109
 Table 10 provides a list of several typical precipitation titrations.

1. The Mohr method uses chromate ions (as 5% K2CrO4sln) as an

indicator in the titration of chloride ions with a silver nitrate secondary
standard solution (normality: 0.0141). This corresponds to 1 mL of 0.0141N
AgNO3 equals to 1 mg chloride in solution. The silver nitrate solution is
standardized against primary standard chloride solution, prepared from
sodium chloride (NaCl). During the titration, chloride ion is precipitated as
white silver chloride:
Ag+ + Cl- = AgCl (Ksp=3×10-10)
titrant analyte white ppt

After all the chloride has been precipitated as white silver chloride, the
first excess of titrant results in the formation of a reddish-brown silver
chromate precipitate, which signals the end point. This stage is taken as
evidence that all chloride ions have been consumed and only excess silver
ions have reacted with chromate ions. The reaction is:
2𝐴𝑔+ + 𝐶𝑟𝑂42− = 𝐴𝑔2 𝐶𝑟𝑂4 (𝑠) (Ksp=5×10-12)
titrant indicator reddish brown ppt

The solution needs to be kept around a neutral pH: silver hydroxide

forms at high pH, and chromate will form H2CrO4 at low pH. This will reduce
the concentration of chromate ions, and delay the formation of the precipitate.
In addition, since carbonates and phosphates both precipitate with silver, they
must be eliminated from the reaction to prevent inaccurate results. The Mohr
method is a relatively simple and accurate method for chloride ion
determination. As such, it has many applications where the concentration of
chloride in water or in food must be determined.

110
 By knowing the stoichiometry and moles consumed at the end point,
the amount of chloride in an unknown sample can be determined.

2. The Volhard’s method was first described by the Jacob Volhard, a

German Chemist, in 1874.
This is an indirect titration procedure, where an excess amount of
standard Ag+ is added to the chloride solution containing Fe3+ as an indicator.
The excess Ag+ is then titrated with standard SCN- solution until a red color is
obtained which results from the reaction:
Ag+ + Cl- = AgCl + Ag+excess
white ppt
Ag+excess+ KSCN → AgSCN + K+
white ppt
At end point: Fe + SCN → Fe(SCN)2+
3+ -

red brown ppt

Here, initially thiocyanate react with silver ions and forms precipitate at end
point, excess of thiocyanate (SCN-) react with Fe(III) and forms reddish
brown complex which indicate the end point of reaction.
The indicator system is very sensitive and usually good results are
obtained. The medium should be acidic to avoid the formation of Fe(OH)3.
However, the use of acidic medium together with added SCN- titrant
increase the solubility of the precipitate leading to significant errors. This
problem had been overcome by two main procedures.
Thiocyante is standardised against a standard silver solution, with the
silver solution being in the titration flask and the thiocyanate in the burette.
This Volhard method is used to determine the concentration of Ag + ions
or concentration of halide ions (i.e. Cl-, Br-, I-) indirectly i.e. by back titration.

3. Fajans Method (indicator adsorption method). The precipitation

titration in which silver ions is titrated with halide or thiocyanate ions in
presence of adsorption indicator is called fajan’s method.
Adsorption indicators function in an entirely different manner than the
chemical indicators and they can be used in many precipitation titrations.
Since the adsorption of indicator takes place at end point the method is also
called indicator adsorption method.
Table 11.Common adsorption indicators
Indicator Colour Change (free Applications
to absorbed)
Fluorescein Yellow-green to pink All halides, pH 7-10
Eosin Pink to red-violet Sample must not
-
contain Cl . pH>1
Diiododimethylfluorescein Orange to blue Iodide (I-) ion only,
pH 4-7
Dichlorofluorescein Yellow-green to red Cl- and Br-, pH 4-7
111
 The indicator, which is a dye, exists in solution as the ionized form,
usually an anion.
The method is generally used for the quantitative analysis of halide ions
or thiocyanate ions.
Fajan’s Method for the argentometric titration of chloride ion with
silver nitrate involved, originally, the use of fluorescein (Ind) as an
adsorption indicator.
Ag+ (aq) + Cl- (aq) = AgCl (colloidal particles)
In an aqueous solution at pH 7, fluorescein will partially dissociate to
form negatively-charged yellow-green fluoresceinate ions (Ind-).
HInd (aq) = H+ (aq) + Ind- (aq)

Because this indicator is weakly basic, the indicator works best above
pH 5. However, the pH must be below about 9 to prevent precipitation of
AgOH.
Ag+ (aq) + OH- (aq) → AgOH(s)
In more current argentometric titrimetric analyses, the preferred
indicator is dichlorofluorescein, which requires a more acidic solution (pH ~
4), but behaves in a manner similar to fluorescein. In the early stages of a
titration of chloride ion with silver nitrate, the colloidal silver chloride
particles formed are negatively charged because of the adsorption of excess
chloride ions onto the particles. The fluoresceinate ions, which are negatively
charged, are repelled by the negatively charged particles and impart a yellow-
green color to the solution. Beyond the equivalence point, where the chloride
ion concentration is very low, the colloidal silver chloride particles strongly
adsorb positively charged silver ions, Ag+. Fluoresceinate ions are now
attracted into the counter-ion layer that surrounds the particles and their color
changes to red.

112
 Adsorption indicators are dyes, such as dichlorofluorescein, that usually
exist as anions in the titration solution. The doubly charged
dichlorofluoroscein anion is attracted into the counterion layer immediately
following the equivalence point, when the surface charge of the particles
changes from negative to positive. For reasons that are not fully understood,
the closer proximity of the dye to the particles changes the color of the
molecule, providing a visual indication of the titration endpoint. In the case of
dichlorofluorescein, the indicator changes to a pinkish color.
Fluorescein and its derivatives are adsorbed to the surface of colloidal
AgCl. After all chloride is used, the first drop of Ag+ will react with
fluorescein (FI-) forming a reddish color.
Ag+ + FI-→AgF
Among these methods, the Volhard Method is widely used because we
can detect the end point of precepitation titration very well.

1ST EXPERIMENT. Standardization of silver nitrate solution against

primary sodium chloride solution
Apparatus: Burette, conical flask, pipette, measuring cylinder.
Reagents:5% K2CrO4 (indicator) solution, 0.1M silver nitrate titrant and solid
NaCl.

Aqueous silver nitrate is photosensitive and should not be exposed to

light any more than is necessary during this procedure. It should be stored in
darkened storage bottles, and be kept in your drawer except when being used.
Silver nitrate is an important precipitating reagent which can also be
used for thedetermination of the halogens, halogenlike anions, mercaptans,
fatty acids, and several divalentinorganic anions.
Silver nitrate solutions of known concentration can be prepared from
known mass of dried AgNO3. However, if we don't have access to the high
purity reagent, or if we have a solution of unknown concentration, we can
easily standardize it against sodium chloride.
Reaction taking place during titration is
113
 AgNO3 + NaCl → AgCl↓ + NaNO3

Preparation of 5% K2CrO4 (indicator): 1.0 g of K2CrO4 was dissolved in 20

mL of distilled water.
Preparation of AgNO3 solution: 9.0 g of AgNO3 was weighed out, transferred
to a 500 mL volumetric flask and made up to volume with distilled water. The
resulting solution was approximately 0.1 M. This solution was standardized
against NaCl.
Preparation of standard NaCl solution: Reagent-grade NaCl was dried
overnight and cooled to room temperature. Accurately weigh about 0.6g of
sodium chloride in a clean dry weighing bottle, and transfer the same to a
clean volumetric flask of 100 cm3 capacity through a glass funnel.Add about
20 mL of distilled water and swirl the contents of the flask until all the
sodium chloride is dissolved. Make the volume upto the mark by adding more
distilled water. In order to adjust the pH of the solutions, small quantities of
NaHCO3 we are added until effervescence ceased.

PROCEDURE:
1. Take with pipette 25 ml NaCl standard solution in a conical flask. Measure
sample pH.
2. Then add 2.0ml 5% K2CrO4 indicator solution.
3. Fill up the burette with AgNO3 solution up to the zero mark (bottom
menisque).
4. Titrate the sodium chloride solution silver nitrate titrant solution. Although
the silver chloride that forms is a white precipitate, the chromate indicator
initially gives the cloudy solution a faint lemon-yellow colour. The endpoint
of the titration is identified as the first appearance of a red-brown colour of
silver chromate Ag2CrO4 and note down volume of titrant used. Also measure
sample pH.
5. All titration processes are done in three trials.
6. Calculate concentration and titer of titrant AgNO3.

Results of titration:
• Volume of standard solution for titration: VNaCl= 10 mL (+2.0 ml 5%
K2CrO4 indicator)
• Normality of standard solution for titration: NNaCl = 0,1N
• Equivalent weight of sodium chloride: EqNaCl =
• Equivalent weight of silver nitrate: EqAgNO =
3
• Volume of titrant consumed for the 1st titration: V1AgNO3 =
• Volume of titrant consumed for the 2nd titration: V2AgNO3 =
• Volume of titrant consumed for the 3rd titration: V3AgNO3 =
• Average amount of titrant consumed for titration: 𝑉𝐴𝑔𝑁𝑂 ∗
3
=
𝑉 1 +𝑉 2 +𝑉 3
=
3
114
Calculation:
The result is expressed as mol-eq/l concentration and based on the
following formula:
𝑉𝑁𝑎𝐶𝑙 𝑁𝐴𝑔𝑁𝑂3 𝑉 ∙𝑁𝑁𝑎𝐶𝑙
∗ = => 𝑁𝐴𝑔𝑁𝑂3 = 𝑁𝑎𝐶𝑙∗
𝑉𝐴𝑔𝑁𝑂3 𝑁𝑁𝑎𝐶𝑙 𝑉𝐴𝑔𝑁𝑂3

𝑁𝐴𝑔𝑁𝑂3 ∙𝐸𝑞𝐴𝑔𝑁𝑂3
𝑇𝐴𝑔𝑁𝑂3 =
1000

𝑁𝐴𝑔𝑁𝑂3 ∙ 𝐸𝑞𝑁𝑎𝐶𝑙
𝑇𝐴𝑔𝑁𝑂3/𝑁𝑎𝐶𝑙 =
1000

The calibration result can be accepted if 3 determinations give a result

with a relative standard deviation of less than 0.5%

2nd EXPERIMENT. Use Mohr’s method to determine the concentration

of chloride ion in solid sample.

Mohr method of determination of chlorides by titration with silver

nitrate is one of the oldest titration methods still in use - it was researched and
published by Karl Friedrich Mohr in 1856.
The Mohr Method uses silver nitrate for titration (normality: 0.0141)
(method applicability: 0.15 to 10 mg/L chloride ions). This corresponds to 1
mL of 0.0141 equals to 1 mg chloride in solution.The idea behind is very
simple - chlorides are titrated with the silver nitrate solution in the presence of
chromate anions. End point is signalled by the appearance of the red silver
chromate.

Initial point white ppt of AgCl End point

Intense yellow color of chromate may make detection of first signs of

formation of red silver chromate precipitation difficult. As some excess of
silver must be added before precipitate starts to form, if concentration of
titrant is below 0.1M, we may expect significant positive error. To correct for
this error we can determine a blank, titrating a solution of the indicator
potassium chromate with standard silver nitrate solution. To make result more

115
realistic we can add small amount of chloride free calcium carbonate to the
solution to imitate the white silver precipitate.
Solution during titration should be close to neutral. The Mohr
method for determination of chloride in water is a pH sophisticated method. It
must be perform between the pH levels 6.5 – 9.0. It is better to carry out
between the pH ranges 7 – 8. At upper pH level, the silver ions react with
hydroxide ions and precipitated as silver hydroxide. In contrast, at lower pH
level, potassium chromate may be converted into potassium dichromate
(K2Cr2O7) and mask the end point. Consequently, accurate result cannot be
obtained. If the water sample is acidic, then gravimetric method or volhard’s
method is appropriate.
Ag+(aq) + OH–(aq) → Ag(OH)(s)
CrO42-(aq) → Cr2O72-(aq)
Both processes interfere with the determination accuracy.
Exactly the same approach can be used for determination of bromides.
Other halides and pseudohalides, like I- and SCN-, behave very similarly in
the solution, but their precipitate tends to adsorb chromate anions making end
point detection difficult.
Most foods have sodium from dissolved salts, either naturally present
or added in cooking or processing. Table salt known as sodium chloride
(NaCl) is the most common source of sodium. It is made up of 40% sodium
and 60% chloride and often used in processed and packaged foods as flavour
enhancer or preservative. Other sources of sodium added in foods are
monosodium glutamate (MSG), sodium nitrite, sodium saccharin, baking soda
(sodium bicarbonate), and sodium benzoate.
The sodium content of food has implications on our health. Sodium is
an essential mineral required in
small amount by the body to
control blood pressure and help the
nerves and muscles to function
properly. However, high sodium
intake can cause health problems
such as high blood pressure and
cardiovascular diseases, which
include heart, stroke, and blood
vessel disease. Thus, knowing the
sodium content in food and
controlling the intake are of utmost
important to keep diseases at bay.
The American Heart
Association1 recommends consumption of less than 1,500 mg per day
sodium for most American adults, which is the level with the greatest effect
on blood pressure. This level does not apply to people who lose large amounts

116
of sodium in sweat, such as competitive athletes, workers exposed to extreme
heat stress, or to those directed otherwise by their healthcare provider.

PROCEDURE:
1. The chloride samples (NaCl) have been dried and stored in a desiccator.
Take a sample and record its number on your data sheet.
2. Zero(tare) the analytical balance with a clean dry, capped weighing bottle.
Add 1.1 to 1.3g of your chloride sample (NaCl) to the bottle; replace the cap
and weigh as accurately as possible. Record on your data sheet.
3. Rinse a 250 mL volumetric flask with distilled water and quantitatively
transfer the chloride sample to the flask. Dissolve the sample and dilute to the
mark. Mix thoroughly.
4. Into each of three 200 - 250 mL erlenmeyer flasks carefully pipet 20.00 mL
of your chloride sample. (Remember to rinse the pipet with the sample
solution before the first transfer.) Use a graduated cylinder to add about 20
mL of distilled water to each flask.
5. Add 2.0 mL 5% K2CrO4 indicator solution to the first sample flask.
6. Rinse and fill a 50 mL burette with standartized AgNO3 titrant solution.
Tap to remove bubbles and make certain that the burette tip is filled with
solution. Adjust the solution level between 0 and 2 mL; read the burette to the
nearest 0.01 mL. (Do not try to set 0.00 mL!) Record the initial reading.
7. Titrate first flask to the first appearance of a persistent brown color. Read
the burette to the nearest 0.01 mL and record the value on your data sheet.
Repeat the procedure with the other samples. You should have three endpoint
volumes within a range of 0.1 - 0.2 mL. If this is not the case, prepare a few
more sample solutions and repeat the titrations.
8. Empty the contents of the titration flasks as well as any excess
AgNO3 solution into a waste container. (There are large bottles in the fume
hoods for this purpose.)
9. Rinse the burette, pipet and volumetric flask with several portions of
distilled water and put them away. Use a brush and soapy water to wash the
Erlenmeyer flasks.

Results of titration:
• Weight of NaCl salt sample: msample =
• Stock volume of NaCl salt solution: Vtotal NaCl = 250 mL
• Equivalent weight of Cl- ion in Mohr salt: 𝐸𝑞𝐶𝑙− =
• Volume of NaCl salt solution for titration: VNaCl = 10 mL
• Normality of standardized AgNO3solution for titration: NAgNO3 =
• Volume of titrant consumed for the 1st titration: V1AgNO3 =
• Volume of titrant consumed for the 2nd titration: V2AgNO3 =
• Volume of titrant consumed for the 3rd titration: V3AgNO3 =

117
 • Average amount of titrant consumed for titration: 𝑉𝐴𝑔𝑁𝑂
∗
3
=
𝑉 1 +𝑉 2 +𝑉 3
=
3

Calculation:
The result is expressed as mol-eq/l concentration and based on the
following formula:

𝑉𝑁𝑎𝐶𝑙 𝑁𝐴𝑔𝑁𝑂3 𝑉𝐴𝑔𝑁𝑂3 ∙𝑁𝐴𝑔𝑁𝑂3

∗ = => 𝑁𝐶𝑙 − =
𝑉𝐴𝑔𝑁𝑂 3
𝑁𝐶𝑙− 𝑉𝑁𝑎𝐶𝑙

𝑁𝐶𝑙− ∙𝐸𝑞𝐶𝑙−
𝑇𝐶𝑙− =
1000

𝑚(𝐶𝑙 − ) = 𝑇𝐶𝑙− ∙ 𝑉𝑡𝑜𝑡𝑎𝑙 𝑁𝑎𝐶𝑙

𝑚(𝐶𝑙 − )
Chloride ion concentration (w/w%): 𝑊𝐶𝑙 − , % = ∙ 100%
𝑚𝑠𝑎𝑚𝑝𝑙𝑒

The calibration result can be accepted if 3 determinations give a result

with a relative standard deviation of less than 0.5%

2nd EXPERIMENT. Use Mohr’s method to determine the concentration

of chloride ion (NaCl content) in liquid sample.
Apparatus: Conical flask, burette with stand, pipette, measuring cylinder,
volumetric flask, beakers, wash bottle.
Reagents: Deionized water, water sample, standard 0.1N silver nitrate
solution, pH test paper, sodium hydroxide solution, nitric acid, Indicator5%
potassium chromate solution.

Chloride in the form of chloride (Cl) ion is one of the major inorganic
anions in water and wastewater. The chloride concentration is higher in
wastewater than in raw water because sodium chloride is a common article of
diet and passes unchanged through the digestive system (Average estimate of
excretion: 6 g of chlorides/person/day; additional chloride burden due to
human consumption on wastewater: 15 mg/L). Along the sea coast chloride
may be present in high concentration because of leakage of salt water into the
sewage system. It also may be increased by industrial process. In potable
water, the salty taste produced by chloride concentration is variable and
depends on the chemical composition of water. Some waters containing 250
mg/L Cl may have a detectable salty taste if sodium cation is present. On the
other hand, the typical salty taste may be absent in waters containing as much
as 1000 mg/L when the predominant cations are calcium and magnesium. In
addition, a high chloride contents may harm metallic pipes and structures as
well as growing plants.
118
 The measured chloride ions can be used to know salinity of different
water sources. For brackish water (or sea water or industrial brine solution), it
is an important parameter and indicates the extent of desalting of apparatus
required. It also interferes with COD determination and thus it requires a
correction to be made on the basis of amount present or else a complexing
agent, such as HgSO4 can be added. Further, chloride ions are used as tracer
ions in column studies to model fate of different contaminants in soil and
liquid media.

PROCEDURES:
1. Measure the pH of the water sample. Adjust the pH with nitric acid or
sodium hydroxide, if needed.
2. Take a 25 ml collected water sample into a conical flask.
3. Add 2-3 drops potassium chromate (K2CrO4) indicator. The color of the
water sample is turn into light yellow.
4. Add standard (normality: 0.0141N) silver nitrate solution from the
burette and shake well. Titrate until the light yellow color changes to
permanent brownish-red color (bricks-red color) precipitate with white color
precipitate.
5. Note the volume of silver nitrate added.
6. Repeat the titration for concordant values.

Results of titration:
• Equivalent weight of Cl- ion: 𝐸𝑞𝐶𝑙− =
• Volume of liquid sample solution for titration: Vsample = 10 mL (+2mL
5% K2CrO4 indicator sln)
• Normality of standardized AgNO3 solution for titration: NAgNO3 =
• Volume of titrant consumed for titration: VAgNO3 =

Calculation:
Chloride ion concentration (mg/l):
𝑉𝐴𝑔𝑁𝑂3 ∙𝑁𝐴𝑔𝑁𝑂3 ∙35,45
𝐶(𝐶𝑙 − ) = ∙ 100%
𝑉𝑠𝑎𝑚𝑝𝑙𝑒 ∙1000

3rd EXPERIMENT. To Determine the Amount of Chloride (Cl) in the

Drinking Water
Aim: To apply Mohr method to the measurement of chloride ion in natural
water
Apparatus: Conical flask, burette, pipette, measuring cylinder, volumetric
flask
Materials: Deionized water, unknown A water sample, unknown B water
sample, 0.075M silver nitrate solution, pH paper, sodium hydroxide solution,
calcium carbonate, 0.25M potassium chromate solution

119
 Mohr method can be used to determine the chloride ion concentration
of water samples from many sources such as seawater, stream water, river
water and estuary water. Two unknown water sample are tested by using the
particular method. The Mohr method works well in a slightly acidic
condition, hence the pH of the water sample should be adjusted to the range
of 6~8 by adding dilute acid or dilute base as needed.
Chlorides are widely distributed in nature as salts of sodium (NaCl),
potassium (KCl), and calcium (CaCl2). These salts of Chlorides are widely
used in the production of different industrial chemicals such as Sodium
Chloride is used for the production of caustic soda, chlorine, sodium chlorite,
and sodium hypochlorite. These salts are extensively used in snow and ice
control. Potassium chloride is used in the production of fertilizers (WHO,
1996).
Sources of Chloride in Environment:
Natural: Usually Chlorides are leached from various rocks into soil and
water due to weathering. The ions of chloride are highly mobile and are
transported to closed basins or ocean. Chloride occurs naturally in foodstuffs
at levels normally less than 0.36 mg/g. (WHO, 1996)
Anthropogenic: Chloride in water may be considerably increased by
treatment processes, used for the purification of water, in which chlorine or
chloride is used. Addition of salt in food during processing, cooking, or eating
can markedly increase the chloride level in food (WHO, 1996).
Chloride ions in a water sample can be determined by Argentometric method.
This method is based on the precipitation and titration in which from
the burette silver nitrate solution is released to the chloride ions and indicator
containing water sample. The silver ions will react with chloride ions and the
chromate ions to form white precipitate of silver chloride and red precipitate
of silver chromate.
Ag+ + Cl– → AgCl
white precipitate
2Ag + CrO4 →Ag2CrO4
+ 2-

red precipitate
In this experiment, the titration of unknown sample was conducted in
the pH range of 7 to 8. This is because at pH lower than 7, the chromate ion
will be converted to dichromate ion: CrO42- (aq) –> Cr2O72- (aq)
Eventually, this dichromate ion cannot form a brick red silver chromate
precipitate with silver ion and hence end point of the titration cannot be
detected. At pH higher than 8, the silver ion will tend to react with the excess
hydroxide ion to form brownish silver hydroxide. Formation of silver
hydroxide will cover the colour of silver chromate precipitate and hence end
point also cannot be seen.
Ag+ (aq) + OH- (aq) → Ag(OH) (s)
Mohr method can only roughly show the concentration of chloride ion
in the water sample. This is because excess silver nitrate is needed to produce
sufficient silver chromate precipitate to be observed in the solution with
120
heavy white precipitate of silver chloride. Besides, the intense yellow colour
of chromate solution causes the brick red silver chromate that formed is
hardly to be observed.
Precaution steps:
1. All solution mixture that involved silver nitrate solution must be discarded
into waste bottle because silver is heavy metal.
2. The burette must be rinsed with silver nitrate solution before titration starts.
3. Wear gloves when handling silver nitrate solution since it will cause skin
staining and chemical burn.
4. Chromate solution needs to be used with care as chromate is a known
carcinogen.

