Department of Physics

School of Physical Sciences

Mizoram University, Aizawl

SIX-MONTHLY PROGRESS REPORT OF Ph.D. WORK DONE

(July 2022- December 2022)

Title of the PhD thesis : Study Of Petroleum Fuel Quality In Mizoram And The Air
Pollutant Emission Of Motor Vehicles

Name of Candidate : Josef Lalhruaitluanga

Registration No. : MZU/Ph.D./1954 of 2021

Name of Supervisor : Dr. Hranghmingthanga

Signature of the Candidate

1.OBJECTIVES

 Estimation and evaluation of Petroleum fuel adulteration by density, distillation and FTIR
spectroscopy.
 Estimation of emission air pollution from combustion of Petroleum fuel by i3sys gas
analyser and its Chemometric analysis.

2. INTRODUCTION
Petroleum is one of the most commonly used fuel that is everyday by billions of people
around the world. The distillation curve of a Petroleum sample (volume vs temperature curve)
can provide various information about the said sample which can affect the starting, warm up
and tendancy to vapor lock at high temperature. It is also important to consider the volatility of
the fuel as it affects the rate of evaporation. Studies have shown that multivariate analysis (PCA,
PLSD-A) of the distillation data of Petroleum samples can yield a very important result in the
classification of different Petroleum samples. The Principal
Component Analysis (PCA) is the core of the different multivariate techniques that are to be
used in the analysis of the samples collected. Since the distillation data is a multivariate data.
Principal Component Analysis (PCA) takes information carried by the original variable and
projects them onto a smaller number of latent variables called Principal Components (PCs). Each
PC explains a certain amount of the total information contained in the original date and the first
PC (or PC1) contains the greatest source of information in the data set. Each subsequent PC
contains, in order, less information than the previous one. By plotting PCs, important sample and
variable interrelationships can be revealed, leading to the interpretation of certain, sample
groupings, similarities or differences.
3.METHODOLOGY

3.1. Sample acquisition

Different Petroleum samples, each of approximately 100ml are collected at random

intervals at different filling stations which is to be subjected to distillation (ASTM D86), density
measurement (ASTM D1298-b), FTIR analysis and Chemometric analysis (using
Unscramblerx).

3.2 Density measurement

Before undergoing any type of other experiment, the density of the Petroleum samples
are first measured using a Hydrometer (ASTM D1298-b). According the transport policy of India
(www.transportpolicy.net), the density of the Petroleum fuels distributed in India should be
around 720–775 kg/m3.

Fig: Density measurement using Hydrometer.

3.3. Distillation (ASTM D86)

The American Standard Method D86 (ASTM D86) covers the atmospheric distillation of
products using a laboratory batch distillation unit to determine quantitatively the boiling range
characteristics of light and middle distillates, automative spark-ignition engine fuels, aviation
gasolines, aviation turbine fuels, 1-D and 2-D regular and low sulfur diesel fuels, special
Petroleum spirits, napthas, white spirits, kerosenes, and Grade 1 and Grade 2 fuels.

The first step involves filling a 100ml cylindrical flask with the samples. The measured
sample is then filled into a distilling flask. A boiling chip is dropped into the flask to prevent
violent flash boiling. The apparatus of the experimental setup involves a distillation chamber, a
thermometer, the distilling flask, a measuring cylinder, a bath, bath cover, a burner, and a
blotting paper. An ice block is filled in the bath to help in the condensation of the water vapour
that will be formed from the distilling flask.

Fig: Experimental Setup of Distillation Chamber

 The table below also shows the conditions for a well set up distillation procedure.

