PROJECT REPORT ON

PREPARATION AND CHARACTERIZATION OF

BIOSILICA (SIO2) FROM RICE HUSK ASH

&
RHA (SIO2) SILICA SUPPORTED BO3H3 A HIGHLY ACTIVE
SOLVENT FREE AND RECYCLABLE CATALYST TO

3,4 DIHYDROPYRIMDIN 2-(1H) ONES ( THIONES) SYNTHESIS.

MASTER OF SCIENCE IN

ORGANIC CHEMISTRY
SUBMITTED BY

PALLAVI MURLIDHAR MALI

Roll Number: 2406

UNDER THE GUIDANCE OF

Miss. PRAJAKTA AWASKAR

Department of Chemistry

(2022-2023)

1
 ACKNOWLEDGMENT

I would like to convey my sincere gratitude to my project

supervisor, Miss. PRAJAKTA AWASKAR for his invaluable
suggestion, constructive criticism, motivation and guidance
for carrying out related experiment and for preparing the
associated reports and presentation.

His encouragement towards the current topic helped me a lot

in this project work which also created an area of interest for
my professional career ahead.

I am also thankful to Miss. komal Tivarekar, Miss.Vedangi

Thakur for giving me their support and encouragement as
well as Lab Assistant’s Mr. H. K. Awaskar, Mr. Akash Jadhav
, Mr. Sarvesh Thakur

I own my thankfulness to Dr.V.D. Bhabad M.sc part-2 co-

ordinator for providing necessary facilities in the departmen t.

M.Sc. II YEAR

DATE :
PLACE: PEN B.N COLLEGE PEN

ORGANIC CHEMISTY

2
 Pen Education Society'sBhausaheb Nene Arts,
Commerce and Science College, Pen, Dist.- Raigad,
Maharashtra, Pin code: 402107, India.
(Permanently Affiliated to MumbaiUniversity)

CERTIFICATE

This is to certify that the report on PREPARATION AND

CHARCTIZATION BIOSILICA (SIO2) FROM RICE HUSK ASH
Submitted by Miss .PALLAVI MURLIDHAR MALI in partial fulfillment of
the requirements for the award of degree of MASTER OF SCIENCE IN
CHEMISTRY BHAUSAHEB NENE A.S.C COLLEGE PEN is an authentic
work carried out by him under my supervision and guidance.

Miss. PRAJKTA AWASKAR DR. V.D. BHABHAD

(GUIDENCE TEACHER) (CO-ORDINATOR)

DR. S. D. DHARAP
(PRINCIPAL) EXTERNAL EXAMINAR

DATE: / /

PALCE: PEN

3
 DECLARATION

I, hereby declare that the present work in the form Of minor research
project report entitled PREPRATION AND CHARACTERIZATIO( Sio2)
FROM RICE HUSK ASH Is an original Work carried out by me under the
guidance of Miss. Prajakta Awaskar , Lecturer in organic chemistry,
Department Of Chemistry PES Bahusaheb Nene Art’s , Science And
Commerce College Pen. Tal. Raigad, Dist. Raigad, 402107 is not
Previously submitted to this institute or any other University for the
award of any degree associate ship Or any other similar title.

DATE :-

PLACE :- PEN

RESEARCH STUDENT

(MISS . PALLAVI MURLIDHAR MALI )

( M.Sc.- ORGANIC CHEMISTRY )

4
 CONTENT

SR. TABLE OF CONTENT PEG.

CHAPTER NO No
1 Abstract 6
2 Introduction 7
3 Literature Review 8
4 Objective 9
5 Silica in Rice Husk and overviews 10
6 Property And composition of Rice Husk 11
Ash
1 7 Preparation and Characterization of 12
Biosilica from Rice Husk Ash
8 Methodology 13
9 Experimental Procedures 14
10 Rice Husk Ash Biosilica Uses 20
2 11 Gravimetric Method Determined total 21
silica
12 Methodology 22
13 Experimental Procedures 24
14 Results 25
3 15 Rice Husk Ash Biosilica (Sio2) supported 28
Bo3H3 A Highly active solvent free and
Recyclable catalyst to
Dihydropyrimdin 2(1H) ones (Thiones)
synthesis
16 Methodology 29
17 Experimental Procedures 31
18 Observation calculation 33
19 Thin Layer chromatography 36
20 Results 35
22 Physical and chemical properties 38
22 Spectral data 39
23 Material safety data sheet 45
24 Conclusion 46
25 Bibliography 47

