CHEMISTRY - VLAB

NAME:B.MYTHRI EXP.NO:
ROLL.NO:249XA05023 DATE:

Aim:

To determine the amount of substance in a solution of unknown concentration using various

titrimetric methods.

Theory:

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:

1.The reaction must be a fast one

2.It must proceed stoichiometrically
3.The change in free energy (ΔG) during the reaction must be sufficiently large for spontaneity of the
reaction
4.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,

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a = activity co-efficient.

Large values of the equilibrium constant K implies that the equilibrium concentration of A & 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,

Where,

R = Universal gas Constant = 8.314 JK-1mol-1,

T = Absolute Temperature.

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.

Acid base titration:

The chemical reaction involved in acid-base titration is known as neutralisation reaction. It involves
the combination of H3O+ ions with OH- ions to form water. 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 undissociated molecule will have 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

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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

Procedure:

• Choose the titrant.

• Choose the titrate.
• Select the normality of the titrate.
• Choose the volume of the liquid to be pipetted out.
• Select the indicator.
• Start titration.
• End point is noted at the colour change of the solution.
• From the final reading the normality of titrant can be calculated by the equation:
N1V1=N2V2
• After finding the normality, the amount of given substance in the whole of the given solution can be
calculated by the equation:
Mass=Equivalent weight*Normality*Volume/1000

Points to Remember while Performing the Experiment in a Real Laboratory:

1.Always wear lab coat and gloves when you are in the lab. When you enter the lab, switch on the
exhaust fan and make sure that all the chemicals and reagents required for the experiment
are available. If they are not available, prepare the reagents using the components for reagent
preparation.
2.Properly adjust the flame of the Bunsen burner. The proper flame is a small blue cone; it is not a
large plume, nor is it orange.
3.Make sure to clean all your working apparatus with chromic acid and distilled water and ensure
that all the apparatus are free from water droplets while performing the experiment.
4.Make sure to calibrate the electronic weigh balance before taking the measurements.
5.Clean all glassware with soap and distilled water. Once the experiment is completed, recap the
reagent bottles. Switch off the light, exhaust fan and gas cylinder before leaving the lab.
6.Discard used gloves in a waste bin.

Procedure:

S.No. Volume of KOH(ml) Burette readings Volume of Concordant

H2SO4(ml)(f-i) Value(ml)(V2)
Initial Final
(i)ml (f)ml
1. 20 0.0 4 4 4

2. 20 0.0 4 4

3. 20 0.0
4. 20 0.0

According to Equimolar formula,

N1V1=N2V2

Where,

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Volume of H2SO4 solution = V2 = 4 ml
Normality of KOH solution = N1 = 0.2N
Volume of KOH solution = V1 = 20 ml
Normality of H2SO4 solution = N2 =1N
N2 = N1V1/V2
N2 = 0.2*20/4
N2 = 1N
The strength of H2SO4 solution = Molecular weight of H2SO4(98)*N2
=98*1
=98 g/litre
Result:

The strength of given acid = 98 g/litre

Viva voce Questions

1.A basic solution can be defined as one in which

a. [H3O+] is not present
b. [H3O+] is equals to OH-

Ans:a

2.Which one is a self indicator?

a. K2Cr2O7
b. Cr2(SO4)2
c. KMnO4
d. H2C2O4.2H2O

Ans:c

3. Which of the following combinations can't produce a buffer solution?

a. HNO2 & NaNO2
b. HCN & NaCN
c. HClO4 & NaClO4
d. NH3 & (NH4)2SO4
e. NH3 & NH4Br

Ans:c

4. What is the pH of a solu/on composed of 0.20 M NH3 & 0.15M NH4Cl?

a. 2.15
b. 4.65
c. 8.26
d. 9.38
e. 8.89

Ans:d

5. Calculate the ra/o [CH3COOH]/[CH3COONa] that gives a solu/on with pH=5.00?

a. 0.28
b. 0.36
c. 0.44
d. 0.56
e. 0.63

Ans:d

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Instrumentation and Working Principles of Infra-Red (IR) Spectroscopy Using

Salt Plates

The infrared region lies between the visible and microwave regions of the electromagnetic spectrum
and works mostly based on absorption spectroscopy. The infrared portion of the electromagnetic
spectrum is usually divided into three regions; near or higher energy IR, mid-IR, and far or low
energy infrared. The mid-infrared which is (4000 - 400 cm-1 ) gives the fundamental vibrations and
associated rotational-vibrational structure of the substance under study. Infrared spectroscopy is the
absorption of infrared radiation by the molecules and is used to elucidate the structure of the molecule
by identifying their functional groups. One of the common laboratory instruments that use this
technique is a Fourier transform infrared (FTIR) spectrometer

Energy levels of molecules

The aim of this experiment is

1.To learn sample preparation and handling procedures to measure an IR spectrum using salt plates.

