CHAPTER 1

INTRODUCTION

1.1 Rationale of the Study

Surface staining is one of the most commonly encountered problems in everyday living. It
is an almost unavoidable occurrence due to the many common substances and materials that can
easily cause staining. Stains can develop on different surfaces such as wood and cement, but most
commonly on clothes and other types of fabric. Different types of stains require different methods
of removal; some are much more difficult to remove than others.

Stains on clothes can be difficult to treat because of the varying nature of material or cloth.
Stains attach more easily to the weaves of the cloth although there are also clothes that repel liquids
and do not easily stain; hydrophobic type cloths. One of the most common stains that almost
everyone encounters is coffee stains. Coffee is widely consumed beverage throughout the world
with at least _ liters consumed daily for almost all ages for people throughout the world (insert
reference) . There are already plenty of coffee shops in almost every place not considering the
coffee people also make in their own homes.

Another common clothes stain is from soy sauce. In the Philippines, it can be immediately
noted that soy sauce is one of the typical seasonings used in a Filipino dish as well as a frequently
used condiment, almost as much as, if not more than, ketchup. Both coffee and soy sauce give dark
brown stains which can be difficult to remove if not immediately treated. There are many stain
removal techniques which can be easily employed in a household. Some common removal
methods are by soaking or washing the cloth with detergent or bleach depending on how much the
stain adheres to the material. Some use solvents, like hydrogen peroxide 𝐻2 𝑂2, as well as by
cleaning it high temperatures, to remove certain stains. But one of the solvents that have been
widely studied as an alternative stain remover is hydrosol.

Hydrosol is

The distillation water with dissolved essential oil components is referred in the literature
by diverse names such as condensate, distillate and hydrosol. The water of hydrosol (Fig. 1) comes
from the water used for generating steam and from the distilled plant biomass.
 Fig.1 Sample hydrosol
Hydrosols are dilute mixtures of varying compositions of essentials oils as well as other
volatile metabolites which can be used as stain remover (Rose, 1999; Catty, 2001) which could be
obtained from plants and plant parts such as fruit and fruit peels, leaves, bark, and flowers.
Hydrosols are milder compared to common bleaching agents such as chlorine and oxygen bleaches
(Rose, 1999) Moreover, these are also more environmentally friendly option for stain removal.

The Philippines is an archipelago with a geographical location 13o to the north and 122o
to the east. It has a rich variety of tropical fruit in which more than 20 different species are grown
throughout the archipelago. The production system stretches from the backyard to a highly
integrated activity with the latter catering to the export market. Among these fruits are pineapple
and calamansi. These raw materials are good sources of hydrosol since its extraction is easily done.
Furthermore, these fruits are abundant and cheap in the Philippines which can turn to another
industry for organic stain removers. To add, Malunggay is also a potential raw material for
hydrosol extraction because of its abundance, price and easiness to grow throughout the year.

Calamansi (Citrofortunella microcarpa), which is indigenous in the Philippines, is among

the widely produced and planted crop in the country. Calamansi has been used in various products
like concentrates, purees, syrups, and juices which are used as a flavouring agent to further enhance
iron absorption. According to Morton 1984, the extracted juice, with the addition of gum
tragacanth, an emulsifier, is pasteurized and bottled commercially then it used to bleach ink stains
from fabrics and serve as a body deodorant in the Philippines (1987, p. 176-178 John
Morton).While pineapple is one of the most popular crops in Philippines.
 The Philippines ranks second in the world in terms of pineapple production next to Costa
Rica, with an estimated 70,000 hectares planted with the fruit, mainly exported, contributing about
17 percent to world supply (Baroña, 2005). On the other hand, Malungay is ……… And
malunggay is a growing, drought-resistant tree of the Moringaceae family, native to South
Asian tropical and subtropical regions.

Wastes from pineapple, like peels, have a potential useful in cleaning purposes because of
garbage enzymes are environment-friendly, it is not known what their optimal amount or
concentration. It has been used in cosmetic industry, detergent industry and food industry due to
their same quality (S. ketnawa, 1990). While calamansi peels can be used in difference applications
such as making juice, cooking, laundry and cleaning. Also in malunggay stem waste, it can be
alternative ingredient in cleaning household chores when added by distilled water.

