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Industrial Pharmaceutical Chemistry
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Hebah Abdel-Wahab
Industrial
Pharmaceutical
Chemistry
Product Quality
Author
Dr. Hebah Abdel-Wahab
Delaware County College
901 Media Lane Road
Media, PA 19063
USA
[email protected]
ISBN 978-3-11-131657-4
e-ISBN (PDF) 978-3-11-131686-4
e-ISBN (EPUB) 978-3-11-131725-0
Library of Congress Control Number: 2023941340
Bibliographic information published by the Deutsche Nationalbibliothek
The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie;
detailed bibliographic data are available on the internet at http://dnb.dnb.de.
© 2024 Walter de Gruyter GmbH, Berlin/Boston
Cover image: Makidotvn/iStock/Getty Images Plus
Typesetting: Integra Software Services Pvt. Ltd.
Printing and binding: CPI books GmbH, Leck
www.degruyter.com
Preface
The book is divided into seven chapters. Chapters 1–5 discuss methods used to im-
prove the quality of some pharmaceutical/industrial products: mouthwashes, acrylic
paints, car-wash shampoos, matt and gloss paints, and some bubble-forming tablets.
The methods used are based on the varying chemical properties, physical properties,
and amounts of the chemical compounds used in the formulation.
Chapter 6 discusses the effect of the obstructed ability to breath by a physical
block limit or by prolonged hypoventilation, or by a pulmonary condition on hypoxia,
hypercapnia, and blood chemical pH imbalance. Mechanism of alternating blood pH
values, methods of identifying blood chemical pH imbalance, methods of measuring
PCO 2 , PO2 , and blood pH, types of joint diseases caused due to blood chemical pH im-
balance, current medicine prescribed in their treatments, and the natural treatments
of such joint diseases are discussed.
Chapter 7 discusses the methods used to calculate thermodynamic parameters for
simple fluorinated organic alcohols including mono and difluorinated ethanol and
multifluorinated ethanol. The methods used to calculate the thermodynamic parame-
ters, enthalpy of formations, and bond dissociation energy values are discussed. The
optimized structures and Cartesian coordinates for molecules studied are included.
Tabulated literature values for enthalpy of formation for molecules studied and for
reference are also included.
This book is based on the actual solutions to industrial problem requests submit-
ted to me through the Association of Consulting Chemists and Chemical Engineers,
Cary, NC, USA, and the actual results of thermodynamic and kinetic independent re-
search studies at NJIT, Newark, NJ, USA, and published articles. I hope you find the
information in this book helpful to your business or project, and I also hope the infor-
mation in this book increases your wealth of knowledge.
Dr. Hebah Abdel-Wahab
Edison, NJ, USA
[email protected]
https://doi.org/10.1515/9783111316864-202
About the Author
Dr. Abdel-Wahab is a Chemical Consultant at the Association of Consulting
Chemists and Chemical Engineers NC, USA, where she is consulted for
independent commercial, industrial, and pharmaceutical chemical projects,
and an Adjunct Professor of Chemistry at Essex County College & Middlesex
County College, NJ, USA, where she has taught chemistry for allied health,
preparatory chemistry, general chemistry, organic chemistry, physical
chemistry, and inorganic chemistry for 17 years. Professor Abdel-Wahab
earned a Ph.D. degree in chemistry from Rutgers University in 2018. She
was scheduled to teach 38 different chemistry courses during her career: CHM-222, CHM-228, CHM-141,
CHM-100, CHE-108, CH-112, CH-314, CHM-116, CHM-115, CHP-111, CHM-103, Chemistry-307, Chemistry-308,
CHEM-4610, CE-241, CHEM-180, CHM-126, CHM-142, CHEM-1105, CHEM- 2208, CHEM- 1033, CHEM-1034,
CHEM-2203, CHEM-2204, CHEM-180, CHEM-181, CH-101, CHEM-1117, CHEM-1028, CHEM-2261, CHEM-100,
CHEM-111, CHEM-208, CH-132, CHE-101, CHE-102, CHEM-3184, CHEM-1083, and she adapted 115 different
textbook and laboratory manuals.
Dr. Abdel-Wahab was conferred an Honorary Doctor of Science (D.Sc.) degree in Physical Chemistry
in December 2022 by the International Agency for Standards and Ratings for her significant contribution
in the field of chemistry and her significant contributions in the transformation of society. Prof. Abdel-
Wahab was also conferred an Honorary Doctor of Science (D.Sc.) degree in Physical Chemistry
in December 2022 by the British National University of Queen Mary, WP Road, London, UK.