2.To carry out spectral analysis of the sample measured.

When two atoms combine to form a stable covalent molecular, there are two repulsion forces acting
between the two heteroatoms. One between the positively charged nuclei of both the atoms and the
other between the negative electron clouds. The other force is the attraction between the nucleus of
one atom with the electrons of the other atom. Balancing the forces between them, the two atoms
settle at a mean internuclear distance or the bond length where the total energy of the system is
minimum. Any change like pulling the atoms away or squeezing them brings a change in the bond
length which requires an input of energy.

A diatomic molecule with the above description is considered as two vibrating masses that are
connected by a spring. The internuclear distance between the atoms at energy minimum is referred to
as the equilibrium distance (re)Any change in this distance is given by Hooke' law as:

f = -k(r-re)

where f is the restoring force and r is the bond length. The energy associated considering the energy
curve to be parabolic is given as :

E= 1/2k(r-re)2

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Vibrational energy levels and allowed transitions between them for a diatomic
molecule in a simple harmonic motion.

For any harmonic oscillator, when the bond vibrates, its energy of vibration is changing
continually and periodically from kinetic to potential energy and back again. The total energy
is proportional to the frequency of vibration, and is given as:

Eosc = hνosc

The elastic nature of the bond has an intrinsic vibrational frequency which is determined by
the force constant K of the spring or its stiffness, the masses of the bonded atoms.

where c is the speed of light, and μ is the reduced mass of the system which is given by:

μ = m1m2/m1 + m2

The value of the force constant varies from the bond to bond. K for a triple bond is three
times those of a single bond and for a double bond, it is twice those of a single bond. There
are two significant features that can be drawn:

1.Strong bonds have force and vibrate at a higher frequency than weaker bonds.
2.Bonds between the heavy atoms (larger reduced mass) vibrate at a lower frequency
than that of bonds between the lighter atoms.

Vibrational modes of an organic molecule.The energy of molecular vibration is quantised. A

molecule can only stretch and bend at certain allowed frequencies.

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Sample preparation for Infrared spectroscopy: The sample to be measured must be taken in a sample
holder or cell which is made of ionic substance. Sodium chloride or potassium bromide plates are
used. Potassium bromide plates are more expensive than sodium chloride but has an advantage over
the sodium chloride because of the asbsorbs at 650cm-1. Glass or platics absorb strongly through the
infrared region.
Liquids: A drop of the liquid sample is placed between a pair of polished IR salt plates. The plates are
pressed together and the sample forms a thin film between the salt plates. A spectrum obtained by this
method is neat for there is no use of solvent in the sample preparation.
Solids: One of the methods used to prepare sample is the Bbr Pellet method. Where the sample is
powdered along with KBr and pressed under high pressure to form a pellet.
The other method is the Nujol method where the sample is ground along with few drops of mineral oil
or nujol and the thick suspension is place between the salt plates.

IR salt plates (Sodium Chloride)

The Infrared Spectrometer: The infrared spectrometer or the spectrophotometer is the instrument
that determines the IR absorption spectra of a compound. There are two types of spectrometers that
are widely used in laboratories. a. Dispersive infrared spectrometers b. Fourie Transform
spectrometers

The main components of a Fourier transform infrared (FTIR) spectrophotometer

FT-IR spectrometers are the modern spectrometers that provide the spectrum more rapidly than the
dispersive ones. The optical pathway produces a pattern called the interferogram. This is a complex
signal which is a plot of intensity versus time. For more practical purposes this time-domine spectrum
is converted to a frequency-domain spectrum, that is intensity versus frequency. This conversion is
done by a mathematical operation called a Fourier-Transform (FT). FT separates the individual

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frequencies from the interferogram producing a virtual spectrum identical to the one obtained from
dispersive spectrometers. The biggest advantage of using FT-IR spectrometers is that it is possible to
collect a number of interferograms of the same sample in less than a second. When a Fourier-
Transform has performed a sum of all the interferograms gives a spectrum that has a better signal-to-
noise ratio. Greater speed and greater sensitivity make FT-IR spectrometers preferred over dispersive
spectrometers.