Fig: Table for conditions during Distillation

The temperature of the burner is adjusted in such a way that the observed recordings
coincides with the above given table. The temperature at which the first condensed liquid drops
into the cylindrical flask is called the Initial boiling temperature (IBP) and is recorded. After the
first drop, the cylindrical flask is alligned to the end tube of the bath in such a way that the liquid
flows into the cylindrical flask without any dropping or spillage. The end of the cylindrical flask
is also covered with a blotting paper in such a way that none of the condensed liquid can
evaporate back. After the Initial boiling point (IBP) is recorded, the corresponding values
oftemperature and volume are recorded with increments as 10ml, 15ml, 20ml, 25ml, 30ml, 40ml,
45ml, 50ml, 55ml, 60ml, 65 ml, 70ml, 75ml, 80ml, 85ml, 90ml, 95ml upto a point where the
Final boiling temperature (FBP) is reached. The recorded volume-temperature data is then
imported into an excel spreadsheet so that Principal Component Analysis (PCA) may be done.
Every time a distillation experiment is carried out, a small quantity of the sample is stored
in a little container and kept in a refrigerator which will be later subjected to Fourier Transform
Infrared Spectroscopy (FTIR).
3.4. Chemometric analysis
As mentioned above, the volume-temperature matrix is arranged in an excel spreadsheet
and the data is sideloaded into the Chemometric tool UnscramblerX. The data is arranged in such
a way that Principal Component Analysis (PCA) will be carried out. (Other analysis including
Partial Least Squares Regression (PLS-R), Linear Discriminent Analysis (LDA), Partial Least
Squares Discriminant Analysis (PLS-DA) and Soft Independent Modelling by Class Analogy
(SIMCA) will also be done. However since the data is still insufficient for such analysis, these
methods are not yet mentioned.)
4.RESULTS AND DISCUSSION

4.1 Density
The measured density of the obtained samples is similar to the required density published
by the Transport Policy of India. The samples obtained are generally 747 kg/m 3 which reveals
that all the samples are obtained are usable for vehicle fuels in one way or the other.

4.2 Graph of Distillation data

The figure below shows the graph of the obtained distillation. The X-axis represents the
Temperature while the Y-axis represents the Volume.

Fig:
Volume-Temperature graph of 22 different Petroleum samples.
4.3 Principal Component Analysis

It is very hard to exploit valuable information from the V-T graph alone. Therefore we
use the UnscramblerX to unscramble the valuable information from the distillation by using said
method of Principle Component Analysis (PCA).

The Principal Component Analysis assimilates the information into variation. When a
measured variable exhibits large systematic variation, this is attributed to information. If a
variable exhibit very little variation, it can be concluded that there is no information associated
with it and it may be contributing to noise. The PCA draws the best fitted line from the different
points on the graph. The best fitted line is measured by the directions in space along which the
distance between the data points is the largest. The best fitted line thus formed is called the first
Principal Component or PC1. We draw a line orthogonal to PC1 which is called PC2. This
process can continue until as many PCs have been computed as there are variables in the data
table. The new set of axes can be described as a new window for looking into the greatest
sources of information contained in the data. This is represented in the figure below as scores
plot.

Fig: Scores plot of PC1 vs PC2 for different Petroleum samples

 When adding the percentage of explained variance between PC1 vs PC2, it results to
86%, which means that the Scores plot of PC1 vs PC2 is a very reliable plot, as scores plot above
70% are a very good representation of the data.

The samples have been grouped by colour codes representing the three Petroleum
supplying companies available in India. The scores plot shows that the samples that are clustered
together share similar qualities and those lying opposite each other exhibit certain differences.
The ellipse shown is known as the Hotelling T2 ellipse. The Hotelling T2 ellipse shows the outlier
samples which in this case is the Zmb sample which is taken from the Bharat Petroleum Filling
station at Zemabawk, Aizawl.

One interesting case which arises from this data is that the obtained sample from said
filling station has been recorded to be of bad quality by the Highland Chevrolet company as it
has caused a stall in the engine of their newly sold car.

Fig: Image of impure Petroleum sample collected.

No conclusion on the cause of this impurity has been found yet. However the sample is
stored in a secured container for further analysis.
CONCLUSIONS

The experiments done has shown that Chemometric analysis of the distillation data of
Petroleum samples can result in the classification and identification of impurities in Petroleum
fuels. With Principal Component Analysis being the building block of all the other analysis
techniques to be involved. It is proved that the other multivariate analysis method i.e, Partial
Least Squares Regression (PLS-R), Linear Discriminant Analysis (LDA), Partial Least Squares
Discriminant Analysis (PLS-DA) and Soft Independent Modelling by Class Analogy (SIMCA)
can very well be used for the classification and prediction of certain impurities when coupled
with distillation as well as Fourier Transform Infrared Spectroscopy (FTIR). As mentioned
before, more samples are required for such analysis’. Therefore further and broader acquisition is
the goal for further progress.