Dr. Abdel-Wahab is the author of several book chapters in academic, commercial, industrial, and
pharmaceutical chemistry. Prof. Abdel-Wahab is the author of five book chapters published by BP
International: Progress in Chemical Science Research Vol. 1, Current Topics on Chemistry and Biochemistry
Vol. 3, Research Aspects in Chemical and Materials Sciences Vol. 2, Progress in Chemical Science Research Vol. 4,
and Research Aspects in Chemical and Materials Sciences Vol. 3, and the author of a book chapter published
by Akinik Publications – Research Trends in Medical Sciences Vol. 19.
Dr. Abdel-Wahab joined the editorial cabinet as an editorial board member in 2022. She is currently an
editorial board member for the Journal of Pharmaceutics and Pharmacology Research, JPPR, 16192 Coastal
Highway, Lewes, DE 19958, USA, International Journal of Anesthesiology and Practice, 1603 Capital Avenue,
Suite 413-A, Cheyenne, WY 82001, the USA, and Clinical Case Reports and Trials, Medires PUBLISHING LLC,
1603 Capital Avenue, Suite 413-A, Cheyenne, WY, 82001, USA. Dr. Abdel-Wahab is currently a reviewer
for Advances in Chemical Engineering and Science (ACES), an SCRIP international journal, and the Royal
Society of Chemistry Journal, RSC Burlington House, Piccadilly, London W1J 0BA, UK.
Dr. Abdel-Wahab belongs to numerous scientific and educational organizations including the
International Society of Female Professionals (ISFP) and the Association of Consulting Chemists and
Chemical Engineers (ACC & CE). Professor Abdel-Wahab has been published in Strathmore’s Who’s Who
Worldwide (Farmingdale, NY, 2021), as an Individual Who Has Exemplified Leadership and Achievement in
Their Occupation, Industry, and Profession, and she has also been published in Marquis’s Who’s Who
(Berkeley Heights, NJ, 2021), as an Individual Who Demonstrates Outstanding Achievement in Their Field
and who has made Innumerable Contributions to Society as a Whole.
https://doi.org/10.1515/9783111316864-203
Acknowledgments
The author wishes to acknowledge the efforts of the Association of Consulting Chem-
ists and Chemical Engineers for making Consultants’ profiles available for our clients
in the USA and worldwide.
https://doi.org/10.1515/9783111316864-204
Contents
Preface V
About the Author VII
Acknowledgments IX
1 Chemical Formulations for Mouthwashes 1
1.1 Overview 1
1.2 Introduction 1
1.3 Experimental 4
1.4 Conclusion 8
References 8
2 Chemical Formulations for Acrylic Matt and Acrylic Gloss Paints 11
2.1 Overview 11
2.2 Introduction 11
2.3 Experimental 17
2.4 Discussion 21
2.5 Conclusion 22
References 23
3 Increase Product Quality for a Car-Wash Shampoo Concentrate 25
3.1 Overview 25
3.2 Introduction 25
3.3 Experimental 27
3.4 Conclusion 32
References 33
4 Modification to an Acrylic Paint Formulation 35
4.1 Overview 35
4.2 Introduction 35
4.3 Detailed Analysis 37
4.4 Conclusion 37
References 38
XII Contents
5 Modification to a Chemical Formulation for Optimal Performance 39
5.1 Overview 39
5.2 Introduction 39
5.3 Experimental 42
5.4 Conclusion 45
References 46
6 The Effect of Lack of Oxygen and Excess Carbon Dioxide Buildup on
Joint Diseases and the Natural Treatments for Some Joint
Diseases 48
6.1 Overview 48
6.2 Introduction and Background 48
6.3 Review and Discussion 51
6.4 Conclusion 56
References 57
7 Enthalpy and Bond Dissociation Energy Values for Multifluorinated
Ethanol and Its Radicals Using Gaussian M-062x/6-31+g (d,p) Method
at Standard Conditions 62
7.1 Overview 62
7.2 Introduction 63
7.3 Experimental and Data 65
7.3.1 Computational Method 65
7.3.2 Isodesmic and Isogyric Reaction 65
7.3.3 Reference Species 66
7.3.4 Standard Enthalpies 67
7.3.5 Bond Energies 74
7.4 Optimized Structures 76
7.5 Cartesian Coordinates 80
7.6 Conclusion 85
References 85
Disclaimer 87
Appendix: The Periodic Table of Elements 89
Index 95
1 Chemical Formulations for Mouthwashes
1.1 Overview
Mouthwash can strengthen the teeth, prevent gum disease, kill bacteria in the mouth
that causes gingivitis and improve your oral health. This chapter discusses the method
used to improve the properties of the current mouthwash formulation, determine the
chemical compounds and safe amounts to be used from the current formulation: dis-
tilled water, sodium chlorite, castor oil, peppermint extract, lemon juice directly from
the fruit, coconut oil, sodium benzoate, citric acid, and tetrasodium EDTA, and recom-
mend a suitable preservative for the current formulation.