PROCEDURE:
A) Titration with the Blank solution: Take 25 ml of the distilled water in a
conical flask and add 3-4 drops of potassium chromate solution. Slowly add
standard silver nitrate solution from the burette and shake the solution well.
At the end point, light yellow colour starts changing to red colour. The
titration is repeated until a concordant volume V1 is obtained.
B) Titration with the Sample Water: Take 25 ml of the given water sample
in a conical flask and add 3-4 drops of potassium chromate solution. Slowly
add standard silver nitrate solution from the burette and shake the solution
well. At the end point, light yellow color starts changing to red colour and red
colour persists. The titration is repeated until a concordant volume V 2 is
obtained.

Results and Calculations:

Titration with the Blank solution: V1 =
Titration with the Sample Water: V2 =
Volume of AgNO3 titrant used Vtitrant = V2 – V1 = ______ ml
Molarity of AgNO3 titrant used 𝑀𝐴𝑔𝑁𝑂3 =
Volume of given water sample, Vwater = 25 ml
Equivalent weigh of chlorine: Eq(Cl-) = 35.45 mol/L
Molarity of given water sample:
𝑉𝑡𝑖𝑡𝑟𝑎𝑛𝑡 ∙ 𝑀𝐴𝑔𝑁𝑂3
𝑀𝑤𝑎𝑡𝑒𝑟 =
𝑉𝑤𝑎𝑡𝑒𝑟

Amount of chloride ions (mg/L): 𝑚(𝐶𝑙− ) = 𝑀𝑤𝑎𝑡𝑒𝑟 ∙ 35.45 ∙ 1000

Environmental Impacts of Chloride ions:

Human Health Impacts: Diseases associated with chloride intake are
rare. Chloride toxicity can be expected only in those who have impaired NaCl
metabolism. Due to deficiency of chloride alkalosis and Hypochlorem can
occur its symptoms include loss of appetite, lethargy, and muscle weakness
heavy sweating (Brazin, 2006)
121
 Plants impacts: Cl- free media results in substantial reduction of growth
of many plants. Cl— deficiency causes reduced leaf growth and wilting,
followed by chlorosis, bronzing and, finally, necrosis. Roots become stunted
and the development of laterals is suppressed. Fruits are decreased in numbers
and size (WHITE & BROADLEY, 2001, Chloride in Soils and its Uptake and
Movement within the Plant: A Review. Annals of Botany, 967-988.).
Table 12. Different Standards for Chlorides in Different Mediums

4th EXPERIMENT. Determination of Sodium chloride (salt content) in

brine: Direct titration of NaCl in brine with standardized silver nitrate
solution based on the Mohr method is adequate for routine analysis.

PROCEDURE:
Take 5 to 10 mg liquid portion from the drained weight determination.
If it is acidic, neutralize it with standard Sodium hydroxide using
phenolphthalein as indicator. Add 1 mL of 5% aqueous potassium chromate
solution and titrate with 0.1N AgNO3 solution to produce red-brown end
point.
• Equivalent weight of NaCl: 𝐸𝑞𝑁𝑎𝐶𝑙 =
• Weight of liquid saple solution for titration: msample = ______mg
• Normality of standardized AgNO3 solution for titration: NAgNO3 =
• Volume of titrant consumed for titration: VAgNO3 =

Results of titration:
• Equivalent weight of Cl- ion: 𝐸𝑞𝐶𝑙− =
• Volume of liquid saple solution for titration: Vsample = 10 mL
• Normality of standardized AgNO3 solution for titration: NAgNO3 =
• Volume of titrant consumed for the 1st titration: V1AgNO3 =
• Volume of titrant consumed for the 2nd titration: V2AgNO3 =
• Volume of titrant consumed for the 3rd titration: V3AgNO3 =
• Average amount of titrant consumed for titration: 𝑉𝐴𝑔𝑁𝑂 ∗
3
=
𝑉 1 +𝑉 2 +𝑉 3
=
3

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Calculation: Sodium chloride concentration (%):
𝑉𝐴𝑔𝑁𝑂3 ∗ 𝑁𝐴𝑔𝑁𝑂3 ∙ 58,5
𝑊𝑁𝑎𝐶𝑙, % = ∙ 100%
𝑚𝑠𝑎𝑚𝑝𝑙𝑒(𝑔) ∙ 1000

Pasteurized or sterilized canned vegetables should contain 1 to 3% of table

salt (NaCl).

CONTROL OF MASTERING THE TOPIC

Typical calculation tasks
1. A mixture containing only KCl and NaBr is analyzed by the Mohr
method. A 0.31720g sample is dissolved in 50 mL of water and titrated to
the Ag2CrO4 end point, requiring 36.85 mL of 0.1120 M AgNO3. A blank
titration requires 0.71 mL of titrant to reach the same end point. Reportthe
%w/w KClinthesample.
2. A 1.963-g sample of an silver alloy is dissolved in HNO 3 and diluted to
volume in a 100-mL volumetric flask. Titrating a 25.00-mL portion with
0.1078 M KSCN requires 27.19 mL to reach the end point. Calculate the
%w/w Ag in the alloy.
3. A 0.0259g sample of primary standard grade NaCl was dissolved in 25
mL of water and titrated to its endpoint using an AgNO3 titrant. The
starting burette volume was 0.33 mL. The ending volume was 21.65 mL.
Calculate the concentration of the AgNO3 titrant and irs titer by primary
standard NaCl.
4. A 0.0531g sample of an unknown powder was dissolved in 25 mL of
water and titrated to its endpoint using an AgNO3 titrant with titer
TAgNO3/KCl = 0.003652 g/ml. The starting and ending burette volumes were
0.15 mL and 32.05 mL respectively. Calculate the percentage chloride ion
in the sample.
5. The %w/w I– ions in a 0.6712-g sample was determined by a Volhard
titration. After adding 50.00 mL of 0.05619 M AgNO3 and allowing the
precipitate to form, the remaining silver was back titrated with 0.05322 M
KSCN, requiring 35.14 mL to reach the end point. Reportthe %w/w I–
inthesample.
6. In the Volhardtitration of 25 mL of 0.05 M of AgNO3 solution with 0.02
M KSCN solution, calculate the molar concentration of Ag + in the conical
flask solution after the following additions of titrant KSCN solution: (1)
30 mL (2) at equivalent point (3) 100 mL. (Ksp (AgSCN) = 1.010-12)
7. The As in a 9.13-g sample of pesticide was converted to AsO43- and
precipitated as Ag3AsO4 with 50.00 mL of 0.02015 M AgNO3. The excess
Ag+ was then titrated with 4.75 mL of 0.04321 M KSCN. Calculatethe %
ofAs2O3inthesample.
8. 400 mg of butter was heated and some water was added. After shaking
and filtration, 10 ml 0.2 M AgNO3 solution, some HNO3, drops of Fe3+
solution and some nitrobenzene were added to the filtrate. The excess Ag+
123
 in the aqueous layer was titrated with 0.1 M NH4SCN standard solution. If
the volume of NH4SCN at the equivalent point was 15 mL. Calculate the
percentage of NaCl in the butter sample.
9. Calculate the concentration of salt in a soy sauce 5.0g of sample, which is
diluted accurately in 250 mL volumetric flask and its 10.25 mL aliquots of
the diluted sample are mixed with 25 mL aliquots of the 0.1025N silver
nitrate standard solution, and back titrated with an average of 14.6 mL of
0.1002N ammonium thiocyanate standard solution.
10.A 0.32 g sample containing KCl is dissolved in 50 mL of water and
titrated with AgNO3to the Ag2CrO4 end point, requiring 16.9 mL of 0.1 M
AgNO3. Reportthe %w/w KClinthesample.
11.The sulphide contents of 100 mL of a water sample was titrated with a
standard solution of 0.01 M AgNO3 according to the following reaction
equation:
2Ag+ + S2- ↔ Ag2S
If the volume of AgNO3 solution at the equivalent point was 8.5 mL.
Calculate the concentration of H2S in the water sample.
12.1.354 g sample of sodium nitrate contaminated with NaCl was dissolved
in small amount of water and filled to the mark in the 100 mL volumetric
flask. To titrate chlorides in 10.00 mL sample 35.70 mL of 0.01021 M
AgNO3 was used. Whatisthepercentpurityofthesample?
13.A 2.2380g sample of a mixture of NaCl and NaI was dissolved in 200.0
mL and 25mL aliquots were titrated to endpoint, using fluorescein
indicator with an average of 24.8 mL. Further 25 mL aliquots were
titrated, using diiododimethylfluorescein indicator with an average of 10.3
mL. Calculate the %w/w of each salt in the mixture.
14.50.0 mL aliquots of a bromide solution were titrated to endpoint with an
average of 12.3 mL of the silver solution with titer 0.001685
g/ml.Calculate the concentration of bromide in mg/L.
15.Calculate the percentage of silver in an ingot, if a 0.9023g sample was
dissolved in 100 mL and its 25 mL aliquots were titrated to endpoint with
an average of 17.9 mL of thiocyanate titrant.
16.A waste water sample from a gold processing plant is analysed for its
cyanide content by titration with silver nitrate. 50 mL aliquots of the
sample are titrated to endpoint with an average of 13.2 mL of silver
nitrate, which has been diluted five times. Does this sample contravene
effluent regulations which limit cyanide waste to 100 mg/L?
17.The organic matter in a 3.776-g sample of a mercuric ointment is
decomposed with HNO3. After dilution, the Hg2+ is titrated with 21.30 mL
of a 0.1144 M soln of NH4SCN. Calculate the percent Hg (200.59 g/mol)
in the ointment.
18.A 1.500-g sample of a chloride ion is diluted with water in volumetric
flask with volume 250 mL. After dilution, 10 mL of the Cl - - ion solution

124
 was titrated with 12.25 mL of a 0.0115 M solution of AgNO 3. Calculate
the percent Cl– ion in the sample.
19.What is the solubility of barium sulfate in pure water at 25 oC? (Ksp for
barium sulfate is 1.1 x 10-10)
20.Calculate the solubility product constant for pure PbSO4 in water. The
solubility of PbSO4 is 1.25 x 10-4mol/L.
21.The solubility of CaF2 is 2.1 x 10 -4 mol/L. Find the Ksp of CaF2.
22.A saturated solution of BaF2 has a [F-] of] of 8.6 x 10-3M at a certain
temperature. Calculate the Ksp at this temperature. Show all your steps in
a logical manner. Correct use of units and significant digits counts.
23.Calculate the [Mg2+] in a saturated solution of Mg(OH)2 at 25°C. Show all
your steps in a logical manner. Correct use of units and significant digits
counts.
24.At a certain temperature 2.2 x 10-4 grams of CuI will dissolve in 1.0 L of
water. Calculate the Ksp for CuI at this temperature. Show all your steps
in a logical manner. Correct use of units and significant digits counts.
25.Calculate the mass of AgIO3 which will dissolve in 2.50 L of water at
25°C. Show all your steps in a logical manner. Correct use of units and
significant digits counts.
26.Calculate the molar solubility of silver chromate in water at 25°C. Show
all your steps in a logical manner. Correct use of units and significant
digits counts.
27.At a certain temperature 0.0558 grams of SrF2 will dissolve in 500.0 mL
of water. Calculate the Ksp for SrF2 at this temperature. Show all your
steps in a logical manner. Correct use of units and significant digits
counts.
28.Which is most soluble in water at 25°C, lead (II) bromide, lead (II)
chloride, lead (II) iodide, or lead (II) iodate?
29.Which is least soluble in water at 25°C, lead (II) bromide, lead (II)
chloride, lead (II) iodide, or lead (II) iodate?

QUESTIONS FOR TEST SELF-CHECK

1. What is the role of chromate ions in chloride determination?
2. As potassium chromate is an oxidizing agent, what would happen to
chloride determination if the sample were consists of organic matter (say 100
mg/L glucose) as well.
3. Why pH range is important in chloride determination?
4. Would the analytical results by the Mohr method for chlorides be higher,
lower or the same as the true color value if any excess of indicator were
accidentally added to the sample? Why?
5. What is the solubility constant expression for: a) Zn 3(PO4)2; b) Ag3PO4, c)
Mg(OH)2?

125
6. In most titrations it does not really matter which solution is in the burette
and which is in the flask. However with Mohr’s method, it is critical that the
silver is in the burette and not in the flask. Explain why.
7. Why is a blank used in Mohr’s method?
8. What indicator would be suitable to analyse the concentration of iodide in
the presence of chloride?
9. How would you analyse the salt content of a sauce which contains a
significant level of ethanoicacid?

References:
1. Harris, Daniel Charles (2003). Quantitative chemical analysis (6th ed.).
SanFrancisco: W.H. Freeman. pp. 142–143.
2. Yoder, Lester (1919). "Adaptation of the Mohr Volumetric Method to
General Determinations of Chlorine". Industrial & Engineering
Chemistry 11(8): pp.75.
3. Sheen R.T. and Kahler H. L. Effects of Ions on Mohr Method for
Chloride Determination, Ind. Eng. Chem. Anal. Ed.; 1938; 10(11); 628-
629.
4. Kraemer E. O. and Stamm A. J. Mohr’s Method for the Determination
of Silver and Halogens in other than Neutral Solutions, J. Am. Chem.
Soc.; 1924; 46(12); pp. 2707- 2709.
5. Nielsen, Suzanne. Sodium Determination Using Ion Selective
Electrodes, Mohr Titration, and Test Strips. Chapter 10.
FoodAnalysisLaboratoryManual. 2nd Edition. USA: Springer. 2015

LABORATORY WORK 7
ARGENTOMETRY
VOLHARD’S METHOD

Objective: Determination of table salt content in food using the Volhard

method of argentometric titration.

Titration is a process by which the concentration of an unknown

substance in solution is determined by adding measured amounts of a
standard solution that reacts with the unknown. Then the concentration of the
unknown can be calculated using the stoichiometry of the reaction and the
number of moles of standard solution needed to reach the so called end point.
Precipitation titrations are based upon reactions that yield ionic
compounds of limited solubility. The most important precipitating reagent is
silver nitrate. Titrimetric methods based upon silver nitrate are sometimes
termed argentometric methods. The most popular are three methods from this
group, named as their inventors: Mohr, Volhard, Fajans. All these methods

126
use AgNO3 solution of known concentration, the Volhard one also solution of
KSCN or NH4SCN.
The sodium chloride content is determined by the well-known Volhard
method. This method uses a back titration with 2 titrants like silver nitrate and
potassium thiocyanate to determine the concentration of chloride ions in a
solution. Before the titration an excess volume of a silver nitrate solution must
be added first, followed by the concentrated HNO3, to the solution containing
chloride ions, forming a precipitate of silver chloride. This order of addition is
critical to ensure complete precipitation of the chlorides. The term ‘excess‘ is
used as the moles of silver nitrate added are known to exceed the moles of
sodium chloride present in the sample so that all the chloride ions present will
react.
Ag+(aq) + Cl-(aq) --> AgCl(s) + Ag+(excess)
titrant analyte white ppt
3+
The indicator Fe (ferric ion) is then added and the solution is titrated
with the potassium thiocyanate solution. The titrate remains pale yellow as the
excess (unreacted) silver ions react with the thiocyanate ions to form a silver
thiocyanate precipitate.
Ag+(excess) + SCN-(aq) --> AgSCN(s)
titrant-2 white ppt
Once all the silver ions have reacted, the slightest excess of thiocyanate
reacts with Fe3+ to form a dark red complex:
Fe3+(aq) + SCN-(aq) --> [FeSCN]2+(aq)
ind titrant-2 red complex
The concentration of chloride ions is determined by subtracting the
titration findings of the moles of silver ions that reacted with the thiocyanate
from the total moles of silver nitrate added to the solution.
This method is used when the pH of the solution after the sample has
been prepared is acidic. If the pH is neutral or basic, Mohr’s method or the
gravimetric method should be used. The method is illustrated below by using
the procedure to determine the concentration of chloride (from sodium
chloride) in cheese.
NOTE: After all the silver has been back-titrated, an excess of
thiocyanate may react with the precipitated AgCl because the solubility
product of AgSCN is 1/100 that of AgCl (SAgSCN = 1.0 x 10-12; SAgCl = 1.1 x
10-10).
The addition of nitrobenzene or diethyl ether overcomes this difficulty
by coating the precipitated AgCl, thereby withdrawing it from the action of
the thiocyanate solution. If results are rounded to 0.1%, precipitate coating is
not needed.
Volhard’s method can be used for the determination of:
• halides (Cl-, Br-,I-),
• anions like phosphate, arsenate, chromate, sulphide, carbonate and
oxalate,
• potassium as potassium tetraphenyl borate,
127
 • flouride as lead chloroflouride.
The Volhard method is more precise than the former ones, but its main
advantage is acidic environment of reaction. Its faults are time-consumption
(more operations) and higher costs, in particular higher consumption of silver
nitrate.

EXPERIMENT. Determination of chloride ion (table salt) concentration

in food by the method of Volhard.

Salt and humans go a long way together. In earlier times, before mining
of rock salt had started, salt was a high-priced and much sought after
commodity. Nowadays, with cheaper salt prices, salt is a key ingredient in
processed foods. In recent times, the negative impact of high levels of dietary
sodium on human health outcomes has attracted increased attention from
public health regulatory authorities.
Table salt, consisting mainly of sodium chloride (NaCl), is the most
commonly used salt in our food. Even after the production process of
customary table salt, either from rock salt or sea salt, 1-3% of other salts are
remaining; unprocessed sea salt contains up to 5% of water. Table salt is a
cleaned and refined salt. To improve attributes such as pourability and
hygroscopy, small amounts of other substances are later on added to the salt.
In table salt, sea salt and stone salt are often distinguished. Both are harvested
in different processes.
Table salt is a common additive to food products and is used as a
preservative and a flavor enhancer. Traditionally, salt was added to food as a
form of preservation. Since the advent of refrigeration, salt is more commonly
used to enhance flavor but its ability to reduce microbial growth, improve
texture, and increase shelf life are still utilized.
In human diet one of the basic roles of table salt is providing the
necessary amounts of sodium which is essential for undisturbed development
of metabolic processes in an organism. However, numerous health problems
such as hypertension, osteoporosis and kidney stone emerge as the result of
excessive salt consumption. The minimum of necessary daily consumption is
usually estimated at 0.5 g of NaCl, while average daily consumption in
developed countries reaches 10-12 g, which is considered to be exaggerated
and dangerous dosage. The recommended adequate and safe dose for adults is
from 2.8 to 8.3 g of NaCl per day.
Table 13. Salt content of few widely used foods expressed as g sodium
chloride per 100 g of food
Food Salt content (g/100 g)
Corn flakes 3
Bacon 5
Parmesan cheese 2.4
Parma ham 6.5
128
Bread 1.5
Camembert cheese 2
Roquefort cheese 3
Emmental cheese 1.5
Sausage 1.4
Salted butter (82.5%) 1%
Unsalted butter (82.5%) 0

The content of NaCl (weight fraction of Cl – ions, in %) was analysed in

different cheeses, which were bought in supermarkets, and made by domestic
manufacturers. Sodium chloride in cheese samples was analysed after the extraction of
chloride by nitric acid solution. Concentration of chloride ions may
be potentiometricly determined, with the chloride selective electrode and
titrimetricly by Volhard method.

Equipment needed: boiling chips, 500 mL volumetric flask, 10 mL and 100

mL measuring cylinders, conical flasks, Bunsen burner, tripod and gauze
burette and stand, 50 mL pipette (2)
Solutions needed:
• Concentrated HNO3 nitric acid (see safety notes): (6 mol/L)
• Silver nitrate solution (0.1 mol/L) in a brown glass bottle. If possible, dry
5 g of AgNO3 for 2 hours at 100°C and allow to cool. Accurately weigh
about 4.25 g of solid AgNO3 and dissolve it in 250 mL of distilled water
in a conical flask. Store the solution in a brown bottle.
• Potassium thiocyanate solution (0.1 mol/L) in a brown glass bottle. Weigh
2.43 g of solid KSCN and dissolve it in 250 mL of distilled water in a
volumetric flask.
• Ferric ammonium sulfate solution (saturated). Add 8g of
NH4Fe(SO4)212H2O to 20 mL of distilled water and add a few drops of
concentrated nitric acid (see safety notes) to completely colorless of
solution.
• Nitrobenzene.
• Potassium Chromate 5 % solution. Add 5 g of K2CrO4 to 100 mL
volumetric flask. Dilute to volume with water and mix.

PROCEDURE:
I. Standardization of titrant solutions AgNO3 and KSCN
1.1 Standardize the AgNO3 solution as follows
• Preparation of 0.1N standard KCl solution. Weigh 0.7450 ± 0.0002 g of
KCl that has been dried at 101 °±1 °C for 1 hour ± 10 min into a 100
mL graduated flask and dissolve in distilled water.
• Pipette 25 mL of standard KCl solution into a 250 mL Erlenmeyer
flask.
• Add approximately 1 mL of K2CrO4 indicator.
129
 • Titrate with the AgNO3 solution to a permanent light brown (salmon
colored) endpoint.
• Calculate concentration of titrant AgNO3 (mol/eq/L) solution:
𝑉𝐾𝐶𝑙 ∙ 𝑁𝐾𝐶𝑙
𝑁𝐴𝑔𝑁𝑂3 =
𝑉𝐴𝑔𝑁𝑂3
1.2 Standardize the KSCN solution as follows
• Pipette 25 mL of standardized AgNO3 solution into a 250 mL
Erlenmeyer flask.
• Add approximately 80 mL of water.
• Add 15 mL of a 1:1 HNO3.
• Add approximately 2 mL of the ferric alum indicator.
• Titrate with KSCN solution to a permanent light brown (salmon
colored) end point. The ratio of the volume of KSCN to the volume of
AgNO3 should be 1:1.
𝑉𝐴𝑔𝑁𝑂3 ∙ 𝑁𝐴𝑔𝑁𝑂3
𝑁𝐾𝑆𝐶𝑁 =
𝑉𝐾𝑆𝐶𝑁

II. Determination of table salt (NaCl) content in different food.

Part A (Analysis of chips, sausage, cheese etc.):
• Weigh 2 g of the food using the analytical balance.
• Grind the cheese (or sausage or chips) into very small pieces. Transfer
it in 100 mL volumetric flask.
• Add 50 mL of hot water (80C) and shake during 2-3 min. To hold it
15 min.
• Filter the solution, washing the remaining solid sample with few small
portions of hot water.
• Wait until the filtrate cools down.

