Analytical method :

The elemental analysis are characterized by simple, safe, economical, Accurate and time
efficient analytical methods. The Sulfur content are determined by Raney Nickel test method,
Phosphorous content determined by colorimetric method , Nitrogen content by Kjeldahl method
& Chloride content are determined by volhards method.
4.1 : Determination of Sulphur (S) Content

4.1.1 SCOPE :- This method is for the determination of low concentrations of Sulphur, ppm to
% range, in distillate free of hydrogen sulphide. It may be applied to non-olefin materials, such
as straight run naphtha, hydrogen treated stocks, reformats & aromatic hydrocarbons. It is limited
to samples containing not more than 2 % olefins. Oxidized Sulphur forms, such as sulfonic acids,
are not determined quantitatively; therefore, this method must be applied with discretion to the
analysis of stocks which have been treated with sulphuric acid.

4.1.2 PRINCIPLE: - The sample is treated with activated Raney nickel to convert
organically-bound sulphur to nickel sulphide. Acid is then added to liberate the sulphur as
hydrogen sulphide. The hydrogen sulphide is absorbed in a sodium hydroxide-acetone solution
& titrated with standard mercuric acetate, using dithizone as the indicator.

4.1.3 APPARATUS :
4.1.3.1 100 ml round bottom flask
4.1.3.2 Heating mantle for 100 ml flask.
4.1.3.3 Nitrogen Cylinder(IOLAR GRADE) : Equipped with pressure regulator. Arrange two
lengths of rubber tubing to independently feed acid reservoir & the flask respectively. Fit a
pinch-cock or needle value in each line to permit regulation of nitrogen flow.
4.1.3.4 Graduated cylinder 10 ml.
4.1.4 REAGENT :
4.1.4.1 RANEY NICKEL CATALYST: Take 0.6 gm nearest to 0.1 mg. Raney catalyst
powder (nickel aluminum alloy) to a 50 ml beaker, & add 10 ml 2.5 N Sodium Hydroxide
solution. Swirl the beaker gently in fume hood until vigorous evolution of hydrogen ceases.
Cover the beaker with watch glass & allow the mixture to activate overnight. Wash the activated
nickel into the 100 ml distillation flask of the apparatus with a minimum amount of water.
Decant the water avoiding loss of catalyst. Wash with two 5 ml portions of water, decant the
wash water, & preserve the activated catalyst under 10 ml of 2-propanol until ready for use.
4.1.4.2 MERCURIC OXIDE (Yellow powder ) :- Reagent grade
4.1.4.3 DITHIZONE INDICATOR : Dissolve 0.1 gm dithizone ( diphenyl thiocarbazone ) in
100 ml of acetone. (Prepare new solution in every week).
4.1.4.4 Dibutyl disulfide ( DBDS )
4.1.4.5 Sodium Hydroxide 2.5 N. and 1N.
4.1.4.6 Concentrated Hydrochloric Acid, AR/GR.
4.1.4.7 Hydrochloric Acid solution : Dilute 1.5 volume of concentrated HCl with 1 volume of
water.
4.1.4.8 ISOOCTANE AR/GR.
4.1.4.9 ISO PROPYL ALCOHOL, AR/GR
4.1.4.10 Mercuric Acetate (30 µg S/ml.) :- Dissolve 0.41 gm. of mercuric oxide in 50 ml.
of aqueous solution containing 2 ml. of acetic acid. Dilute to 2 liter with water in a volumetric
flask. Standardise this titrant by pipetting 2 ml. of sulfur standard and following the analysis as
sample as described under PROCEDURE.
CD
CALCULATION µg S/ml. = ------------ = T
E

Where C = Sulfur standard (µg S/ml.)

D = Volume of sulfur standard used. ml.
E = Titration volume of mercuric acetate. ml.

Sulfur Standard Solution. :- Place several gm. of dibutyl disulphide into a dropping bottle.
Weigh the bottle and components to the nearest 0.1 mg. add 60 – 100 mg. of disulphide to 1 liter
of sulfur free isooctane. Reweigh the dropping bottle to obtain the weight of dibutyl disulphide
removed. Dilute the contents of the 1 liter flask to the mark with isooctane and mix by inverting
the flask several times. Calculate the titer in µg S /ml as follows.

360.5 X A
µg S/ml. (standard) = --------------------- = C
 B

Where A = Weight of DBDS in mg.

B = Volume of isooctane, ml.

4.1.5 SAFETY : Each analyst should be acquainted with the potential hazards of the
Equipment, Reagents, Products, solvents and procedure before beginning laboratory work.

4.1.6 PROCEDURE :
Thoroughly clean the reduction apparatus glassware with soap and water and then rinse at least
two times with sulfur free alcohol. Dry in an oven at 110°C for one & half hour or until dry. An
excess of water inhibits the reduction of organic sulfur.