1.2 Introduction
An independent business owner in New Jersey is looking to produce a small amount
of homemade mouthwash to be sold and distributed locally. The ingredient included
the following chemicals: distilled water, sodium chlorite, castor oil, peppermint ex-
tract, and lemon juice directly from the fruit, coconut oil, sodium benzoate, citric
acid, and tetrasodium EDTA. The chemical compounds to be used in the formulation
and the safe amounts of each chemical in the formulation are identified.
Mouthwash can strengthen the teeth, prevent gum disease, kill bacteria in the
mouth that causes gingivitis, and improve your oral health. If the mouthwash con-
tains fluoride, it reduces the cavity when used correctly. It is recommended by den-
tists to use mouthwash daily in addition to daily brushing and flossing. People with
medical conditions, tooth sensitivity, dry sockets, and xerostomia find mouthwash es-
sential in their daily routine.
Mouthwash is used to refresh and clean the oral cavity. To prevent the develop-
ment of caries, a formulation containing fluorides has been used, as it destroys and
inhibits the oral microbial population that generates malodors or dental plaque.
Mouthwash formulation mainly consists of ethanol, water, a humectant, a surfactant,
flavor, color, and an active ingredient. Ethanol is used to enhance the flavor impact
and adds freshness. Humectant such as glycerin, sorbitol, or propylene glycol adds
body to the formulation and improves the mouth feel when using the mouthwash.
The surfactant is usually nonionic such as poly oxypropylene or poly oxyethylene co-
polymers; it produces foams, dissolves the flavor oil, and removes debris. The flavor
is an oil used to make the mouthwash pleasant to use. The mouthwash may include
an active ingredient, for example, an anticares effect or antibacterial effect.
Dental caries is a multifactorial disease produced within the dental plaque by mi-
croorganisms. It involves a process of enamel demineralization and remineralization
due to the act of organic acids produced within the dental plaque by microorganisms.
https://doi.org/10.1515/9783111316864-001
2 1 Chemical Formulations for Mouthwashes
Enamel demineralization is the process of dissolution of hydroxyapatite by the act of
extrinsic or intrinsic acids, according to equation (1.1), leading to erosion or dental
cares. Dental caries are caused by acetic or lactic acid that diffuses into the enamel
pores through the plaque, decreasing the pH of the fluid surrounding the enamel crys-
tals. To prevent dental caries, fluorides, calcium, and phosphates and antimicrobials
can be used as additives in the mouthwash formulation. The presence of fluorides in
the microenvironment or around the teeth inhibits demineralization and promotes the
remineralization of the tooth surface. The incorporation of fluoride as fluorapatite into
enamel decreases its solubility. Casein phosphopeptide amorphous calcium phosphate
(CPP–ACP), has been added to mouthwash, tropical pastes, and chewing gums to in-
crease remineralization and decrease demineralization. Antibacterial has some role in
caries prevention, it helps with plaque and microbial control, chloro-hexadiene and tri-
closan-containing gels, toothpastes, and rinses have been used:
Ca10 ðPO4 Þ6 ðOHÞ2 + 2H +!10Ca2 + + 6PO4 3 − + 2H2 O (1:1)
Mouthwash can be classified into two main types: therapeutic and cosmetic. Thera-
peutic mouthwash reduces plaque, bad breath, tooth decay, and gingivitis. Children
under the age of 6 shouldn’t be using mouthwash as they may inadvertently swallow
large amounts of liquids unless directed by a dentist. Cosmetic mouthwash has no bio-
logical or chemical application beyond its temporary relief; they temporarily control
bad breath and give a pleasant taste and smell.
Active ingredients used in a therapeutic mouthwash are peroxides, fluorides,
chlorhexidine, essential oils, and cetyl-pyridinium chlorides. Peroxides are used in
whitening mouthwash. Fluorides are used to prevent tooth decay. Chlorhexidine and
essential oils are used to fight gingivitis and plaque. Cetyl-pyridinium chlorides is
used to prevent bad breath.
Antimicrobial, fluoride, anesthetic, and chlorhexidine mouthwashes are examples
of therapeutic mouthwashes.
Antimicrobial mouthwashes are used in the treatment of oral malodor and bad
breath. Volatile sulfur compounds (VSCs) are the major factor causing bad breath;
they arise from the breakdown of food, bacteria associated with dental disease, and
dental plaque. Cosmetic mouthwash can also temporarily mask bad breath, but it
doesn’t kill the bacteria that causes bad breath and has no effect on VSCs causing bad
breath. Therapeutic mouthwash containing an antimicrobial is more long term and
can control bad breath. Antimicrobials in mouthwash formulations can include chlor-
hexidine, cetyl-pyridinium chloride, essential oils (e.g., methyl salicylate, eucalyptol,
thymol, and menthol), and chlorine dioxide. Antimicrobial mouthwashes are also
used in the treatment of gingivitis and plaque.