5
 ABSTRACT
Rice is a one of the major crops grown through the world.Once the
paddy is separated from the rice grain, the kernel (hull) is removed from
the rest of the rice grains. This constitute about , one third of the total mass
of grains , commonly termed as ' Rice Husk' or ‘Rice Hull ' .Rice husk is an
agricultural residue abundantly available in rice producing countries. The
annual rice husk is produced in India amounts genrally approximately 12
million tones . Rice husk is generally not recommended as cattle feed since
it cellulose and other sugar content are low . Furfural and rice bran oil are
extracted from rice husk. Industries use rice husk as a fuel in boilers and
for power generation. Among the different types of biomass used for
gasification, rice husk has a high Ash varying from 18-20% . Silica is the
major constituent of rice husk ash varying from 85-95% . with such a large
Ash content silica content in the rice husk it becomes economical to extract
silica from the Ash , which has wide market and also takes care of the Ash
disposal.
In this project an attempt is made to introduce a simple process
to manufacture precipitated silica from this waste rice husk. It solves the
disposal problem of rice husk as well as valuable product is manufactured
from it. Experimental data shows better performance as well as easy
industrial implementation of the process.

Keywords:- Extraction, Silica, Silica gel preparation, 1N HCL,1N NaOH,

Concentrated H2S04, Rice husk, Filter press.

6
 INTRODUCTION

Silica (SiO2) is one of the valuable inorganic multipurpose

chemical compounds. It can exist in gel, Crystalline and amorphous forms.
It is the most abandon material on the earth‟s crust. However,
manufacture of Pure silica is energy intensive. A variety of industrial
process, involving conventional raw materials require high Furnace
temperatures (more than 700 degree C). In our Project, a simple chemical
process is described which Uses a non-conventional raw material rice husk
ash for extraction of silica. Rice Husk ash is one of the most Silica rich raw
materials containing about 90-98% silica (after complete combustion)
among the family of other Agro-wastes. Rice husk is a popular boiler fuel
and the ash generated usually creates disposal problems. The Chemical
process discussed not only provides a solution for waste disposal but also
recovers a valuable silica Product, together with certain useful associate
recoveries. The other associate recovery is sodium sulphate. Effluent wash
water obtained after washing precipitated silica (wet impure silica)
contains sodium sulphate. By Evaporation of water in multiple effect
evaporators, followed by crystallization, filtration and drying, crystals of
Sodium sulphate are obtained. The residue ash in sodium silica
production can be utilized for making good Quality bricks. Retained
sodium silicate in residue ash acts as a binder and with incorporation of
suitable Ingredients high quality bricks can be manufactured.From rough
estimation the production of paddy in the Country about twenty five
million tons of rice husk is obtained from rice mills. This is usually burnt
resulting in Mounts of ash in and around the mills, causing major health
problem and pollution. Using rice husk as the raw Material two million
tons of pure high grade silica can be produced to meet the high demand
of various Industries that are using it. The main states with large number
of rice mills are Andhra Pradesh, Tamil Nadu, Karnataka, and Kerala
Maharashtra etc. The conventional process of manufacturing silica in Rice
Husk Ash.

7
 LITERATURE REVIEW
Crystalline Silica is a basic segments of material which have a plenitude of
employment in industry and are a fundamental part in numerous things
utilities as a part of our regular Daly existence .It is difficult to envision
houses without block ,mortar or windows ,autos without mortars or
windscreen, existence without streets or other transport framework and
ordinary things made of glass or stoneware . Hence production of silica in
large amounts economically can be proved beneficial for all the industrial
that uses silica for various purposes.

Rice husk (RH) is a side effects from rice factories and is a standard
amongst the most generally accessible horticulture deposit on the ground
that rice is an essential wellspring of nourishment for billions of
individuals, According to the sources, the India’s rice generation came to
a record high of 104.32 millions tons in 2021-2022 harvest years ( June –
July) . The RH has a hard surface , little mass thickness and high
amorphous silica content ( the most astounding among the Gramineae
plant) .more than 90% pure silica can be extracted from rice husk
cantaning approximately 60% silica.

Thermal Treatment of burning of rice husk is the primary method used to

extract silica via several chemical treatment silica can be extracted in
various forms like some research are done to extract silica in gel from
either as aerogel or xerogels using the gelatinous process or in it
amorphous from .

According to the past work done, initially the produce by thermally was
pretreated with hydrochloric acid to remove the impurities , then boiled ,
filtered and brought to a neutral pH .As a Silica is a known to be dissolved
in an alkaline solution of pH decreased 10 , thus on alkali NaOH is added
neutralize mass and then precipitated or titrated with acid again.

8
 OBJECTIVE

• Extraction of silica from rice husk .

• To study effect of washing RHA and treatment with HCl to obtain

silica gel.

• To study the application of silica.

• Determine the procedure of maximum yield of silica .

• Greenary extraction of silica.

9
RICE HUSK

• Rice husk are the hard protecting covering of grain of rice.

• It is a by- product of rice production.
• It also contains 15 to 28 et % of silica.
• The high content of silica in RH present opportunities for the
presentation of value – added silica based materials.

