Euromed Faculty of Pharmacy

LEVEL/SEMESTER: First year/S2

MODULE: Analytical Chemistry I

Lab Manual
Analytical Chemistry I

 Pr. RAKASS Souad

2024-2025

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 The Analytical chemistry
Analytical chemistry is the study of the separation, identification, and
quantification of the chemical components (elements or compounds) of natural and
artificial materials (sample), and the separation of components are often performed
prior to analysis.

There are two types of chemical analysis:

A- Qualitative analysis:
Qualitative analysis gives an indication of the identity of the chemical species
(elements or compounds) in the sample.
Example: If you have a solution, you obtained by extraction
medical1-Sugars 2-Poly saccharine 3-acids
B-Quantitative analyses:
Quantitative analysis determines the amount of certain components (elements
or compounds) in the sample.
Example: In medicine it is important to know the level of drug in blood or urine.
Methods of analysis:
A- Classical methods.
B- Instrumental methods.
Qualitative Analysis

Classical methods Instrumental methods

1. Simple chemical test (inorganic & organic). 1. Gas chromatography (G.C).
2. Paper chromatography 2.Infrared (IR).
3. Thin layer chromatography 3.Nuclear magnetic resonance (NMR).
4. Analysis of ignition. 4. Mass Spectroscopy (MS).

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 Quantitative Analysis

Instrumental methods Classical methods

1. Electrochemical analysis. 1- Gravimetric
analysis.2- Spectrophotometer. 2- Volumetric analysis.
3. Thermal analysis. a).Acid-base titration.
b).Redox titration.
c).Precipitation titration.
d).Complex formation
titration.

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 SAFETY RULES
The chemistry laboratory is not a dangerous place to work as long as all necessary precautions are
taken seriously. In the following paragraphs, those important precautions are described. Everyone
who works and performs experiments in a laboratory must follow these safety rules at all times.
Eye Protection: Because the eyes are particularly susceptible to permanent damage by corrosive
chemicals as well as flying objects, safety goggles must be worn at all times in the laboratory.
Prescription glasses are not recommended since they do not provide proper side protection. No
sunglasses are allowed in the laboratory. Contact lenses are a potential hazard because the chemical
vapors dissolve in the liquids covering the eye and concentrate behind the lenses. If you have to
wear contact lenses consult with your instructor. If possible try to wear prescription glasses under
your safety goggles. In case of any accident that a chemical splashes near your eyes, immediately
wash your eyes with lots of water and inform your instructor. Always assume that you are the only
safe worker in the lab. Work defensively. Never assume that everyone else is as safe as you are.
Be alert for other’s mistakes.
Cuts and Burns: Remember you will be working in a chemistry laboratory and many of the
equipment you will be using are made of glass and it is breakable. When inserting glass tubing or
thermometers into stoppers, lubricate both the tubing and the hole in the stopper with water. Handle
the tubing with a piece of towel and push it with a twisting motion. Be very careful when using a
mercury thermometer. It can be broken easily and may result in mercury contamination. Mercury
vapor is extremely toxic.
When you heat a piece of glass it gets hot very quickly and unfortunately hot glass look just like a
cold one. Handle glass with tongs. Do not use any cracked or broken glass equipment. It may ruin
an experiment and worse, it may cause serious injury. Place any broken glass in the proper waste
glass container. Do not throw them into the wastepaper container or regular waste container.
Poisonous Chemicals: All of the chemicals have some degree of health hazard. Never taste any
chemicals in the laboratory unless specifically directed to do so. Avoid breathing toxic vapors.
When working with volatile chemicals and strong acids and bases use ventilating hoods. If you are
asked to smell the odors of a substance do so by wafting a 7 bit of the vapor toward your nose. Do
not stick your nose in and inhale vapor directly from the test tube. Always wash your hands before
leaving the laboratory.

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Eating and drinking any type of food are prohibited in the laboratory at all times. Smoking is not
allowed. Anyone who refuses to do so will be forced to leave the laboratory.
Clothing and Footwear: Everyone must wear a lab coat during the lab and no shorts and sandals
are allowed. Long hair should be securely tied back to avoid the risk of being set on fire. If large
amounts of chemicals are spilled on your body, immediately remove the contaminated clothing and
use the safety shower if available. Make sure to inform your instructor about the problem. Do not
leave your coats and back packs on the benchs because they may be contaminated. Cell phones
must be turned off.
Fire: In case of fire or an accident, inform your instructor at once. Note the location of fire
extinguishers and, if available, safety showers and safety blankets as soon as you enter the
laboratory so that you may use them if needed. Never perform an unauthorized experiment in the
laboratory. Never assume that it is not necessary to inform your instructor of small accidents. Notify
him/her no matter how slight it is.
Laboratory Care and Waste Disposal
Remember that the equipment you use in this laboratory will also be used by many other students.
Please leave the equipment and all workspaces as you wish to find them. After the end of each lab,
clean off your work area. Wash your glassware. When weighing any material on the balances, do
not weigh directly onto the balance pan. Weigh your material on a piece of weighing paper. The
balances are very sensitive instruments and should be treated with great care.
If you take more reagents than you need, do not put excess back into the bottle. It may be
contaminated. Threat it as waste and dispose of it accordingly. It is most likely that, during any
experiment you will perform, you will generate some waste chemicals and solutions to dispose of.
Never put them down the sink unless specifically told to do so by your instructor. There will be
inorganic, organic, and solid waste containers in the lab. Dispose of your waste in the appropriate
container.