Fluoride mouthwashes are used to prevent tooth decay in children and can also
be used in the treatment of xerostomia, a condition where the amount of saliva bath-
ing the oral mucous membrane is reduced. It is found that rinsing weekly with 0.2%
1.2 Introduction 3
NaF mouthwash or daily with a 0.02% NaF would reduce dental caries by 20–40% in
children.
Anesthetic mouthwashes are used to relieve pain, and they contain anesthetics, dyclo-
nine hydrochloride, phenol, lidocaine, benzocaine, tetracaine hydrochloride, or butamin.
Whitening mouthwash mostly contains 1.5–2% hydrogen peroxide or 10% car-
bamide peroxide.
Chlorhexidine mouthwash, without the use of antibiotics, is found to be effective
for AO prevention following extractions. Dry socket, alveolar osteitis, is a condition that
might follow an extraction procedure and intense pain 2–3 days after the procedure.
Additives that make a therapeutic mouthwash can be classified into either anti-
bacterial agents or compounds that effect VSC formation. Antibacterial agents help re-
duce the number of anaerobic bacteria in the mouth. Examples of antibacterial
agents that are used in mouthwash formulation are cetyl pyridinium chloride, essen-
tial oils/antiseptic formulations, triclosan, and chlorhexidine gluconate. It is found
that the use of 0.75% cetyl pyridinium chloride mouth rinse reduces plaque by 35%
over a 6-month period, and the use of 0.2% chlorhexidine gluconate oral rinse solu-
tion causes reduction in VSC level (it shows some side effects and alters the sense of
taste and causes staining of mouth and tongue).
Compounds that effect VSC formation neutralize VSCs to improve quality of breath.
Examples of ingredients that effect VSCs are zinc compounds and chlorine dioxide (so-
dium chlorite is an oxidizing agent and is able to degrade sulfur-containing amino acids,
which is the building block of VSCs, making fewer of them available to bacteria, leading
to fewer VSCs formed). It is found that using mouthwash containing 1% sodium chlorite
reduces VSC for a period of 8 h. Some metal ions have the ability to oxidize the thiol,
sulfur-based molecules found on VSCs. Examples of metal ions are zinc, copper, magne-
sium, tin, and sodium; zinc also has an antibacterial property, doesn’t cause tooth staining
like other metal ions, and has low toxicity. A 1% zinc acetate mouthwash has a significant
effect on VSC levels, even 3 h after use. A typical formulation for essential oils/antiseptic
mouthwash is 0.092% eucalyptol, 0.042% menthol, 0.06% methyl salicylate, and 0.064%
thymol in a solution containing 21.6% to 26.9% alcohol, high concentration of alcohol in
the formulation (25% ethanol) may cause drying effect on oral tissue, increasing breath
malodor. The most effective mouthwash for bad breath is found to use a multifaceted
approach using a combination of formulations. Other products used for breath control
may include gum, toothpaste, mints, drops, lozenges, and sprays. It is found that six com-
pounds are mainly used in the formulation of mouthwash designed to fight bad breath
(halitosis); zinc chloride, triclosan, essential oils/antiseptic formulations, chlorhexidine
gluconate, cetyl-pyridinium, and chlorine dioxide. Studies show that using a 0.09% zinc
chloride mouth rinse is effective in reducing the formation of calculus in people.
Sodium chlorite is the main ingredient used in the newer classes of mouthwashes
such as ProFresh, CloSYS, TheraBreath, and Oxyfresh. It is sometimes used as a water
purifier. These mouthwashes are said to freshen breath up to 6 h. SmartMouth uses
sodium chlorite as a main ingredient, but it must be mixed with zinc chloride right
4 1 Chemical Formulations for Mouthwashes
before use. The zinc ions block receptor sites of amino acids after eating food contain-
ing amino acids, so the bacteria can’t produce rancid gases, and it lasts for up to 12 h
before another rinse is needed.
Flavors are one of the main ingredients that make a mouthwash, as it gives flavor
to the formulation and makes the mouthwash pleasant to use. The different known
flavors that can be used in a mouthwash ingredient are: clove leaf oil, cubeb oil, ce-
darwood oil, eucalyptus oil, lemon oil, Italian type, coldpressed, myrrh oil, mentha ar-
vensis oil, sweet orange oil, peppermint oil, sucralose, saccharin sodium, dihydrate,
granular, spearmint oil, camphor, methyl salicylate, and cinnamon extract.