RICE HUSK ASH

• They are obtained from burning protective outer cover of rice husk.
the RHA can be found as natural materials, by- product or
industrial waste.
• RHA contain incompletely burned organic components and a
mixture of crystalline and amorphous silica .

10
 SILICA IN RICE HUSK AND OVERVIEW
The plants belonging to graminae family, namely, rice, wheat, barley, oats,
maize are the main sources Of biogenic the roots as dissolved monosilicic
acid, Si(OH)4& precipitated within around cells as hydrated Deposits.(4,6)
The monosilicic and moves by evaporation of polymerized to force a
cellulose silica membrane. It Has been formal that silica is highly
concentrated in the inner and outermost surfaces of the epidermal twice.
As A result, rice husks are relatively friable, brittle and abrasive. The term
white ash refers to residue obtained from Complete combustion of rice
husk. It if chiefly composed of silica (86-97%). This silica has following
structure, In which the atom is bonded to four surrounding O atoms by Si-
O-Si bonds. Above fig. shows that each Si atom Is surrounded by four O
atoms and O atom serves as a neighbor to two Si atoms there by leading to
a Condensation product with a formula SiO2.Silica occurs in nature mainly
in three crystalline fours namely quartz (hexagonal), cristobolite (white)
and tridymite (hexagonal) and also in amorphous form like opal and silica
in Rice husk being of bioquenic origin is essentially of amorphous nature.
But it can be connected into any of above Three crystalline forms by heat
treatment at different temperature.

11
PROPERTY AND COMPOSITION OF RICE HUSK
ASH

PROPERTIES OF RAW MATERIAL

Molecular weight 60.06

Nature Amorphous powder
Odour Odorless
Melting point 1740°C
Boiling point 2230°C
Specific gravity 2.650 at 20°C
Partical size 1-10um

COMPOSITION OF RICE HUSK ASH

Elements Percentage

Carbon 37.5

Hydrogen 5.4
Oxygen 36.6

Nitrogen 0.5
Ash 20.0

12
PREPRATION AND CHARACTERIZATION OF BIOSILICA
(SIO2) FROM RICE HUSK ASH

METHODOLOGY

ROW MATERIALS / CHEMICAL :-

• Rice Husk
• Sodium Hydroxide (1N NaOH)
• Hydrochloric acid (1N HCL)
• Con.Sulfuric acid (con.H2So4)

REQUIRED EQUIPMENT :-
• Oven.
• 500ml beaker
• Glass rod
• Thermometer
• Filter paper
• Whatman filter paper
• pH meter
• Burette
• Water bath
• Round bottom flask

13
 EXPERIMENTAL PROCEDURES
METHODS:-

A)General Procedure For The Preparation of Rice Husk Ash

Biosilica (Sio2) By Thermal Method.

1)RICE HUSK ASH PREPARATION :

• 100 mg of rice husk is taken as a burnt to open air.

• 100 °C is burnt off black Ash, at a temperature range between 80-
90°C with the h100 of digital temperature probe.
• Heating is continued , till white Ash is formed.

RICE HUSK RICE HUSK BURNING

RICE HUSK ASH. WHITE RICE HUSK ASH

14
 2) SODIUM SILICATE SOLUTION PREPARATION :-

• 5gm of rice husk ash is mixed with 250 mL of 1N NaOH aqueous

solution.
• The mixture is boiled for b2h at (100-110°C).
• The solution is filtered through filter paper and carbon residue are
washed out with boiling water.
• Then the filtrate and washings are stored in a re refrigerator for
further
• Usage.

SiO2 (Ash) + 2NaOH 80-90ºC Na2SiO3 + H2O

Heating with 1 N NaOH at 2 hours Sodium Silicate Solutions titrated 1N

100°C HCL Decrease pH 7

15
 3) SILICA GELPREPARATION
• 5 ml sample of prepared sodium silicates solution was taken
titration against 1N HCL with constant stirring to pH 7.
• Silica gel started to Precipitate when the pH decreased to 10.
• The silica gels formed were aged for 24 h. And distilled water 100
ml was added to gels and then the gels are broken to make slurry.
• Centrifugal at 2.500 rpm (15 min).Discard the supernatant and
repeat the washing.
• The gels were transferded into a beaker and dried at 80°C for 2 h to
produce white amorphous silica powder.
Na2SiO3 + H2SO4 80°C SiO2 + Na2SO4+H2O

o (Sodium Silicate) +(Sulphuric acid) (Silica) + (Sod. Sulphate)