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 General notions in analytical chemistry

1- Preparation & Standardization of solutions

Standardization: the process whereby the concentration of a standard solution is determined by
titration of a primary standard.
Reagents
1-1. Standard Solutions
 Volumetric analysis: Analysis using measurements of volumes
 Standard solution: A solution that has an accurately known concentration
 Primary Standards
- Primary standard: A substance of known high purity that may be dissolved in
a known volume of solvent
- Requirements:
- readily obtainable in pure form
- have a known chemical formula
- be easy to store without deteriorating or reacting with the atmosphere
- have a high molar mass to minimize the effect of errors in weighing
- Inexpensive
 Standard Solutions
Prepared by dissolving the accurately measured mass of a primary standard in an accurately
measured volume of water
- Volumetric flask / standard flask is used to prepare a solution that has an accurately
known volume
- filled so that the bottom of the meniscus is level with the graduation line on the neck
of the flask
- ensure that your eye is level with the line (avoids parallax errors)

- Equations needed:

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 1-2. The process:

Concentration of Standard Solutions

2- Volumetric Analysis
2-1. The Titration:
One of the most important techniques in analytic chemistry is "titration", the addition of a
carefully measured volume of one solution containing substance (A) in known concentration, to a
second solution containing substance (B) in an unknown concentrate, with which it will react
quantitatively, the solution of known concentration used in titration is called a standard solution,
the goal of every titration is the addition of standard solution in an amount that is chemically
equivalent to a substance (solution B) with which it reacts, this condition is achieved at the
equivalent point, completion of reaction at the (endpoint) is signaled by a change in some physical
properties of solution at or near the endpoint such as color due to reagent indicator substance or
formation precipitation.
 Simple and easy.
 Fast and can be done on-site.
 Less expensive.
 Estimation of content or Assay.
 Precise and accurate.

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 2-2. Some terms used in titration
Equivalence point (Veq):
The point in a titration where stoichiometrically equivalent amounts of analyte and titrant react
(theoretical end of titration).
End point (Vep):
The point of titration at which the completion of a reaction is practically observed. Unfortunately,
the endpoint and the equivalence point are not the same. The difference between the two is called
the titration error.
Titration error:
The difference between the end point and the equivalence point Et = Vep – Veq
Titrant: The standard solution of known concentration added from the burette.
Analyte: An unknown solution that is to be determined.
Indicator:
A colored compound reagent is added to the analyte solution to produce an observable physical
change (usually change in color) at or near the equivalence point when the titration reaction is
complete, and so mark the endpoint e.g: Phenolphthalein, Methyl Orange, Methyl red, etc.
Examples of some indicators

Back titration:
A technique used to determine the excess of a reagent used in the neutralization of the sample by
titration with a second reagent
2-3. Types of titration
2-3-1. Acid-Base (Neutralization) titrations:
Many compounds, both inorganic and organic, are either acids or bases and can be titrated with a
standard solution of a strong base or a strong acid. The end points of these titrations are easy to
detect, either by means of an indicator or by following the change in pH using a pH meter.
acide1 + base2⇌ base1 + acide2
2-3-2. Reduction-Oxidation (Redox) titrations:
The “redox” titrations involve the titration of an oxidizing agent with a reducing agent, or vice
versa. An oxidizing agent gains electrons and a reducing agent loses electrons in a reaction
between them.
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 oxydant 1 + n1 e- ⇌ réducteur 1 (x n2)
réducteur 2 ⇌ oxydant 2 + n2 e- (x n1)

n2.ox 1 + n1.réd2 ⇌ n2.réd1 + n1.ox2

2-3-3. Precipitation titrations:
In this type of titration, the titrant forms a precipitate with the analyte. An example is the titration
of chloride ions with silver nitrate solution to form silver chloride precipitate. Again, indicators
can be used to detect the endpoint,...
Cl- + Ag+ → AgCl(s) (white ppt) 2Ag+ + K2CrO4 → Ag2CrO4 (brick red ppt)
2-3-4. Complexometric titrations:
In complexometric titrations, the titrant is often a chelating agent (Ligand) that forms a water-
soluble complex with the analyte (metal ion). Ethylenediaminetetraacetic acid (EDTA) is one of
the most useful chelating agents used for titration. It will react with a large number of elements,
and the reaction can be controlled by the adjustment of the pH. Indicators can be used to form a
highly colored complex with the metal ion.
M + n L ⇌ MLn
2+
Cu + 2NH3 ⇌ [NH3-Cu-NH3]2+ complexe de couleur bleu.