1.3 Experimental
The chemical composition of the ingredients used in the making of the mouthwash is
identified in Tab. 1.1.
Distilled water (purified water) is used as a solvent in which the ingredients are
soluble in. It is a cooled boiling water steam returned to its liquid state after removing
99.9% of the minerals dissolved in water.
Sodium chlorite is used as an antimicrobial agent in mouthwash. It reduces bacte-
ria living in the mouth causing bad breath. It also degrades building blocks of the
VSCs causing bad breath, and it degrades sulfur-based amino acids, causing fewer of
them being available to bacteria, and fewer VSCs are formed. It is found that one-time
use of mouthwash containing 1% sodium chlorite is effective in reducing the RVS
level for 8 h and beyond.
Castor oil has the ability to break biofilm, a protective coating created by detri-
mental bacteria in the microbiome. It makes the environment more hospital to
healthy bacteria and eradicates the bad bacteria. It also reduces inflammation of the
gums [25]. Castor oil is a slightly toxic chemical, and a safe amount of castor oil is
found to be below 5 g/kg, below mass per cent (m/m) of 0.099%.
Peppermint extract is used as a flavoring agent, antiseptic, and antiviral agent.
There is no evidence that it has the ability to treat any medical condition. However,
the high concentration of menthol in the extract causes side effects in children and
infants when annihilated.
Sodium benzoate is used as a preservative in food, medicine, and cosmetics. It is
converted to benzoic acid under these conditions, which are fungistatic and bacterio-
static. Due to the insolubility of benzoic acid in the water, it isn’t used directly as a
preservative. Its concentration as a preservative is determined as 0.1% by the FDA.
Lemon juice is a good source of citric acid, containing 1.44 g/oz citric acid, which
is 4.83% by mass citric acid in lemon juice [29]. Citric acid is known to cause tooth
enamel to dissolve quickly. More dentin is exposed as enamel dissolves, causing teeth
cracks and chips, and the edges of the teeth to become more irregular.
1.3 Experimental 5
Tetrasodium EDTA is a water-soluble acid with chelating properties and is an
emulsion stabilizer. It bonds with metal ions in solution, causing them to be inactive,
and is used as a preservative for cosmetic formulation and skin care products,
creams, lotions, etc. It prevents the change in pH, texture, and color of skincare prod-
ucts. And it is used as a copreservative in skincare formulations. Also, it can enhance
foaming and cleaning ability when binding to iron, calcium, or magnesium.
Tab. 1.1: Structures, molecular formulas, and molecular weights of all household chemical compounds
used in the current formulation.
Household Chemical Structure Molecular Molecular
Chemical and Formula Weight
Chemical Name (g/mol)
Distilled water HO .
H H
Sodium chlorite NaClO .
O O–
Cl Na+
Castor oil CH .
18
H3C 8 7 6
17 9 5
16 10 4
11
15 3
14 12
H 2
13 1 O
OH
o
O
o 1 2
O o 5 4
3
1 6
2 7
4
5 3 OH 8
6
H 11
H
9 OH
11 12
7 13 10 12
8 14 13
10 18
9
15
14 CH3
16 15 17
16
17
18 CH3
Major component of castor oil, triester of glycerol
and ricinoleic acid
6 1 Chemical Formulations for Mouthwashes
Tab. 1.1 (continued)
Household Chemical Structure Molecular Molecular
Chemical and Formula Weight
Chemical Name (g/mol)
Peppermint CH .
extract/Oil
O
HO
O O
(Menthol), (3,7-Dimethyl-l-oxaspiro[3.5]nonane),
(Menthyl acetale), (p-Menthan-3-one) and
(Menthofuran)
Sodium benzoate CHNaO .
Na+
O O–
Lemon Juice CHO .
H
(Citric acid)
O O
H
O O
O
H
H
O O
1.3 Experimental 7
Tab. 1.1 (continued)
Household Chemical Structure Molecular Molecular
Chemical and Formula Weight
Chemical Name (g/mol)
Tetrasodium EDTA CHNNaO .
Na+
O– O–
N Na+
O O
O
Na+ N
–O
O O–
Na+
Lemongrass oil CHO .
H
O
H
O H
O
O
HO
(Methyleugenol), (L-Borneol), (Nerol),
(Dihydromyrcene) and (Neral)
Coconut oil contains 80–90% unsaturated fat, is 100% fat, and contains a trace of
minerals and vitamins. It is used for cooking food, as a fuel source in industry, and as
a base ingredient for the manufacture of soap.
Lemongrass oil is known to be used as an herbal alternative (0.25%) to chlorhexi-
dine (0.2%) in mouthwash. It prevents and treats periodontal diseases.