Silica gel formed were aged 24 h. RHA Silica gel Dried at 80°C

RHA Biosilica Amorphous powder

16
 B)General Procedure For The Preparation of Rice
Husk Ash Biosilica (Sio2) By Conventional Method.
• 100 mg of rice husk is taken as a feed to a muffle furnace.
• 100It is burnt off, at a temperature range between 800-850ºC, with
the help of digital temp probe. Heating is continued, till white ash
is formed.
• Total time required for burning the husk is about 1.5 to 2 hrs.
• In a round bottom flask, we are adding ash and caustic soda in 1:7
ratio i.e. 25 gm of ash an175ml of NaOH (to make wet all ash by
caustic soda).
• The flask is then kept for heating on a heating mantle provide with
a temperature probe. Both the Reaction time and the temperature
for heating mantle provided with a temperature probe.
• Then sample is filtered out from any unburned, carbon impurities
by using filter press. Clear filtrate obtained is aqueous sodium
Silicate solution.
• This solution is further concentrated in the oven by keeping
temperature Range between 100 to 150ºC for 60-90min.
• The final concentrated solution is the gelatinous sodium silicate and
its quantity is measured by using Electronic weight balance.
• The concentrated solution is the gelatinous sodium silicate taken in
200ml beaker and concentrated sulfuric acid added until solution
become acidic
• Silica is precipitated from the solution , and sodium Sulphate as a
product remain at a bottom . Little quantity of water is added to
reduce to high exothermic temperature solutions is kept as it is for
half an hour to become cool.
• Solution is filtered by using filter press by giving water wash. Cake
formed is silica and dried at 80°C for 2 hours to produce white
amorphous silica powder.
Sio2 + 2NaOH 80-90ºC Na2SiO3 + H2O

Na2SiO3 + H2SO4 85ºC SiO2+ Na2SO4+ H2O

17
.

Conventional Method.

Reflux Heating with White RHA Ash

White Rice Husk Ash
+1 N NaoH at 100°c ,2 hours

At

Sodium Silicate Solutions

18
 Solution concentrated in the oven range
between 100°C for 60 min. -

Add Con H2SO4 , solution become acidic

RHA Biosilica Amorphous Powder
then silica gel is started , Dried at 80°C

19
 RICE HUSK ASH BIOSILICA USES

• Reinforcement of elastomeric product like shoe soles.

• Reinforcement of elastomeric products like shoe soles.
• Reinforcement of silicone rubber.
• Reinforcing material in tires.
• In sheathing compounds for cables.
• Constituent of adhesives in for bonding of unvulcanized rubber to
textiles or steel tire cord.
• In thermoplastics used to act as anti-blocking agents and to prevent
plate out effects in films and film Production.
• To improve mechanical properties of PVC flooring.
• As carrier silica for materials and as free flow agents for powder
formulation, particularly of Hygroscopic and adhesive substances.
• As adsorbent.
• In toothpaste to control rheological properties and as a cleansing
agent.
• Hydrophobic precipitated silica is used in mineral oil and silicone
oil antifoaming effect.
• Purification and stabilization of beer.
• Analysis of blood.
• Cosmetics.
• Food industry as an anti-caking Cosmetic
• Specially prepared silica gels from silica are used for making
thermal insulation material.
• As a dehumidifying agent for air and other gases.
• As a filtering agent to clarify of juices.
• Uses as a catylist.

20
 GRAVIMETRIC METHOD DETERMIN TOTAL SILICA
RICE HUSK ASH BIOSILICA

GRAVIMETRIC METHOD :
Principal :
Hydrochloric acid decomposes silicates and dissolved silica, forming
silicic acids that Are precipitated as partially dehydrated silica during
evaporation and baking. Ignition completes Dehydration of silica, which
is weighed and then volatilized as silicon tetrafluoride, leaving any
Impurities behind as non-volatile residue. The residue is weighed and
silica is determined as loss on Volatilization.

Apparatus :

crucibles -With covers, evaporating dishes ,250 cm-3 beaker, glass rod,
filter paper, funnel , sand bath, watch glass.

Reagents:

Hydrochloric acid ( HCL) , Sulphuric acid( H2SO4), . Perchloric acid

(HCLO4)

Procedure :

Before determining silica, test sulphuric acid and hydrochloric acid for
interfering non-roIatiIe matter by carrying out procedure given ,Use an
empty clean platinum crucible. If any Increase in weight is observed,
make a correction in the silica determinations.

21
1 ) Hydrochloric acid dehydration –
To a clear sample containing at least 10 mg of silica, add 5 ml of 1 : 1
Hydrochloric acid. Evaporate to dryness in a 200 ml platinum or acid
leached glazed porcelain dish, in Several portions if necessary, on a
waterbath or over a hot plate. Protect against contamination from
Atmospheric dust. During evaporation add a total of 15 ml of 1 : 1
hydrochloric acid in several portions, dry the dish and place it in an oven
at 110°C or over a hot plate to bake for 30 minutes.

2) First Filtration:
Add 5 ml of I : 1 hydrochloric acid, warm and add 50 ml of hot distilled
Water. While the mixture is hot, filter through an ashless medium textured
filter paper, decanting as Much liquid as possible. Wash dish and residue
with hot I : 50 hydrochloric acid and then with a Minimum volume of
distilled water until washings are chloride-free. Save all washings. Set
aside Filter paper with its residue.