3- Acid-Base Titrations

- Volumetric Equipment:

- Equivalence point: The point in a titration at which the reactants have reacted in their

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 correct mole ratios → Reaction is complete when the equivalence point is reached
- End point: A point in titration at which the indicator changes color, usually marking
the completion of the reaction
- Indicator: A substance that is different colors in its acid and base forms → used in
titration to determine when the reaction is complete → determines the endpoint
(when the color change happens)

 Reading A Burette Scale

- Three concordant tires (titers that are within 0.10 ml of each other) are obtained and
the average is used → minimizes errors
- A single drop from a burette has a volume of 0.05 ml
2-4. Calculations involving Acids and Bases
 Reacting Quantities of Acids and Bases
- The coefficients in a balanced chemical equation give the ratio in which substances
react
- m = nM - m is in grams – M is in g.mol-1
- n = CV – C is in mol.L-1
- N = p.C- N is in mol d’éq/L
- At the equivalence point in a neutralization, the moles of acid are equal to the moles
of base.
NA×VA=NB×VB

3- Evaluation of titration accuracy and calculation of uncertainty

The results obtained are always subject to uncertainty. The causes of errors are diverse and can be
classified into two categories:

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a) Errors that can be minimized by repeating measurements; are often caused by clumsiness
of the experimenter, instability of the devices used, and fluctuation in ambient conditions.
b) Systematic errors: a consistent or proportional difference between the observed and true
values of something (e.g., a miscalibrated scale consistently registers weights as higher than they
actually are, …).
These errors can be evaluated.
It is therefore always necessary to evaluate the uncertainties involved in measuring volumes and
calculate the errors before the final presentation of the results.
3-1. Absolute uncertainty
It defines a range of values in which we are sure to find the exact value. If V X= V ± V, it means
that:
V -V ≤ VX ≤ V+V
When we have a sum or a difference of values, the absolute uncertainty is the sum of the absolute
uncertainties of each value. Note that we never remove an uncertainty.

If V is written V=V1 + V2 – V3  V= V1 + V2  V3

Absolute uncertainty has the same unit as the value.

3-2. Relative uncertainty

It is a factor of proportionality allowing communication between different units.

It is noted and has no unity

Example:

NA. VA = NB. VB
.
𝑁 =

If the Log function is applied to this equality:

N .V
LogN = Log = LogN + LogV − LogV
V

The derivative leads to:

dN dN dV dV
= + −
N N V V
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Which brings us to the relationship between relative uncertainties:
N dN V V
= + +
N N V V

  
 N = N ( + + )
Note :
For y = .x we have: dy = .dx  y = .x ( is a constant).
Example :
C’ =M C  C’ = M C.
Expression of the results:
Two main rules to respect:
a) Absolute uncertainties have only one significant digit.
Example:
m = 0.00061 g ≤ 0.0007 g (only 7 is considered a significant digit).
We always round up to the next number.
b) The value can only be rounded after determining the uncertainty: the value must have as
many digits after the decimal point as the uncertainty.
In the case where: N = 0.0012 ≤ 0.002 N and if N = 0.1264 N
We must write:
N = (0.126 ± 0.002) N

General rules for rounding results:

1. We leave the last significant digit unchanged if the digit following it is less than 5.
2. The last significant digit is increased by one if the following number is greater than 5.
Example :
C’ = 3.238 g/L and C’ = 0.021 g/L
We always increase the uncertainty: C’ = 0.021 g/L ≤ 0.03 g/L;
For the result given that the uncertainty concerns the 2 nd digit after the decimal point and
the 3rd digit 8 is greater than 5 we will have:

C’ = (3.24 ± 0.03) g/L

3. If the significant digit is followed by a number equal to 5, we keep the number 5 but place
it in parentheses.
Example:
C = 0.003651 mol/L and C = 0.00021 mol/L ≤ 0.0003 M
C = (0.0036(5) ± 0.0003) mol/L

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If m = 25.4 g and m = 1.3 g ≤ 2 g  m = (25 ± 2) g.
If m = 1025 g and m = 12g ≤ 20 g  m = (102(5) ± 20) g.
For : VM = 7.15 mL and VM = 0.1 mL (burette)  VM = (7.1(5) ± 0.1) mL and for Vpipette = 10 ml
and Vp = 0.05 ml ; Vp = (10.00 ± 0.05) ml
In the case where: N = 0.1 N and N = 0.001 N  N = (0.100 ± 0.001)N.
Uncertainties about glassware in chemistry

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 Experiment N°1
Acid-base titration
I. Aim
 Preparation of titrated solutions and verification of their titers
 Titration of phosphoric acid
 Titration of tiaprofenic acid (SURGAM)

II. Experimental part

1) Titration of an active ingredient in a pharmaceutical specialty
SURGAM (tiaprofenic acid), a propionic acid derivative, is a nonsteroidal anti-inflammatory
agent with analgesic and antipyretic properties.
The objective of this lab is to perform a titration to determine the concentration of tiaprofenic
acid in a Surgam 100 mg tablet using a standardized solution of NaOH

Preparation of the NaOH titrant solution

1-1. Procedure.