8 1 Chemical Formulations for Mouthwashes
1.4 Conclusion
The therapeutic mouthwash formulation shouldn’t include the following chemical
compounds: citric acid, lemon juice, EDTA, and coconut oil. Citric acid/lemon juice is
known to weaken and dissolve tooth enamel, and both EDTA and coconut oil are
known neither to be used in the pharmaceutical industry nor in mouthwash formula-
tions. EDTA is commonly used in skin products as a chelating agent, and coconut oil is
a fat that is known to be used in cooking, fuel, and in the making of soaps.
The therapeutic mouthwash formulation may include 1.0% Sodium chlorite as an
active ingredient, 0.1% sodium benzoate as a preservative, water as the solvent, and
less than 0.09% by mass castor oil. To improve the quality of the mouthwash formula-
tion, other chemical compounds may be used: glycerin as a humectant and poly oxy-
propylene co-polymer as a surfactant. Color and flavor may be used to improve the
quality of the mouthwash. Some other additives, such as zinc chloride, may also be
used; it Is known to freshen up breath 12 times higher when combined with sodium
chlorite.
The recommended preservative for mouthwash is sodium benzoate. The safe
amount of hydrogenated castor oil is below 5 g/kg.
Chapter Questions
1) What’s the aim of the chapter?
2) What’s the chemical composition of peppermint extract?
3) What are types of mouthwashes?
4) What are the chemicals used in the current formulation? Which chemicals are
found to be harmful to the current formulation? What is the preservative recom-
mended and its safe amount?
5) Write the equation for enamel demineralization? And methods to prevent tooth
decay?
References
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[18] https://www.animated-teeth.com/bad_breath/t5_halitosis_cures.htm
[19] https://www.webmd.com/diet/distilled-water-overview#1
[20] https://www.animated-teeth.com/bad_breath/t5_halitosis_cures.htm
[21] https://pubchem.ncbi.nlm.nih.gov/compound/Castor-oil
[22] Andrade IM, Andrade KM, Pisani MX, et al. Trial of an experimental castor oil solution for cleaning
dentures. Braz Dent J. 2014;25(1):43–47.
[23] Badaró MM, Salles MM, Leite VMF, et al. Clinical trial for evaluation of Ricinus communis and
sodium hypochlorite as denture cleanser. J Appl Oral Sci. 2017;25(3):324–334.
[24] Salles MM, Badaró MM, Arruda CN, et al. Antimicrobial activity of complete denture cleanser
solutions based on sodium hypochlorite and Ricinus communis – a randomized clinical study. J Appl
Oral Sci. 2015;23(6):637–642.
[25] Vieira C, Evangelista S, Cirillo R, et al. Effect of ricinoleic acid in acute and subchronic experimental
models of inflammation. Mediators Inflamm. 2000;9(5):223–228.
[26] Gosselin, R.E., H.C. Hodge, R.P. Smith, and M.N. Gleason. Clinical Toxicology of Commercial
Products. 4th ed. Baltimore: Williams and Wilkins, 1976., p. II-152.
[27] https://en.wikipedia.org/wiki/Peppermint_extract
[28] https://en.wikipedia.org/wiki/Sodium_benzoate
[29] Penniston K.L., Nakada S.Y., Holmes R.P., Assimos D.G., Quantitative Assessment of Citric Acid in
Lemon Juice, Lime Juice, and Commercially-Available Fruit Juice Products, National Library of
Medicine, Journal of Endourology, 2008;22(3):567–70.
10 1 Chemical Formulations for Mouthwashes
[30] https://pubchem.ncbi.nlm.nih.gov/compound/Citric-acid
[31] https://www.glowdental.co.uk/how-citric-acid-affects-your-teeth/
[32] https://en.wikipedia.org/wiki/Tetrasodium_EDTA
[33] https://www.lorealparisusa.com/ingredient-library/disodium-edta
[34] https://www.hsph.harvard.edu/nutritionsource/food-features/coconut-oil/
[35] https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4625327/
[36] https://pubchem.ncbi.nlm.nih.gov/compound/Water
[37] https://en.wikipedia.org/wiki/Sodium_chlorite
[38] https://en.wikipedia.org/wiki/Castor_oil
[39] https://pubchem.ncbi.nlm.nih.gov/compound/Peppermint-oil
[40] https://pubchem.ncbi.nlm.nih.gov/compound/Sodium-benzoate
[41] https://pubchem.ncbi.nlm.nih.gov/compound/Castor-oil
[42] https://pubchem.ncbi.nlm.nih.gov/compound/Lemongrass-oil
[43] Charles C.H, Cronin M. J., Dembling W. Z., Petrone D. M., McGuire J. A., Anticalculus efficacy of an
antiseptic mouthrinse containing zinc chloride, Journal of American Dental Association, 2001;132
(1):94–8, doi: 10.14219/jada.archive.2001.0033.