Part B (The sample is butter):

• Weigh 2 or 5 g of the butter (depending on the butter is salted or not)
using the analytical balance.
• Add 100 mL of boiling water (100C) and mix 5-10 min until
homogeneous emulsion is formed.
• Check pH – if it is below 6.5, add ≈0.1 g of solid CaCO3.
• Wait until the mixture cools down.

Titration Part:
1. Take 10 mL by pipette of the analyzed sample solution to the Erlenmeyer
flask, add 5 mL of HNO3 (1+1 – it is in the fume hood) and add water to
ca. 100 mL.
2. Add from burette exactly 50 mL 0.05 mol/L AgNO3 titrant solution.
3. Add 3 mL of nitrobenzene (it is in fume hood) and 1 mL 10% iron-
ammonium alum acidified with nitric acid; shake the flask during 1 min.
130
4. Titrate the excess of silver added using 0.1 mol/L KSCN. The end-point is
visible as red-brown color.
5. Repeat titration, if necessary even three times.
6. For each titration, calculate the weight percent chloride in the sample (to
two decimal places).

Calculation:
(VAgNO3 − VKSCH ) ∙ CKSN ∙ 58,45 ∙ Vtotal
WNaCl % = ∙ 100%
1000 ∙ msample ∙ Vfiltrate

CONTROL OF MASTERING THE TOPIC

Typical calculation tasks
Task 1. The As in a 9.13-g sample of pesticide was converted to AsO43- and
precipitated as Ag3AsO4 with 50.00 mL of 0.02015 M AgNO3. The excess
Ag+ was then titrated with 4.75 mL of 0.04321 M KSCN. Calculate the % of
As2O3 in the sample.
Task 2. 400 mg of butter was heated and some water was added. After
shaking and filtration, 10 ml 0.2 M AgNO3 solution, 2 ml HNO3, few drops of
Fe3+ solution and some nitrobenzene were added to the filtrate. The excess
Ag+ in the aqueous layer was titrated with 0.1 M NH4SCN standard solution.
If the volume of NH4SCN at the equivalent point was 15.05 mL. Calculate the
percentage of NaCl in the butter sample.
Task 3. Calculate the concentration (%) of salt in a soy sauce 5.0g of sample,
which is diluted accurately in 250 mL volumetric flask and its 10.25 mL
aliquots of the diluted sample are mixed with 25 mL aliquots of the 0.1025N
silver nitrate standard solution, and back titrated with an average of 14.6 mL
of 0.1002N ammonium thiocyanate standard solution.
Task 4. A 0.4025 g sample containing KI is dissolved in 100 mL of water and
titrated to the Ag2CrO4 end point, requiring 20.15 mL of 0.1 M AgNO3. A
blank titration requires 2.50 mL of titrant to reach the same end point. Report
the %w/w KI in the sample?
Task 5. The %w/w I– in a 0.7005-g sample was determined by a Volhard
titration. After adding 50 mL of 0.05521 M AgNO3 and allowing the
precipitate to form, the remaining silver was back titrated with 0.05239 M
KSCN, requiring 36.15 mL to reach the end point. Report the %w/w I – in the
sample?
Task 6. A 500.0 mg sample of butter was warmed and shaken vigorously
with water. The undissolved material was removed by filtering and the
aqueous portion was made 1.0 M in HNO3 and 0.025 M in Fe(NO3)3. This
acidified solution was treated with 10.00 mL of 0.1755 M AgNO 3 to
precipitate the chloride ion and, after the addition of a small amount of
nitrobenzene, 14.22 mL of 0.1006 M KSCN was required to back titrate the
excess Ag+. Calculate the % NaCl in the butter.

131
Task 7. The %w/w KBr in a 0.6712-g sample was determined by a Volhard
titration. After adding 50.00 mL of 0.05211 M AgNO3 and allowing the
precipitate to form, the remaining silver was back titrated with 0.05105 M
NH4SCN, requiring 33.14 mL to reach the end point. Report the %w/w Br –
and KBr in the sample.
Task 8. The %w/w Br- in a 100 ml sample solution was determined by a
Volhard titration. Its 1.00 mL aliquot of the sample is mixed with 2.0 mL of
the 0.02N silver nitrate standard solution. The excess of AgNO3 was then
titrated with 1.5 mL of 0.015 M KSCN.
Task 9. The %w/w NaI in a 1.0-g sample was determined by a Volhard
titration. After adding 30.00 mL of AgNO3 with titer TAgNO3/KCl =
0.000568g/mL and allowing the precipitate to form. The excess of Ag+ was
then titrated with 13.05 mL of 0.0235mol/L NH4SCN solution. Report the
%w/w NaI and I- in the sample.
Task 10. 2.5g of cheese was weighted in 250 ml conical flask and dissolved
with hot water. After shaking and filtration, to the 10 ml aliquot of the sample
add 35mL 0.1050 M AgNO3 solution, 2 ml HNO3, few drops of Fe3+ solution
and some nitrobenzene were added to the filtrate. The excess Ag + in the
aqueous layer was titrated with 0.1112 M NH4SCN standard solution. If the
volume of NH4SCN at the equivalent point was 11.06 mL. Calculate the
percentage of NaCl in the cheese sample.
Task 11. Calculate the concentration (%) of salt in a soy sauce 3.0g of
sample, which is diluted accurately in 100 mL volumetric flask and its 10 mL
aliquots of the diluted sample are mixed with 30 mL aliquots of the silver
nitrate standard solution with titer 0.00164g/mL, and back titrated with an
average of 12.05 mL of 0.1018 N ammonium thiocyanate standard solution.
Task 12. A 1.0250 g sample containing NaBr is dissolved in 20 mL of water.
After adding 40.00 mL of AgNO3 with titer TAgNO3= 0.000328g/mL and
allowing the precipitate to form. The excess of Ag+ was then titrated with
20.03 mL of 0.0501 mol/L NH4SCN solution. Report the %w/w NaC and Cl-
in the sample.

Reference:
1 Official Methods of Analysis of the Association of Official Analytical
Chemists, 15th Edition: 935.47, 941.18.
2 Skoog D. A.; West D. M.; Holler F. J. Fundamentals of Analytical
Chemistry, 7th Edition, Thomson Learning, Inc, USA, 1996.

LABORATORY WORK 8
COMPLEXOMETRIC TITRATION

Objective:
After completing the experiment, we are able to:
• define a complexometric titration;
132
 • describe the reaction between a metal cation and EDTA;
• calculate the concentration the unknown solution given the titration
data;
• standardize the EDTA solution;
• determine the hardness of some natural water samples and tap water;
and concentration of calcium ions in milk;
• apply the techniques involved in the preparation of solutions,
standardization of solutions, and analysis of unknown solutions
for titrations.

Complexometric titration is based on the fact that certain organic

compounds (as chelates) form stable complexes with metal ions in solution.

analyte titrant

Many metal ions form slightly dissociated complex ions. The formation
of these can serve as the basis of accurate and convenient titrations for such
metal ions. Such determinations are referred to as complexometric titrations.
The accuracy of these titrations is high and they offer the possibility of
determinations of metal ions at concentrations at the millimole level. Many
cations will form complexes in solution with a variety of substances that have
a pair of unshared electrons (e.g. on N, O, S atoms in the molecule) capable of
satisfying the coordination number of the metal. The metal ion acts as a Lewis
acid (electron pair acceptor) and the complexing agent is a Lewis base
(electron pair donor). The number of molecules of the complexing agent,
called the ligand, will depend on the coordination number of the metal and on
the number of complexing groups on the ligand molecule.

Structure of complexes
Complex is formed by the reaction of metal ion (M+n) with either an
anion e.g. [Ag(CN)2]- or neutral molecule e.g. [Ag(NH3)2]+. The metal ion is
known as Central metal atom. The anion or neutral molecule is known as
Ligand (L).
CENTRAL TYPE: in general the central atom is a metal ion in
transition which tends to form complexes after interaction between type d
orbitals with s and p type orbitals on the ligands. The resulting bonds have
such energy that the wave lengths of the visible lead to electronic transition.
This is why the complexes, also known as coordination compounds, are
coloured.

133
 Table 14. Transition metals

LIGANDS: are those ions which have at least one lone electron pair
available to form a bond.
COUNTERION: the ion necessary for electroneutrality if the complex
is charged. It is an ion having a charge opposite to that of the substance with
which it is associated.
The number of complexes any cation tends to form with the electron
donors (ligands) is referred to as its coordination number.

CHELATES. An organic agent which has two or more groups capable

of complexing with a metal ion is called a chelating agent. The complex
which is formed in this manner is called a chelate. Most chelating agents
contain N or O (see Fig. 18).
Titration with such a chelating agent is called a chelometric titration
which is a particular type of complexometric titration.
Ligands can be grouped in different ways depending on the number of
coordination bonds they manage to form with the transition metal.
The equilibrium constant for the reaction between a metal ion (M +n)
and a chelating agent (L-P) is known as a formation constant or stability
constant.

134
 𝑀𝑛+ + 𝐿−𝑃 = 𝑀𝐿𝑛−𝑃
[𝑀𝐿𝑛−𝑃 ]
𝐾𝑓 =
[𝑀 +𝑛 ] ∙ [𝐿−𝑃 ]

Figure 18. Important chelating agents

The term monodentate refers to a type of chemical that forms only one
coordination bond; while bidentate, tridentate, tetradentate,
penatadentate and hexadentate chemicals have more electron pairs available
and so form more bonds.
The complexes that polydentate ligands form are referred to as chelates.
• MONODENTATES: NH3, Cl-, CH3COO-;
• BIDENTATES: H2N-CH2-CH2-NH2 (Ethylenediamene);
• TRIDENTATES: H2N-CH2-CH2-NH-CH2-CH2-NH2
(Diamminodimetiletilammina);
• TETRADENTATES: (HOOC-CH2)3N (Nitric acid-triacetate);
• HEXADENTATES: (HOOC-CH2)2N-CH2-CH2-N(CH2-COOH)2
(Ethylen-diamminotetraacetatic acid).

Titration curve
The image shows how tridentate
and hexadentate bonds produce a very
clear end point. Other reasons why these
are the titrants of choice in
complexometric titration are:
• their reaction with the cations is
more complete;
• they tend to form 1:1 complexes
In case of complexometric
determination of metal ions we compute
pM; the negative log of the free metal
ion concentration present in the solution
135
at different stages of the titration. The plot is similar to the one obtained in
acid base titration. The schematic plot showing the titration curve of a metal
EDTA titration is given in Figure.
The schematic titration curve shown in Figure has three distinct
regions, the initial region where there is an excess of the metal ion the
inflection region corresponding to the equivalence or end point and the third
region where there is an excess of the titrant EDTA. The jump or the rise in
the pM value around the equivalence point depends on many factors like the
stabilities of the metal indicator and metal EDTA complexes besides pH.

COMPLEXOMETRIC TITRATION WITH EDTA

EDTA, ethylenediaminetetraacetic acid (formula C10H16N2O8, Molar

mass: 292.24 g/mol, often written as H4Y), has four carboxyl groups and two
amine groups that can act as electron pair donors, or Lewis bases. The ability
of EDTA to potentially donate its six lone pairs of electrons for the formation
of coordinate covalent bonds to metal cations makes EDTA a hexadentate
ligand. However, in practice EDTA is usually only partially ionized, and thus
forms fewer than six coordinate covalent bonds with metal cations.

Disodium EDTA is commonly used to standardize aqueous solutions of

transition metal cations. Disodium EDTA (often written as Na2H2Y) only
forms four coordinate covalent bonds to metal cations at pH values ≤ 12. In
this pH range, the amine groups remain protonated and thus unable to donate
electrons to the formation of coordinate covalent bonds. Note that the
shorthand form Na4-xHxY can be used to represent any species of EDTA, with
x designating the number of acidic protons bonded to the EDTA molecule.

EDTA forms an octahedral complex with most 2+ metal cations, M 2+,

in aqueous solution. The main reason that EDTA is used so extensively in the
standardization of metal cation solutions is that the formation constant for
most metal cation-EDTA complexes is very high, meaning that the
equilibrium for the reaction:
M2+ + H4Y → [MH2Y] + 2H+
lies far to the right. Carrying out the reaction in a basic buffer solution
removes H+ as it is formed, which also favors the formation of the EDTA-
metal cation complex reaction product. For most purposes it can be
considered that the formation of the metal cation EDTA complex goes to
136
completion, and this is chiefly why EDTA is used in titrations /
standardizations of this type.
So, disodium EDTA
• Molecular Formula C10H14N2Na2O8
• Molecular Weight: 336.208 g/mol
• is the most common complexometric titrant;
• forms 1:1 stable complexes with the majority of metals like earth-
alkaline Ba2+, Ca2+, Mg2+, Sr2+ and d-elements Cd2+, Fe2+, Fe3+, Hg2+,
Mn2+, Ni2+, (except group IA metals);
• forms stable water soluble complexes;
• is a primary standard;
• is normally used like sodium salt to increase the solubility.
Ethylenediaminetetraacetic acid and Na2H2Y form complexes with
most cations in a 1:1 ratio, irrespective of the valency of the ion:
M2+ + [H2X]2- = [MX]2- + 2H+
M3+ + [H2X]2- = [MX]- + 2H+
M4+ + [H2X]2- = [MX] + 2H+
where M is a metal cation and [H2X]2- is the anion of the disodium salt
(disodium EDTA) which is most frequently used. The structures of these
complexes with di-, tri- and tetravalent metals contain three, four and five
rings respectively:
The generalised reaction between the metal ion and the EDTA can be
described as given below.
Y4− + Mn+ = MY n−4
where, Y4– is a shorthand notation for the fully dissociated molecule of
EDTA. The formation constant for the complex will be given as following.
[𝑀𝑌 𝑛−4 ]
𝐾𝑓 =
[𝑀 𝑛+ ] ∙ [𝑌 4− ]

For example, the formation of a metal-EDTA complex with Cd2+ can be

represented as
Cd2+ (aq) + Y4– (aq) = CdY2– (aq)
The equilibrium constant (better called as formation constant) for the
reaction is given as follows and has a value of 2.9 × 1016 implying that the
complex is quite stable and the reaction goes far to the right.
[𝐶𝑑𝑌 2− ]
𝐾𝑓 =
[𝐶𝑑 2+ ] ∙ [𝑌 4− ]

During a complexometric titration, the pH must be constant by use of a

buffer solution. Control of pH is important since the H+ ion plays an
important role in chelation. Most ligands are basic and bind to H + ions
throughout a wide range of pH. Some of these H+ ions are frequently

137
displaced from the ligands (chelating agents) by the metal during chelate
formation.
Thus, stability of metal complex is pH dependent. Lower the pH of the
solution, lesser would be the stability of complex (because more H + ions are
available to compete with the metal ions for ligand). Only metals that form
very stable complexes can be titrated in acidic solution, and metals forming
weak complexes can only be effectively titrated in alkaline solution.

Preparation of an EDTA
Standard Solution Primary standards of EDTA cannot be prepared from
accurately weighted sample. EDTA solutions should be standardized against
ZnSO4 or MgSO4 of very high purity. Water used in EDTA solution
preparations should be free from polyvalent metal ions and preferably
distilled through all Pyrex glass. Calmagite is a suitable indicator. The
titration is conducted at a buffered solution at about pH 10.
Another important note concerns storage of standardized EDTA
solutions where these solutions should never be stored in soda based glass.
Preferably, polyethlene bottles should always be used.

Indicators in complexometric titration

The equivalence point of a complexation titration occurs when
stoichiometrically equivalent amounts of analyte and titrant have reacted. For
titrations involving metal ions and EDTA, the equivalence point occurs when
the concentrations of the metal ion and EDTA are equal. The accuracy of the
end point depends on the relative strength of the metal–indicator and metal-
titrant complex. If the metal-indicator complex is too strong, the color change
occurs after the equivalence point. If it is too weak, the end point is observed
before reaching the equivalence point.
As the concentration of metal ion decreases abruptly at the end point, in
principle, any method, which can determine this disappearance of free metal
ions, can be used to detect equivalence point in complexometric titrations.
This is usually detected with a metallochromic indicator wherein the end
point is determined by change in the colour of a metal ion indicator that
responds to change in metal ion concentration. In addition, we may resort to
instrumental determination of the equivalence point. Spectrophotometric,
potentiometric and conductometric methods are commonly employed
instrumental methods. Let us learn about the different methods of
determination of the end point of complexometric titrations.

Metallochromic Indicators
The most practical and versatile method is the visual end point
detection by using metallochromic indicators. Metallochromic indicators or
metal ion indicators are the compounds that are capable of forming a colored
complex with the metal ion being determined. In favourable conditions the
138
metal-indicator complex formed has an intense color which is distinctly
different from the uncomplexed indicator. The metal-indicator has a low
stability constant than the chelate-metal complex. Therefore, in the course of
the titration the colour of the solution remains that of the metal-indicator
complex until the end point, when an equivalent amount of the titrant has
been added. At the equivalence point the titrant decomposes metal-dye
complex to produce free dye which is manifested by a change in the colour.
Mn+ + Ind ⎯→ [M – Ind]
[M – Ind] + EDTA ⎯→ [M – EDTA] + free Ind

It is important that the stability constant for the metal-indicator

complex is lower than the metal-titrant complex and has an optimum value. If
it is too large, the sample will be over titrated, and if it is too small, an under
titration is possible. Let us try to visualise the changes occurring during the
course of complexometric titration involving metallochromic indicator.
The end point in complexometric titrations is shown by means of pM
indicators. The concept of pM arises as follows:
If K is the stability constant, K = [MX]/[M][X]
then, [M] = [MX]/[X]K
or log [M] = log [MX]/[X] – log K
and pM = log [X]/[MX] – pK
Therefore, if a solution is made such that [X] = [MX], pM = -pK (or
pM = pK’, where K’ = dissociation constant). This means that, in a solution
containing equal activities of metal complex and free chelating agent, the
concentration of metal ions will remain roughly constant and will be buffered
in the same way as hydrogen ions in a pH buffer. Since, however, chelating 8
agents are also bases; equilibrium in a metal-buffer solution is often greatly
affected by a change in pH. In general, for chelating agents of the amino acid
type (e.g., edetic acid and ammonia triacetic acid), it may be said that when
[X] = [MX], pM increases with pH until about pH 10, when it attains a
constant value. This pH is, therefore, usually chosen for carrying out titrations
of metals with chelating agents in buffered solutions.
The pM indicator is a dye which is capable of acting as a chelating
agent to give a dye-metal complex. The latter is different in colour from the
dye itself and also has a low stability constant than the chelate-metal complex.
The colour of the solution, therefore, remains that of the dye complex until
the end point, when an equivalent amount of sodium EDTA has been added.
As soon as there is the slightest excess of EDTA, the metal-dye complex
decomposes to produce free dye; this is accomplished by a change in colour.
Over 200 organic compounds form colored chelates with ions in a pM
range that is unique to the cation and the dye selected. To be useful, the dye-
metal chelates usually will be visible at 10-6 – 10-7 M concentration. Many of
these indicators also have the typical properties of acid-base indicators and
the colour changes are the result of the displacement of the H+ by a metal ion.
139
 Metal indicators must comply with the following requirements:
• Compound must be chemically stable throughout the titration.
• It should form 1:1 complex which must be weaker than the metal
chelate complex.
• Colour of the indicator and the metal complexed indicator must be
sufficiently different.
• Colour reaction should be selective for the metal being titrated.
• The indicator should not compete with the EDTA.
Mechanism of action of indicator: Let the metal be denoted by M,
indicator by I and chelate by EDTA. At the onset of the titration, the reaction
medium contains the metal-indicator complex (MI) and excess of metal ion.
When EDTA titrant is added to the system, a competitive reaction takes place
between the free metal ions and EDTA. Since the metal-indicator complex
(MI) is weaker than the metal-EDTA chelate, the EDTA which is being added
during the course of the titration is chelating the free metal ions in solution at
the expense of the MI complex. Finally, at the end point, EDTA removes the
last traces of the metal from the indicator and the indicator changes from its
complexed colour to its metal free colour. The overall reaction is given by:
[M-Ind] + EDTA = [M-EDTA] + Ind

Many compounds have been used as indicators (Table-1), like:

• Triphenyl methane dyes
• Phthalein and substituted phthaleins
• Azo dyes
• Phenolic compounds
Common indicators are organic dyes such as Fast Sulphon Black,
Eriochrome Black T. Color change shows that the indicator has been
displaced (usually by EDTA) from the metal cations in solution when the
endpoint has been reached. Thus, the free indicator (rather than the metal
complex) serves as the endpoint indicator.
In case of an important complexometric determination viz., hardness of
water we use Eriochrome black T or solochrome black as metal ion
indicator. Eriochrome black T is sodium 1-(1-hydroxy-2-napthylazo)-6-nitro-
2napthol-4-sulphonate. Its structure is as shown below.

In the beginning of the titration, eriochrome black –T forms a wine red

complex with the metal ions subsequent addition of the EDTA is used in
140
complexing the free metal ion. At the end point of the titration, when the
available metal ions are fully complexed with EDTA, the colour changes to
blue ‒ the colour of the free indicator.
MIn− + H2Y2− → MY2− + HIn2−
wine red blue
where H2Y2− represents disodium salt of EDTA and HIn2− represents
eriochrome black T in a buffer solution of pH 10.
While using the metallochromic indicators one must be careful about
the pH of the reaction solution. This is so because most visual metallochromic
indicators, in addition to being complexing agents, are also acid-base
indicators. In other words, they are capable of undergoing a color change with
a corresponding change in pH of the solution. For example, calmagite is an
indicator for the determination of calcium ions which may be represented as
H3In, undergoes a change in color from the red (H2In–) to blue (HIn2–) at a pH
of about 8.1. The blue of HIn2– changes to the red-orange (In3–) at a pH of
about 12.4. As the color of metal-indicator complexes are red, it can be used
as a metallochromic indicator only in the range of pH = 9 – 11, at which
almost all the indicator is present as HIn2– (blue). It is, therefore, important to
maintain the pH of the solution in the course of the complexometric titrations.