From a concentrated NaOH solution (0.25 N), take 10 ml using a volumetric pipette and introduce it in a
100 ml flask.

complete up to the gauge

10 ml pipette mark with distilled
jaugée water

Concentrated Diluted NaOH

solution of NaOH solution
Homogenize the
solution by stirring

1-2. Standardization of the prepared NaOH solution

Standardization of sodium hydroxide is done by acid-base titration. When oxalic acid is allowed
to react with sodium hydroxide, sodium oxalate and water are obtained. In this titration, to locate
the end point phenolphthalein indicator is used. The appearance of the pale pink color which
persists for 30 sec is the endpoint.

Sodium hydroxide NaOH, in the form of tablets, is hygroscopic (strong tendency to absorb
humidity from the air). In addition, its composition changes over time. It is therefore necessary to
standardize it, that is to say, determine its real concentration. For this, we use a standard solution
of oxalic acid, the latter is a stable solid with a guaranteed purity of 99.9%.

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1-2-1. Procedure

1. Rinse your burette twice with about 5 mL of the NaOH solution.

2. Fill the burette with the NaOH solution and position it above an Erlenmeyer flask (Note:
be sure there are no air bubbles in the tip of the burette).
3. Obtain a 5.00 mL pipette and rinse it twice with about 2 mL of the standard oxalic acid of
N = 0.05 N solution.
4. Transfer 5.00 mL of the standardized oxalic acid of N = 0.05 N solution into the
Erlenmeyer flask.
5. Add 1-2 drops of phenolphthalein indicator solution into the flask (NB: phenolphthalein
is colorless in an acidic medium and pink in a basic medium).
6. Record the initial volume of NaOH in the burette before you begin the titration.
7. Begin the titration, swirling the solution in the Erlenmeyer flask as you add NaOH in a
drop-wise approach (Note: Your solution will initially turn pink, and then fade back to
colorless when swirled. The pink color will remain longer as you approach the end point
of the titration).
8. Record the final volume of NaOH in the burette when the solution in the Erlenmeyer
flask remains light pink for about 10 seconds.
9. Repeat this procedure two more times, refilling the NaOH in the burette as needed.

1-2-2. Titration scheme

A few drops of 5.00 ml of oxalic acid of N=0.05N

phenolphthalein
Ve of NaOH

1-3. Titration of H3PO4 acid solution using standardized NaOH solution

1-3-1. Procedure:

1- Fill the burette with the NaOH solution and position it above an Erlenmeyer flask (Note: be
sure there are no air bubbles in the tip of the burette).
2- Obtain a 10.00 mL pipette and rinse it twice with about 2 mL of phosphoric acid solution.
3- Transfer 10.00 mL of phosphoric acid of unknown normality solution into the Erlenmeyer
flask.
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4- Add 1-2 drops of methyl orange indicator solution into the flask (NB: methyl orange is red in
an acidic medium and yellow in a basic medium).
5- Record the initial volume of NaOH in the burette before you begin the titration.
6- Begin the titration, swirling the solution in the Erlenmeyer flask as you add NaOH in a drop-
wise approach (Note: Your solution will initially turn red, and then fade back to yellow when
swirled. The yellow color will remain longer as you approach the end point of the titration).
7- Record the volume of NaOH (V1) in the burette when the solution in the Erlenmeyer flask
remains yellow for about 10 seconds.
8- Add 1-2 drops of phenolphthalein indicator solution into the flask (NB: phenolphthalein is
colorless in an acidic medium and pink in a basic medium).
9- Continue the titration, swirling the solution in the Erlenmeyer flask as you add NaOH in a
drop-wise approach (Note: Your yellow solution becomes pink color as you approach the end
point of the titration).
10- Record the volume of NaOH (V2) in the burette when the solution in the Erlenmeyer flask
remains pink for about 10 seconds.
11- Repeat this procedure two more times, refilling the NaOH in the burette as needed.

1-3-2.Titration scheme

A few drops of
10 mL (of H3PO4 of unknown
methyl orange
concentration)
V1 of NaOH
A few drops of
phenolphthalein V2 of NaOH

1-4. Titration of Tiaprofenic acid using the NaOH titrated solution

After determining the normality of NaOH which will be used to determine the mass of
tiaprofeinic acid which is the active ingredient of the drug Surgam 100 mg per tablet.