[44] https://usatoday30.usatoday.com/news/health/2008-05-13-bad-breath_N.htm
[45] http://dentalingredients.spectrumchemical.com/products/oral-care-flavorants
2 Chemical Formulations for Acrylic Matt
and Acrylic Gloss Paints
2.1 Overview
Paints are used to prolong the life of natural and synthetic materials and to protect it;
it acts as a barrier against environmental conditions. Mainly paints are made up of
solvent, binder, extenders, pigment(s), and some additives. A solvent can be either or-
ganic or inorganic, and it is used as a medium to dissolve paint contents together and
make them uniform. It can also be used as a thinner. Pigments are used to give color
to the paint. Binders are used to hold pigments in place. Extenders have large pigment
particles to improve the adhesion properties of the paint, and they are also used to
strengthen the film and save the binder. This chapter discusses the methods used to
improve the properties of acrylic matt paint and methods used to increase the scrub
resistance test of the current formulation. This chapter also presents the types of addi-
tives and chemical compounds that would potentially increase the quality and in-
crease the scrub resistance test for acrylic paints.
2.2 Introduction
Professional Specialty Chemicals Factory, a polymer production unit in Saudi Arabia,
are looking to improve its formulation for acrylic paints to give a better scrub resis-
tance test after decades of using the same formulation. The current formulation consists
of the following chemical compounds: 0.4% natrosol 250-HHBR, 44.39% water, 0.14% so-
dium bicarbonate, 2.0% polyoxyethylene 25 octyl phenol, 2.0% octyl phenol polyglycol
ether sulfate sodium salt, 0.5%, provichem, 2.0% butyl acrylate, 47% vinyl acetate,
0.1258% potassium persulfate, 0.0234% tertiary butyl hydrogen peroxide, 0.06% hydro-
gen peroxide, 0.05% sodium formaldehyde sulfoxylate, 1.0% dibutyl phthalate, 0.1% for-
maline, 0.05% biocide, 0.1% Silquest A-171, and 0.06% defoamer. The scrub resistance
test of the current formulation shows 60% effectiveness compared to the reference; the
coat breaks and gloss change were observed after 60 cycles for the current formulation
compared to 100 cycles for the reference.
Paints are used to prolong the life of natural and synthetic materials and to pro-
tect it; it acts as a barrier against environmental conditions. Paints contain pigment
(s), binder, extender, solvent, and some additives. The pigment is used to give color
and opacity. Binders are matrices and are used to hold the pigment in place. Extend-
ers have larger pigment particles to improve adhesion and to strengthen the film and
save the binder. A solvent can be either an organic solvent or water and is used as a
thinner and to dissolve paint components and make it uniform. Additives are com-
monly used to improve the properties of the paint. Contents of an acrylic white matt
https://doi.org/10.1515/9783111316864-002
12 2 Chemical Formulations for Acrylic Matt and Acrylic Gloss Paints
emulsion paint are known as follows: pigments 25%, extender pigments 12%, additive
5%, solvent 44%, and binder 14%.
To control paint gloss, extender pigments are used. Extender pigments give extra
weight to the paint and are low-cost pigments. There are two types of pigments: ex-
tender pigments and prime pigments. Prime pigments are those that contribute to
both dry and wet hide in paint. There are two main types of prime pigments: inor-
ganic and organic prime pigments. Inorganic prime pigments are earthy colors, duller
and more durable for exterior paint application. Examples are yellow ochre, umber,
and red oxide. TiO2, titanium dioxide, provides the actual color within the container.
Organic prime pigments aren’t very durable for exterior paint application and pro-
vide brighter colors; examples are phthalo blue and hansa yellow. An extender pig-
ment is a naturally occurring chemical substance (usually having a white color) that
is added to paint or coating to improve its properties, such as durability, cost, and
resistance to corrosion or wear.
Ingredients that provide a binding effect that holds the pigments together as dry
film after the liquid solvent evaporates are called binders. Paint binders directly re-
late to paint performance, including gloss retention or fade resistance, washability,
adhesion, and scrub resistance. The binder in many emulsion paints is based on ho-
mopolymers or copolymers of vinyl acetate and a propenoate (acrylic) ester. Other
acrylic esters used as comonomers with ethenyl ethanoate are ethyl propenoate, butyl
propenoates, or a copolymer of butyl propenoate and methyl 2-methylpropenoate.
Many commercial extenders are glycerin-based. In fact, glycerin is already an ingredi-
ent in most acrylic paints. It gives the paint viscosity in addition to extending the dry-
ing time. We can heighten this effect by using glycerol mixed with water. Propylene
glycol is also used for thicker applications.