Test the sample for the presence of hydrogen sulfide by holding a piece of water moistened lead
acetate paper in the vapor space of the sample container. If hydrogen sulfide is present the paper
will darken or a silver sheen will appear. If hydrogen sulfide is not present proceed with the
analysis. If hydrogen sulfide is present it must be removed as this method is applicable for
organic sulfur only.
Transfer the Raney nickel to the reaction flask with 10 ml. of isopropyl alcohol, rinsing down.
Decant the isopropyl alcohol without loss of nickel .

Take appropriate quantity of sample in the reaction flask

Suggested sample size for analysis.

Sulfur, ppm Sample size, gm. Concentration of titrant

µg. S ml. (ppm)
0-1 50 30
1-10 50 100
10-20 20 100
 20-100 5 100
100-200 2 100

Rinse the walls of the flask with about 25 ml. of isopropyl alcohol to ensure contact of the entire
sample with the Raney nickel. Place the flask in the heating mantle, Charge the absorber with 10
ml. of 1 N. Sodium hydroxide, 10 ml. of Acetone and 5 drops of dithizone solution. Assemble
and connect the apparatus as indicated in the drawing. Set the nitrogen pressure regulator for 2-5
psig and allow the nitrogen to flow through the reaction vessel and on into the absorber at a rate
of one bubble every 1 or 2 seconds. Turn on the heater and allow the reactants to warm to a
temperature at which no sample will be lost as a results of distillation during the sulfur reduction
stem (i.e. use a temperature which is just short of inducing boiling). Allow the sulfur reduction to
proceed for 30 minutes, agitating the contents of the flask several times during this period.
Charge the acid reservoir of the connected head with 10 ml. of 1.5: 1 hydrochloric acid after the
desulfurization is completed. Attach the nitrogen line loosely to the acid reservoir using the glass
tube inserted in neoprene stopper. Flush the air from the acid reservoir with a rapid flow of
nitrogen and then reduce the rate of flow of nitrogen and put the stopper firmly in to the place.
Add the acid drop wise to the reaction flask while maintaining the nitrogen flow through the
reaction flask and into the absorber. Add just enough of the appropriate mercuric acetate titrant
to the absorber liquid to change the color of the solution from yellow to pink. After the vigorous
reaction of the acid with the nickel has taken place, the remaining acid can be added rapidly.
Maintain the nitrogen flow through the flask and reservoir. Increase the temperature to the point
where the content of the flask just barely reflux.
As the evolved hydrogen sulphide begins to be absorbed in the caustic solution, the color of the
solution will change from pink back to yellow. Titrate with the mercuric acetate solution until the
absorber solution is definitely pink. Continue boiling the reaction flask contains for at least 30
minutes and then stop the nitrogen flow. Cool the reaction flask by applying a cold wet cloth
above the heating mental when the liquid approaches the side-arm, turn on the nitrogen to force
the liquid back into the absorber. Repeat this operation several times, being careful not to allow
any absorber solution to wet the horizontal portion of the delivery tube. If the absorber solution
changes color from pink to yellow following this operation titrate further with mercuric acetate
to bring the solution to the permanent end point. Record the total volume of mercuric acetate
titrant used. Obtain the net titration volume for the sample by subtracting the titration volume
determine for Raney nickel blank.

Determination of blank for Raney nickel :

Transfer the active nickel to the reaction flask with 10 ml. of isopropyl alcohol. Rinse down the
wall of the flask with about 5 ml of isopropyl alcohol and attach the greased connected head.
From this point on follow the procedure as described for the analysis of the sample with the
exception that the sample is omitted. The total volume of mercuric acetate required to reach the
end point is Raney nickel catalyst blank. The blank should be 0.1 to 0.2 ml. of the 100 µg S
titrant or 0.3 to 0.6 ml. of 30 µg S titrant. This amounts to 17-34 ppm sulfur in the Raney nickel
alloy.

4.1.7 Calculations :
(V – Vo ) X T
Sulfur % = -------------------------
W x 10

Where,

V = Volume of mercuric acetate solution required for sample, ml.

Vo = Volume of mercuric acetate solution required for blank, ml.
T = Titer of the mercuric acetate solution µg S/ml.
W = Weight of sample in mg.

4.1.8 Analytical data of Sulphur content :

Table 4.1 : Determination of sulphur content
Sample Name Step Weight of Vol. of Vol. of Titer of % S
Sample M.A. M.A. the
(mg) required required M.A.
for sample for blank
in ml (V) in ml (V)
SPBDC-PIP-NPS II 4 14.85 0.35 4.5 15.92
SPBDC-PIP-NPS III 4 8.440 0.35 4.5 9.10
SPBDC-PIP-NPS IV 4 11.683 0.35 4.5 12.75
SPBDC-PIP-NPS V 4 8.181 0.35 4.5 8.81
NPS-PIP-NPS -- 4 14.003 0.35 4.5 15.36
NPS-EDA-NPS -- 4 14.972 0.35 4.5 16.45
DOPS-PIP-DOPS I 4 12.527 0.35 4.5 13.70
DOPS-PIP-DOPS II 4 10.758 0.35 4.5 11.71
DOPS-EDA- -- 4 11.247 0.35 4.5 12.26
DOPS
CYN-PIP-NPS -- 4 10.661 0.35 4.5 11.60