Murexide (NH4C8H4N5O6), also called ammonium purpurateor MX, it

is the ammonium salt of purpuric acid. It can be represented by H4Ind –:

Murexide can be used for the direct titration of calcium at pH 11 and

this give a colour change at end point from red to blue violet. In the direct
titration of murexide with nickel at pH 10-11 there is a colour change from
yellow to blue-violet. Murexide forms a complex with many metal ions.
Murexide solution has various colour change at various pH range. It is reddish
brown up to pH 9, violet from pH 9 to pH 11 and blue-violet (or blue) when it
is above pH 11.

The colour change are due to the progressive displacement of protons

from imido group. The application of murexide that are sufficiently stable in
141
analysis of metals is with copper (Cu), nickel (Ni), cobalt (Co), calcium (Ca)
and the lanthanides. Their colours in alkaline solution are orange in copper,
yellow in nickel and cobalt and red in calcium. The colour also varies with the
pH of the solution.
Murexide may be prepared by suspending 0.5g of the powered
dyestuff in water, shake it thoroughly and allow the undissolved portion to
settle.
Murexide in its dry state has the appearance of a reddish purple powder,
slightly soluble in water. In solution, its color ranges from yellow in strong
acidic pH through reddish-purple in weakly acidic solutions to blue-purple in
alkaline solutions. The pH for titration of calcium is 11.3.
The useful pH range for some common metallochromic indicators is
compiled in Table 15.
Table 15. Indicators used in complexometric titration

Types of Complexometric Titrations

Complexometric titrations are of 4 types:
1. Direct Titration: It is the simplest and the most convenient method
used in chelometry. In this method, the standard chelon solution is added to
the metal ion solution until the end point is detected. This method is
analogous to simple acid-base titrations. E.g.-calcium gluconate injection,
calcium lactate tablets and compound sodium lactate injection for the assay of
calcium chloride (CaCl26H2O).
Limitations:
• slow complexation reaction
• interference due to presence of other ions
2. Back Titration: In this method, excess of a standard EDTA solution
is added to the metal solution, which is to be analyzed, and the excess is back
titrated with a standard solution of a second metal ion.
142
 Determination of Mn. This metal cannot be directly titrated with EDTA
because of precipitation of Mn(OH)2. An excess of known volume of EDTA
is added to an acidic solution of Mn salt and then ammonia buffer is used to
adjust the pH to 10 and the excess EDTA remaining after chelation, is back
titrated with a standard Zn solution kept in burette using Eriochrome blackT
as indicator. This method is analogous to back titration method in acidimetry.
3. Replacement Titration: In this method the metal, which is to be
analyzed, displaces quantitatively the metal from the complex. When direct or
back titrations do not give sharp end points, the metal may be determined by
the displacement of an equivalent amount of Mg or Zn from a less stable
EDTA complex.
Mn+2 + Mg-EDTA-2 = Mg+2 + Mn-EDTA-2
Mn displaces Mg from Mg-EDTA solution. The freed Mg metal is then
directly titrated with a standard EDTA solution. In this method, excess
quantity of Mg EDTA chelate is added to Mn solution. Mn quantitatively
displaces Mg from Mg EDTA chelate. This displacement takes place because
Mn forms a more stable complex with EDTA. By this method Ca, Pb, Hg
may be determined using Eriochrome blackT indicator.
4. Indirect Titration: This is also known as Alkalimetric titration. It is
used for the determination of ions such as anions, which do not react with
EDTA chelate. Protons from disodium EDTA are displaced by a heavy metal
and titrated with sodium alkali.
Mn+ + H2X-2 = MX (n-4) + 2H+
Some important elements which could be determined by
complexometric titration are as follows:
• Direct Titration: Analysis of Cu, Mn, Ca, Ba, Br, Zn, Cd, Hg, Al,
Thallium, Sn, Pb, Bi, Vanadium, Cr, Mo, Gallium, Fe, Co, Ni, and Pd.
• Indirect Titration: Analysis of Na, K, Ag, Au, As, C, N, P, S, Cl, Br, I
and F.
• Water hardness.
• Amount of calcium in milk and dairy products.

Selectivity in Complexometric Titrations

EDTA is a very unselective reagent because it complexes with
numerousdoubly, triply and quadruply charged cations. When a solution
containingtwo cations which complex with EDTA is titrated without the
addition of a complex-forming indicator, and if a titration error of 0.1 per cent
ispermissible, then the ratio of the stability constants of the EDTA
complexesof the two metals M and N must be such that KM/KN > 106 if N is
not to interfere with the titration of M. Strictly, of course, the constants KM
and KN considered in the above expression should be the apparent stability
constants of the complexes. If complex-forming indicators are used, then for a
similar titration error KM/KN > 108.The following procedures will help to
increase the selectivity:
143
 a) Suitable control of the pH of the solution. This, of course, makes
use of the different stabilities of metal-EDTAcomplexes. Thus bismuth and
thorium can be titrated in an acidicsolution (pH = 2) with xylenol orange or
methylthymol blue as indicatorand most divalent cations do not interfere.A
mixture of bismuth and lead ions can be successfully titrated by firsttitrating
the bismuth at pH 2 with xylenol orange as indicator, and thenadding
hexamine to raise the pH to about 5, and titrating the lead.
b) Use of masking agents. Masking may be defined as the process in
which a substance, withoutphysical separation of it or its reaction products, is
so transformed that it does not enter into a particular reaction. Demasking is
the process inwhich the masked substance regains its ability to enter into a
particular reaction. By the use of masking agents, some of the cations in a
mixture can often be 'masked' so that they can no longer react with EDTA or
with the indicator. An effective masking agent is thecyanide ion; this forms
stablecyanide complexes with the cations of Cd, Zn, Hg(II), Cu, Co, Ni, Ag,
and the platinum metals, but not with the alkaline earths, manganese, and
lead.
It is therefore possible to determine cations such as Ca2+, Mg2+, Pb2+,
and Mn2+ in the presence of the above-mentioned metals by masking with an
excess of potassium or sodium cyanide. A small amount of iron may be
masked by cyanide if it is first reduced to the iron(II) state by the addition of
ascorbic acid. Titanium(IV), iron(III), and aluminium can be masked with
triethanolamine; mercury with iodide ions; and aluminium, iron(III),
titanium(IV), and tin(II) with ammonium fluoride (the cations of the alkaline-
earth metals yield slightly soluble fluorides). Sometimes the metal may be
transformed into a different oxidation state: thus copper(II) may be reduced in
acid solution by hydroxylamine or ascorbic acid. After rendering ammoniacal,
nickel or cobalt can be titrated using, for example, murexide as indicator
without interference from the copper, which is now present as Cu(I). Iron(III)
can often be similarly masked by reduction with ascorbic acid.
c) Selective demasking. The cyanide complexes of zinc and cadmium
may be demasked with formaldehydeacetic acid solution or, better, with
chloral hydrate : The use of masking and selective demasking agents permits
the successive titration of many metals. Thus a solution containing Mg, Zn,
and Cu can be titrated as follows:
1. Add excess of standard EDTA and back-titrate with standard Mg
solution using solochrome black as indicator. This gives the sum of al1 the
metals present.
2. Treat an aliquot portion with excess of KCN (Poison !) and titrate as
before. This gives Mg only.
3. Add excess of chloral hydrate (or of formaldehyde-acetic acid
solution, to the titrated solution in order to liberate the Zn from the cyanide
complex, and titrate until the indicator turns blue. This gives the Zn only. The
Cu content may then be found by difference.
144
1st EXPERIMENT. Preparation of an EDTA standard solution and
standardization it.
Chemicals:
• EDTA (Na2H2Y2H2O);
• pH 10 ammonia-ammonium buffer. Dissolve 7.0 g of ammonium
chloride in 57 mL concentrated ammonia (see safety notes); dilute to
100mL with distilled water in a volumetric flask. The pH should be
10.5.;
• Eriochrome Black T (ground 1:10 with NaCl),
• Eriochrome Black T indicator solution. Dissolve 0.2 g of Eriochrome
Black T indicator in 15 mL of concentrated ammonia solution (or 15
mL of triethanolamine) (see safety notes) and 5mL absolute ethanol.
Do not store more than one to two days before use;
• Standard Zn solution.
Equipment: volumetric flask, graduated cylinder 100 mL, pipette, burette 25
mL and beakers

The disodium dehydrate of EDTA, Na2H2Y2H2O is commonly used to

prepare standard EDTA solutions. This salt is readily available from many
commercial sources, and often in such a high purity that solutions need not be
standardized for routine work. Primary standard Zn, CaCO3, ZnSO4, MgCl2
solutions can be used to standardize EDTA solution.

PART 1. PREPARATION OF STANDARD 0.01 N Na2H2EDTA

SOLUTION
1. Weigh about 3.8 g of the disodium EDTA salt (Na2H2Y2H2O) (what
balance should you use?) into a 1 liter volumetric flask, dissolve and dilute to
the mark with deionized water and mix well.

PART 2. PREPARATION OF STANDARD Zn SOLUTION

Standard Zn solution: (This has been prepared for you.) An accurate
mass (~1.3g) of pure zinc has been dissolved in a small volume (~15 mL) of
6M HCl. The dissolve zinc was quantitatively transferred to a 2 L volumetric
flask and diluted to the mark. This ~0.01 M (you need to find the exact
concentration!!) solution serves to standardize the EDTA solution. Remember
that the results from your calcium and magnesium determination depend on
the accurate preparation of this solution.

PART 3. STANDARDIZATION OF THE EDTA SOLUTION

1. Pipet exactly 25 mL of standard Zn solution into each of three Erlenmeyer
flasks.

145
2. Then add 20 mL of pH 10 buffer (in the hood), 15 mL of water, stir, and
add a few crystals of the Eriochrome Black T indicator. It is critical to add
only enough indicator to produce a light wine-red color.
3. Rinse and fill a 25 mL buret with standartized Na2H2EDTA titrant solution.
Tap to remove bubbles and make certain that the buret tip is filled with
solution. Adjust the solution level between 0 and 2 mL; read the buret to the
nearest 0.01 mL. (Do not try to set 0.00 mL!) Record the initial reading.
4. Titrate with your EDTA solution until the color changes from wine-red to a
clear blue.
5. Use these results to determine the molar concentration of the EDTA
solution for use in the titration of your unknown solution.

Results of titration:
• Volume of standard Zn solution taken for titration: VZn = 25 mL
• Normality of standard Zn solution: NZn = 0.01 M
• Volume of titrant consumed for the 1st titration: 𝑉𝐸𝐷𝑇𝐴
1
=
• Volume of titrant consumed for the 2 titration: 𝑉𝐸𝐷𝑇𝐴 =
nd 2

• Volume of titrant consumed for the 3rd titration: 𝑉𝐸𝐷𝑇𝐴

3
=
𝑉 1 +𝑉 2 +𝑉 3
• Average amount of titrant consumed for titration: 𝑉𝐸𝐷𝑇𝐴
∗
= =
3

Calculation:
The result is expressed as mol-eq/l concentration and based on the
following formula:
𝑉𝑍𝑛 𝑁 𝑉 ∙𝑁
∗ = 𝐸𝐷𝑇𝐴 => 𝑁𝐸𝐷𝑇𝐴 = 𝑍𝑛 𝑍𝑛
𝑉𝐸𝐷𝑇𝐴 𝑁𝑍𝑛 𝑉𝐸𝐷𝑇𝐴
𝑁𝐸𝐷𝑇𝐴 ∙𝐸𝑞𝐸𝐷𝑇𝐴
𝑇𝐸𝐷𝑇𝐴 =
1000
𝑁𝐸𝐷𝑇𝐴 ∙𝐸𝑞𝑍𝑛
𝑇𝐸𝐷𝑇𝐴 =
1000

2nd EXPERIMENT. Determination of total water hardness and

concentration of Ca2+ and Mg2+ ions in water through EDTA
complexometry.
Chemicals: 0.05N standardized EDTA (Na2H2Y2H2O) solution; pH 10
ammonia-ammonium buffer; 9M NaOH solution, Eriochrome Black T and
Murexide indicators.
Equipment: volumetric flask, graduated cylinder 100 mL, pipette, burette 25
mL

One of the factors that establish the quality of a water supply is its
degree of hardness. Hardness of water measures the sum of calcium and
magnesium ions present in the water. The above-mentioned standard lays
down a titration with EDTA at pH 10.00, using a NH4Cl – NH4OH buffer and
a colorimetric detection of the equivalent point.

146
 The concentration of Ca2+ and Mg2+ cations dissolved in 1 L of water is
described as the hardness of water.
𝑚𝐶𝑎2+ 𝑚𝑀𝑔2+
𝐻= + = 𝑚𝑚𝑜𝑙𝑒 − 𝑒𝑞/𝐿
20.04 12.16
The two cations are essential for humans and other living organisms,
but it is also vital to control their concentration in drinking water and water
for industrial use because of the practical consequences of their presence. In
fact, calcium and magnesium form insoluble compounds with carbonated
anions cumulatively termed lime.
Determining the hardness of water is therefore a necessary test as a
measure of water quality for domestic and industrial use. If there are too many
of these ions it can lead to the formation of limescale inside electrodomestic
appliances like washing machines and dishwashers making them less
efficient. The formation of lime deposits in tubes or pipes is also a problem
for industry where the equipment is water-cooled. Water which is too rich in
calcium also makes soaps precipitate, making household detergents less
foamy. In areas where the water is very hard, people need to use more
detergent to get things clean.
TEMPORARY HARDNESS is due to the presence of Ca2+ and
Mg2+ salts like bicarbonates which, when boiled, decompose to form
insoluble compounds of the two metal ions.
Ca(HCO3)2 ↔ CaCO3 + CO2 + H2O
At high temperatures, the equilibrium of the reaction is towards the
right (CO2 gas is released and calcium carbonate precipitates).
PERMANENT HARDNESS is due to those salts that remain in the
water despite prolonged boiling (chlorides, sulphates, nitrates, carbonates).
The sum of the temporary and permanent hardness is called general
(total).
GH = TH + PH
Table 16. Classification of water depending on hardness
Hardness Types of water Examples
interval (mmol-eq/L)
H < 1.5 Very soft Rainfall
H = 1.5 – 4.0 Soft Fresh water pond like
rivers and lakes
H = 4.0 – 8.0 Medium hard Drinking water
H = 8.0 – 12.0 Hard
H > 13.0 Very hard Seas and oceans

The hardness of water is expressed like:

• French degrees 1g CaCO3/100 L of water;
• German degrees (°t) 10 mg CaO/100 ml of water;
• English degrees 1 grain CaCO3/gallon of water. They use a different
unit for both weight and volume,
147
 • Our degrees mg of Ca2+ and Mg2+ ions in 1 Liter of water.
Concentrations of calcium and magnesium in water are normally
expressed in french degrees. 1 german degree = 0.56 french degree.
The disodium EDTA solution can then be used to determine the
hardness of an unknown water sample. Both magnesium and calcium can be
easily determined by EDTA titration in the pH 10 against Eriochrome Black
T. If the sample solution initially contains also other metal ions, one should
first remove or mask them, as EDTA react easily with most of the cations
(with the exception of alkali metals).
Reactions taking place during titration are:
[Me-In]+ + H2EDTA2- → [Me-EDTA]2- + 2H+ + In-
wine red dark blue
(where Me – Mg or Ca, In - indicator).
The end point of magnesium titration can be easily detected with
Eriochrome Black T, which forms redorange complex with both Ca2+ and
Mg2+ ions. Addition of EDTA causes gradual expulsion of indicator from
complexes (because those with EDTA are stronger). Finally, only blue color
of free (non-bonded) indicator is present. The change of color is, however,
gradual, and titration should be carried with overtitrated sample as color
reference.
Another indicator, Murexide, forms red complexes with calcium at
pH=12 (and higher). At this pH, magnesium precipitates as Mg(OH) 2. So, for
simultaneous determination of Mg and Ca one needs two titrations: one at
pH=10 and using Eriochrome Black T (the sum of moles of both metals is
obtained) and second, at pH=12 and using Murexide (only calcium is titrated).
Important: the change of indicator’s color is gradual. So, the titration has to be
carried to total change of color, using overtitrated sample as the color
reference.
Determination of magnesium and calcium is important in many fields.
The examples are:
1. Analysis of drinking (technological, etc.) water. Surface waters
always contain dissolved minerals, in particular well soluble bicarbonates of
Mg and Ca. Because there is always CO2 present in air, when rains fall of the
limestone, the following reaction occurs:
CaCO3 + H2O + CO2 → Ca2+ + 2HCO32-
This reaction can be reversed by boiling and the carbonate precipitates
forming so called “fur” or “boiler scale”. Moreover, metal ions in water react
with soap causing its increased consumption when washing. So, the content of
Ca and Mg is one of the most important factors, known as “water hardness”.
Look in textbooks for information how this factor is calculated.
2. Analysis of minerals – the content of magnesium in
limestone/dolomite determines sometimes its technological usefulness.
Cations of other metals can disturb these analyses – sometimes it is necessary
to mask them using a ligand forming colorless complexes with these ions, but

148
not with magnesium or calcium ones (CN-, F- etc.). Find in textbooks
additional information about masking.

PROCEDURE:
PART 1. DETERMINATION OF TOTAL HARDNESS
1. Pipet exactly 100 mL of analyzed water into each of three Erlenmeyer
flasks using graduated cylinder.
2. Then add 2 mL of pH 10 buffer (in the hood), stir, and add a 7 – 10 drops
of the Eriochrome Black T indicator. It is critical to add only enough indicator
to produce a light wine-red color.
3. Titrate with your EDTA solution until the color changes from wine-red to a
clear blue.
4. Use these results to determine the molar concentration of the EDTA
solution for use in the titration of your unknown solution.

Results of titration:
• Volume of analyzed water sample taken for titration: 𝑉𝐻2 𝑂 = 100 𝑚𝐿
(+ 2 mL buffer + 7-8 drops of Eriochrome black Ind)
• Normality of standardized Na2H2EDTA: NEDTA = 0.05N
• Volume of titrant consumed for the 1st titration: 𝑉𝐸𝐷𝑇𝐴
1
=
• Volume of titrant consumed for the 2 titration: 𝑉𝐸𝐷𝑇𝐴 =
nd 2

• Volume of titrant consumed for the 3rd titration: 𝑉𝐸𝐷𝑇𝐴

3
=
𝑉 1 +𝑉 2 +𝑉 3
• Average amount of titrant consumed for titration: 𝑉𝐸𝐷𝑇𝐴
∗
= =
3

Calculation:
The result is expressed as mmol-eq/l concentration and based on the
following formula:
∗
𝑉𝐸𝐷𝑇𝐴 ∙𝑁𝐸𝐷𝑇𝐴
𝑇𝑜𝑡𝑎𝑙 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = ∙ 1000
𝑉𝐻2 𝑂

Conclusion. Describe the source of your water sample. Use the USGS
classification system to describe the hardness of your water sample. Where
does Astana’s drinking water come from? Based on the source of the water,
explain the presence of the magnesium and calcium ions in the water.

PART 2. DETERMINATION OF ONLY CALCIUM

CONCENTRATION IN WATER
Calcium can be determined by EDTA titration in solution of 9 M
sodium hydroxide (pH 12-13) against murexide. Murexide solutions are
not stable and should be not stored longer than a week. Murexide indicator
exist either in the form of solution, or ground with NaCl - 100 mg of indicator
plus 20 g of analytical grade NaCl.
Titration against EDTA at pH around 12.5 gives the hardness due to
2+
Ca only. A pH of about 12.5 required for this titration can be obtained by
149
adding diethyl amine base with 3 – 4 drops of calcon indicator or NaOH base
with murexide indicator. At this high pH, the Mg2+ ion is quantitatively
precipitated as Mg(OH)2 and Ca2+ ion alone can be estimated by
complexometric method using EDTA. At the end point color changes from
pink to pure blue.
Before starting titration:
Ca2+ + H2In3- ↔ CaH2In
sample murexide complexed murexide
ind (red rose)
During titration:
Ca2+ + H2Y2- ↔ CaY2- + 2H+
EDTA
(titrant)
Just before & at the E.P.:
CaH2In- + H2Y2- ↔ CaY2- + 2H+ + H2In3-
free murexide
(bluish violet)
This reaction occurs because Ca-EDTA complex is more stable than Ca-
murexide complex.

PROCEDURE:
1. Pipette 25.0 mL of water sample into conical flask, add the 1 mL 9M
NaOH solution to change the pH value of solution to 12. Then add the
Murexide powder indicator. The color of water sample change to rose red.
2. Titrate the water sample by standardized Na2H2EDTA solution from rose to
violet colour. Consumption of titrant EDTA solution for this titration
represents the content of Ca2+ in titrated solution.
3. The sample for the blank test contains 25.0 mL of distilled water, 1 ml
volume of 9M NaOH solution necessary for pH regulation and a punch of
Murexide powder indicator. And titrate it by standardized Na2H2EDTA too.

Results of titration:
• Volume of analyzed water sample taken for titration: 𝑉𝐻2 𝑂 =
50 𝑚𝐿 (+1 𝑚𝐿 9𝑁 𝑁𝑎𝑂𝐻 + 𝑚𝑢𝑟𝑒𝑥𝑖𝑑𝑒)
• Normality of standardized Na2H2EDTA: NEDTA = 0.05N
• Volume of titrant consumed for the 1st titration: 𝑉𝐸𝐷𝑇𝐴
1
=
• Volume of titrant consumed for the 2 titration: 𝑉𝐸𝐷𝑇𝐴 =
nd 2

• Volume of titrant consumed for the 3rd titration: 𝑉𝐸𝐷𝑇𝐴

3
=
𝑉 1 +𝑉 2 +𝑉 3
• Average amount of titrant consumed for titration: 𝑉𝐸𝐷𝑇𝐴
∗
= =
3

Calculation:
The result is expressed as mmol-eq/l concentration and based on the
following formula:

150
 ∗
𝑉𝐸𝐷𝑇𝐴 ∙𝑁𝐸𝐷𝑇𝐴
[𝐶𝑎2+ ] = ∙ 1000
𝑉𝐻2 𝑂

PART 3. CALCULATION OF MAGNESIUM CONCENTRATION IN

WATER
The difference between total content and calcium content in the sample
represents the content of magnesium in the sample.