3 ) Second filtration :
Evaporate filtrate and washings from the above operation to dryness in
The original platinum dish. Bake residue at 110°C in an oven or over a hot
plate for 30 minutes. Repeat steps given in 2. Use a separate filter paper
and rubber policeman to aid in transferring Residue from dish to filter.
Take special care with porcelain dishes because silica adheres to the dish.

22
4) Ignition –
Transfer the two filter papers and residues to a Covered platinum crucible
dry at 1IO’C and ignite at 1 2OO’C to constant mass. Avoid mechanical
loss Of residue when first charring and burning off paper by gradual
heating at minimum temperature. Too Rapid heating may form black
silicon carbide. Cool in desiccator, weigh and repeat of ignition and
Weighing until constant mass is attained. Record mass of crucible and
contents.

5 )Volatilization with hydrochloric acid-

Thoroughly moisten weighed residue with distilled Water. Add 4 drops of
1 : 1 sulphuric acid, followed by IO ml of hydrochloric acid, measuring the
latter In a plastic graduated cylinder. Slowly evaporate to dryness over an
air bath or hot plate in a hood And avoid loss by splattering. Ignite crucible
to constant mass at 1 2OO’C. Record mass of crucible And contents.

6) Perchloric acid dehydration –

Follow procedure as given in5.1 until all but 50 ml of Sample has been
evaporated. Add 5 ml of perchloric acid and evaporate until dense white
fumes appear. Continue dehydration for 10 minutes Cool, add 5 ml of 1 I
hydrochloric acid and 50 ml of hot distilled Water. Bring to boil and filter
through an ashless quantitative filter paper. Wash thoroughly ten times
With hot distilled water and proceed as directed in step 5.4 and step 5 For
many purposes, the silica Precipitate is often sufficiently pure for the
purpose intended and may be weighed direct, omitting Hydrochloric acid

23
 GRAVIMETRIC ANALYSIS

ALIQUOT SOLUTION
HYDROCHLORIC ACID DEHYDRATIO
DEHYDRATIO

IGNITION BLACK SILICON CARBIDE

1 :-Empty weight of crucibl

gravimetric analysis pure silica

2 PERCHLORIC
:-InsolubleACID DEHYDRATIO
Residue

24
 RESULTS

1: Empty weight of crucible = 10.582 gm

2: Insoluble Residue = 1.458 gm

INSOLUBLE MASS OF MASS OF

RESIDUE CRUCIBLE CRUCIBLE
CONTENT W1 CONTENT W2

1.458 1.458 1.458

10.585 4.991 3.684
9.124 3.533 2.226

3:- insoluble Residue :- 9.124 gm .

Pure silica (sio2) = W1×1000 ÷V

=3.533×1000÷50

W1:- 70.66 gm

Pure silica (sio2) =W1×1000 ÷ V

=2.226×1000÷5

W2 = 44.52gm

25
RICE HUSK ASH BIOSILICA (SIO2) SUPPORTED BO3H3 A

HIGHLY ACTIVE SOLVENT FREE AND RECYCABLE

CATALYST TO

3,4 DIHYDROPYRIMDIN 2(1H) ONES( THIONES) SYNTHESIS

Dihydropyrimidin-2(1H)ones(thiones) (DHPM) are obtained in excellent

To good yield by employing green catalyst under sol-Vent-free condition.
The condensation of substituted benzaldehyde , ethyl acetoacetate
urea/thiourea in the Presence of green catalyst after 1 h of stirring at 50°C
Resulted in DHPM. The reaction of substituted presence of DHPM Here,
we have used Lewis acid catalyst RHA–SiO2–BO3H3 derived from the
agro-waste of rice husk, a heteroge-neous catalyst for important organic
scaffold synthesis The reaction required low catalyst loading (1.2 mg) to
achieve a target product under solvent-free Condition. A series of other
derivatives of heterogeneous catalysts synthesized are RHA–SiO2, RHA–
SiO2–BO3H3. We examined their Catalytic activity in the synthesis of
DHPM a. Only the reaction catalysed By RHA–SiO2–BO3H3 gave excellent
yield of the Product. The final isolated pure product has been
fullyCharacterized by various spectroscopic methods and Confirmed.

Keywords: Agro-waste, dihydropyrimidin-2(1H)ones(thiones),

heterogeneous catalyst, rice husk.

26
 RHA–SiO2-derived catalysts for the synthesis of 3,4
Dihydropyrimidin-2(1H)ones (thiones)

Reaction

Mechanism

27
28
 3,4 DIHYDROPYRIMDIN 2(1H) ONES( THIONES)
SYNTHESIS

METHODOLOGY

REQUIRMENTS :

A)CHEMICALS :-

• Benzaldehyde
• Ethyl Acetoacetate
• Thiourea
• RHA Biosilica
• Boric acid

B) APPARATUS:-

• 50 cm -3 borosil becker
• Glass rod
• watch glass
• Buchner funnel
• Whatman filter paper

29
 EXPERIMENTAL PROCEDURE

METHODS

A) Procedure for the Synthesis of – 3,4 Dihydropyrimidin 2

(1H) Ones/Thiones. By microwave Method.