4.2 Determination of Nitrogen content %

4.2.1 PRINCIPLE :
A known weight of the nitrogenous compound is decomposed by digestion with conc. Sulphuric
acid, preferably in the presence of a catalyst (e. g. mixture of selenium; copper sulphate &
potassium sulphate ) to accelerate the process, ammonium sulphate is produced. An excess of
sodium hydroxide solution is added to the diluted reaction mixture, % the ammonia is distilled in
steam, & absorbed in excess of 1 N hydrochloric acid. Titrate of the residual mineral acid with 1
N sodium Hydroxide gives the equivalent of the ammonia obtained from the weight of the
sample taken.
4.2.2 REACTION :
heat
Nitrogenous Compound + H2SO4 (NH4)2SO4
 (NH4)2SO4 + 2 NaOH Na2SO4 + 2NH3 + 2 H2O
The ammonia absorbed in 1 N Hydrochloric Acid.
NH3 + HCl NH4Cl
4.2.3 REAGENT :
• Copper sulphate A.R. grade.
• Selenium powder
• Potassium sulphate A.R.grade
• Conc.Sulphuric Acid . A.R. grade
• 1 N Hydrochloric acid solution
• 1 N Sodium Hydroxide solution
• Mixed indicator
a) Dissolve 0.1 gm of methyl red indicator in 50 ml of absolute industrial methylated
spirit.
b) Dissolve 0.15 gm of bromocreasol green in 150 ml of absolute industrial methylated
spirit
c) Mix (a) & (b).

4.2.4 PROCEDURE :
Digestion : Weigh accurately about 1.0 gm sample and transfer it to a clean and dry 500 ml.
Kjeldahl flask. Add catalyst mixture ( prepare from 0.1 gm of selenium, 1 gm of cupric sulphate
and 10 gm of potassium sulphate.) Measure out 25 ml of concentrate sulphuric acid A.R.grade
and pour it carefully in to the flask. Insert the glass bids and support the Kjeldahl flask in a stand
so that it is slightly inclined from the vertical. Heat the mixture slowly until 30 minutes and then
increase the heating so that the solution boil vigorously and continue the heating for a further 4
hours, the liquid should be colourless or light green at the end of this period. Allow the Kjeldahl
flask to cool and dilute it cautiously with 150 ml-distilled water.
Distillation: Before the distillation all the parts should have been cleaned with chromic acid
mixture and thoroughly rinsed with distilled water. Fit the Kjeldahl distillation apparatus. Place
a500 ml conical flask containing 50 ml 1 N hydrochloric acid and 2 drops of mix indicator below
the condenser and adjust its height on a wooden support so that the end of the condenser dips 3-4
mm below the level of liquid. Add drop wise 40.0 % Sodium Hydroxide solution it to digested
material via additional funnel until the solution in the Kjeldahl flask becomes dark brown colour,
then add 10 ml of excess 40.0 % Sodium Hydroxide solution and heat the digested material
continue the distillation for 30 minutes. Disconnect the additional funnel before stop the heating.
Wash out the condenser tube rinse the liquid on the outside of condenser tube in to the acid with
the add of distilled water. Titrate the excess Hydrochloric acid with 1 N Sodium Hydroxide .End
point gives blue colour. And run a blank also .

4.2.5 CALCULATION :
Nitrogen % = (B -V) X N X 1.4
M

Where,
B = Blank reading.
V = Volume of 0.1 N Sodium Hydroxide added in the titration.
N = Normality of 0.1 N Sodium Hydroxide
M = Weight of sample taken for the titration.

4.2.6 Analytical Data of Nitrogen content

Table : 4.2 : Determination of Nitrogen content
Sample Name Weight BR BL Normality %N
SPBDC-PIP-NPC 0.5120 19.45 49.2 0.1020 8.30
Step-3
SPBDC-PIP-NPC 0.4752 9.75 49.2 0.1020 11.85
Step-4
SPBDC-PIP-NPC 0.5075 20.6 49.25 0.1020 8.06
Step-5
SPBDC-PIP-NPS 0.5002 22.15 49.25 0.1020 7.72
Step-3
SPBDC-PIP-NPS 0.4896 11.00 49.25 0.1020 11.15
Step-4
SPBDC-PIP-NPS 0.5196 21.25 49.25 0.1020 7.70
Step-5
 NPC-PIP-NPC 0.5066 23.35 49.05 0.1025 7.28
NPC-EDA-NPC 0.5214 20.7 49.05 0.1025 7.80
NPS-PIP-NPS 0.5175 25.05 49.50 0.1015 6.71
NPS-EDA-NPS 0.4925 24.7 49.50 0.1015 7.16
DOPO-PIP-DOPO 0.5296 29.2 49.25 0.1020 5.41
DOPO-EDA-DOPO 0.5330 28.0 49.25 0.1020 5.70
DOPS-PIP-DOPS 0.5075 31.3 49.60 0.1011 5.10
DOPS-EDA-DOPS 0.4862 8.8 49.60 0.1011 11.88
CYN-PIP-NPC Step-1 0.2560 13.75 49.60 0.1011 19.82
CYN-PIP-NPC Step-2 0.1020 22.7 49.80 0.1015 37.75
CYN-PIP-NPC Step-3 0.4040 3.85 49.80 0.1015 16.17
CYN-PIP-NPS 0.4103 5.9 49.80 0.1015 15.21