Results:
From 1 Part take value of Total Hardness: ______
From 2 Part take value of Ca2+ ion concentration: _____

Calculation:
The result is expressed as mmol-eq/l concentration and based on the
following formula:
𝑇𝑜𝑡𝑎𝑙 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = [𝐶𝑎2+ ] + [ 𝑀𝑔2+ ]
[𝑀𝑔2+ ] = 𝑇𝑜𝑡𝑎𝑙 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 − [𝐶𝑎2+ ]

3rd EXPERIMENT. Estimation of calcium content in milk through

EDTA complexometry.
Aim: to estimate the amount of calcium in milk powder by complexometric
titration using disodium EDTA.
Chemicals: sample of milk, standardized EDTA (Na2H2Y2H2O) solution;
9M NaOH solution, Murexide indicator, distilled water.
Equipment: volumetric flask, graduated cylinder 100 mL, pipette, burette 25
mL

Calcium is a macroelement that is very important for the human body:

its content and circulation in the body is large, it serves as the electrolyte, it
has a building role and participates in the process of metabolism. Calcium
comprises 1.5 – 2.0 % of our body weight. It is required by the body to
produce strong bones and teeth, and 99%of the calcium of our body is present
in bones and teeth. Milk is a heterogeneous mixture of proteins, sugar, fat,
vitamins and minerals. Milk and milk products are some of the natural
sources of calcium.
The present analysis is concerned with the determination of Ca by the
use of a complexometric titration of the type that is described above. The
titration is performed by adding a standard solution of EDTA to the sample
containing the Ca. The reaction that takes place is the following:
Ca2+ + H2Y2- <===> CaY2- 2H+
Before the equivalence point, the Ca2+ concentration is nearly equal to
the amount of unchelated (unreacted) calcium since the dissociation of the
chelate is slight. At the equivalence point and beyond, pCa is determined from
the dissociation of the chelate at the given pH. The equivalence point is

151
detected through the use of an indicator which is itself a chelating agent. The
specific indicator used is Murexide. It is an indicator exist either in the form
of solution, or ground with NaCl - 100 mg of indicator plus 20 g of analytical
grade NaCl.

PROCEDURE:
1. Combine 2 mL of sample, 48 mL distilled water, and 2 mL of 9M sodium
hydroxide solution into an Erlenmeyer flask and allow solution to stand
for about 5 minutes with occasional swirling.
2. A small of magnesium hydroxide may precipitate during this time. Do not
add the indicator until you have given this precipitate a chance to form.
3. Then add few specks of murexide indicator
4. After that start to titrate with standardized 0.01 M EDTA solution
5. Repeat titration for the sample for the blank sample test contains 50 mL of
distilled water, 2 ml volume of 9M NaOH solution necessary for pH
regulation and a punch of Murexide powder indicator. And titrate it by
standardized Na2H2EDTA too.

Results of titration:
• Volume of analyzed milk sample taken for titration: 𝑉𝑠𝑎𝑚𝑝𝑙𝑒 = 2 𝑚𝐿
• Molecular weight of calcium: M(Ca) = 40.78g/mole
• Normality of standardized Na2H2EDTA: NEDTA =
• Volume of titrant consumed for the sample titration: 𝑉𝐸𝐷𝑇𝐴
1
=
• Volume of titrant consumed for the blank sample titration: 𝑉𝐸𝐷𝑇𝐴
2
=

Calculation:
The result is expressed and based on the following formula:
1 ml of 0.01 M EDTA = 0.4008 mg Ca
1 2
𝑚𝐶𝑎2+ = (𝑉𝐸𝐷𝑇𝐴 − 𝑉𝐸𝐷𝑇𝐴 ) ∙ 0.4008

𝐶𝐸𝐷𝑇𝐴 ∙ 𝑉𝐸𝐷𝑇𝐴(𝑖𝑛 𝐿𝑖𝑡𝑒𝑟) ∙ 40.78

𝑊𝐶𝑎 , % = ∙ 100%
𝑚𝑠𝑎𝑚𝑝𝑙𝑒
* Calcium content is average 240 mg in 100 mL of milk. The adult reference
nutrient intake for calcium is 700 mg a day. This is the amount considered sufficient to
meet the requirements of most people. Teenagers have a higher requirement (1000 mg for
males and 800 mg for females aged 11-18).

CONTROL OF MASTERING THE TOPIC

Typical calculation tasks
Task 1. A 0.3205 g sample of CaCO3 was dissolved in HCl and the resulting
Solution diluted to 250.0mL in a bolumetric flask. A 25.00 mL sample of the
solution repuired 18.75mL of an EDTA solution for titration to the

152
Eriochrome Black T end point. What is the concentration (in mol/L) of the
EDTA solution?
Task 2. A 100.0 mL aliquot of city drinking water was treated with a small
amount of an ammonia – ammonium chloride buffer to bring the pH to 10.
After the addition of Calmagite indicator the solution required 21.46 mL of
5.140*10-3 M EDTA for titration. Calculate the hardness of water.
Task 3. A 50.00 ml aliquot of a solution containing Ca2+ and Mg2+ was
buffered at pH 10 and titrated with 0.04865 M EDTA. The endpoint volume
was 44.27 ml. A second aliquot of the same mixture was made strongly basic
by the addition of NaOH – this causes the Mg2+ to precipitate as Mg(OH)2.
The solution was then titrated with the 0.04865 M EDTA and the endpoint
volume was found to be 34.26 ml. Calculate the molar concentrations of Ca 2+
and Mg2+.
Task 4. A 25.00 ml aliquot of a solution containing Cu2+ and Fe3+ was titrated
with 16.06 ml of 0.05083 M EDTA. A second 25.00 ml aliquot of the Cu/Fe
mixture was treated with NaF to form a stable iron-fluoride complex
(complexed Fe will not react with EDTA). This mixture was then titrated with
0.05083 M EDTA and the endpoint volume was found to be 5.43 ml.
Calculate the molar concentrations of Cu2+ and Fe3+.
Task 5. A sample of Epsom Salt of mass 0.7567 g was dissolved uniformly in
distilled water in a 250 mL volumetric flask. Portions of the magnesium ion
solution of volume 10 mL were titrated using a 0.01000 M solution of EDTA
by the method of this experiment. The mean corrected titration volume was
12.25 mL. Calculate the percentage by mass (% w / w) of the magnesium in
the Epsom Salt sample.
Task 6. A supplement tablet containing (nominally) about 300 mg of calcium
ion was dissolved, filtered, and diluted to 100 mL volume. Several 2.00 mL
samples of the total solution were titrated with 0.0100 M EDTA solution by
the method of this experiment. The mean corrected titration volume was
13.65 mL. Calculate the calcium content of the supplement tablet in mg units.
Task 7. A 100 mL (0.100 L) sample of tap water was titrated with 0.0100 M
EDTA solution. The corrected titration volume was 14.80 mL. Determine the
total hardness of water.
Task 8. A solution of 0.00599 M EDTA is used to titrate 250 mL of a
solution formed by adding MgSO4 to water. The volume of EDTA solution
required to reach the endpoint was 10.10 mL. What was the concentration
(g/L) of MgSO4 in the solution?
Task 9. Determine the molarity of an EDTA solution, if 1.2534g of zinc
sulfate is dissolved in acid and made up accurately to 100 mL. 25mL aliquots
of this solution are buffered and titrated to endpoint with an average of 21.4
mL of EDTA.
Task 10. A 0.2054 g sample of CaCO3 (primary standard) is dissolved in
hydrochloric acid and the solution is diluted with water to 250.0 mL (solution

153
A). A 50.0 mL aliquot of solution A is titrated with 41.12 mL of EDTA
solution. Calculate the molarity and titer of EDTA solution.
Task 11. A 1.4581g sample of powdered milk was dissolved in 100 mL. 25
mL aliquots were titrated to endpoint with an average of 13.8 mL of 0.0109 M
EDTA. Calculate the %w/w of calcium in the sample.
Task 12. A sample of brass is analysed for its zinc and copper content.
0.2076g sample is dissolved in acid and made up to 250.0 mL 25 mL aliquots
are titrated to endpoint with an average of 31.7 mL of 0.0102 M EDTA.
Further 25 mL aliquots are treated with cyanide, and then methanal, and
titrated with an average of 10.9 mL of the sae EDTA. Calculate the %w/w of
zinc and copper in the sample.

QUESTIONS FOR TEST SELF-CHECK

1. What is the indicator used in this titration?
2. Why can Eriochrome Black T not be used directly as an indicator?
3. What is the color of the doubly ionized Eriochrome Black T indicator in
slightly basic solution?
4. What is the purpose of adding NaOH solution dropwise to the Mg-EDTA
mixture?
5. Is it possible to use the sodium salt of EDTA as a primary standard?
6. At what pH is the Ca titration carried out?
7. What are the conditional constants for Mg2+ and Ca2+ at the pH at which
the titration is carried out?
8. What is a metal ion indicator? Briefly explain how it functions in an
EDTA titration?
9. Why do we use murexide as the indicator for the second set of titrations?
10.How can you determine the water hardness due to calcium and magnesiu
m individually?
11. What causes water hardness in nature? Why don’t we measure the water ha
rdness of distilled water?
12. Complexometric titration (sometimes chelatometry) is a form
of ________ in which the formation of a colored complex is used to
indicate the end point of a titration.
13. ________, ethylenediaminetetraacetic acid, has four carboxyl groups and
two amine groups that can act as electron pair donors, or Lewis bases.
14. In complexometric titration, the most common used chelating agent is
EDTA (ethylenediamine tetraacetic acid). EDTA's molecules will
combine with metals to form chelate. EDTA is classified as a?
a) Bidentate ligand b) Monodentate ligand
c) Tetradentate ligand d) Hexadentate ligand
15.The complexometric titration where EDTA is used, carried out at basic
pH. Why?
a) For the stability of complex formed
b) reaction rate is optimum in basic pH
154
c) there is less number of side reaction
d) all

References:
1 D. A. Skoog, D. M. West, F. J. Holler, and S. R. Crouch, Analytical
Chemistry: An Introduction, 7th ed. Chapter 15, pp. 345-381.
2 Vogel's Textbook of Qualitative Inorganic Analysis by Vogel, A.I., 3rd,
Ed., Longman (1961) 444, 445.
3 James N Miller & Jane C Miller, Statistics and Chemometrics for Analytical
Chemistry, 5th Ed (2005) Publ. Pearson Education Limited pg 1143.
4 Online sources:
http://www.csudh.edu/oliver/che230/labmanual/calcium.htm[Accessed3/22/2
011]
http://www.ajcn.org/cgi/reprint/83/2/310.pdf [Accessed3/22/2011]5.
http://www.cerlabs.com/experiments/10875404367.pdf[Accessed3/22/2011]6
http://www.chemteach.ac.nz/investigations/documents/calcium.pdf{\[accesse
d 3/22/2011]

LABORATORY WORK 9
REDOX TITRATION
PERMANGANATOMETRY

Objective: to determine the strength of KMnO4 solution by titrating it

against a primary standard solution of Sodium oxalate (Na 2C2O4) and to
determine an amount of iron (Fe2+) in Mohr’s salt (Ferrous ammonium
sulphate FeSO4(NH4)2SO46H2O)
Learning Outcome:
• Students acquire the knowledge to calculate the strength of
KMnO4 using molarity equation.
• Students understand the purpose of addition of dil. H2SO4 and the
purpose of heating of oxalic acid before titration.
• Students acquire the skill to prepare standard solutions of oxalic acid
and Mohr’s salt.
• Students understand the apparatus used for a titration.
• Students acquire the skill to perform the redox-titration in the real lab
after understanding the different steps.

The titration based on oxidation and reduction reaction between the

titrant and analyte is called Redox titration.
Oxidation is the process of the addition of oxygen or removal of
hydrogen/electron and reduction involves the process of addition of
hydrogen/electrons or removal of oxygen.

155
 Oxidizing agents are substances that gain one or more electrons and are
reduced. Reducing agents are substances that lose one or more electrons and
are oxidized. That is, oxidizing agents are electron acceptors, and reducing
agents are electron donors.
In redox systems, the titration method can be adopted to determine the
strength of a reductant/oxidant using a redox sensitive indicator.
Redox titrations were introduced shortly after the development of
acid–base titrimetry. The earliest methods took advantage of the oxidizing
power of chlorine. In 1787, Claude Berthollet introduced a method for the
quantitative analysis of chlorine water (a mixture of Cl2, HCl, and HOCl)
based on its ability to oxidize solutions of the dye indigo (indigo is colorless
in its oxidized state). In 1814, Joseph Louis Gay-Lussac (1778–1850),
developed a similar method for chlorine in bleaching powder. In both
methods the end point was signaled visually. Before the equivalence point,
the solution remains clear due to the oxidation of indigo. After the
equivalence point, however, unreacted indigo imparts a permanent color to
the solution.
The number of redox titrimetric methods increased in the mid-1800s
with the introduction of MnO4–, Cr2O72– and I2 as oxidizing titrants, and
Fe2+ and S2O32– as reducing titrants. Even with the availability of these new
titrants, however, the routine application of redox titrimetry to a wide range of
samples was limited by the lack of suitable indicators. Titrants whose
oxidized and reduced forms differ significantly in color could be used as their
own indicator. For example, the intensely purple MnO4– ion serves as its own
indicator since its reduced form, Mn2+, is almost colorless. The utility of other
titrants, however, required a visual indicator that could be added to the
solution. The first such indicator was diphenylamine, which was introduced in
the 1920s. Other redox indicators soon followed, increasing the applicability
of redox titrimetry.
The equivalent weight of a participant in an oxidation reaction is that
amount that directly or indirectly produces or consumes 1 mole of electrons.
The equivalent weight of an oxidizing and reducing agent can be
obtained by dividing molecular weight of the compound by the total number
of electrons that are gained or lost in a reaction per molecule of the substance:
1
𝐸𝑞𝑂𝑥/𝑅𝑒𝑑 = ∙ 𝑀𝑂𝑥/𝑅𝑒𝑑
±𝑛𝑒 −
The relative strengths of oxidizing and reducing agents can be inferred
from their standard electrode potentials. The standard electrode potential
enables us to predict which ions will oxidize or reduce other ions.
The standard reduction potential is defined relative to a standard
hydrogen electrode (SHE) reference electrode, which is arbitrarily given a
potential of 0.00 volts. The values below in parentheses are standard
reduction potentials for half-reactions measured at 25 °C, 1 atmosphere, and
with a pH of 7 in aqueous solution.
156
 The electrode potential which is established when an inert or
unattackable electrode is immersed in a solution containing both the oxidant
and the reductant is given by the expression
𝑅𝑇 𝑎𝑜𝑥
𝐸𝑇 = 𝐸 ° + ∙ 𝑙𝑛
𝑛𝐹 𝑎𝑟𝑒𝑑
where ET is the observed potential of the redox electrode at temperature T , E
is the standard reduction potential, n the number of electrons gained by the
oxidant in being converted to the reductant.
The Electrochemical series enlists a number of systems according to
decreasing standard reduction potentials at 25C. The most powerful
oxidizing agents lie at the top of electrochemical series (High positive Ered
values) and the most powerful reducing agents are present at the bottom (High
negative Ered values).
Table 17. Standard Reduction Potentials at 25°C (298K) for many
common half-reactions

Oxidation-Reduction Potentials. The propensity for a species to

undergo oxidation or reduction, as well as the propensity of a particular
reaction, can be given by the change in a thermodynamic value as in
the Gibbs free energy change, ∆G, for the reaction,

• the electrical potential or "electromotive force" for the reaction, and

157
 • the pE or electron activity for the reaction.
All of these are quantitative measures of propensity of the reaction and
do not take into account the kinetics or rate at which a reaction can occur.
Chemical systems that are at equilibrium are characterized by these
quantities throughout the volume.
Chemical systems that are not at equilibrium may still be characterized
by these quantities, but each species, each location, or each time, will have a
different characteristic value.
Chemical Potential. There are two chemical potentials used by
chemists.
The first is the potential for an oxidation or reduction system at
"standard-state conditions". It is given by the symbol Eo.
The standard-state potential is given as either a standard oxidation
potential or a standard reduction potential. The two are related only through a
sign change and are specified in Volts.
The reduction potential is the IUPAC standard. A reduction potential is
stated such that the species is being reduced. For example, the standard
reduction potentials for the Fe2+/H+ half reactions are

The second potential used by chemists is the actual or measured

potential. This potential varies with activity (concentration) of the species.
The equation that describes how the potential changes with activity is the
Nernst equation:

ln10 = 2.303. At room temperature

and

Predicting Spontaneous Direction of a Redox Reaction. The

direction of a redox reaction depends on the relative strengths of the oxidants
and reductants in a solution.
Value of standard redox potential can be used to determine tendency for
electron transfer and hence, the direction of the reaction. The E.M.F. which is
difference between the redox potential of oxidizing and reducing agent is used
for this.
E.M.F. = EOx – ERed
If E.M.F. > 0, reaction occurs, but if E.M.F. <0 reaction does not occur.
The relationship between the Gibbs free energy change and the
standard reaction potential is:
ΔG= − nFE

158
in this equation: ΔG is the change in free energy, n is the number of moles,
E is the standard potential (or EMF), F is the Faraday constant.
For example, whether the redox reaction proceeds Fe2(SO4)3 + NaI ->
The redox potential of oxidizing and reducing agent are
° °
𝐸𝐹𝑒 2+/𝐹𝑒 3+ = 0.77𝑉 𝑎𝑛𝑑 𝐸2𝐼 − /𝐼 = 0.53𝑉
2
E.M.F. = Eox – Ered = 0,77 – 0,53 = 0,24 V.
This reaction is possible because the value of E.M.F. is positive.

Selecting and Standardizing a Titrant

In quantitative work the titrant’s concentration must remain stable
during the analysis. Since titrants in a reduced state are susceptible to air
oxidation, most redox titrations are carried out using an oxidizing agent as the
titrant. The choice of which of several common oxidizing titrant is best for a
particular analysis depends on the ease with which the analyte can be oxidized.
Analytes that are strong reducing agents can be successfully titrated with a
relatively weak oxidizing titrant, whereas a strong oxidizing titrant is required
for the analysis of analytes that are weak reducing agents.
The two strongest oxidizing titrants are MnO4– and Ce4+, for which the
reduction half-reactions are
MnO4– + 8H+ + 5e– = Mn2+ + 12H2O
Ce4+ + e– = Ce3+
1. Solutions of Ce4+ are prepared from the primary standard cerium
ammonium nitrate, Ce(NO3)4 2NH4NO3, in 1 M H2SO4. When prepared from
reagent grade materials, such as Ce(OH)4, the solution must be standardized
against a primary standard reducing agent such as Na 2C2O4 or Fe2+ (prepared
using Fe wire). Ferroin is a suitable indicator when standardizing against
Fe2+ (Table 3). Despite its availability as a primary standard and its ease of
preparation, Ce4+ is not as frequently used as MnO4– because of its greater
expense.
2. Solutions of MnO4– are prepared from KMnO4, which is not
available as a primary standard. Aqueous solutions of permanganate are
thermodynamically unstable due to its ability to oxidize water.
4MnO4– + 2H2O = 4MnO2¯ + 3O2 + 4OH–
This reaction is catalyzed by the presence of MnO2, Mn2+, heat, light,
and the presence of acids and bases. Moderately stable solutions of
permanganate can be prepared by boiling for an hour and filtering through a
sintered glass filter to remove any solid MnO2 that precipitates. Solutions
prepared in this fashion are stable for 1–2 weeks, although the standardization
should be rechecked periodically. Standardization may be accomplished using
the same primary standard reducing agents that are used with Ce 4+, using the
pink color of MnO4– to signal the end point (Table 3).
Table 3. Standardization Reactions for Selected Redox Titrants
2Ce(SO4)2 + 2FeSO4 = Ce2(SO4)3 + Fe2(SO4)3
2Ce(SO4)2 + H2C2O4 = Ce2(SO4)3 + 2CO2 + H2SO4
159
 2KMnO4 + 10FeSO4 + 16H2SO4 = 2MnSO4 + 5Fe2(SO4)3 + K2SO4 + 8H2O
2KMnO4 + 5H2C2O4 + 3H2SO4 = 2MnSO4 + 10CO2 + K2SO4 + 8H2O
I2 + 2Na2S2O3 = 2NaI + Na2S4O6
3. Potassium dichromate is a relatively strong oxidizing agent whose
principal advantages are its availability as a primary standard and the long-
term stability of its solutions. It is not, however, as strong an oxidizing agent
as MnO4– or Ce4+, which prevents its application to the analysis of analytes
that are weak reducing agents. Its reduction half-reaction is
Cr2O72– + 14H+ + 6e– = 2Cr3+ + 21H2O
Although solutions of Cr2O72– are orange and those of Cr3+ are green,
neither color is intense enough to serve as a useful indicator. Diphenylamine
sulfonic acid, whose oxidized form is purple and reduced form is colorless,
gives a very distinct end point signal with Cr2O72–.
4. Iodine is another commonly encountered oxidizing titrant. In
comparison with MnO4–, Ce4+, and Cr2O72–, it is a weak oxidizing agent and is
useful only for the analysis of analytes that are strong reducing agents. This
apparent limitation, however, makes I2 a more selective titrant for the analysis
of a strong reducing agent in the presence of weaker reducing agents. The
reduction half-reaction for I2 is:
I2 + 2e– = 2I–
Because of iodine’s poor solubility, solutions are prepared by adding an
excess of I–. The complexation reaction
I2 + I– = I3–
increases the solubility of I2 by forming the more soluble triiodide ion, I3–.
Even though iodine is present as I3– instead of I2, the number of electrons in
the reduction half-reaction is unaffected.
I3– + 2e– = 3I–
Solutions of I3– are normally standardized against Na2S2O3 (see Table 3)
using starch as a specific indicator for I3–.
Oxidizing titrants such as MnO4–, Ce4+, Cr2O72– and I3–, are used to
titrate analytes that are in a reduced state. When the analyte is in an oxidized
state, it can be reduced with an auxiliary reducing agent and titrated with an
oxidizing titrant. Аlternatively, the analyte can be titrated with a suitable
reducing titrant. Iodide is a relatively strong reducing agent that potentially
could be used for the analysis of analytes in higher oxidation states.
Unfortunately, solutions of I– cannot be used as a direct titrant because they
are subject to the air oxidation of I– to I3–.
3I– = I3– + 2e–
Instead, an excess of KI is added, reducing the analyte and liberating a
stoichiometric amount of I3–. The amount of I3– produced is then determined
by a back titration using Na2S2O3 as a reducing titrant.
2S2O32– = S4O62– + 2e–
5. Solutions of Na2S2O3 are prepared from the pentahydrate
Na2S2O35Н2О and must be standardized before use. Standardization is
160
accomplished by dissolving a carefully weighed portion of the primary
standard KIO3 in an acidic solution containing an excess of KI. When
acidified, the reaction between IO3– and I–
IO3– + 8I– + 6H+ = 3I3– + 9H2O
liberates a stoichiometric amount of I3–. Titrating I3– using starch as a visual
indicator allows the determination of the titrant’s concentration.
Although thiosulfate is one of the few reducing titrants not readily
oxidized by contact with air, it is subject to a slow decomposition to bisulfite
and elemental sulfur. When used over a period of several weeks, a solution of
thiosulfate should be restandardized periodically. Several forms of bacteria
are able to metabolize thiosulfate, which also can lead to a change in its
concentration. This problem can be minimized by adding a preservative such
as HgI2 to the solution.
6. Another reducing titrant is ferrous ammonium sulfate,
Fe(NH4)2(SO4)2  6H2O, in which iron is present in the +2 oxidation state.
Solutions of Fe2+ are normally very susceptible to air oxidation, but when
prepared in 0.5 M H2SO4 the solution may remain stable for as long as a
month. Periodic restandardization with K2Cr2O7 is advisable. The titrant can
be used in either a direct titration in which the Fe2+ is oxidized to Fe3+, or an
excess of the solution can be added and the quantity of Fe 3+ produced
determined by a back titration using a standard solution of Ce4+ or Cr2O72–.
There are some techniques of redox reaction rate rising:
1. Temperature increasing.
2. The pH value and reactants concentration change.
3. Catalyst addition.
4. Inducted reactions running.
The redox titration divides on titration with reducing agents – for
oxidisers determination, and titration with oxidisers – for reducing agents
determination. Common standard titrants are named below:
Standard titrants E0, V Standardised with Indicator
Oxidants
Potassium + 1,51 Na2C2O4, Fe, As2O3 pink colour
permanganate, disappearance
KMnO4
Potassium bromate, + 1,45 is primary standard methyl orange,
KBrO3 methyl red, starch
Cerium(IV) + 1,44 Na2C2O4, Fe, As2O3 ferroin
sulphate, Ce(SO4)2
Potassium + 1,33 is primary standard diphenylamine,
dichromate, K2Cr2O7 starch, yellow colour
disappearance
Sodium nitrite, + 1,20 sulphanilic acid, starch (internal
NaNO2 KMnO4 indicator), tropeoline
00
161
Ammonium + 1,02 K2Cr2O7, Mohr salt diphenylamine,
vanadate, (NH4)VO3 phenylanthranilic
acid
Reductants
Iron(II) solutions, + 0,77 is primary standard KSCN
Fe(NH4)2(SO4)2
Iodine, I2 + 0,54 Na2S2O3, BaS2O3 starch
Sodium + 0,08 K2Cr2O7, KIO3, starch
thiosulphate, KBrO3,
Na2S2O3 K3[Fe(CN)6]
Titanium sulphate, + 0,04 K2Cr2O7, KMnO4, diphenylamine,
Ti2(SO4)3 Fe2(SO4)3 violet colour
disappearance