FT-IR spectrophotometers collect the interferograms of the sample and Fourier-transform them
to an absorption spectrum

Salt plates : While using solutions of samples is a common technique in IR spectroscopy, use of salt
plated for the same is also a conventional use. The process of mulling is a common method of sample
preparation for salt plates. The principle here is by grinding the particles to below the wavelength of
incident radiation that will be passing through there should be limited scattering. To suspend those
tiny particles, an oil is used. IR-transparent salt plates are used to hold the sample in front of the beam
in order to acquire data. To prepare a sample for IR analysis using a salt plate, first decide what
segment of the frequency band should be studied for the materials best suited for the sample. Figure
shows the materials needed for preparing a mull.

Preparing the mull is performed by taking a small portion of the sample and and adding approximately
10% of the sample volume worth of the oil and grinding this in an agate mortar and pestle. The
resulting mull should be transparent with no visible particles. Another method involves dissolving the
solid in a solvent and allowing it to dry in the agate pestle. If using this method, ensure that all of the
solvent has evaporated since the solvent bands will appear in the spectrum. Some gentle heating may
assist this process. This method creates very fine particles that are of a relatively consistent size. After
addition of the oil further mixing (or grinding) may be necessary.

Plates should be stored in a desiccator to prevent erosion by atmospheric moisture and should appear
roughly transparent. Some materials such as silicon will not, however. Gently rinse the plates with
hexanes to wash any residual material off of the plates. Removing the plates from the desiccator and

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cleaning them should follow the preparation of the mull in order to maintain the integrity of the salt
plates. Of course, if the plate is not soluble in water then it is still a good idea just to prevent the threat
of mechanical trauma or a stray jet of acetone from a wash bottle.

Once the mull has been prepared, add a drop to one IR plate, place the second plate on top of the drop
and give it a quarter turn in order to evenly coat the plate surface. Place it into the spectrometer and
acquire the desired data. Always handle with gloves and preferably away from any sinks, faucets, or
other sources of running or spraying water. Spectra acquired by this method will have strong C-H
absorption bands throughout several ranges 3,000 – 2,800 cm-1 and 1,500 – 1,300 cm-1 and may
obscure the signal.

Cleaning the plate as previously mentioned with hexanes or chloroform can easily be performed by
rinsing and leaving them to dry in the hood. Place the salt plates back into the desiccator as soon as
reasonably possible to prevent damage. It is highly advisable to polish the plates after use, no
scratches, fogging, or pits should be visible on the face of the plate. Chips, so long as they don’t cross
the center of the plate, are survivable but not desired. The damaged salt plates show common
problems associated with use or potentially mishandling. Clouding, and to an extent, scratches can be
polished out with an iron rouge. Areas where the crystal lattice is disturbed below the surface are
impossible to fix and chips cannot be reattached.

Follow the procedure given below once all the apparatus has been introduced into the workspace:

1. Click on the Sample Beaker to transfer small amount (around 1mg) of the Sample substance into
the empty Mortar.
2. Click on the Solvent Beaker to transfer 5 ml of the Solvent (Nizol) to the Mortar.
3. Click on the Mortar to grind the mixture and make a paste.
4. Click on the Mortar to draw 1 ml of the solution prepared to load on to the IR Plate.
5. Click on the IR Plate to put it into the Desiccator.
6. Click on the Observe button in the Control Menu to observe what is happening inside the
Desiccator.
7. Click on the Observe button again to observe the Intensity graph plotted.
8. Click on the Restart button in the Control Menu to repeat the experiment from scratch.

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Model Graph

Viva voce Questions

1.Infrared spectroscopy provides valuable information about:

A. Functional groups

2.The most effective method of IR spectroscopy is the:

A. Fourier-Transform spectrometer

3.The desiccator is used before sample testing in FT-IR to:

A. Remove any water molecules present due to moisture

4.The O-H group in alcohol and carboxylic acids show at:

A. Alcohol at 3300cm-1 and carboxylic acid at 3000cm-1

5.What occurs when a molecule absorbs infrared radiation?

A. It vibrates fast

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