4.3 Determination of phosphorous content .

4.3.1 PRINCIPLE :
The Total Phosphate Content is obtained via a hot acid digestion with Potassium Persulphate to
completely oxidize all the Phosphonate to Orthophosphates. Then the Orthophosphate
concentration is determined by the reaction of ammonium molybdate in an acid medium to
form a hetropoly acid, molybdoPhosphoric acid (Phosphomolybdic acid).
The heteropolyacid is reduced to an intensely colored complex, molybdenum blue by the
combination of Metol, Citric Acid and Sodium disulfite reducing agents.
4.3.2 EQUIPMENTS AND REAGENTS :
4.3.2.1 SPECTROPHOTOMETER :
Any colorimeter suitable for absorbance measurements at 720 nm.
4.3.2.2 METOL-DISULPHITE-CITRIC ACID SOLUTION :
Dissolve 20 gm. Metol, 100 gm Sodium Disulphite (Na2S205) and 20 gm. Citric Acid
separately in sufficient amount of distilled water (say about 200 ml each). Transfer
all the solutions in one liter volumetric flask and make up the volume to the mark
by distilled water. Filter if necessary. Store the solution in an amber colored glass stopper
bottle at a temperature not exceeding 30°C.
4.3.2.3 AMMONIUM MOLYBDATE SOLUTION :
Dissolve 50 gm. of (NH4) 6 Mo7O24. 4H2O in about 200 ml distilled water in a beaker.
Cautiously add 50 ml Concentrated Sulphuric Acid to about 400 ml distilled water taken in one
litre volumetric flask. Cool to room temperature. Add molybdate solution in volumetric
flask & dilute it upto one litre with distilled water.
4.3.2.4 APPROX. 6 M SULPHURIC ACID SOLUTION :
Cautiously add one part by volume concentrated Sulphuric Acid to two parts by volume of
water. Cool to room temperature.
4.3.2.5 Potassium Persulphate (K2S208):A.R.
4.3.2.6 STANDARD PHOSPHATE (PO4) SOLUTION : (1 ml = 0.5 mg. PO4.)
Preparation of Standard Solution (1 ml = 0.5 mg. PO4) :
Weigh accurately 0.716 gms of Potassium Dihydrogen Phosphate, KH2PO4 (dried in an
oven at 100 - 110_ø“C) and dissolve it in little quantity of water in a beaker. Transfer the
solution in one litre volumetric flask and dilute it up to the mark with distilled water. Shake
well.
4.3.3 PROCEDURE :
4.3.3.1 PHOSPHATE CONTENT :
Weigh accurately about 1 gm sample in a 250 ml. conical flask containing about 25 ml of
distilled water. Add 1 ml. of 6 M. Sulphuric Acid, 0.5 gm. Potassium Persulphate. Heat the
solution to concentrate it up to 10 ml. Cool it to room temperature. Transfer the solution in to
100 ml volumetric flask with help of minimum distilled water. This flask marked as `A'
Pipette out 1 ml of Standard Phosphate (PO4) Solution (1 ml = 0.5 mg PO4) in 100 ml
volumetric flask. Add to it about 50 ml of distilled water and 1 ml of 6 M Sulphuric Acid. This
flask marked as `B'
To each volumetric flask (marked as `A' and `B' )add by pipette, swirl ing with each addition, 5
ml Metol-disulphite-citric Acid Solution and 5 ml Ammonium Molybdate Solution.
Dilute each volumetric flask up to mark with distilled water and mix thoroughly and allow to
stand for 30 minutes.
Prepare a reagent blank treated in a same way and allow to stand for 30 minutes.
After 30 minutes adjust the Spectrophotometer to read zero optical density (100 % transmittance)
at 720 nm with the reagent blank solution. Measure the optical density (or percent transmittance)
of each Phosphate solution.

4.3.4 CALCULATION :

O.D.(s) M (std.)
Phosphate Content %, = --------------X ------------ X 100 = A
. O.D.(std.) M (s)
31
Phosphorous (as P) % = A X -----
. 95

Where,
O.D.(s) = Optical density of Sample.
O.D.(std.) = Optical density of Standard.
M(s) = Mass of Sample in mg.
M(std.) = Mass of Standard in mg.