1-4-1. Procedure

1. Fill the burette with the NaOH solution and position it above an Erlenmeyer flask (Note:
be sure there are no air bubbles in the tip of the burette).
2. Dissolve the Surgam tablet in a volume of water (10 ml) in the Erlenmeyer flask.
3. Add 1-2 drops of phenolphthalein indicator solution into the flask (NB: phenolphthalein
is colorless in an acidic medium and pink in a basic medium).
4. Record the initial volume of NaOH in the burette before you begin the titration.
5. Begin the titration, swirling the solution in the Erlenmeyer flask as you add NaOH in a
drop-wise approach (Note: Your solution will initially turn pink, and then fade back to
colorless when swirled. The pink color will remain longer as you approach the end point
of the titration).
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 6. Record the final volume of NaOH in the burette when the solution in the Erlenmeyer
flask remains light pink for about 10 seconds.
7. Repeat this procedure two more times, refilling the NaOH in the burette as needed.

1-4-2. Titration scheme

1 tablet in 10 ml of water
A few drops of
phenolphthalein
Ve of NaOH

III. Results
II-4-1 Part 1
1) Give the average volume of NaOH for the first titration with oxalic acid.
2) Write the neutralization reaction of oxalic acid with sodium hydroxide.
3) Calculate the normality N of NaOH and its uncertainty.
II-4-2 Part 2

4) Write the equations for the neutralization reactions of the 1 st and 2nd acidity of phosphoric
acid and name the reactants and the products formed.
5) Deduce, from these results, a simple relationship between the values of volumes V 1 and V2.
6) Calculate the normality N, and the molar concentration of H 3PO4 solution and their
uncertainty.

II-4-3 Part 3
7) Give the average volume of NaOH for the titration with Tiaprofeinic acid.
8) Calculate the normality N of Tiaprofeinic acid and its uncertainty.
9) Calculate the experimental mass of Tiaprofeinic acid and its uncertainty.
10) Calculate the active ingredient content (T%)

𝒎𝒂 (𝑻𝒊𝒂𝒑𝒓𝒐𝒇𝒆𝒊𝒏𝒊𝒄 𝒂𝒄𝒊𝒅 𝒎𝒂𝒔𝒔)

𝑻(%) = 𝐱 𝟏𝟎𝟎
𝑻𝒉𝒆𝒐𝒓𝒊𝒕𝒊𝒄𝒂𝒍 𝒎𝒂𝒔𝒔 𝒐𝒇 𝒕𝒊𝒂𝒑𝒓𝒐𝒇𝒆𝒊𝒏𝒊𝒄 𝒂𝒄𝒊𝒅
NB. Give the results in the following form
Y = (X + X) unity

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 Experiment N°2
REDOX TITRATION:
MANGANIMETRY AND IODOMETRY
Generality
Reminders

The process of oxidation or reduction boils down to an exchange of electrons

 Oxidation: corresponds to a loss of electrons
(Zn ⇌ Zn2+ + 2e-)
 Reduction: corresponds to a gain of electrons
(Sn4+ + 2e- ⇌ Sn2+)
Electrons do not exist in the free state, oxidation cannot take place without simultaneous
reduction and vice versa.
 An oxidant: is an atom, molecule or ion that captures electrons
(Cu2++2e- ⇌ Cu)
 A reductant: is an atom, molecule, or ion that gives up electrons
(Fe2+⇌ Fe3++ e-)
The Oxidizer and the reducer are linked by the following relationships:

Ox1 + n1 e- ⇌ Red1 (x n2)

Red2 ⇌ Ox2 + n2 e- (x n1)

n2 Ox1 + n1 Red2 n2 Red1 + n1 Ox2

⇌
Example :
MnO4- + 5 e - + 8H+ ⇌ Mn2+ + 4 H2O

(Fe2+ ⇌ Fe3+ + 1e - )  5

MnO4- + 8H+ + 5Fe2+ ⇌ 5Fe3+ + Mn2+ + 4H2O

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 Part I: Manganimetry
Manganimetry is the set of redox titrations in which potassium permanganate KMnO 4 is
used.
Aim of manipulation
The manipulation consists of:
- Titer a solution of potassium permanganate KMnO4 of unknown concentration with a
solution of ferrous sulfate FeSO4 of known normality.

1. Titration of KMnO4 per FeSO4

1-1. Theory
In an acidic environment, ferrous sulfate FeSO4 reacts with potassium permanganate
according to the reaction equation:
Dissociation of the 2 salts:
KMnO4  K+ + MnO4 –
FeSO4 Fe2+ + SO4 2-
MnO - + 5 e- + 8H+ ⇌ Mn2+ + 4H O
4 2
2+ 3+ -
Fe ⇌ Fe + 1e
Write the global redox reaction.
1-2. Procedure
1- Rinse and fill a clean burette with potassium permanganate solution. Remove the air
bubble, if any, from the nozzle of the burette by releasing some solution through it. The
burette used in the permanganate titration must have a glass stop cock as rubber is
attacked by permanganate ions.
2- Obtain a 10.00 mL pipette and rinse it twice with about 2 mL of FeSO 4 of N = 0.02 N
solution.
3- Transfer 10.00 mL of FeSO4 of N = 0.02 N solution into the Erlenmeyer flask.
4- Add 1 ml of 2.0 N H2SO4.
5- Record the initial volume of KMnO4 in the burette before you begin the titration.
6- Begin the titration, swirling the solution in the Erlenmeyer flask as you add KMnO4 in
a drop-wise approach until a persistent pink color appears, indicating the end of the
titration reaction.
7- Record the final volume of KMnO4 in the burette when the solution in the Erlenmeyer
flask remains pink for about 10 seconds.
8- Repeat this procedure two more times, refilling the KMnO4 in the burette as needed.