• In a 50 cm3 borosil becker mixture of benzaldehyde (2.mmol),Ethyl

acetoacetate (2 mmol), urea/thiourea (3 gm) and RHA Silica (1
gm)Boric acid (1 gm), was stirred at 50◦C under solvent free
condition.
• A Clear solution will be obtained , allow the Reaction mass to cool.
• Add few pieces of ice ,A solid product will be obtained .
• Filter the product and wash with cold water .
• Recrystallized by aqueous ethanol
• Fined out weight and melting point of the Product The progress Of
reactions was monitored by TLC (ethyl acetate/n- Hexane .

30
 THIN LAYER CHROMATOGRAPHY (TLC)

Thin layer chromatography(TLC) is a chromatographic technique used to

Separate non-volatile mixtures, verify a substances identify or monitor the
progress Of a reaction.The two solvents used in this experiment of thin
layer chromatography are n- hexane and Ethyl acetoacetate.

Solvent system : 8.2( n- Hexane : Ethyl acetate)

RF value : Distance traveled by solute / Distance traveled by Solvent

= 4.2÷4.5
= 0.96

31
 OBSERVATION AND CALCULATION

Observation:

1: weight of crude product :- 3.184 gm

2: weight of dry purified product : 2.122 gm

Calculation:
1: Theoretical tiled:

106.12 gm of Benzaldehyde ,260 gm of Dihydropyrimdin -2 (1H) thiones.

2 gm of Benzaldehyde = 260×2 ÷ 106.12
= 4.900gm
2: Percentage Yield :

% = Practical Yield ÷ Theoretical Yield×100

% = 2.122 ÷ 4.900×100
= 43.30 %

Melting point: 202°C

32
 B)General Procedure for the synthesis
of3,4Dihydropyrimidin-2(1H) Ones/Thiones. By Thermal
stirring Method.

• In a 50 cm3 borosil becker mixture of benzaldehyde (2.mmol),Ethyl

acetoacetate (2 mmol), urea/thiourea (3 gm) and RHA Silica (1
gm)Boric acid (1 gm), In microwave oven for 50 -55°C solvent free
conditions.

• A Clear solution will be obtained , allow the Reaction mass to cool.

• Add few pieces of ice ,A solid product will be obtained .
• Filter the product and wash with cold water .
• Recrystallized by aqueous ethanol. Fined out weight and melting
point of the Product
• The progress Of reactions was monitored by TLC (ethyl acetate/n-
hexane).

33
 THIN LAYER CHROMATOGRAPHY (TLC)

Thin layer chromatography(TLC) is a chromatographic technique used to

Separate non-volatile mixtures, verify a substances identify or monitor the
progress Of a reaction.The two solvents used in this experiment of thin
layer chromatography are n- hexane and Ethyl acetate.

Solvent system : 8:2 ( n- Hexane : Ethyl acetate)

RF Value = Distance traveled by solute ÷ Distance traveled by Solvent

= 4.2 ÷ 4.5
= 0.93

34
 OBSERVATION AND CALCULATION

Observation:
1: weight of crude product :-0.820 gm
2: weight of dry purified product. :-0.520 gm

Calculation:

1: Theoretical Yield :
106.12 gm of Benzaldehyde ,260 gm of Dihydropyrimdin -2 (1H) thiones.
2 gm of Benzaldehyde = 260×2÷ 106.12
= 4.900gm

2: Percentage Yield :
% = Practical Yield ÷ Theoretical Yield ×100
= 4.900 ÷ 0.520×100
= 94.23%
Melting point: 202°C

35
 PHYSICAL AND CHEMICAL PROPERTY
Chemical Name 6-methyl -2-oxo-4phenyl 1,2,3,
4 tetrahydropyrimidine
5carboxylic acid Ethyl ester.

STRUCTURE

Molecular Formula C14H16N2O

Molecular Weight 260.29

Physical State Solid

Colors white

Solubility in water Insoluble

Melting Point 202-203°C

Time For Reaction 1 hours

36
 RESULTS

A)General Procedure for the synthesis of 3,4Dihydropyrimidin-

2(1H) Ones/Thiones. By Microwave Method.

Method Catalyst Time (h) Yield (%) Melting

point
Microwave RHA 20 min. 43.30% 202°C
Biosilica – At 50°C
Bo3H3

B)General Procedure for the synthesis of 3,4Dihydropyrimidin-

2(1H) Ones/Thiones. By Thermal Method.