Analytical Data of Phosphorous content

Table -4.3 : Determination of phosphorous content
Sample Name Step Weight of Weight of OD of OD of % P
Sample (mg) Std. (mg) Sample Std.
SPBDC-PIP-NPC I 1.0 0.5 0.1865 0.1460 20.81
SPBDC-PIP-NPC II 1.0 0.5 0.1501 0.1460 16.75
SPBDC-PIP-NPC III 2.0 0.5 0.1652 0.1460 9.21
SPBDC-PIP-NPC IV 1.5 0.5 0.1763 0.1460 13.13
SPBDC-PIP-NPC V 1.0 0.5 0.1600 0.1460 17.85
SPBDC-PIP-NPS II 1.0 0.5 0.1380 0.1460 15.37
SPBDC-PIP-NPS III 2.0 0.5 0.1582 0.1460 8.84
SPBDC-PIP-NPS IV 1.5 0.5 0.1656 0.1460 12.33
SPBDC-PIP-NPS V 1.0 0.5 0.1527 0.1460 17.05
NPC-PIP-NPC -- 1.0 0.5 0.1444 0.1460 16.13
NPC-EDA-NPC -- 1.0 0.5 0.1557 0.1460 17.39
NPS-PIP-NPS -- 1.0 0.5 0.1333 0.1460 14.89
NPS-EDA-NPS -- 1.0 0.5 0.1424 0.1460 15.90
DOPO-PIP-DOPO -- 1.5 0.5 0.1605 0.1460 11.95
DOPO-ED-DOPO -- 1.5 0.5 0.1700 0.1460 12.65
DOPS-PIP-DOPS I 1.5 0.5 0.1190 0.1460 13.29
DOPS-PIP-DOPS II 1.5 0.5 0.1516 0.1460 11.29
DOPS-EDA-DOPS -- 1.5 0.5 0.1596 0.1460 11.88
CYN-PIP-NPC -- 1.5 0.5 0.1600 0.1460 11.90
CYN-PIP-NPS -- 1.5 0.5 0.1504 0.1460 11.20

4.4 Determination of chloride content (%)

4.4.1. Apparatus
Reflux Apparatus, consisting of a 250-mL Erlenmeyer flask attached to a reflux
condenser.
Hot Plate, with variable heat control.
Magnetic Stirrer, with polytetrafluoroethylene (PTFE)-Magnetic Stirrer, with
polytetrafluoroethylene (PTFE)-coated stirring bar.
Glass Burette or Automatic Potentiometric Titrator.
Silver electrode or equivalent.
Boiling Chips.
Analytical Balance, capable of weighing to 0.001 g.

4.4.2. Reagents and Material

 Acetone.
Bromcresol Green Indicator Solution (0.1 %)— Dissolve 0.1 g of bromo cresol green in
100 mL of water.
Nitric acid, (HNO3) (1 + 1) diluted with water.
Potassium Hydroxide, alcohol solution (0.1 N)— Dissolve 5.6 g of potassium hydroxide
(KOH) in 1 L of methanol (99 %). No standardization of the solution is necessary.
Silver Nitrate, alcohol solution (0.1 N)—Dissolve 1.698 g of silver nitrate (AgNO3),
weighed to the nearest 0.001 g, in L of methanol (99 %). Standardize against hydrochloric acid
or sodium chloride (NaCl) solution either gravimetrically or potentiometrically
Toluene.
Glacial Acetic Acid

4.4.3 Procedure
Weigh 0.2 to 0.3 g of sample, to the nearest 0.005 g, into a 250-mL Erlenmeyer flask.
Add 20 mL of toluene, 20 mL of acetone, and 50 mL of 0.1 N alcoholic KOH. Swirl or mix until
dissolution is complete.
Prepare a blank in a separate 250–mL Erlenmeyer flask, adding 20 mL of toluene, 20 mL
of acetone, and 50 mL of 0.1 N alcoholic KOH. Swirl to mix.
Add several boiling chips, connect the flasks to separate reflux condensers, and gently
reflux each for 15 min on a hot plate.
Remove the hot plate from under the flask and allow the flask and contents to cool to
room temperature. Rinse down the condenser with approximately 20 mL of acetone then remove
from the flasks.
Quantitatively transfer the contents of each flask to separate 250-mL titration vessels
using acetone as wash solution. Dilute each solution to about 125 mL with acetone.
For manual titrations, insert a stirring bar into each flask, and place on a magnetic stirrer.
Add five drops of bromo cresol green indicator.
Titrate with 0.10 N silver nitrate While stirring add 50 mL of glacial acetic acid.
Alternatively, 1 + 1 nitric acid can be added drop wise just until the permanent color changes
from blue to yellow instead of adding the acetic acid. (Warning—If using nitric acid, do not add
any excess. Do not acidify the solution until ready to begin the titration. Make certain that the
solution is at room temperature before acidifying. These cautions are necessary to prevent the
chloride results from being low due to recombination with the resin.)
to the first blue endpoint, stable for 20 seconds.
For automated potentiometric titrations, insert a stirring bar and place on a magnetic
stirrer or attach to the titration device equipped with a stirrer.

4.4.4. Calculation
Calculate the % chloride content of the specimen as follows:
(V – B ) X N X 3.546
Cl % = ---------------------------
W
where:
B = AgNO3 required for the titration of the blank, mL,
V = AgNO3 required for the titration of the hydrolyzed specimen, mL,
N = Normality of the AgNO3,
W = specimen weight, g.