Redox Indicators
The most important class of indicators for redox titrations are
substances that do not participate in the redox titration, but whose oxidized
and reduced forms differ in color. When we add a redox indicator to the
titrand, the indicator imparts a color that depends on the solution’s
potential. As the solution’s potential changes with the addition of titrant, the
indicator changes oxidation state and changes color, signaling the end point.
A redox indicator should be such that it produces a sudden change in
the electrode potential in the vicinity of the equivalence point during a redox
titration. This is possible when the indicator itself is redox active i.e., capable
of undergoing oxidation or reduction process which is a reversible one. The
oxidized and reduced form of the indicator should have a contrast difference
in the colours.
Indox + ne = Indred
To predict the potential range over which the indicator colour will
change, we first write a Nernst equation for the indicator. At potential E, the
ratio of the concentration of two forms is given by the equation:
°
𝑅𝑇 𝐼𝑛𝑑𝑜𝑥 °
0.059 𝐼𝑛𝑑𝑟𝑒𝑑
𝐸𝐼𝑛𝑑 = 𝐸𝐼𝑛𝑑 + ∙ 𝑙𝑛 = 𝐸𝐼𝑛𝑑 − ∙ 𝑙𝑔
𝑛𝐹 𝐼𝑛𝑑𝑟𝑒𝑑 𝑛 𝐼𝑛𝑑𝑜𝑥

As discussed, if we assume that the indicator’s color changes from that

of Indox to that of Indred when the ratio [Indred]/[Inox] changes from 1 to 10
(full color changes for most redox indicators take place over a 100-fold
change in the concentration ratio of the oxidized and reduced forms of the
indicator):

162
 then the end point occurs when the solution’s potential is within the range
and if the quotients from the previous slide are inserted in the Nernst
equation, we get the range over which the indicator colour change will occur:
°
0.059
(∆𝐸𝐼𝑛𝑑 = 𝐸𝐼𝑛𝑑 ± ) 𝑣𝑜𝑙𝑡𝑠
𝑛
As illustrated here below, the change in color occurs over a range of
potentials centered on the indicator’s standard state reduction potential. The
size of this range is ±0.05916/n volts where n is the number of electrons in the
indicator’s oxidation or reduction reaction.

Type of Redox Indicators:

1 Self Indicators. Many a times the titrant itself may be so strongly
coloured that after the equivalence point, a single drop of the titrant produces
an intense colour in the reaction mixture. Such Indicators are called self
indicators. Self indicators generally are strongly coloured as a result of charge
transfer transitions in them.
For example, the oxidized and reduced forms of some titrants, such as
MnO4 , have different colors. A solution of MnO4– is intensely purple. In an
–

acidic (2N H2SO4) solution, however, permanganate’s reduced form, Mn2+, is

nearly colorless. When using MnO4– as a titrant, the analyte’s solution
remains colorless until the equivalence point. The first drop of excess MnO 4–
produces a permanent tinge of purple, signaling the end point.
2 Specific indicators. Some indicators form a colored compound with
a specific oxidized or reduced form of the titrant or the analyte. Starch, for
example, forms a dark blue complex with iodine I3–. We can use this distinct
color to signal the presence of excess I3– as a titrant (a change in color from
colorless to blue) or the completion of a reaction consuming I 3– as the analyte
(a change in color from blue to colorless). Another example of a specific
indicator is thiocyanate, SCN–, which forms a soluble red-colored complex of
Fe(SCN)2+ with Fe3+ .
3 True redox indicators. The most important class of indicators are
substances that do not participate in the redox titration, but whose oxidized
and reduced forms differ in color. When we add a redox indicator to the
analyte, the indicator imparts a color that depends on the solution’s potential.
As the solution’s potential changes with the addition of titrant, the indicator
changes oxidation state and changes color, signaling the end point
163
 a) Internal indicator. Such indicators are added into the reaction
mixtures Such indicators always have reduction potential values lower
than the analyte system so that they react with the titrant only when
whole of the analyte has been consumed, producing a readily detectable
color change.
b) External indicator. In case a suitable redox indicator is not available
for a given system, an indicator may be employed which will indicate
the completion of reaction by physically or chemically reacting with
the analyte (not through redox reaction). This reaction between
indicator and the analyte may sometimes be an irreversible one and in
some cases may even lead to precipitation. In those case indicators are
not added to the reaction mixture on the whole, rather used externally
on a grooved tile. Such indicators are called external indicators.
Table 17. Redox indicators

4. Potentiometric Methods. The most accurate method to judge the

completion of redox titration is however potentiometric method which deals
with the measurement of E.M.F. between a reference electrode and the
indicator (redox) electrode during the stages of redox titration. This method
infact tells us the equivalence point of the reaction and not the end point.

Redox Titration Curves

To evaluate a redox titration we need to know the shape of its titration
curve. In an acid-base titration or a complexation titration, the titration curve
shows how the concentration of H3O+ (as pH) or Mn+ (as pM) changes as we
164
add titrant. For a redox titration it is convenient to monitor the titration
reaction’s potential instead of the concentration of one species Eanalyte – Vtitrant.

Figure 19. Titration curve for the titration of 50.0 mL of 0.100 M Fe2+ with 0.100 M Ce4+.

PERMANGANATOMETRY

Redox titrations involving potassium permanganate are called

permanganometric titrations. In these reactions, MnO4- ions acts as the self
indicator.
Potassium permanganate, KMnO4, is a strong oxidizing agent.
Permanganate, MnO4–, is an intense dark purple color. Reduction of purple
permanganate ion to the colorless Mn+2 ion, the solution will turn from dark
purple to a faint pink color at the equivalence point. No additional indicator is
needed for this titration. Thus, a slight excess of KMnO4 solution at the end
point imparts a persistent pale pink colour to the warm reaction mixture and,
therefore KMnO4 acts as a self-indicator.

Figure 20. Permanganate acts as self indicator. Since MnO4– is intense purple while Mn2+
is colourless, the reaction mixture at equivalence point is colourless and even a single
drop of the permanganate would impart sufficient pink colour to the solution acting as self
indicator.

165
 The reduction of permanganate requires strong acidic conditions. In this
experiment, permanganate will be reduced by oxalate, C2O42- in acidic
conditions. Oxalate reacts very slowly at room temperature so the solutions
are titrated hot to make the procedure practical. The unbalance redox reaction
is shown below.
MnO4- + C2O42- → Mn2+ + CO2 (acidic solution)

Titrations involving potassium permanganate are usually carried out in

acidic medium. This is due to higher oxidizing power of permanganate ion in
acidic medium than in neutral or alkaline medium; secondly, the formation of
brown coloured, MnO2 in alkaline medium interferes with the detection of the
end point.
For acidification of KMnO4 solution, only H2SO4 is suitable whereas
the other mineral acids like HCl and HNO3 are not. HCl is not used because
some of the KMnO4 will oxidize Cl- ions to chlorine gas according to the
following equation and thus interferes in the quantitative estimations of
reducing agents.
2MnO4−+16H+ +10Cl− → 2Mn2+ +8H2O+5Cl2

Nitric acid cannot be used because it is itself a strong oxidizing agent

and may oxidize the reducing agent, thereby introducing error.
Potassium permanganate is not a primary standard i.e., a standard solution
of KMnO4 cannot be prepared by weighing because
• it can never be obtained in the purest form (99.99%) and is always
associated with organic impurities
• its normality changes on standing
• KMnO4 may react with organic matter present in water in which it is
dissolved.
KMnO4 solution can be standardized by titrating with a suitable
primary standard solution such as Mohr’s salt, oxalic acid, sodium oxalate or
arsenious oxide etc. KMnO4 solution needs to be added to a known volume of
reducing agent containing dilute H2SO4, gradually in small amounts. Rapid
addition of KMnO4 results in the formation of hydrated manganese dioxide,
MnO2H2O, which is brown in colour.
2KMnO4 + 3MnSO4 + 7H2O → K2SO4 + 5MnO2H2O + 2H2SO4
The above reaction also occurs if the medium is not sufficiently acidic.
Potassium permanganate is such a powerful oxidizing agent that it oxidizes
even water, according to the following equation,
4MnO4- + 2H2O → 4MnO2 + 4OH- + 3O2
An aqueous solution of potassium permanganate, therefore, should be
unstable. However, this reaction is extremely slow; hence the permanganate
solution attains reasonable stability in the absence of light. Thus, potassium
permanganate solution is stored in dark coloured bottles since the above
reaction is catalyzed by light.
166
 In part I of this experiment, a potassium permanganate solution will be
standardized against a sample of sodium oxalate. Once the exact normality
(eq/L) of the permanganate solution is determined, it can be used as a
standard oxidizing solution.
Sodium oxalate is commonly used as a primary standard for
determining the concentration of many strong oxidizers used in oxidation/
reduction analyses. In this experiment, sodium oxalate will be used to
determine the concentration of the strong oxidizer potassium permanganate.
In part II of this experiment, the standard permanganate solution will be
used to find the concentration of iron (II) in a ferrous solution (g/L). The
unbalanced redox reaction is shown below.
MnO4– + Fe2+ → Mn2+ + Fe3+ (acidic solution)
Phosphoric acid will be used to ensure that the ferric product, Fe 3+
remains in its colorless form.
Table 18. Analytical application of permanganate titration

Precaution:
1) All the glass apparatus should be washed thoroughly with distilled water
before use.
2) Burette and pipette should be rinsed with the solution to be taken in it.
167
3) There should not be any leakage in the burette.
4) KMnO4 solution should be kept in dark.
5) KMnO4 solution should not be filtered through filter paper, it should be
taken by decantation.
6) Freshly prepared KMnO4 should be used.
7) H2SO4 should be added in excess otherwise brown precipitate of MnO 2
may appear.
8) The titration (conical flask) should be placed on white paper or board to
identify properly the color change at the end point.
9) Each drop of KMnO4 solution should be decolourized and then only
next drop should be added.
10) Near the end point, the reaction becomes slow and the colour is
discharged slowly.
11) Sometimes during titration of KMnO4 with oxalic acid, a brown
precipitate may be formed. It is either due to the rapid addition of KMnO4
or due to insufficient addition of dil. H2SO4 to the titration mixture. The
brown colour appears due to the formation of hydrated manganese dioxide.
2KMnO4 + 3MnSO4 + 7H2O → K2SO4 + 5MnO2H2O + 2H2SO4
brown colour
12) During the titration, if the temperature of titration flask decreases,
heat it again and titrate.

1st EXPERIMENT. Standardization of Potassium Permanganate

Solution with Sodium Oxalate
Equipment and Materials: magnetic stirrer / hotplate, stir bar, 25 mL
burette with stand and clamp, 400 mL beaker, weigh boat, analytical balance,
~0.01N KMnO4, reagent grade Na2C2O4, 100 mL graduated cylinder, 2N
H2SO4

Sodium oxalate is widely used to standardise permanganate solution. In

acidic solutions the oxalate ion is converted to the undissociated acid:
Na2C2O4 + H2SO4 = H2C2O4 + Na2SO4
Thus, its reaction with the permanganate ion can be described as
2KMnO4 + 5H2C2O4 + 3H2SO4 = K2SO4 + 2MnSO4 + 10CO2 + 8H2O

The reaction between permanganate ion and oxalic acid is complex and
proceeds slowly even at elevated temperature unless manganese (II) is present
as a catalyst. Thus, when the first few millilitres of the standard permanganate
are added to a hot solution of oxalic acid, several seconds are required before
the colour of the permanganate ion disappears. Solution of sodium oxalate are
titrated at 60C to 90C. After the added permanganate is completely
168
consumed (as indicated by the disappearance of colour), the solution is heated
to about 60C and titrated to a pink colour that persists for about 30 seconds.

PROCEDURE:
I. Preparation the primary standard solution Na2C2O4 (0,01 N sodium
oxalate)
1. Calculate a primary standard sample (𝑚1 𝑁𝑎2𝐶2𝑂4 ) for preparation 0.01N
100 ml of solution:
𝑁𝑁𝑎2𝐶2 𝑂4 ∙ 𝑉𝑡𝑜𝑡𝑎𝑙 𝑠𝑙𝑛 ∙ 𝐸𝑞𝑁𝑎2𝐶2𝑂4
𝑚1 𝑁𝑎2𝐶2𝑂4 =
1000
2. Weight sodium oxalate sample on hand balance with 0,1 g accuracy
and put powder into weighting bottle. Weight weighting bottle with
sodium oxalate on analytical balance.
3. Transfer the sodium oxalate into volumetric flask and weight empty
weighting bottle on analytical balance. Calculate the real sodium
oxalate sample weight: 𝑚2 𝑁𝑎2𝐶2 𝑂4 = 𝑚𝑜𝑥𝑎𝑙𝑎𝑡𝑒+𝑏𝑜𝑡𝑡𝑙𝑒 − 𝑚𝑒𝑚𝑝𝑡𝑦 𝑏𝑜𝑡𝑡𝑙𝑒
4. Dissolve sodium oxalate in 40-50 ml of 1 M H2SO4 and establish exact
volume of solution with 1 M H2SO4.
5. Calculate precision normal concentration of prepared solution of
𝑚2 𝑁𝑎2 𝐶2 𝑂4
sodium oxalate: 𝑁𝑁𝑎2𝐶2 𝑂4 =
𝐸𝑞𝑁𝑎2 𝐶2𝑂4 ∙𝑉𝑡𝑜𝑡𝑎𝑙 𝑠𝑙𝑛

6. Calculate the correction factor for prepared 0,1 N sodium oxalate

solution:
2
𝑚𝑁𝑎 𝐶 𝑂
𝐶𝐹𝑁𝑎2𝐶2 𝑂4 = 1 2 2 4
𝑚𝑁𝑎2𝐶2𝑂4

II. Preparation of a 0.01 N KMnO4 Solution.

1. On a centigram balance, weigh about 0.2 g KMnO4 crystals on a piece
of weighing paper. Add the crystals to a 500 mL Florence Flask.
2. Add about 350 mL of distilled water to the flask.
3. Heat the solution with occasional swirling to dissolve the KMnO4
crystals. Do not boil the solution. This may take about 30 minutes.
4. Allow the solution to cool and stopper. You will need this solution for
both day 1 and day 2.

III. Standardization of potassium permanganate solution with 0,1 N

sodium oxalate
• Load a burette with potassium permanganate solution.
• 20 ml of of (1:4) H2SO4 solution are pipetted into a 250ml conical
flask. Heat solution to 80C to 90C.
• Now 10 ml aliquot of standard sodium oxalate solution is added by
pipette.

169
 • Now mixture is titrated with potassium permanganate solution. The
pink colour imported by one addition should be permitted to disappear
below any father titrant is introduced.
• Reheat if the temperature drops below 60C. Take the first persistent
(≈30s) pink colour as the end point. Read the burette mark.
• Repeat titration also two times. Calculate the approximate value of used
potassium permanganate solution.
• Calculate the exact concentration of the potassium permanganate
solution accordance to equivalents law.

Results of titration:
• Volume of standard solution for titration: Vsodium oxalate = 10 mL
• Normality of standard solution for titration: Nsodium oxalate = 0,01N
• Equivalent weight of sodium oxalate: EqNa2C2O4 =
• Equivalent weight of potassium permanganate: EqKMnO4 =
• Volume of titrant consumed for the 1st titration: V1KMnO4 =
• Volume of titrant consumed for the 2nd titration: V2KMnO4 =
• Volume of titrant consumed for the 3rd titration: V3KMnO4 =
• Average amount of titrant consumed for titration: 𝑉𝐾𝑀𝑛𝑂 ∗
4
=
𝑉 1 +𝑉 2 +𝑉 3
=
3

Calculation:
The result is expressed as mol-eq/l concentration and based on the
following formula:
𝑉𝑁𝑎2 𝐶2𝑂4 𝑁𝐾𝑀𝑛𝑂4 𝑉𝑁𝑎2 𝐶2𝑂4 ∙𝑁𝑁𝑎2 𝐶2 𝑂4
∗ = => 𝑁𝐾𝑀𝑛𝑂4 = ∗
𝑉𝐾𝑀𝑛𝑂4 𝑁𝑁𝑎2 𝐶2𝑂4 𝑉𝐾𝑀𝑛𝑂4

𝑁𝐾𝑀𝑛𝑂4 ∙𝐸𝑞𝐾𝑀𝑛𝑂4
𝑇𝐾𝑀𝑛𝑂4 =
1000

𝑁𝐾𝑀𝑛𝑂4 ∙𝐸𝑞𝑁𝑎2 𝐶2 𝑂4
𝑇𝐾𝑀𝑛𝑂4/𝑁𝑎2𝐶2 𝑂4 =
1000

The calibration result can be accepted if 3 determinations give a result

with a relative standard deviation of less than 0.5%

2nd EXPERIMENT. Determination of the percentage of iron (II) in a

sample using permanganomerty
Aim of experiment: Estimation of Fe(II) ions in given Mohr salt
solution by titrating it with standardized KMnO4 solution.
Apparatus: Burette, pipette, conical flask, burette stand and clamp
Chemicals: solutions of 0.01N KMnO4 and 2N H2SO4, mixture
H2SO4:H3PO4, Mohr’s salt [(NH4)2SO4FeSO46H2O].
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 Estimation of Fe+2 was done in the supplied Mohr’s salt solution by
redox titration using KMnO4 as oxidizing agent. The reaction between Mohr’s
salt solution and potassium permanganate solution in acid medium is redox
reaction where potassium permanganate solution is the oxidizing agent and
Mohr’s salt solution is the reducing agent.
MnO4 - + 8H+ + 5e = Mn+2 + 4H2O
5Fe+2 = Fe+3 + 5e
MnO4- + 5Fe+2 + 8H+ = 5Fe+3 + Mn+2 + 4H2O
All the apparatus were well cleaned with distilled water prior to the
experiment. If the apparatus are not cleaned properly, then sole determination
of Fe+2 in the Mohr’s salt solution is not possible as water may contain trace
amount of Fe+2 ions.
The use of (H2SO4:H3PO4) in the Mohr’s salt solution is to maintain the
proper pH and H3PO4 reacts with Fe+3 to form FePO4 and complete oxidation
of Fe+2 proceeds and the equilibrium shifts to the right (Fe +2 to Fe+3). As
redox reaction is temperature dependent, estimation of Fe+2 is done at a fixed
temperature i.e. room temperature.
The permanganate ion acts as its own indicator, as MnO4- is highly
colored while Mn2+ is essentially colorless. The product of oxidation, the Fe 3+
ion, is itself, slightly colored. To avoid any possible interference with the
equivalence point determination a little phosphoric acid, H3PO4, is added so
as to complex Fe3+ to a completely, colorless ion. You will have 3 hours to
complete this assignment; lab and calculations, so come prepared!