Knowing these, the researchers are determined in solving this prevailing matter of
pineapple wastes utilization and as well as using calamansi peels and malungay as hydrosols for
stain removal. Previous researches are focused on using lemon and other citrus fruits in the other
countries as stain remover and found out the big potential of citrus fruits as a stain remover (insert
citation). However, there are few studies focusing on Calamansi peels, pineapple peels and
malungay, especially here in the Philippines. Also, the process that will be used in this study is
hydrodistillation, a type of steam distillation.

This research will give a new knowledge and information regarding the use of these raw
materials as stain remover and might as well open a new industry for organic based stain removers.
This might be used as well as an additive in the already existing industry of commercially produced
stain removers.

1.2 Stain Removal

Researchers are

1.3 Hydrosol

1.3.1 Pineapple Peels

 1.3.2 Calamansi Peels

1.3.3 Malungay stem

1.4 Significance of the Study

First and foremost, there hasn’t been any studies focusing in the extraction of hydrosol
from pineapple peels, calamansi peels and malunggay using steam-distillation. Moreover, there
are existing manufacturing companies already utilizing pineapple peels but aren’t extracting
hydrosols which is a good alternative for removing stains.

Also, this study impacts the community by providing livelihood e.g. Small to Medium
Enterprises (SMEs) specifically to places with abundant pineapple, calamansi and malungay
production by utilizing the peels in making hydrosols. Moreover, the results of this study can be
incorporated in soap and detergent production by using these organic hydrosols as additives.
Finally, to the future researchers, this will provide additional information in the utilization of
abundant pineapple, calamansi and malungay hydrosol extracts in many fields not just in stain
removal.
1.5 Objectives of the Study

This study sought to determine the following:

1.) Efficacy of hydrosols derived from

a) Pineapple peels
b) calamansi peels
c) malunggay stem

2.) Efficacy of the derived hydrosols in terms of

a) Degree of whiteness
b) Time it takes to remove stains
3.) Degree of changes in stain removal with varying volume of hydrosols
4.) Reflectance spectra for each hydrosol with changing volumes of hydrosols
5.) Effects of varying pH in the efficacy of removing the stain
6.) Chromatography of the stain for each hydrosol

1.6 Scope and Limitations

This study will be only focusing on the efficacy of different hydrogels derived from
Malunggay (Moringa Oleifera), Calamansi (Citrofortunella microcarpa) peels and Pineapple
(Ananad Comosus) peels as stain remover. Different parameters like purity, temperature (in
application) and visco-elasticity of the hydrosol are not included and will not be studied.
Furthermore, only coffee, soy sauce, ink and mud stains will be used.
 CHAPTER II

Review of Related Literature

2.1 pH

pH stands for power of hydrogen, which is a measurement of the hydrogen ion

concentration in a solution. The total pH scale ranges from 1 to 14, with 7 considered to be neutral.
A pH less than 7 or 0-6 is said to be acidic and solutions with a pH greater than 7 or 6-14 are basic
or alkaline. (Felicetti, 2012). pH is scaled from 0 – 14, with 7 as neutral ……….

insert mathematical interpretation/solution for Ph

Diagram or acidic, neutral and basic solutions

Insert the chemistry of pH

According to the KALAMANSI® PLG-4 EXTRACT (Author, Year, Page) , the pH level
of calamansi was recorded as 2 – 4, which means to be acidic (Please edit syntax). According to
the FDA, pineapple juice falls at 3.5 on the pH scale, right in the middle between most acid and
neutral, or moderately acidic. In contrast, the fresh fruit itself ranges from 3.5 to 5.2 pH, making
pineapple potentially less acidic than its juice. (Fredenburg, 2017). Show this in table

2.2 Stain Removal

 Define what stains are first. Coffee, lipstick, red wine, and tea stains are some
common examples of oxidizable stains (R. Benckiser, (2017)). Oxidizable stains go
through chemical reactions, specifically oxidation-reduction reactions, or redox reactions.