4.4.5 Analytical Data of Chloride content

Table -4.4 : Determination of Chloride content
Sample Name Step Weight of BR Bl Normality % P
Sample (gm)
SPBDC-PIP- I 0.2530 16.736 0.10 0.1010 23.55
NPC
 SPBDC-PIP- II 0.2586 13.927 0.10 0.1010 19.15
NPC
SPBDC-PIP- II 0.2625 12.999 0.10 0.1010 17.60
NPS

4.5 : Infra red Spectral Analysis :

Introduction : IR spectral analysis involves the interaction of IR radiation with matter and it is
based on absorption spectroscopy technique. All spectroscopic technique used to identify and
study of chemicals may be solid, liquid or gas. The technique or method of IR spectroscopy is
conducted on instrument to produce infra red spectrum called IR spectrometer. IR spectrum can
be visualized in a graph of IR light transmittance IR Absorbance on the vertical axis verses
wavelength or frequency on the horizontal axis. In IR spectra typical unit of frequency are wave
number or reciprocal centimetre with the symbol cm-1. Unit of Infra red wavelength are
commonly given micrometer (Symbol µm) which are related to wave number in reciprocal way.
In this technique common laboratory instruments is Fourier Transform infra red spectrometer.
The two dimensional infra red is also possible.
The IR portion of the electromagnetic spectrum is divided into three region, near, mid & Far IR
region
Near IR- Higher energy, 0.8 – 2.5 µm ( 14000-4000 cm-1), can excite overtone or harmonic
vibration.
Mid IR – 2.5 - 25 µm (4000 – 400 cm-1)used to study the fundamental vibration & associated
rotational vibrational structure. It is divided into four regions and the nature of the group
frequency may generally be determined by the region in which it is located. The region are
generalized as below;
Stretching region : The fundamental vibrations regions between 4000-2500 cm-1due to O-H, C-
H and N-H stretching. The O-H stretching showing broad band between range 3700-3600 cm-1.
The N-H stretching produce sharper absorption than O-H and observed in the range 3400-3300
cm-1. The C-H stretching bands from aliphatic compounds observed in the range 3000-2850 cm-
1. if the C-H bond is adjuscent to double bond or aromatic ring the C-H stretching wavenumber
increases and absorb between 3100-3000 cm-1.
Triple bond stretching : The triple bond stretching observe between 2500-2000 cm-1 due to
force constant of bonds. C≡C bonds shows absorption between 2300 - 2050 cm-1 & it is normally
very weak stretching. The nitrile group C≡N bonds absorb between 2300 – 2200 cm-1 and
stretching is of medium intensity. The some time observe X-H stretching absorption where X is
atom such as phosphorous & silicon & these absorption occur near 2400 & 2200 cm-1
respectively.
Principle band stretching : The principle bands are observed between 2000-1500 cm-1 region
between due to C=C and C=O stretching. The carbonyl bond stretching observe between 1830-
1650 cm-1 region and it is most intense band in the spectrum also metal carbonyl bond absorb
between 2000 cm-1. The C=C stretching is much weaker and occurs at around 1650 cm-1 but
this band is often absent for dipole moment reasons. The C=N Stretching also observe in this
region.
Finger Print region : Each band in IR spectrum can be assigned to a particular deformation of
the molecule, movement of the group of atom or bending or stretching of a particular bond,
Many vibration are not so behave and may vary by hundred of wave numbers even for similar
molecules. This applies bending and skeletal vibrations which is absorb between 1500-650 cm-1
region. In this region smalls steric or electronics effect in the molecule lead to large shift also
spectrum of a molecule may have a hundred or more absorption bands present but no need to
assign majority.
Far IR – low energy, 25-1000 µm (400-10 cm-1) Lying adjacent to the microwave region and
may be used for rotational spectroscopy. The classification and the names of these sub regions
are based on relative molecular or electromagnetic properties
The IR spectroscopy exploit the fact that molecule absorbs frequencies that are characteristic of
their molecule structure and these absorption occur at resonance frequency i.e. the frequency of
the absorption radiation matches the vibrational frequency. The energy are affected by the shape
of the molecular potential energy surfaces, the masses of the atom and the associated vibrational
coupling.
In order for a vibrational mode in sample to be IR active it must be associated with change in the
dipole moment. A covalent bond can vibrate in many ways including stretching, rocking &
scissoring. The most useful bands in an IR spectrum corresponding to the stretching frequency
and those are asymmetric stretching, asymmetric stretching, scissoring, rocking, wagging &
twisting. Infra red spectroscopy useful in providing information about presence or absence of
specific functional group in the molecule, it also provide molecular finger print that can be used
when comparing sample. If the two pure samples shows the same IR spectrum it can be argued
that that they are the same compound. IR shows information about molecular fragments
specifically functional group but does not provide detail information or proof of molecular
structure or molecular formula. Therefore IR is very limited in scope and must be used in
conjugation with other technique to provide a more complete picture of the molecular structure
4.6 Nuclear magnetic resonance spectroscopy (NMR)
Nuclear magnetic resonance spectroscopy (NMR), as mentioned in name it’s about the change of