PROCEDURE:
I. Preparation the solution of Mohr salt
1. On weighing paper, weigh about 1.0 g of Mohr salt on the analytical
balance. Record the exact mass. Transfer the sample to a 100 mL
Erlenmeyer flask.
2. Add about 100 mL of distilled water to the flask.
3. Heat the solution with occasional swirling to dissolve the crystals. Do not
boil the solution. This may take about 30 minutes.
4. Allow the solution to cool and stopper.

II. Determination of the mass of iron in a ferrous solution

1. Pipette out 20 mL of unknown Fe(II) solution in a 250 mL conical flask.
2. Add 20 mL of dilute H2SO4 (1:8 V/V).
3. Rinse and fill the buret with the standardized KMnO4 solution.
4. Titrate with standardized KMnO4 solution to a stable pink color.
5. Take minimum 3 readings.

Results of titration:
• Weight of Mohr salt sample: msample =
• Stock volume of Mohr salt solution: VMohr salt = 100 mL
171
 • Equivalent weight of Fe2+ ion in Mohr salt: 𝐸𝑞𝐹𝑒 2+ =
• Volume of Mohr salt solution for titration: VMohr salt = 10 mL
• Normality of standardized KMnO4 solution for titration: NKMnO4 =
• Volume of titrant consumed for the 1st titration: V1KMnO4 =
• Volume of titrant consumed for the 2nd titration: V2KMnO4 =
• Volume of titrant consumed for the 3rd titration: V3KMnO4 =
• Average amount of titrant consumed for titration: 𝑉𝐾𝑀𝑛𝑂 ∗
4
=
𝑉 1 +𝑉 2 +𝑉 3
=
3

Calculation:
Calculate the percent by mass of Fe+2 in a sample based on the
following formula:
𝑉𝑀𝑜ℎ𝑟 𝑠𝑎𝑙𝑡 𝑁𝐾𝑀𝑛𝑂4 𝑉𝐾𝑀𝑛𝑂4 ∙𝑁𝐾𝑀𝑛𝑂4
∗ = => 𝑁𝐹𝑒 2+ =
𝑉𝐾𝑀𝑛𝑂4 𝑁(𝐹𝑒2+ ) 𝑉𝑀𝑜ℎ𝑟 𝑠𝑎𝑙𝑡

𝑁𝐹𝑒2+ ∙𝐸𝑞𝐹𝑒2+
𝑇𝐹𝑒 2+ =
1000

𝑚(𝐹𝑒 2+ ) = 𝑇𝐹𝑒 2+ ∙ 𝑉𝑡𝑜𝑡𝑎𝑙 𝑀𝑜ℎ𝑟 𝑠𝑎𝑙𝑡

𝑚(𝐹𝑒 2+ )
𝑊𝐹𝑒 2+ , % = ∙ 100%
𝑚𝑠𝑎𝑚𝑝𝑙𝑒

The calibration result can be accepted if 3 determinations give a result

with a relative standard deviation of less than 0.5%

CONTROL OF MASTERING THE TOPIC

Typical calculation tasks
Task 1. What is the molarity of oxalic acid solution prepared by dissolving
0.63g of oxalic acid in 100ml water?
Task 2. The weight of Ferrous ammonium sulphate required to prepare 250ml
solution is___.
Task 3. Which mass of KMnO4 should be taken to prepare 2L of the solution
with CN(KMnO4) = 0,02 mol/L? (feq (KMnO4) = 1/5).
Task 4. A 5.00 gram sample of impure sodium oxalate required 36.91 mL of
0.100 M KMnO4 to reach the endpoint. What was the percent purity of the
sample?
Task 5. A standardized 4 M solution of KMnO4 is titrated against a 100 mL
sample of an unknown analyte containing Fe2+. A student conducts the redox
titration and reaches the endpoint after adding 25 mL of the titrant. What is
the concentration of the analyte?
Task 6. A 0.5585 g sample of ferrous ammonium sulfate hexahydrate,
Fe(NH4)2(SO4)2(H2O)6, requires 21.45 mL of a KMnO4 solution to reach a
pink endpoint. What is the molarity of the KMnO4 solution?
172
Task 7. A 1.787 g sample containing some Fe+2 ion requires 31.50 mL of a
0.02188 m KMnO4 solution to reach a stable pink endpoint. What is the
percent by mass of Fe+2 in the sample?
Task 8. What is the concentration of permanganate ion if there is spent 36.90
mL potassium permanganate, for titration of 250 mg Na2C2O4?
Task 9. Calculate the molar masses of the equivalents: a) Fe2+; b) Na2C2O4; c)
KI in reactions with KMnO4 in the acidic medium.
Task 10. To titrate 0.0244 g of H2C2O4·2H2O we used 19.5 mL of KMnO4
solution. Calculate the normality of KMnO4 solution.
Task 11. To titrate 25.0 mL 0.0500 N of KMnO4 solution in the acidic
medium we used 10.2 mL of sodium nitrite solution. How many grams of
NaNO2 are in 100 mL of its solution?
Task 12. 2.50 g of hydrogen peroxide solution were diluted by water till 200
mL. To titrate 5.0 mL of the obtained solution in the acidic medium we 50
used 20.0 mL 0.0500 N of KMnO4 solution. Which is the mass fraction of
H2O2 in the initial concentrated solution?
Task 13 We added 20.0 mL 0,1N of FeSO4 solution to 10.0 mL of the
analyzed solution of K2Cr2O7 solution acidated by sulphuric acid. To titrate
the excess of FeSO4 we used 28.0 mL 0.0500 N of KMnO4 solution.
Calculate, how many grams of K2Cr2O7 are in 200 mL of the analyzed
solution.
Task 14. To determine the content of calcium in blood serum it is precipitated
in the form of CaC2O4 adding ammonium oxalate to 0.50 mL of the serum.
The precipitate is filtered, washed and dissolved in sulphuric acid. The
obtained solution is titrated by 0.0100 N KMnO4 solution till the appearance
of rosy colouring. Calculate the amount of calcium in milligrams per 100 mL
of the serum if to titrate it we used 0.25 mL of KMnO4 solution.

QUESTIONS FOR TEST SELF-CHECK

(with multiple responses «correct-incorrect»)
1. Why is it necessary to perform the titration in strong acid?
2. Speculate on what would happen if the titration were attempted in neutral
or basic conditions.
3. Why is it necessary to heat the solution?
4. Why is it necessary to make sure all air is removed from the tip of the
buret?
5. Write an expression for the equilibrium constant of the reaction.
6. Define the term “primary standard.”
7. Why KMnO4 cannot be taken as a primary standard?
8. Can HCl or HNO3 be used in place of H2SO4 for making the medium
acidic in a redox titration where KMnO4 is used as an oxidant?
9. Why is potassium permanganate solution not filtered through a filter paper?
10. Why is KMnO4 solution not taken in a burette with a rubber tube

173
11. Why is brown turbidity sometimes observed in the titration flask while
titrating KMnO4 solution with a reducing agent?
12. Why is Mohr’s salt used in place of hydrated ferrous sulphate for
preparing standard solution?
13. Why is dil. H2SO4 added while preparing a standard solution of Mohr’s
salt?
14. What happens if you heat Mohr’s salt solution in the titration between
KMnO4 and Mohr’s salt?
15. Refer to Table Standard Electrode Potential to predict
a) Which species – Sn4+(aq), Cl−(aq), Ag+(aq), Cr3+(aq), and/or H2O2(aq) –
can oxidize MnO2(s) to MNO4− under standard conditions.
b) Which species – Sn4+(aq), Cl−(aq), Ag+(aq), Cr3+(aq), and/or H2O2(aq) –
is the strongest oxidizing agent in aqueous solution.
16. What do you mean by a standard solution?
a) solution of known volume
b) an aqueous solution
c) solution of known strength
d) 1M solution
17. The indicator used in KMnO₄ titration is …
a) KMnO₄ acts as a self indicator b) Methyl orange
c) Phenolphthalein d) Phenol red
18. Mohr’s salt is chemically___.
a) Ferric sulphate
b) Ferrous sulphate heptahydrate
c) Ferric oxide
d) Ferrous ammonium sulphate
19. The type of reaction involved in permanganometric titration is___.
a) Displacement b) Decomposition
c) Neutralization d) Redox
20. In acidic medium MnO₄⁻ is reduced to ___.
a) Mn²⁺ b) Mn⁵⁺ c) Mn⁷⁺ d) Mn⁴⁻
21. A standard solution of which of the following is used to determine the
concentration of potassium permanganate solution?
a) Potassium aluminium sulpahte
b) Sodium aluminium sulphate
c) Ferrous ammonium sulphate
d) Ferric ammonium sulphate
22. An example of a primary standard is___.
a) Potassium hydroxide
b) Sodium carbonate
c) Potassium permanganate
d) Sodium hydroxide

174
References:
1 D. C. Harris, Quantitative Chemical analysis, 6th ed, Freeman: New York,
1999
2 Christian G. D. Analytical Chemistry. John Wiley & Sons, Washington.
2002. P. 828.
3 Patnaik P. Dean's Analytical Chemistry Handbook (2nd Edition).
McGraw-Hill, New York, 2004. P. 11

LABORATORY WORK 10
REDOX TITRATION
IODOMETRY

Objective: to determine the Vitamin C in grug tablet and in orange juices

After completing the experiment, we are able to:
• define an iodometric and iodimetric titration.
• know differences between Iodometic and Iodimetric titrations.
• standardize the Iodine solution

The titration based on oxidation and reduction reaction between the

titrant and analyte is called Redox titration. Oxidation-reduction titration is a
volumetric analysis that relies on a net change in the oxidation number of one
or more species. The titrant is a commonly an oxidising agent although
reducing titrants can be used. Common oxidising agents are:
1) Permanganate ion (MnO4-)
MnO4-(aq) + 8H+ + 5e- → Mn2+(aq) + 4H2O Eo = +1.51 V
purple permanganate ion (MnO4-) is reduced to colourless manganese(II) ion
(Mn2+)
2) Dichromate ion (Cr2O72-)
Cr2O72-(aq) + 14H+ + 6e- → 2Cr3+(aq) + 7H2O Eo = +1.23 V
orange dichromate ion (Cr2O72-) is reduced to green chromium(III) ions (Cr3+)
3) Cerium IV Ce4+
Ce(ClO4)6 2- + e- = Ce3+ + 6 ClO4 - Eo = +1.7 V
4) Iodine is another commonly encountered oxidizing titrant. In
comparison with MnO4–, Ce4+, and Cr2O72–, it is a weak oxidizing agent and is
useful only for the analysis of analytes that are strong reducing agents. This
apparent limitation, however, makes I2 a more selective titrant for the analysis
of a strong reducing agent in the presence of weaker reducing agents. The
reduction half-reaction for I2 is:
I2 + 2e– = 2I– Eo = +0.521 V
Because of iodine’s poor solubility, solutions are prepared by adding an
excess of I–. The complexation reaction
I2 + I– = I3–

175
increases the solubility of I2 by forming the more soluble triiodide ion, I3–.
Even though iodine is present as I3– instead of I2, the number of electrons in
the reduction half-reaction is unaffected.
I3– + 2e– = 3I–
Solutions of I3– are normally standardized against Na2S2O3 using starch
as a specific indicator for I3–.
Iodine titration:
1. Direct method: Iodine is used as the titrating agent.
2. Indirect method: The liberated iodine is back titrated with the sodium
thiosulphate.

Iodine is red-brown and forms colourless iodide ion in its redox

reaction. With experience this endpoint can be identified without the presence
of an indicator. The endpoint is enhanced with the addition of a starch based
indicator. Starch forms an intense blue colour in the presence of excess
iodine. Starch is not a true redox indicator but a specific indicator for iodine.
Iodine can be used to titrate easily oxidised species without reacting
with other species. It is common for analysis of:
• Sulfur dioxide
• Sulfide
• Ascorbic acid
Back titration may be used if the analyte reacts with oxygen in solution.
This occurs in the case of Vitamin C which decomposes when in solution.
With sulfide and SO2 reaction is best in acidic solution, but this risks
the loss of the analyte as a partly soluble gas (H2S or SO2). With these
analytes the titration may be performed in the reverse ie the sample in the
burette and the standard in the flask.
Solutions of Na2S2O3 are prepared from the pentahydrate
Na2S2O35Н2О and must be standardized before use. Standardization is
176
accomplished by dissolving a carefully weighed portion of the primary
standard KIO3 in an acidic solution containing an excess of KI. When
acidified, the reaction between IO3– and I–
IO3– + 8I– + 6H+ = 3I3– + 9H2O
liberates a stoichiometric amount of I3–. Titrating I3– using starch as a visual
indicator allows the determination of the titrant’s concentration.
Although thiosulfate is one of the few reducing titrants not readily
oxidized by contact with air, it is subject to a slow decomposition to bisulfite
and elemental sulfur. When used over a period of several weeks, a solution of
thiosulfate should be restandardized periodically. Several forms of bacteria
are able to metabolize thiosulfate, which also can lead to a change in its
concentration. This problem can be minimized by adding a preservative such
as HgI2 to the solution.
In acidic conditions or in the presence of bacteria thiosulfate can
decompose to hydrogen sulfite and elemental sulfur. Anti-bacterial agents
such as trichloromethane or sodium benzoate should be added to maintain
solution stability. The solution is also prone to layering when stored. The
container should therefore be shaken thoroughly before use. When iodine is
being titrated (ie present in significant quantities) an insoluble and irreversible
complex forms with starch resulting in loss of iodine and therefore an
artificially low endpoint value. Starch should therefore not be added to the
reaction vessel until almost all the iodine has been reduced. Alternative
indicators such as Vitex do not have this problem.
Iodine is a weak oxidising agent, only reacting with species that are
easily oxidised. Solution conditions are normally neutral or acidic since
iodine reacts with hydroxide. Where iodine is used to directly titrate the
analyte the reaction is termed iodimetric method.
Iodine has solubility in water of only 0.304 g/100 mL of water. In the
presence of an excess iodide ions soluble triiodide ion I3- is formed.
I2 + I- →I3-
A 0.05M iodine solution has an iodide concentration of 0.15M. A
typical 0.05 M solution of I3- for titrations is prepared by dissolving 0.12 mol
of KI plus 0.05 mole of I2 in 1 L of water. This can be standardized against
arsenic (III) oxide or sodium thiosulfate.
Iodometry is the process used for the quantitative use of thiosulfate to
analyse a range of oxidised species. The analyte reacts quantitatively with an
excess of iodide ion to form iodine, which can then be titrated with a
standardised thiosulfate solution, as shown in Fig 20.

Figure 20. The process of iodometry

177
 The reaction does not involve a back titration as the iodide (added as
KI) is not added quantitatively, simply in excess. The titration determines the
moles of iodine which indicates the moles of analyte.
The excess iodide can be a problem since it can be oxidised by the
oxygen in air and in solution to form iodine introducing an error. The error is
known as the oxygen error and can be minimised by avoiding high
concentrations of acid and titrating as soon as possible.
O2 + 4I- + 4H+ → 2I2 + 2H2O
Typical iodometric analyses include:
• Copper II
• Hydrogen peroxide
• Hypochlorite ion
For copper II analyses the formation of copper II iodide is prone to
error as the iodine may adsorb onto the precipitate. Thiocyanate is added to
replace iodide in the precipitate and prevent loss of iodine.
Starch Indicator. As described earlier, starch is used as an indicator
for iodine. In a solution with no other coloured species, it is possible to see
the colour of ~5 μM I3-. With starch, the limit of detection is extended by
about a factor of 10.
In iodimetry (titration with I3-), starch can be added at the beginning of
the titration. The first drop of excess I3- after the equivalence point causes the
solution to turn dark blue.
In iodometry, I3- ion is present throughout the reaction up to the EP.
Starch should not be added until right before the EP (as detected visually, by
fading of the I3-); otherwise, some iodine tends to remain bound to starch
particles after the equivalence point is reached.

Iodometric titration needs to be done in a weak acid environment which

is why we need to remember that:
1. The iodine solution used needs to be at pH < 8.5 because at a base pH
iodine disproportionates (a particular kind of oxidoreduction reaction where
one substance partly oxidises and partly reduces);
2. Iodine is a volite substance, so titration is taken in cold condition.
2. Sodium thiosulphate needs a neutral or weak acid environment to oxidise
with tetrathionate (in an alkaline solution we would get sulphate oxidation);
178
3. In a strong acid environment thiosulphate decomposes to S2;
4. In acid environments the iodide is oxidised to iodine as in the reaction
below: O2 + 4I- + 4H+ ↔ 2I2 + 2H2O

Titrations with standard I3- (iodimetric)

Titrations of I3- from analyte (iodometric)

179
1ST EXPERIMENT. Iodometric Determination of Vitamin C
The goal of this laboratory exercise is to determine the amount of vitamin
C in samples, such as fruit juice.
Equipment and apparatus: volumetric flask 250.00 ml. beaker 500.00 ml,
500.00 ml, 100 ml, burette 50.00 ml, graduated cylinder 50.00 ml, Erlenmeyer
flask 250.00 ml, balance, heater, glass rod
Chemicals: potassium iodide (KI) 15.00g (± 0.001 g), iodine powder 5g,
starch powder 0.25g, distilled water, vitamin C tablet

Vitamin C (ascorbic acid, ascorbate, AA) is a water soluble organic

compound that participates in many biological processes and the most
common electroactive biological compound found in some fruit species. It is
the most widely taken nutritional supplement worldwide. More than 90% of
the vitamin C in human diets is supplied by fruits and vegetables (including
potatoes)4-6. Citrus fruits and juices are particularly rich sources of vitamin C
but other fruits including cantaloupe and honeydew melons, cherries, kiwi
fruits, mangoes, papaya, strawberries, tangelo, tomatoes, and water melon
also contain variable amounts of vitamin C.
Vitamin C is essential for human life and is required for a range of
physiological functions in human body. It can be found either in fresh fruits
and vegetables naturally or in medical forms such as normal tablets,
effervescent tablets and liquid vials. Though daily requirements of vitamin C
are changeable according to the age, sex and conditions, it is around 75 to 90
mg per day for healthy adults and no more than 2000 mg per day is
recommended. It is one of the most ubiquitous vitamins ever discovered.
Besides plays a paramount role as an antioxidant and free radical scavenger, it
has been suggested to be an effective antiviral agent. Vitamin C is an essential
nutrient that plays a vital role in protecting the body from infection and
disease. It is needed for the formation of collagen, the protein that makes up
connective tissue, and is essential to muscles, bones cartilages, blood vessels,
capillaries, tissues, skin and teeth7-9. It is also functions in absorption of
inorganic iron, reduction of plasma cholesterol level, inhibition of
nitrosoamine formation, enhancement of the immune system, and reaction
with singlet oxygen and other free radicals. As an antioxidant, it reportedly
reduces the risk of arteriosclerosis, cardiovascular diseases, infectious
diseases, asthma, cataract, Diabetes Mellitus and some forms of cancer
In addition, ascorbic acid has been widely used in the pharmaceutical,
chemical, cosmetic and food industry as antioxidant. Therefore, there is a
need to find an accurate, reliable, rapid, and easy-to implement method for
measuring the amount of ascorbic acid in a sample. However, there have been
difficulties in quantifying ascorbic acid due to its instability in aqueous
solution. The instability of ascorbic acid is due to its oxidation to
dehydroascorbic acid, which is a reversible reaction, and subsequently to 2,3-
diketo-L-gulonic acid. The later reaction is irreversible.
180
 Figure 21. Chemical structure of vitamin C

Ascorbic acid is a water soluble vitamin with molecular weight of

176.12 g/mol and melting point of 193˚C. World-wide accepted daily
requirement of ascorbic acid is about 60 – 95 mg. Ascorbic acid is a reducing
agent which reverses the oxidation in aqueous solution. Increased amounts of
free radicals trigger the condition called oxidative stress which is kept under
control by antioxidants. If there are not enough antioxidants some stress
related diseases including hypertension, atherosclerosis, chronic inflammatory
diseases and diabetes might occur.
The following Iodometric titration is performed and the amount of
vitamin C was evaluated in given tablet using iodometric titration method. In
this method the reaction between iodine and starch suspension, will indicate
the endpoint by producing the blue-black product. The tri-iodide ions are
quickly converted into iodide ions when ascorbic acid is present. However,
when all of the ascorbic acid is oxidized, the excess iodide will react with
starch and will result in blue-black color.

Figure 22. Left to right: iodine solution, starch solution, starch solution + I2.

Triiodide, I3−, is a mild oxidizing agent that is widely used in

oxidation/reduction titrations. Triiodide is prepared by combining potassium
iodide, KI, and potassium iodate, KIO3, in acidic solution according to the
following stoichiometry:
IO3– + 8 I– + 6 H+ →3 I 3– + 3 H2O

181
 In preparing triiodide, excess KI is used, so the concentration of I 3‐ is
determined by the amount of KIO3 added to the solution. Triiodide reacts with
ascorbic acid (vitamin C, a mild reducing agent) to form dehydroascorbate
and three iodide ions according to the reaction:

Notice that one mole of iodine is consumed for each mole of ascorbic
acid. In this experiment, you will determine the amount of ascorbic acid in a
vitamin pill using the triiodide reaction in a “back titration”. After extracting
the ascorbic acid from vitamin pills with acid, you will convert it to
dehydroascorbate using a known excess of triiodide. The amount of triiodide
remaining after reaction 2 will be determined by titration of the triiodide with
a standardized thiosulfate solution. Note that you do not titrate the analyte
directly, but rather titrate an added reagent after excess has been added. This
is known as a back titration. The back titration reaction is
I3‐ + 2 S2O32‐ → 3 I‐ + S4O62‐

Note that 2 moles of thiosulfate are consumed for each mole of triiodide
present. The endpoint is determined using a starch indicator. Mixtures of
starch and triiodide have a deep violet color, but when the triiodide is
consumed the solution becomes colorless. Over time the starch‐triiodide
complex can stabilize, and it becomes difficult to reduce all of the triiodide.
Therefore it is preferable to add the starch just before the endpoint.
Fortunately the triiodide solution itself has a yellow‐to‐brown color,
depending on concentration. When the solution turns pale yellow, you know
that most of the triiodide has been consumed, and you are near the endpoint.
Then you can add the starch indicator. You know how much I 3‐ is added to the
vitamin sample, and with the titration results you can determine how much is
left after the oxidation of ascorbate. The difference between these is the
amount of triiodide consumed in the oxidation of ascorbate, which is related
to the amount of vitamin C present in the sample by the stoichiometry of
reaction 2.
Ascorbic acid is determined by using an oxidation-reduction reaction.
The solubility of iodine is increased with iodide and tri-iodide is occurred:
–
I2 (aq) + I ↔ I3
I3– then oxidizes vitamin C to dehydroascorbic acid:
- +
C6H8O6 + I3 + H2O → C6H6O6 + 3I + 2H
Vitamin C dehydroascorbic acid
182
 The endpoint is production of a blue-black color which occurs as a
result of the reaction of iodine with starch suspension. When ascorbic acid is
present, I3 is converted to iodide and no color change is observed. However,
when all ascorbic acid was utilized, expected blue-black color occurs due to
the reaction between starch and excess tri-iodide.
This titration procedure is widely accepted and is appropriate for
testing the amount of vitamin C in the tablets, liquids and fruits and
vegetables.