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 KMnO4

FeSO4+ H2SO4

Titration scheme

10 ml of FeSO4 solution
1 ml of concentrated (0.02N)
H2SO4 (2N)
Ve of KMnO4

Results:
1- Establish the redox half equations.
2- Deduce the global equation.
3- Calculate the average volume of KMnO4
4- Calculate the normality, molarity, and mass concentration of KMnO 4 and evaluate
the uncertainties in these quantities.
5- Give the results in the form:
NKMnO4±MnO4 = ( ± )
CKMnO4 ± CKMnO4 = ( ± )
C'KMnO4 ± C'KMnO4 = ( ± )
2- Characteristics of Fe2+ and Fe 3+ ions
To highlight the presence of Fe2+ and Fe3+ ions; perform the following tests in two test
tubes.
-2ml of the solution containing Fe2+ ions + 2ml of NaOH (0.5N)
-2 ml of the titrated solution + 2 ml of NaOH (0.5 N)
-Let it rest and note the difference in colors observed

3- Back-titration of a potassium dichromate solution using an aqueous ferrous salt

solution of known title.
Aim
 Determination of the titer (concentration) of potassium dichromate.
 Back titration of potassium dichromate K2Cr2O7 solution
Principle
 In an acid medium, Cr2O72- ions oxidize ferrous Fe2+ ions giving rise to the
formation of Cr3+ and Fe3+ ions.
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  However, potassium dichromate cannot titer directly with ferrous sulfate, because
the change in color that accompanies the change is very difficult to identify. To do
this, we use the technique known as: back titration method.
 Dichromate ions are reduced by an excess of ferrous salt (iron sulfate FeSO 4) in a
solution of known concentration. This excess ensures that the reaction is complete.
 The remaining ferrous ions are then determined using a solution of potassium
permanganate KMnO4 of known concentration in the presence of sulfuric acid
H2SO4.
 The couples involved are: Cr2O72-/ Cr3+ ; Fe3+/Fe2+, MnO4-/Mn+2
Procedure
1- Fill the burette with potassium permanganate solution. Remove the air bubble, if
any, from the nozzle of the burette by releasing some solution through it.
2- Obtain a 20.00 mL pipette and rinse it twice with about 5 mL of FeSO 4 of N = 0.02
N solution.
3- Transfer 20.00 mL of FeSO4 of N = 0.02 N solution into the Erlenmeyer flask.
4- Add 10.00 mL of potassium dichromate solution (Obtained by 10.00 mL pipette)
into the Erlenmeyer flask.
5- Add 1 ml of 2.0 N H2SO4.
6- Record the initial volume of KMnO4 in the burette before you begin the titration.
7- Begin the titration, swirling the solution in the Erlenmeyer flask as you add KMnO4
in a drop-wise approach until a persistent pink color appears, indicating the end of
the titration reaction.
8- Record the final volume of KMnO4 in the burette when the solution in the
Erlenmeyer flask remains pink for about 10 seconds.
9- Repeat this procedure two more times, refilling the KMnO4 in the burette as
needed.

K2Cr2O7+FeSO4

Titration scheme
20.00 ml of FeSO4 (0.02N) +
1 ml of concentrate 10.00 ml K2Cr2O7
H2SO4
Ve of KMnO4

26
 Results
1- Write the half-equations of the Cr2O72-/Cr3+ and Fe3+/Fe2+ couples in an acidic
medium.
2- Write the equation for the titration reaction between Cr2O72- and Fe2+ ions.
3- Write the half-equations of the MnO4-/Mn2+ and Fe3+/Fe2+ couples in an acidic
medium.
4- Write the equation for the titration reaction between MnO4- and Fe2+ ions.
5- Calculate the average volume of KMnO4 and its uncertainty.
6- Calculate the normality, molarity, and mass concentration of K2Cr2O7 and evaluate
the uncertainties in these quantities.

Part II: Iodometry

I) Titration of an aqueous solution of iodine with an aqueous
solution of sodium thiosulfate.