the spin state of a nuclear magnetic movement when the nucleus absorbs electromagnetic
radiation in strong magnetic field.
Basically two types of NMR spectroscopy are commonly used i.e. H NMR and C NMR. By H
NMR spectroscopy we can study three things which are follows.
1) Number of different kinds of hydrogen atoms in molecule also different environments of
hydrogen atoms in molecule.
2) The areas underneath each signal are in the same ratio as number of hydrogen atoms
causing each signal.
3) We can also predict on the splitting pattern of signal the number of neighbouring
hydrogen atom, thus spin-spin splitting help us to know molecular structure.
Theory of H-NMR spectroscopy
NMR spectroscopy is based on transition between nuclear spin states when these nuclei are
subjected to strong magnetic field. Spinning nuclei behave like a small bar magnet with a South
and North Pole. The nuclear spin have only two values associated with quantum numbers which
are represented as α and β. There is no difference between energy states of these two nuclear spin
states. When the nuclei are placed in the magnetic field the energies of two states become
unequal. There magnetic movement tends either to align with field (corresponding to α spin) or
against the field (corresponding to β spin). When nuclei are subjected to right combination of
magnetic field and electromagnetic radiation to flip its spin it is said to be in resonance. After
excitation the nuclei relax and return to their original state via several pathways and release the
absorbed energy as heat. Therefore at resonance nuclei gas continuous excitation and relaxation.
The Logic says that same energy would be required for the resonance condition of all hydrogen
nuclei in molecule if the magnetic environment is identical for all. But the nuclei however, are
not all magnetically equivalent due to three-dimensional structure of molecule which produces
different magnetic environment for each hydrogen atom. This condition results in achieving the
resonance condition requires varying amounts of energy and results spectrum containing
valuable information for determining structure of molecule.
NMR is phenomenon for limited number of atoms which have isotopes with either odd atomic
number or odd atomic mass number.
The 1H NMR spectrum
To know the spectrum of other compounds some standard has been created which having known
spectrum. So in HNMR spectroscopy Tetramethyl silane (TMS) acts as internal standard. To
know this position small quantity of TMS was directly added to the sample whose spectrum is to
be measured. TMS, therefore, acts as internal standard. The zero hertz line also exactly set to 60
MHz at the right hand side of spectral paper. The differences in positions of chemical shifts are
measured between TMS and the compound under observation. Before running the sample
absorption of TMS protons is set at zero. The protons which absorbs to left side of TMS are
downfield or deshielded protons and those which absorbs on right side are upfield or shielded
protons. Most of the protons in organic compound absorbs to the left i.e. downfield to TMS. The
distance between ɠ values from TMS to each signal is known as chemical shift.
13
CNMR Spectroscopy
By 13CNMR spectroscopy following information has been given.
13
1) the common range for energy absorption C is wide δ 0-200 relative to TMS thus
overlapping of peaks in this case is less hence we can easily interpret 13C NMR spectra.
 13 13
2) Only 1.1% carbon in compound is C so C-13C coupling is negligible and thus is not
13
observed. Therefore in C NMR spectrum each magnetically non equivalent carbon gives a
single unspilt peak
13
3) The areas under peaks in C NMR are not necessarily proportional to the number
carbons giving rise to the signal, therefore one dose not consider the area ratios.
13
C NMR Spectrum
An advantage of low abundances 13C is the absence of carbon-carbon coupling.
If two adjacent carbons are magnetically non-equivalent they can split each other. Coupling can
occur only if two 13C isotopes come next to each other but due to low abundance this situation
has very low possibility.
Most of the 13C nuclei are surrounded by 12C nuclei, which having no spin, do not gives to
spin-spin splitting, consequently 13C NMR spectra appreciably simplified, reducing problem of
their analysis to a determination of the coupling patterns to any attached hydrogen
Moreover the effects of substituent on 13C shifts are not confined to the nearest atom as is so in
proton chemical shift, but the effect of substituent, two, three and four bonds from the carbon
atom whose chemical shift under study must be evaluated .
4.7 : Thermal Analysis:
It is branch of material science where properties of material are studied against change in the
temperature. Various methods are commonly used where these are distinguished from one
another by the property which is measured. Some of the following analysis technique are as
follows,
• Differential scanning calorimetry (DSC) : Heat flow changes verses temperature or time
• Differential thermal analysis (DTA) : Temperature differences verses temperature or
time.
• Dielectric thermal analysis (DEA) : Dielectric permittivity and loss factor
• Thermogravimetric analysis (TGA) : Mass change verses temperature or time
• Thermo mechanical analysis (TMA) : Dimension changes verses temperature or time
Simultaneous determination of thermo gravimetric analysis ( TGA) and Differential
scanning calorimetry (DSC) :
Simultaneous thermal analysis refers to the simultaneous application of thermo gravimetric