PROCEDURE
1 Preparation of iodine solution. For preparation of 0.1 M iodine solution,
10 g of KI was taken in a 250 ml volumetric flask and 35 ml of distilled water
was added followed by heating the solution; the mixture was cooled to room
temperature and 3.15 g of solid Iodine powder was dissolved.
Similarly, to prepare 0.005M of iodine solution 2g of KI was taken in a
500 ml beaker and dissolving in 100 ml of distilled water and 1.3 g of iodine
powder was stirred with small quantity of water and qs (quantum satis) to 1
liter.
For preparation of 0.05M Iodine solution from 5% medicine iodine
solution in ethanol you may take this solution and dilute it in 40 times.
Solution prepared that way will be has 0.05M concentration.

2 Preparation of starch solution. Addition of 0.25 g of starch powder in 50

ml warm distilled water, as the starch is insoluble in cold water and needs to
be boiled to stay in solution.

3 Preparation of vitamin C standard solution. 250 mg (0.25g) Ascorbic

acid in tablet form was taken in a 100.00 beaker and dissolved with distilled
water. Dilute to 250 ml with distilled water in a volumetric flask. Label the
flask as your vitamin C standard solution.

4 Standardizing Iodine Solution

• Add 25.00 ml of vitamin C standard solution to a 125 ml Erlenmeyer
flask.
• Add 10 drops of 1% starch solution.
• Rinse your buret with a small volume of the iodine solution and then
fill it. Record the initial volume.
• Titrate the solution until the endpoint is reached. This will be when you
see the first sign of blue color that persists after 20 seconds of swirling
the solution.
• Record the final volume of iodine solution. The volume that was
required is the starting volume minus the final volume.
• Repeat the titration at least twice more. The results should agree within
0.1 ml.
183
Results of standard solution titration:
• Volume of standard solution for titration: 𝑉𝐴𝑠𝑐𝑜𝑟𝑏𝑖𝑐 𝑎𝑐𝑖𝑑 = 25 𝑚𝐿
• Volume of titrant consumed for the 1st titration: 𝑉𝐼12 =
• Volume of titrant consumed for the 2nd titration: 𝑉𝐼22 =
• Volume of titrant consumed for the 3rd titration: 𝑉𝐼32 =
𝑉 1 +𝑉 2 +𝑉 3
• Average amount of titrant consumed for titration: 𝑉𝐼∗2 = =
3

Calculation:
In the beginning of the experiment 25 ml of sample was taken from 250
ml of prepared standard solution containing 250 mg of Ascorbic acid. As 𝑉𝐼∗2
ml of iodine is required for the color change containing 25 ml ascorbic acid
solution, the dilution was done 10 times to that of the solution.
Hence, the final volume of the iodine solution = 𝑉𝐼∗2 ×10 = VI2 ml

5 Preparation of samples
• Vitamin C Tablet. Dissolve the tablet in ~100 ml distilled water. Add
distilled water to make 250 ml of solution in a volumetric flask.
• Fresh Fruit Juice. Strain the juice through a coffee filter or cheesecloth
to remove pulp and seeds, since they could get stuck in the glassware.
• Packaged Fruit Juice. This also may require straining.
• Fruits & Vegetables. Blend a 100 g sample with ~50 ml of distilled
water. Strain the mixture. Wash the filter with a few milliliters of
distilled water. Add distilled water to make a final solution of 250 ml in
a volumetric flask.
Titrate these samples in the same way as the juice sample described above.

5.1 Titrating Juice Samples

• Add 25.00 ml of juice sample to a 250 ml conical flask.
• Add 10 drops of 1% starch solution.
• Titrate until the endpoint is reached. (Add iodine solution until you get
a dark blue color that persists longer than 20 seconds.)
• Repeat the titration until you have at least three measurements that
agree to within 0.1 ml.

Results of standard solution titration:

• Volume of juice sample for titration: 𝑉𝑗𝑢𝑖𝑐𝑒 = 25 𝑚𝐿
• Volume of titrant consumed for titration: 𝑉𝐼2 =
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5.2 Titrating Real Lemon
Real Lemon is nice to use because the maker lists vitamin C, so you can
compare your value with the packaged value. You can use another packaged
lemon or lime juice, provided the amount of vitamin C is listed on the
packaging. Keep in mind, the amount can change (diminish) once the
container has been opened or after it has been stored for a long time.
• Blend a 100 g sample with ~50 ml of distilled water. Strain the mixture.
Wash the filter with a few milliliters of distilled water. Add distilled
water to make a final solution of 250 ml in a volumetric flask.
• Add 25.00 ml of Real Lemon into a 250 ml conical flask.
• Add 10 drops of 1% starch solution.
• Titrate until you have at least three measurements that agree within 0.1
ml of iodine solution.

Results of standard solution titration:

• Volume of fruit juice sample for titration: 𝑉𝑓𝑟𝑢𝑖𝑡 𝑗𝑢𝑖𝑐𝑒 = 25 𝑚𝐿
• Volume of titrant consumed for titration: 𝑉𝐼2 =

Calculation:
Mass of ascorbic acid in sample will be calculated from expression
below:
Mass Ascorbic acid = Mole iodine × Volume of iodine × 176.12

2nd EXPERIMENT. Iodometric determination of Peroxides Number of

Oil And Fats

In the food industry, iodometry is widely used to determine the

concentration of hydroperoxides in any given lipid matrix (oils and fats for
human consumption).
Oxidation is a chemical process which is catalysed by various factors
(presence of oxygen, levels of unsaturation in the oil, presence of metals,
temperature) and leads to the formation of hydroperoxides. Determining the
concentration of these chemicals is important because hydroperoxides have a
negative effect on the acceptability of the fat matrix used, and on the food
fried in it, and they also decompose easily, forming molecules which are
dangerous for human health.
Oxidative process
• Initiation: in the presence of a catalyst, alkyl radicals (L·) form and
these tend to accumulate.
• Propagation: the alkyl radicals which have formed react with
atmospheric oxygen to form a peroxyl radical (LOO·). This radical can
react with another available hydrogen atom (LH) to form another free
radical (L·) and a hydroperoxide (LOOH).
185
 • Termination: hydroperoxides, which are highly unstable chemicals,
decompose to produce additional free radicals and /or secondary
oxidation products which accumulate and so increase the rancidity of
oil.

Figure23. Reaction of radicals responsible for formation of hydroperoxides in edible fats

and oils. LH is a monosaturated or polyunsaturated acid

Table 19. Number of peroxides (mEq/kg) legally permitted in different types

of oil

Principles of method
Hydroperoxides in the presence of KI reduce as shown in the redox
reaction below (Fig.24). The reaction is illustrated as the sum of the two half-
reactions.
The iodine released is titrated using sodium thiosulphate at a known
concentration with a starch indicator (blue colour). The number of equivalents
of titrated iodine is the same as the number of hydroperoxides present in the
186
sample as shown in the reaction in fig. 5. Thiosulphate is added until the blue
colour disappears and the solution turns colourless. The turning point
indicates that all the iodine released has been titrated.

Figure24. Redox reactions of peroxides

Scheme of performing the titration

The number of peroxides (NP) expressed in mole-eq/Kg results from

the following calculation:
NP = (N*V*1000) / p
where:
V = ml of standard solution of Na2S2O3 used;
N = normality of Na2S2O3 solution;
p = weight of oil expressed in grams.

187
3rd EXPERIMENT. Iodimetric determination of SO2 in wine

The term iodimetry, on the other hand, refers to titration using an iodine
solution and is useful for determining substances that have reducing
properties. The half-reaction is as follows:
I3- + 2e- ↔ 3I- E0 = + 0.536 V

Triodide ion I3- (iodide ions have to be added to increase the solubility
of iodine in water and these form the triodide complex).
Standard iodine solutions are of fairly limited use compared to oxidants
because of their small electrode potential. This characteristic of the I 3- /I- pair
can sometimes be an advantage, however, because it makes it selective and
therefore means that strong reducing agents can be determined in the presence
of weak ones.
One interesting application of iodometry in the food industry is for
determining sulphur dioxide (SO2) in wine.
Sulphur dioxide has several important functions:
• regulates the fermentation of the alcohol;
• acts as an antioxidant;
• acts as a purifier;
• is useful for stopping the fermentation of the must;
• aids in the extraction of polyphenolic substances;
• lowers the fermentation temperature.
Sulphur dioxide is added to the must and wine in the form of salts, like
potassium bisulphate (KHSO3) which contains 53% in weight of sulphur
dioxide, and the potassium metabisulphite (K2S2O5) which has a 69.5%
concentration of sulphur dioxide.
The legal limit for white and rose wines is 210mg/L, and for reds
160mg/L.
Forms of SO2 in wine. Once sulphur dioxide is added to wine it does
not remain free but oxidates in part and in part combines with other molecues:
Free SO2: found as such, or in the form of sulphurous acid (H2SO3) or
potassium bisulphite, which is less efficient than gaseous sulphur dioxide and
has no smell. The free form (either as a gas or an acid) is the most important
because it inhibits the action of microoganisms and acts as an antioxidant.
Oxidated sulphur dioxide appears in the form of sulphur trioxide (SO3),
sulphuric acid or potassium bisulphate.
Combined SO2: has no smell or taste and results from combination
with substances which have aldehyde and/or ketone groups to form bisulphate
compounds. The SO2, therefore, can combine with sugars, proteins and
polyphenols. Combined sulphur dioxide is in equilibrium with the free form.
This means that any reduction in the free form will result in a significant
quantity of the combined form moving towards the free form. Thi is another

188
of the advantages of using sulphur dioxide because it guarantees the stability
of the product over time.

Principles of the method

The total sulphur dioxide in the wine sample is determined through
direct iodimetric titration using starch as the indicator. Before proceeding to
titration, a 10% solution of sulphuric acid is added to the wine, thus reducing
the sulphur trioxide (SO3) to sulphur dioxide (SO2). The titration reaction can
be represented as:
SO2 + I2 + H2O → 2I- + SO3 + 2H+
The addition of an excess of I2 makes the solution turn dark blue
indicating that all the sulphur dioxide in the sample has been titrated.
With red wines it is difficult to see the equivalence point because their
intense red colour makes it difficult to perceive the colour change in the
indicator. In this case it is better use potentiometric titration which indicates
the equivalence point on the basis of changes to the solution’s potential.
Carrying out the titration (1)

Carrying out the titration (2)

189
 Calculating amount of sulphur dioxide in wine using formula:

A = ml of I2 used in the titration

N = normality of titrant solution
V = ml of wine used in the analysis
32 = equivalent weight of SO2
The calculation is applied for the three forms of SO2, the sum equals total
SO2.

CONTROL OF MASTERING THE TOPIC

Typical calculation tasks
1. An iodine disinfectant solution was analysed by titration with 0.0822 M
thiosulfate solution. The iodine solution was diluted from 10.0 to 100.0 mL
and 25.0 mL aliquots titrated to endpoint by 17.9 mL of the thiosulfate
solution. Calculate the %w/v of the original iodine solution
2. Calculate the SO2 content (mg/L) in 100 mL of a white wine sample which
was titrated to endpoint with 14.9 mL of 0.01505 M I2.
3. Calculate the molarity of a thiosulfate solution, given the following data.
1.1362g of potassium iodate is dissolved and made up to 250 mL. 25 mL
aliquots of the iodate are made acidic and reacted with KI. Titration of the
liberated iodine required an average of 22.4 mL of thiosulfate solution.
4. The concentration of oxygen in water can be determined by iodometry.
Oxygen oxidizes the Mn(OH)2 to Mn(OH)3, and is itself reduced to water.
The manganese (III) then reacts in acidic conditions with iodide to form
iodine. This is titrated with thiosulfate. Calculate the concentration of oxygen
in water if a 250 mL sample requires 7.8 mL of 0.0101 M thiosulfate in the
titration.
5. How many grammes of sodium thiosulfate is required for preparation 1,5L
of a solution Na2S2O3 with molarity of an equivalent 0,1 mol/l.
6. At iodimetric definition of a potassium dichromate in a solution on titration
of assay 10 ml of a decomposed solution are spent on the average 2,5 ml of a
solution Na2S2O3 with molarity of an equivalent 0,1mol/l. How many gram of
a dichromate contain in 50 ml of a solution?
7. 10,0 ml of a solution Na2S2O3 with molarity of an equivalent 0,0192 mol/l
spent for titration 10,5 ml of a solution of iodine. Spot molarity of an
equivalent of a solution of iodine.
8. How many ml of 0.01n iodine solution are needed for titration of
50ml of the solution, where 0.24 g of Na2S2O3 has been dissolved?
9. For preparation 1 L of a potassium dichromate solution the shot 3,5 g
К2Cr2О7 is taken. Spot a molarity and molarity of an equivalent of a received
solution (the factor of equivalence К2Cr2О7 is peer 1/6).
10. Make the ionic equations of the given below reactions. Specify an
oxidizing agent and reducer.
190
 a) КI + К2Cr2О7 + Н2SO4 → I2 + Cr2(SO4)3 +...
b) КI + КМnO4 + Н2SO4 → I2 + MnSO4 +...
c) I2 + CI2 + Н2О → HCI + HIO3

QUESTIONS FOR TEST SELF-CHECK

1. Why is hydrated sodium thiosulfate not suitable as a primary standard?
2. Why are iodine solutions made up using potassium iodide solution?
3. Why does starch solution have to be freshly prepared?
4. Which of the three pieces of titration apparatus, the pipette, the burette or
the conical flask, should not be rinsed with the solution it is to contain? Give
a reason for your answer.
5. Why is starch indicator added close to the end-point? What happens at the
end-point?
6. What is the main characteristic of the analyte in Iodimetric and Iodometric
Titrations?
6. Explain why a true redox indicator could be used in the titration of iodine
with thiosulfate, but a specific indicator, such as starch could not be used in a
titration of iron (II) with permanganate.
7. Give two reasons why an iodometric titration should be performed as soon
as possible after addition of the iodide.
8. Which titrate is used in the iodimetric process?
a) sodium thiosulphate
b) iodine
9. Which titrate is used in the iodometric process?
a) sodium thiosulphate
b) iodine
10. Is it necessary to use an indicator in an iodometric titration?
a) Yes, because the brown colour of iodine disappearing as iodine is
consumed.
b) No, because the brown colour of iodine in an aqueous solution is
sufficiently intense to serve as an indicator.
11. When should the starch be added?
a) Starch should be added at the beginning of the titration.
b) Starch should be added after most of the iodine has been consumed.
12. Why is it necessary to add any tyiociante ion?
a) There is a problem, the CuI forms a complex with the I2, and therefore the
I2 shouldn’t be titrated by the thiosulfate. That means that we have reached
the end point before the equivalent point, and consequently there is a
determinate error.
b) The addition of an tyiocianate ion allows the formation of the complex
[CuI – I2], and so the standard solutions reacts directly with the generated
iodine.

191
References:
1. Dietary Reference Intakes for Vitamin C, Vitamin E, Selenium, and
Carotenoids: consensus report. Institute of Medicine of the National
Academies. (www.iom.edu. Retrieved: 30th November 2009)
2 W. Zeng, F. Martnuzzi, A. MacGregor, J. Pharm. and Biomed. Anal., 36
(2005)1107
3 http://www.chemistry.wustl.edu/~edudev/LabTutorials/Vitamins/images/
Ascorbat.jpg> retrieved: 19 November 2009
4 Dietary Reference Intakes for Vitamin C, Vitamin E, Selenium, and
Carotenoids: consensus report. Institute of Medicine of the National
Academies. (www.iom.edu. Retrieved: 30th November 2009)
5 Mohammed sohel Chowdhury, Akib Ahmed, and others. Determination of
amount of Vitamin C (ascorbic acid) from supplied drug by using iodometric
titration. Department of Pharmacy, International Islamic University
Chittagong. March 2016

192
 Glossary of Analytical Terms

The following glossary defines common terms encountered in analytical chemistry.

Many of these terms are used interchangeably in day-to-day language. Describing chemical
measurement procedures and results requires the use of accepted terminology to avoid
confusion. I follow IUPAC recommendations for most terms, noting any deviations. See
references 1 and 2 for general terminology. Other fields of science and engineering might
have slightly different conventions, so use the context to eliminate ambiguity. As an
example, speciation has very different meanings between chemists and biologists.
A−B
accuracy The nearness of an experimental measurement to the true
value. For test portions containing unknown amounts of analytes, the
accuracy of a given method is inferred from the accuracy when measuring
certified reference materials.
analysis, qualitative Making measurements to determine the identity,
structure, or physical properties of a substance.
analysis, quantitative Making measurements to determine the amount
of an analyte in a sample.
analyte The chemical species to be identified or quantitated. Can be a
pure substance or one constituent in a multi-component sample.
blank A standard that contains no analyte, i.e., a concentration of 0.0.
The composition, solvent, electrolyte, etc, should otherwise match the sample
test portion. Variations include method, equipment, and instrument blanks for
blanks that go through all or only part of the sample processing procedures.
C–D
calibration The process of measuring a known quantity to determine
the relationship between the measurement signal and the analyte amount or
concentration.
calibration curve A plot of signal versus analyte amount or
concentration. Used to calibrate a measurement over an extended range. Good
practice is to measure five to ten standards that are equally spaced through the
measurement range.
calibration function The mathematical equation that is the best fit to
the data for a set of calibration data.
control samples (quality control samples) The blanks, standards, and
spiked test portions that are measured to determine the accuracy of a
measurement.
E− L
EPA action level The concentration of a contaminant that requires a
response such as public notification, exposure monitoring, or remediation.
error, random The spread in replicate measurements due to random
fluctuations. Will be both higher and lower than the true value.

193
 error, systematic A consistent difference either higher or lower
between an experimental measurement and the true value. Can differ from
sample to sample depending on variability in sample matrix effects.
IUPAC (International Union of Pure and Applied Chemistry) A non-
governmental agency that recommends standardization of chemical
nomenclature, terminology, and chemical and physical data.
limit of detection (LOD) The minimum measured concentration at
which an analyte may be reported as being detected in the test portion or
sample. There are several accepted methods to determine an LOD. A simple
method is to calculate the concentration that corresponds to a signal level that
equals the baseline plus 3 times the noise. See also method detection limit.
limit of quantitation (LOQ) The minimum measured concentration at
which an analyte concentration may be reported. A simple method is to
calculate the concentration that corresponds to a signal level that equals the
baseline plus 10 times the noise.
M−Q
masking reagent A reagent added to a test portion to prevent sample
components from interfering in an analytical method. An example is the
chelating ligand in total ionic strength adjustment buffer (TISAB) that is used
with a fluoride ion selective electrode (ISE). The ligand prevents metal ions
such as Fe3+ and Al3+ from forming fluoride complexes.
precision The repeatability in making replicate measurements.
Imprecision, or the lack of precision, is probably a better term to describe the
repeatability of measurements, but precision is the more common term.
Quantitative measures include standard deviation, standard error, and
confidence limits.
protecting reagent A reagent added to a test portion to prevent the
analyte(s) from being lost or otherwise not detected. An example is a weak
complexing agent to prevent metal ions from precipitating as insoluble
hydroxides at high pH.
qualitative and quantitative analysis See analysis, qualitative and
analysis, quantitative.
quality assurance Auditing of methods and procedures to ensure
accurate results.
quality control A system of instrument calibration and method
validation procedures to produce accurate results.
R
range, measurement The range from the minimum to the maximum
measurable analyte concentrations. The minimum may be taken as zero or
chosen as the limit of detection (LOD). The maximum is determined by the
point at which the signal no longer increases with increasing analyte
concentration. For linear dynamic range, the maximum is the point at which
the signal deviates from linearity. Not to be confused with dynamic range,
which is a ratio.
194
 ruggedness The degree to which variable experimental conditions,
such as temperature, pH, ionic strength, etc, will affect the accuracy and
precision of a measurement result.
S
sample A portion of material selected from a larger quantity of
material.
sample, laboratory A sample as delivered to the testing laboratory.
sample, test A sample that has been processed in the laboratory and is
ready to divide into test portions.
sampling plan The method by which samples are collected from a
population. Common selection methods use random, systematic, or stratified
strategies.
selectivity The ability of a method or instrument to measure an analyte
in the presence of other constituents of the sample or test portion.
sensitivity The slope of the calibration function, i.e., the change in
detector signal versus the change in amount of analyte. For non-linear
calibration functions, the sensitivity will be a function of concentration. Not
to be confused with limit of detection. A higher sensitivity may allow
measurement of a lower analyte concentration, depending on the signal-to-
noise ratio.
signal The detector output that is displayed or recorded.
species, chemical A specific form of an atomic or molecular entity.
spectrum A plot of signal versus wavelength or energy.
spike An internal standard or standard addition added to a test portion
or blank.
stability Retention of analyte over time or during sample preparation
and analysis steps.
standard A sample or test portion of known composition prepared
from a certified reference material.
standard, internal A standard that is added directly to the test portion.
The internal standard is then measured simultaneously with the analyte.
standard, primary A reagent that is extremely pure, stable, has no
waters of hydration, and has a high formula weight.
standard, secondary A standard that is prepared in the laboratory or
by a third party for a specific analysis. It is usually standardized against a
primary standard.
T−Z
test portion A portion of a sample that is tested or analyzed.
trace analysis Measurement of analyte concentrations of less than
approximately 100 ppm.
unknown A term with no standard definition. The source of the sample
is usually known. Calling a sample an “unknown” is common usage to
indicate that the analyte concentration in the sample is unknown

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Nazira Mukhanbetova

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