Insert Diagram(OXIDATION)

The color in the pigment of the stain is produced when molecules absorb light in the visible
spectrum with a wavelength ranging from 400-780 nm (W. Reusch, (2017)). The
wavelengths that are not absorbed will be reflected instead and will be visible to the human
eye. Red wine stains are red because every wavelength that is not in the red range are
absorbed by the molecule, and the red wavelengths ranges from 500-600 nm are then
reflected shown in the figure below.

INSERT ELECTROMAGNETIC SPETRUM

Figure 3: Visible Wavelength by Reusch, W. Visible and Ultraviolet Spectoscopy (2017).

A stain is a discoloration that can be distinguished clearly from the surface substance or
medium on which it is found. These are caused by two dissimilar materials ' chemical or physical
contact. There may be deliberate stains (such as wood stains or paint), suggestive stains (such as
coloring food or applying a substance to make bacteria visible under a microscope) in the stains
categories are present (Limos, 2013).

INSERT FIGURES OF STAINS

KIND OF STAINS
2.3 Acid-Base Reaction Theories

Acids and bases are everywhere. Some foods contain acid, like the citric acid in lemons
and the lactic acid in dairy. Cleaning products like bleach and ammonia are bases. Chemicals that
are acidic or basic are an important part of chemistry.

2.3.1 Acids

INSERT DIAGRAMS

INSERT THE CHEMISTRY OF ACIDS

 Acids are substances which produce hydrogen ions in solution.

 An acid is a substance, which dissociates in solvent to produce one or more

hydrogen ions (H+).
2.3.2 Bases
INSERT DIAGRAMS
INSERT THE CHEMISTRY OF BASES

 Bases are substances which produce hydroxide ions in solution.

 A base is a substance, which dissociates in solvent to produce one or more

hydroxide ions (OH-).

Based on this definition, you can see that Arrhenius acids must be soluble in water.
Arrhenius acid-base reactions can be summarized with three generic equations:
 An acid will dissociate in water producing
𝐻𝐴 → 𝐻 + + 𝐴−
hydrogen ions.

A base (usually containing a metal) will

𝑀𝑂𝐻 → 𝑀+ + 𝑂𝐻 −
dissociate in water to produce hydroxide
ions.
Acids and bases will neutralize each other
𝐻𝐴(𝑎𝑞) + 𝑀𝑂𝐻(𝑎𝑞) → 𝐻2 𝑂(𝑙) + 𝑀𝐴(𝑎𝑞)
when mixed. They produce water and an
ionic salt, neither of which are acidic or
basic

2.4 Bleach

A bleaching agent is a substance that by chemical reaction lightens or shades a surface.

Typically, bleaching reactions include oxidizing or reducing processes that destroy color systems.
Such processes that include the destruction or alteration in the substratum of chromophoric groups
as well as the degradation of color bodies into smaller, more soluble units that are easier to remove
in the bleaching process.

There are usually two types of the most common bleaching agents: chlorine and its
associated compounds (such as sodium hypochlorite) and eroxygen bleaching agents, such as
hydrogen peroxide and sodium perborate. Bleach reduction is another class. Enzymes are a modern
bleaching agent class. These are used for bleaching textiles, paper and pulp as well as for washing
at home. The most cost-effective bleaching agents known are chlorine-containing bleaching
agents. These are also active disinfectants, and the most common use of most chlorine-containing
bleaching agents is often water disinfection. These can be classified into four classes: chlorine,
hypochlorites, compounds of N-chloro and dioxide of chlorine. Chlorine itself is seldom used as a
bleaching agent except for bleaching wood pulp and flour. Sodium hypochlorite is the main form
of hypochlorite produced.

Calcium hypochlorite and bleach alcohol, bleaching dust and marine bleach are other
hypochlorites. The chlorinated isocyanurates, e.g. sodium dichloroisocyanurate dihydrate, are the
main solid chlorine bleaching agents. Other compounds of N-chloro include halogenated
hydantoins and N -chlorobenzenesulfonamide (chloramine B) sodium. Chlorine dioxide is a more
volatile gas than chlorine. Large amounts of pulp bleaching are produced through several processes
in which complex reactions reduce sodium chlorate in highly acidic solutions with chloride,
methanol, or sulfur dioxide.