REFERENCES

ASTM D6277-01 (2017), Standard Test Method for Determination of Benzene in Spark-Ignition

Engine Fuels Using Mid Infrared Spectroscopy, ASTM, Vol: 05.03, DOI: 10.1520/D6277-

07R17.

ASTM D5845-01 (2016), Standard Test Method for Determination of MTBE, ETBE, TAME,

DIPE, Methanol, Ethanol and tert-Butanol in Gasoline by Infrared Spectroscopy, ASTM,

Vol: 05.02, DOI: 10.1520/D5845-01R16.

ASTM D5986 (2015), Standard Test Method for Determination of Oxygenates, Benzene,

Toluene,C8-C12 Aromatics and Total Aromatics in Finished Gasoline/ Fourier Transform

Infrared Spectroscopy, Vol: 05.02, ASTM, DOI:10.1520/D5986-96R15.

ASTM E1655-17(2017), Standard Practices for Infrared Multivariate Analysis, ASTM, Vol:

03.06, DOI: 10.1520/E1655-17.

Asfaha Iob*, Rick Buenafe and Nurredin M. Abbas (1998), Determination of oxygenates in

gasoline by FTIR, Fuel Vol.77 : No.15, pp. 1861-1864.

Calvert J.G., Heywood J.B., Sawyer. R.F., and Seinfeild, J.H. (1993), Achieving Acceptable Air

Quality: Some Reflections on Controlling Vehicle Emission, Science, 261: 37-45.

Central pollution control Board (CPCB) (2010), Status of the vehicular pollution control

programme in India, PROBES, 136.

David M. Haaland, Edward V. Thomas (1988), Partial least-squares methods for spectral

analyses. 1. Relation to other quantitative calibration methods and the extraction of

qualitative information, Anal. Chem., 60 (11): pp 1193–1202. DOI: 10.1021/ac00162a020.

Gisele Mendes, Paulo J.S. Barbeira (2013), Detection and quantification of adulterants in

gasoline using distillation curves and multivariate methods, Fuel, 112: 163–171.

Honorato, F.A., Neto, B.B., Pimental, M.F., Stragevitch, L., Galvao, R.K.H., (2008), Using

principal component analysis to find the best calibration settings for simultaneous

spectroscopic determination of several gasoline properties, Fuel, 87: 3706-3709.

Mohammad A. Al-Ghouti, Yahya S. Al-Degs, Mohammad Amer (2008), Determination of motor

gasoline adulteration using FTIR spectroscopy and multivariate calibration, Talanta, 76:

1105–1112.

Mohsen Forouzangohar, Rai S. Kookana, Sean T. Forrester, Ronald J. Smernik and David J.

Chittleborough (2008), Mid infrared Spectroscopy and Chemometrics to Predict Diuron

Sorption Coefficients in Soils, Environ. Sci. Technol, 42 (9), pp 3283–3288, DOI:

10.1021/es702750d.

Paulo Leonardo S.G. Teixeira, Fa´bio S. Oliveira, Hilda C. dos Santos d, W.L. Cordeiro a, Selmo

Q. Almeida (2008), Multivariate calibration in Fourier transforms infrared spectrometry as

a tool to detect adulterations in Brazilian gasoline, Fuel, 87 (3): 346–352.

Pereira, R.C.C., Skrobot, V.L., Castro, E.V.R., Fortes, I.C.P., and Pasa, V.M.D., (2006),

Determination of Gasoline Adulteration by Principal Components analysis-Linear

Discriminant Analysis Applied to FTIR Spectra, Energy and Fuels, 20: 1097-1102.
 REPORT OF THE DEPARTMENTAL RESEARCH COMMITTEE

i) No. of publication in this semester :

ii) No. of Conferences/Workshops attended :

iii) Attendance (%) of the Scholar :

iv) Total No. of Publications in Journals and Conferences attended since registered for
Ph.D.

 Publications in Journals :

 Publication in Conferences :

Comments of the Supervisor

Signature of the Supervisor Signature of DRC Chairman

Performance of the Scholar (based on assessment by the DRC members)

1. Satisfactory

2. Fair

3. Average

4. Below Average