Principle
- Iodometry is a redox titration method which consists of measuring the diode I2
present in a medium using sodium thiosulfate Na2S2O3.
- Oxidizing/reducing couples: I2 /I -; S4O62-/S2O32-.
Procedure
1- Rinse and fill a clean burette with the aqueous sodium thiosulfate solution. Remove
the air bubble, if any, from the nozzle of the burette by releasing some solution
through it.
2- Obtain a 10.00 mL pipette and rinse it twice with about 2 mL of diode solution to be
measured
3- Transfer 10.00 mL of diode solution to be measured into the Erlenmeyer flask, and
placed on the magnetic stirrer.
4- Add a few drops of starch.
5- Record the initial volume of sodium thiosulfate solution in the burette before you
begin the titration.
6- Begin the titration, swirling the solution in the Erlenmeyer flask as you add the
sodium thiosulfate solution in a drop-wise approach until a persistent blue color
appears, indicating the end of the titration reaction.
7- Record the final volume of sodium thiosulfate in the burette when the solution in the
Erlenmeyer flask remains blue for about 10 seconds.
8- Repeat this procedure two more times, refilling the sodium thiosulfate in the burette
as needed.

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 Na2S2O3.5H2O

10 ml I2+ starch

Titration scheme

10 ml I2
A few drops of
starch
Ve of Na2S2O3.5H2O

Results
1- Make an annotated scheme of the titration setup.
2- Write the redox half-equations of the following couples: I2 / I - et S4O62- / S2O32-.
3- Write the equation for the titration of I2 by S2O32-
4- Define equivalence.
5- What is the role of starch?
6- Calculate the normality, the molar concentration C diiod, and the mass concentration
of the solution to be determined and its uncertainty.
We give the molar mass of I2=254g/mol

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 Part III: Iodometric titration of vitamin C
INTRODUCTION
A Vitamin C
Vitamin C is an essential vitamin not synthesized by the human body. It is provided
through food or in medicinal form. Its deficiency leads to scurvy. Ascorbic acid is
characterized by its reducing properties due to the ene-diol function.

Chemical formula of ascorbic acid

Its oxidation reaction is as follows:

The standard potential of the couple is 0.13 V. Due to the complex structure of the
molecule, the redox reactions in which they occur are generally slow: in the laboratory,
they are carried out in a few minutes with stirring.
The aim is to carry out an iodometric titration to determine the ascorbic acid content
per effervescent tablet of Vitamin C at 500 mg.
Principle
The transformation of vitamin C with diiodine is slow to consider a direct titration.
First reaction:
C6H8O6 + I2 => C6H6O6 + 2 I- + 2 H+(aq)
Second reaction: titration of excess diode.
I2 + 2 S2O32- => 2 I- + S4O62-

29
Which leads to: n(I2 having reacted with C6H8O6) = n(C6H8O6) and n(I2 having reacted
with S2O32-) = (1 / 2) (S2O32-)

Procedure

 Grind a vitamin C tablet in a mortar. Place the powder in a 100 mL beaker and
dissolve it in 20 to 30 mL of distilled water.
 Filter the solution obtained by collecting the filtrate in a 100 mL volumetric
flask. The flow is slow, so you can stir with a glass rod, taking care not to
puncture the filter.
 Rinse the beaker, mortar, and pestle above the filter. Complete with distilled
water. The solution obtained is called (S1).
 Make a tenth dilution of the solution (S1), which forms the solution (S2).
 Into a beaker, introduce 20.00 mL of the solution (S2) and 10.00 mL of the diode
solution using a volumetric pipette. The solution obtained is called (S 3). Place
under agitation and wait a few minutes
 Titer the solution (S3) with sodium thiosulfate.

Titration scheme

+ 10 ml I2
A few drops of
starch
Ve of Na2S2O3.5H2O

Results
1. Write the reactions involved in this titration step and note the titration volumes
with the uncertainties.
2. Determine the concentration of iodine in molarity and normality with
uncertainties.
3. Determine the ascorbic acid content per 500 mg Vitamin C effervescent tablet.

30
 Experiment N°3
Precipitation and complexometry
I. Introduction
Gravimetric analysis is a type of laboratory technique that determines the mass or
concentration of a substance by measuring a change in mass. Gravimetric titration uses
two types of methods:
 Volatilization method
 Precipitation method
Precipitation titrations, based on the formation of compounds with limited solubility,
constitute one of the oldest analytical techniques (mid-19th century). Halides Cl -, Br-, I-,
except fluorides, cyanides CN-, thiocyanates SCN-, and some organic acids form insoluble
compounds with Ag+ ions. These compounds can therefore be measured in a solution by
forming a precipitate with the silver ion. Titration methods based on silver nitrate are
called argentimetric methods.
Argentimetry refers to a set of precipitation titration methods having the common point of
using a solution containing Ag⁺ ions.

Mohr's method
The solution to be dosed contains chloride ions and the titrant solution is a solution of
silver ions, or vice versa.

It is necessary to work in a neutral medium because in a basic medium pH > 7.5,

there is precipitation of silver ions into silver hydroxide AgOH and in an acidic medium
pH < 6.5, silver chromate is soluble.