analysis ( TGA) and Differential scanning calorimetry (DSC).to one and the same sample in a
single instrument. For theses analysis the test conditions like same atmosphere, gas flow rate,
vapor pressure of the sample, heating rate sensor, thermal contact to the sample crucible,
radiation effect etc are perfectly identical for the DSC & TGA signals. The information gathered
can even be enhanced by coupling the simultaneous thermal analysis (STA) instrument to an
evolved gas analyses like FTIR or mass spectrometry (MS)
Other less common methods measure the light or sound emission from a sample or the
mechanical relaxation in a stressed specimen or the electric discharge from a dielectric material.
The essence of all these technique is that the sample response is recorded function of time and
temperature.
It is useful to control temperature in a predetermined way either by continuous decrease or
increase in temperature at a constant linear cooling or heating rate or by carrying out a series of
determination at different temperature or stepwise isothermal measurement. More advance
temperature profile have been developed which use an oscillating usually square or sine wave
heating rate modulated temperature thermal analysis. Modify the heating rate in response to
changes in the system property like sample controlled thermal analysis.
Thermogravimetric analysis test method capable of measuring the mass evolution of a milligram
scale sample. Gas atmosphere is well defined at all time during the experiment. The atmospheric
temperature is well defined and follow a predefined programme. In TGA analysis data is
collected from mass of sample with respect to time and temperature. Heterogeneous reaction /
thermal degradation kinetics, temperature range of pyrolysis like properties / properties are
determined from the data.
In TGA analysis micro thermo balance measure any change in the mass of the sample, whether
due to adsorption of oxygen, thermal degradation, oxidation or other heterogeneous reaction
Differential scanning calorimetry analysis test method capable of measuring the heat flow rate to
a milligram scale sample also gas atmosphere is well defined at all time during all over the
experiment. As like TGA analysis the atmospheric temperature is well defined and follows a
predefined programme. In DSC analysis data is collected from heat flow to sample with respect
to time and temperature. Properties like heat capacity, enthalpy of reaction/ thermal degradation,
Enthalpy of melting / fusion and glass transition temperature has determined from data.
Heat Flux DSC
Th ≠ Tsm ≠ Ts
R ≠ R’ ≠ O
Δ T = T rm – T sm = R (dT/dt) ( Cs – Cr )
Power compensation DSC
Power is varied such that :
T sm = T rm – T h
R=0
Δ (dq/dt) = (dT/dt) ( C s – C r )
Simultaneous thermal analyser incorporates TGA and DSC to measure mass change and heat
flow rate simultaneously.
Operational Procedure :
• Make sure sample and reference crucible are perfectly clean prior to test .
• For heat capacity determination make sure that orientation of sample and reference
crucibles are consistent all replicate tests.
• Make sure the crucible material will not react or interfere with the sample material and
vice versa.
• Always build in isothermal period prior to linear heating to allow the sample to reach
equilibrium with the furnace condition.
In TGA & DSC analysis conduct baseline experiment with empty sample a crucible along a pre
defined temperature program in a well defined gas atmosphere. Prepare sample crucible by
evenly packing sample material into crucible and measure mass of entire crucible. Conduct
experiment with sample along the same temperature program in the same gas atmosphere as in
the baseline experiment. Allow furnace to cool and clean the sample crucible. Temperature,
Heating rate and sample are considered in simultaneous analysis.
Data Analysis :
TGA analysis :
A general homogenous reaction is of the form :
A --- B+C
The rate of the reaction is assumed to be the product of a rate constant k and a function of conc.
of a reactant & product where k is given by,
K = AT m e –E/RT
A similar analysis can be applied to heterogeneous reaction :
A (s) --- B (s) + C (g)
Concentration does not hold the same meaning with heterogeneous reaction and degree of
reaction or conversion is used :
α = ( m o – m) / ( m o – m f )
For constant heating rate measurement ( Φ = dT/ dt )
dα/dT = (dα/dt) (dt/dT) = (1/Φ) (dα/dt)
dα/dT = (1/Φ) (dα/dt) = (A/Φ) e –E/RT g (α)
f (α) = kt g(α) = (1/k) (dα/dt)
many method to determine A, E and function al form of f(α) or g(α)
DSC analysis :
Thermal events in the sample manifest as deviation from the baseline, most likely as exothermic
or endothermic peaks.
Q = Δ h r – c p dT / dt
Specific heat capacity is determined by comparing the heat flow rate curves yielded from the
sample and a standard references:
Displacement = B Φ Cp
TGA and DSC analysis are both sensitive to the heating rate and sample masses and either can
result in shift in the temperature.
Limitation of TGA and DSC analysis :
TGA analysis only provide meaningful data when a change in mass occurs. Some time liquid
can be measured but this is generally very difficult to do for the liquid sample. For testing very
small weight are used so non homogeneous material generally can not be analysed.
DSC analysis has very sensitive o any change in the sample or crucible. At the time of analysis
requires very good thermal contact with bottom of sample crucible. Heating rate is very sensitive
factor in DSC analysis.