Method Catalyst Time (h) Yield (%) Melting

point
Thermal RHA 1 hours 94.23% 202°C
Method Biosilica –
At 50-55°C
Bo3H3

37
 3,4 DIHYDROPYRIMDIN 2(1H) ONES( THIONES)
SYNTHESIS

MICROWAVE METHOD THERMAL METHOD

38
 SPECTRAL DATA
Name of compounds IR value ( cm-1 ) 1 H NMR value
and structure
Benzaldehyde 3600-3650 cm-1 a = 7.61 ppm
(C-H) aromatic b = 7.51 ppm
ring. c = 7.87 ppm

2860-2775 cm-1
C-H streching of
aldehyde
C6H5CHO
2900cm-1 a = 4.202ppm
Ethyl Acetoacetate unsaturated group b =3.451ppm
CH bonds. c =2.273ppm
d=1.288ppm
1600cm-1 (-c=o) .
o
1710cm-1 (-c-) .

2200cm-1(-c=c).
C6H10O3

Thiourea
3260cm-1. and a=8.2 ppm
3156cm-1(NH2)
group

CH4N2S

39
 MATERIALS SAFETY DATA SHEET

1)MSDS FOR BENZALDEHYDE

Section 1 :- Hazards Identification

Potential Acute Health Effects:

Hazardous in case of skin contact (irritant), of eye contact (irritant), .
Slightly hazardous in case of skin contact (permeator), of ingestion. Non-
corrosive for skin. Non-corrosive to the eyes. Non-corrosive for lungs.

Section 2 :- First Aid Measures

Eye Contact: Check for and remove any contact lenses. Immediately
flush eyes with running water for at least 15 minutes, keeping eyelids
open. Cold water may be used. Get medical attention.

Skin Contact: In case of contact, immediately flush skin with plenty of

water. Cover the irritated skin with an emollient. Remove contaminated
clothing and shoes. Cold water may be used.Wash clothing before reuse.
Thoroughly clean shoes before reuse. Get medical attention
.

Serious Skin Contact: Wash with a disinfectant soap and cover the
contaminated skin with an anti-bacterial cream. Seek medical attention.

Inhalation: If inhaled, remove to fresh air. If not breathing, give artificial

respiration. If breathing is difficult, give oxygen. Get medical attention if
symptoms appear.

40
Serious Inhalation: Evacuate the victim to a safe area as soon as
possible. Loosen tight clothing such as a collar, tie, belt or waistband. If
breathing is difficult, administer oxygen. If the victim is not breathing,
perform mouth-to-mouth resuscitation. Seek medical attention.

Ingestion: Do NOT induce vomiting unless directed to do so by medical

personnel. Never give anything by mouth to an unconscious person.
Loosen tight clothing such as a collar, tie, belt or waistband. Get medical
attention if symptoms appear.

Section 3: Handling and Storage

Precautions:
Keep locked up.. Keep away from heat. Keep away from sources of
ignition. Ground all equipment containing material. Do not ingest. Do not
breathe gas/fumes/ vapor/spray. Wear suitable protective clothing. In
case of insufficient ventilation, wear suitable respiratory equipment. If
ingested, seek medical advice immediately and show the container or the
label. Avoid contact with skin and eyes. Keep away from incompatibles
such as oxidizing agents, acids, alkalis, moisture.

Storage:
Store in a segregated and approved area. Keep container in a cool, well-
ventilated area. Keep container tightly closed and sealed until ready for
use. Avoid all possible sources of ignition (spark or flame). Do not store
above 23°C (73.4°F).

41
 2)MSDS FOR ETHYL ACETOACETATE

Section 1 :- Hazards Identification

Potential Acute Health Effects:

Hazardous in case of skin contact (irritant), of eye contact (irritant), .
Slightly hazardous in case of skin contact (permeator), of ingestion. Non-
corrosive for skin. Non-corrosive to the eyes. Non-corrosive for lungs.

Section 2 :- First Aid Measures

Eye Contact: Check for and remove any contact lenses. Immediately
flush eyes with running water for at least 15 minutes, keeping eyelids
open. Cold water may be used. Get medical attention.

Skin Contact: In case of contact, immediately flush skin with plenty of

water. Cover the irritated skin with an emollient. Remove contaminated
clothing and shoes. Cold water may be used.Wash clothing before reuse.
Thoroughly clean shoes before reuse. Get medical attention.

Serious Skin Contact: Wash with a disinfectant soap and cover the
contaminated skin with an anti-bacterial cream. Seek medical attention.

Inhalation: If inhaled, remove to fresh air. If not breathing, give

artificial respiration. If breathing is difficult, give oxygen. Get medical
attention if symptoms appear.

42
Serious Inhalation: Evacuate the victim to a safe area as soon as
possible. Loosen tight clothing such as a collar, tie, belt or waistband. If
breathing is difficult, administer oxygen. If the victim is not breathing,
perform mouth-to-mouth resuscitation. Seek medical attention.