Charpentier - Volhar
It consists of precipitating the halide anions in an acidic medium with an excess quantity
of silver nitrate solution (back titration):

The excess silver nitrate is then measured in an acidic medium using potassium
thiocyanate in the presence of ferric ammoniacal alum (colored indicator):

It is necessary to work in an acidic environment because, in a basic environment, we

observe the precipitation of silver oxide Ag2O and other metal hydroxide.

II. Experimental part

1. Application: Titration of barium chloride by gravimetry

Objective : Determination of the titer in (g/l) of a solution of BaCl 2, 2H2O

Principle : Gravimetric determination of the Ba2+ ion by precipitation of barium chromate
BaCrO4
31
1-1. Procedure

1. Obtain a 50.00 mL pipette and rinse it twice with about 3 mL of the solution to be
measured.
2. Transfer 50.00 mL of the solution to be measured into the Erlenmeyer flask.
3. Add 200 ml of water
4. Add 2 ml of 30% ammonium acetate
5. Add 20 ml of 10% potassium chromate
6. Heat for 1 hour on a hot plate
7. Weigh the empty sintered glass (m0)
8. Vacuum filtration on sintered glass of porosity No. 4
9. Wash with boiling water until the chromate disappears
10. Dry at 120°C for 1 hour in an oven
11. Weigh the sintered glass + dry precipitate (m)

Étapes 1-4 Étape 5 Étapes 6-7

1-2 Titration scheme

2 ml of 30% 50 ml of BaCl2 ,2H2O

ammonium acetate

() For 1 hour 20 ml of 10% potassium

chromate

Formation of a BaCrO4
precipitate

2. Titration of Silver Nitrate by Sodium Chloride (Argentimetry)

Objective: Determination of the molarity of a silver nitrate solution.

Principle: Titration of an AgNO3 solution with NaCl using the Mohr method

2-1. Procedure

1. Rinse your burette twice with about 5 mL of the AgNO3 solution.

2. Fill the burette with the AgNO3 solution and position it above an Erlenmeyer flask
(Note: be sure there are no air bubbles in the tip of the burette).
32
3. Obtain a 10.00 mL pipette and rinse it twice with about 2 mL of NaCl at 0.05 mol/l
solution.
4. Transfer 10.00 mL of NaCl at 0.05 mol/l into the Erlenmeyer flask.
5. Add a few drops of Potassium Chromate (CI)
6. Record the initial volume of AgNO3 in the burette before you begin the titration.
7. Begin the titration, swirling the solution in the Erlenmeyer flask as you add AgNO 3
in a drop-wise approach up to the bend (persistent red precipitate).
8. Record the final volume of NaOH in the burette when the solution in the
Erlenmeyer flask remains light pink for about 10 seconds.
9. Repeat this procedure two more times, refilling the AgNO3 in the burette as needed.

AgNO3

NaCl +Chromate de
potassium (IC)

2-2. Titration scheme

A few drops of potassium 10 ml of NaCl solution at

chromate (CI) 0.05mol/l

V equivalence of AgNO3

3. Titration of a mixture of halides

Objective: Determination of the molarity of a mixture of halides (KI and NaCl).

Principle: Titration of a mixture of halides by NH4SCN using the Charpentier - Volhar
method.

3-1. Procedure

1. Rinse your burette twice with about 5 mL of the NH4SCN solution.

2. Fill the burette with the NH4SCN solution 0.05 mol/l and position it above an
Erlenmeyer flask (Note: be sure there are no air bubbles in the tip of the burette).
3. Obtain a 10.00 mL pipette and rinse it twice with about 2 mL of the mixture of
halides (I- and Cl-) solution.
4. Transfer 10.00 mL of the mixture of halides (I- and Cl-) into the Erlenmeyer flask.
5. Add 100 ml of distilled water.

33
6. Add 40 ml of AgNO3 (its concentration is already calculated in the second part).
7. Add 3 ml of nitrobenzene (to coagulate the precipitate).
8. Add 5 ml of nitric acid HNO3
9. Add 4 ml of ferric alum (CI).
10. Add NH4SCN drop by drop, until the color changes (orange-red precipitate).
11. Repeat this procedure two more times.

NH4SCN

- -
(I et Cl )+H2O+ AgNO3+ (IC)
+ nitrobenzène + HNO3

3-2. Titration scheme

3 ml of nitrobenzene 10 ml of the halide mixture to

titrate

40 ml of an AgNO3 solution at C
5ml of HNO3 mol/l
4 ml of ferric alum
(IC) V equivalence of NH4SCN

III. Results
II-1 Part 1
1) Write the reaction involved between BaCl2 and K2CrO4.
2) Determine the mass of the precipitate obtained.
3) Determine the concentration of BaCl 2, 2H2O en g/l.
II-2 Part 2
4) Give the average volume of AgNO3.
5) Determine the molarity of AgNO3 and its uncertainty.

II-3 Part 3
6) Give the average volume of NH4SCN.
7) Determine the molarity of the mixture of halides (I-, Cl-) and its uncertainty:
NB. Give the results in the form
Y = (X + X) unity

34