Using oxidizing agents is one of the best ways to remove oxidizable stain, which gain
electrons to create the new compound, becoming more negative. Bleach is a common oxidizing
agent that can remove oxidizable stains.Bleach functions as a stain remover by breaking the bonds
within the chromophore to produces smaller fragments which do not absorb light in the visible
region that is visible to human eye (R. Benckiser, (2017)). Bleach removes the double bonds from
chromophores through a redox reaction by breaking the double bonds into single bonds that do not
reflect color (The Science of Stain Removals, (2017)).

Figure 4: Double bonds into single bonds that do not reflect color (The Science of Stain
Removals, (2017)).

Broken Chromophore under the Influence of Bleach

There are two different types of laundry bleaches: chlorine bleach and oxygen bleach.
Chlorine bleach is one of the most powerful stain removals. The main constituent of chlorine
bleach is sodium hypochlorite. Sodium hypochlorite has a pH level of about 11, making it basic,
and is very unstable and reactive, making it a strong oxidizer (J. Rowe, (2017)).

Chlorine bleach is based on sodium hypochlorite (NaClO) that is diluted with water to
create an approximately 5.25% concentration (L. Bramble, (2017)). Oxygenbased bleaches is safer
to use on many fabrics. Oxygen bleach is based on sodium percarbonate (Na2CO3·1.5H2O2).
 As shown below, when sodium percarbonate is combined with water, it is broken down
into sodium carbonate (Na2CO3) and hydrogen peroxide (H2O2) (R. Benckiser, (2017)).

Reaction:

2Na2CO3 . 3H2O2(aq) → 2Na2CO3(aq) + . 3H2O2 (aq)

2.5 Hydrogen Peroxide

Hydrogen peroxide is one of the most common bleaching agents. It is the textile industry's
primary bleaching agent and is also used in pulp, paper and home laundry applications. Hydrogen
peroxide reacts to give peroxy compounds or peroxyhydrates with many compounds, such as
borates, carbonates, pyrophosphates, sulfates, etc. Due to the greater electrophilicity of the peracid
peroxygen moiety. peracids have superior cold water bleaching capacity versus hydrogen
peroxide. The recent use and vast literature of peracids in textile bleaching account for lower wash
temperatures and phosphate reductions or bans in detergent systems. Sulfur dioxide, sulfuric acid,
bisulfites, sulfites, hydrosulfite (dithionites), sodium sulfoxylate formaldehyde, and sodium
borohydride are the reduction agents generally used in bleaching. Such products are primarily used
in blanching of pulp and textiles.

The main constituent of oxygen bleach is hydrogen peroxide. Hydrogen peroxide is a very
pale blue, clear fluid in its pure form, somewhat more viscous than water. It is the simplest peroxide
(a single oxygen bond compound) and it is used as an oxidizer, antiseptic and bleaching agent.
Concentrated hydrogen peroxide, or "high-test peroxide," is a very reactive oxygen species, its
chemistry is dominated by its unstable peroxide bond nature. For nearly all other oxygenbased
bleaching systems, hydrogen peroxide (H2O2) is one of the starting materials for common
bleaching agent. Here are some advantages in using Hydrogen peroxide: It does not contaminate
the soil, does not damage the aquifer, indirectly provides the soil and crops with more oxygen and
it is appropriate for oxidizing iron and manganese. Hydrogen peroxide is consumed instantly after
contact with water, its velocity allows it to quickly oxidize and disinfect the water source as well
as the filters.

History of Bleach
 Bleaching is a method that is rather old process. The influence of sun on various substances
was also known to ancient human beings. In fact, we can find examples of items that are exposed
to sunlight for bleaching purposes, even in primitive times. Some of them were concentrated in
Egypt, China, Africa, and Europe.