Ingestion: Do not induce vomiting unless directed to do so by medical

personnel. Never give anything by mouth to an unconscious person.
Loosen tight clothing such as a collar, tie, belt or waistband. Get medical
attention if symptoms appear.

Section 3: Handling and Storage

Precautions:
Keep locked up.. Keep away from heat. Keep away from sources of
ignition. Ground all equipment containing material. Do not ingest. Do
not breathe gas/fumes/ vapor/spray. Wear suitable protective clothing.
In case of insufficient ventilation, wear suitable respiratory equipment. If
ingested, seek medical advice immediately and show the container or the
label. Avoid contact with skin and eyes. Keep away from incompatibles
such as oxidizing agents, acids, alkalis, moisture.

Storage:
Store in a segregated and approved area. Keep container in a cool, well-
ventilated area. Keep container tightly closed and sealed until ready for
use. Avoid all possible sources of ignition (spark or flame). Do not store
above 23°C (73.4°F).

43
 3) MSDS FOR THIOUREA

Section 1 :- Hazards Identification

EMERGENCY OVERVIEW -Harmful if swallowed.

Potential Health Effects :-

Eye: May cause eye irritation. Causes redness and pain.

Skin: May cause skin irritation. Causes redness and pain. May be
harmful if absorbed through the skin. Contact with the skin defats the
skin. Substance is readily absorbed through the skin.

Ingestion: Harmful if swallowed. May cause irritation of the digestive

tract. May cause a narcotic effect with possible coma. May cause central
nervous system depression. May cause headache, nausea, fatigue, and
dizziness. May cause convulsions.

Inhalation: May cause respiratory tract irritation. May cause asthma

and shortness of breath. May be harmful if inhaled.

Chronic: Prolonged or repeated skin contact may cause

dermatitis.Chronic exposure may cause degenerative muscle and
myocardium changes.

44
Section 2 :- First Aid Measures

Eyes: Flush eyes with plenty of water for at least 15 minutes,

Occasionally lifting the upper and lower eyelids. Get Medical aid.

Skin: Get medical aid. Flush skin with plenty of water for at least 15
minutes while removing contaminated clothing and Shoes.

Ingestion: Get medical aid. Wash mouth out with water.

Inhalation: Remove from exposure and move to fresh air immediately.

If not breathing, give artificial respiration. If breathing is Difficult, give
oxygen. Get medical aid.

Section 3: Handling and Storage

Handling: Use with adequate ventilation. Avoid breathing dust, vapor,

mist, or gas. Avoid contact with skin and eyes. Take precautionary
measures against static discharges.

Storage: Keep away from sources of ignition. Store in a cool, dry place.
Do not store in direct sunlight. Store in a tightly closed container. Store
protected from moisture. Store under nitrogen.

45
 CONCLUSION

Rice husk is not just a waste material but more than that thus instead of
just disposing it off one can add Value to it. By effectively utilizing silica
content present in it and to produce precipitated silica from it.From the
Experiment, it has been observed that the approximately more than 90% of
SiO2 is recovered. An accurate cost Estimation of this process is not
possible, although rough estimation gives same cost estimation as that of
Traditional process, the main advantage of this proposed process is that
waste disposal problem of rice husk is Eliminated and also valuable
product is obtained. The amorphous silica obtained using this method
have many Application In summary, we have demonstrated one-pot
synthesis of DHPM and coumarin-3-craboxylic acid derivatives using
Agricultural waste rice husk-derived silica-supported BO3H3As a
heterogeneous catalyst 50°C with 1 h stirring and thermal conditions
respectively. The present Method is greener, solvent-free, economical, easy
work-Up, mild reaction condition, with good to excellent yield Isolation. .
Additional advantage of This method is recyclability of the catalyst and
the process Is also cost-effective as silica is derived from natural Agro-
waste that falls in the area of ‘green chemistry’.

46
 BIBLIOGRAPHY

❖. Y. Khatavi1, K. Kantharaju1,, H. Yamanappa2 and S.

Raghothama21Department of Chemistry, Peptide and Medicinal
Chemistry Research Laboratory, Rani Channamma University,
Vidyasangama, P-B, NH-4, Belagavi 591 156, India2NMR Research
Centre, Indian Institute of Science, Bengaluru 560 012, India

❖ Hooman Sharifnasab, Mohammad Younesi Alamooti*(Agricultural

Engineering Research Institute, Agricultural Research Education
and Extension Organization (AREEO), Karaj, Iran)

❖ Kalapathy, U., Proctor, A. and Shultz, J., A simple method for

Production of pure silica from rice hull ash. Biosensors.
Technology2000

❖ Ghorbani, F., Santi, A. M. and Malaki, M., Production of Silica

nanoparticles from rice husk as agricultural waste environmental
friendly technique. Environ. Stud. Persian Gulf, 2015,

47