In the Egyptian civilization (around 5000BC) the earliest traces can be found. Therefore,
when it came to applying the whitening power of the sun to bleach objects, Egyptians are
considered to be experts. Through exposing their garments to sunlight, they used to discolor their
linens.

Before the third millennium BC, leach was found. The people of that time had adequate
knowledge about a solution that could be developed from wood ashes, which, after mixing with
water, turned into lye (a substance that is obtained by leaching or removing soluble or other
components by percolating a liquid). They knew that the resultant liquid would lighten colors.

They also realized that steeping or soaking stuff in lye would blanch linen to the point that
it would completely disintegrate linen if it was allowed to remain dipped for a long period of time.
With this lye form, the whitening process is a bit tricky. Furthermore, because it takes many hours,
it is tedious. However, because it is pretty strong, it warrants extra care.

The Dutch are attributed in the 11th and 12th centuries AD for the modification they
brought about in this sphere. They emerged as experts on the science of laundering in the European
community as a whole during this time. They seasoned lye with sour milk in order to mitigate the
harsh results. They never let anyone know about their secret, and the system has been a mystery
for many years as a result.

Till the mid-18th century, the Dutch dominated and maintained their supremacy in the
bleaching trade. Thus, all brown linen, manufactured at the time principally in Scotland, was
shipped to Holland for the purpose of bleaching.
 2.6 Hydrosols

Steam distillation is a separation method used to purify or insulate temperature-sensitive

materials, such as natural aromatic compounds. Steam or water is added to the distillation
apparatus, reducing the boiling point of the compounds. The goal is to heat and isolate the
components at temperatures below their decomposition level.

2.7 Steam Distillation

HISTORY OF STEAM DISTILLATION

Objectives of steam distillation

The advantage of steam distillation over simple distillation is that the lower boiling point
limits the decomposition of temperature sensitive compounds. Steam distillation is useful for
purifying organic compounds, while vacuum distillation is more common. The vapor is diluted
when the organics are distilled. Since water and organic matter appear to be immiscible, the
resulting liquid generally consists of two phases: water and organic distillate. Decantation or
partitioning may be used to separate the two layers in order to obtain a purified organic material.

Principle of steam distillation

When heating and agitating a mixture of two immiscible liquids (e.g. water and organics),
the surface of each liquid exerts its own vapor pressure as if the other component of the mixture
were absent. Therefore, the system's vapor pressure increases beyond what it would be if only one
of the components was present as a function of temperature. Boiling starts when the amount of the
vapor pressure equals the atmospheric pressure. Because the boiling temperature is increasing,
damage is minimized to heat-sensitive components.

INSERT DIAGRAM

Use of steam distillation

 The preferred method used to separate essential oils is steam distillation. Throughout
petroleum refineries, it is also used for "steam cleaning" and for separating commercially important
organic compounds, such as fatty acids.

Set-up of steam distillation

The distillation setup includes a flask (solution), a three-way adapter, a water-jacked

condenser, a vacuum adapter, and a round-bottom flask to catch the condensing liquid. At the
bottom end, the water supply (inlet) is attached, while the outlet either goes back to the sink or to
the inlet of another water-jacketed condenser. Only in two places should the device be clamped:
the neck of the round bottom flasks. A water bath (~50-60 degree Celsius) is used here as a heat
source since there is no high boiling point of diethyl ether (36 degree Celsius). The configuration
must have an opening of pressure release (usually the vacuum adapter). In figure shows the set-up
of steam distillation in Physical and Chemical Laboratory in Cebu Institute of Technology-
University.

Figure 4: Set-up of steam distillation

 CHAPTER 3
RESEARCH DESIGN AND METHODOLOGY

Methodology

The experiment was conducted in CIT-U ……………

3.1 Materials
3.2 Sample Preparation
3.2.1 Sample Collection
3.2.2 Drying and Grinding
3.2.3 Steam Distillation
3.3 Staining
3.4 Visual Testing
3.5 Chromatography
3.6 Spectroscopy
3.6.1 Transmittance
3.6.2 Reflectance
3.6.3 Intensity vs Wavelength