Binders in various emulsion paints are based on copolymers or homopolymers of
a propenoate (acrylic) ester and ethenyl ethanoate (vinyl acetate)
O
O catalyst
CH 3 C
CH3 C + H2C CH2 + ½ O2 O + H 2O
OH
H 2C CH
Fig. 2.1: Homopolymers of an acrylic ester and vinyl acetate.
Solvents are liquids that allow the paint to be applied to the surface directly from the
containers. Solvents allow the uniform combination of binders, considered solids, and
pigments with the liquid solvent. Types of liquid solvents depend on the type of paint.
For alkyd paints, the liquid solvent is thinner and is typically another type of solvent;
for latex paints, water is the main liquid solvent. More solids in the ingredients allow
for higher quality paints, 35–40%. How much paint will remain on the surface after the
liquid solvent is evaporated depends on the amount of solid in the paint formulation.
2.2 Introduction 13
The make-up of the solids effects the overall paint performance. High solids by volume
don’t always give a high-quality product.
To modify the properties of paint and create additional performance properties,
additives are used. The percent of additives in the formulation is known to be 0.1–1%.
Additives may include algaecides, bactericides, anti-settling agents, driers, thixotropic
agents, dispersants, silicones, and cross-linkers. The molar mass of a polymer is
greatly increased by using a cross-linker, silicates, causing the polymer to become a
three-dimensional molecule and form a hard film to become resistant to chemical
and environmental conditions. Algaecides are used to protect exterior paint films
from being disfigured from lichen, algae, and molds, and bactericides are used to pre-
serve water-based paints in their containers. To prevent pigment settling, antisettling
agents (surfactants) may be used. To accelerate drying time, driers are used. Thixotro-
pic agents are known to be used to create a jelly-like texture of the paint that would
break down to liquid when the paintbrush is placed in it or when stirred. To improve
weather resistance, silicones are used. To stabilize and separate pigment particles and
prevent them from aggregating, dispersants are used.
Water-borne emulsion paints are better for the environment than paints made
with organic liquid solvents. Emulsion paints are made using emulsion polymeriza-
tion, and monomers are dispersed in water as an emulsion. The molecular weight of
the polymers produced is 500,000–1,000,000 a.m.u. For a better application of paint, a
solvent thinner can be used, and it is either water or organic solvent.
An ideal paint has high scratch and heat resistance, high color stability against
ultraviolet and visible light, high water and corrosion resistance, high opacity, a rela-
tively quick drying time and is easily applied to the surface, has high durability and
flexibility, has a good flow out of the application, and forms a strong protective film.
Surfactants, surface active agents, are compounds that lower the surface tension
of liquid or interfacial tension between solid and liquid making them more soluble.
Stabilizing effects for latex paints are caused by using a soluble surfactant, as they
can form micelles and aggregate structures in solutions. In paints, surfactants are
used as an emulsifier. Surfactants have a positive and negative role in being used in a
paint formulation. The positive effect would be stabilizing the dispersion of polymer
molecules during emulsion polymerization, improving the mechanical stability of
paints, and allowing the paint to coat the surface more easily. The negative effect
would be decreasing the resistance of the coating as it can be washed out of the coat-
ing and enter the environment; some of these surfactants are toxic to the environ-
ment, problems with adhesion, and loss of optical clarity. Other chemicals in paint
can alter the overall effect of surfactants on paint. The amount of TiO2 affects the elas-
ticity in latex paint. Chains that consist of alternating silicon and oxygen atoms and
siloxane chains with siloxane tails in polymers have been found to resist hydrolysis
and prevent the breakdown of polymer chains; breakdown of polymer chains can
cause cracking in the paint film. Siloxane is used in soaps, cosmetics, defoamers, and
deodorants.
14 2 Chemical Formulations for Acrylic Matt and Acrylic Gloss Paints
S O–
(a) Hydrophobic tail
O
H
+
N R
(b) Hydrophobic tail
Fig. 2.2: (a) and (b) are the general formula for a surfactant.
cross-linker
polymer
Fig. 2.3: A cross-linker.
Polymers are high molecular substances that are made up of small low-molecular
weight chemical species held together by a chemical bond called monomers. Polymers
are used in coatings, polyurethane, and plastics, and they are used as a binder in
paints. The first polymer studied by chemists is natural or biological polymers such as
protein, starch, and cellulose. An example of a polymer would be polyethylene con-
sisting of ethylene monomers that are chemically bonded.
Polyethylene is a polymer consisting of thousands of ethylene units. The name
polyethylene is a name arousing from the prefix poly, which means “many,” and the
monomer name (ethylene). Synthetic polymers can be either condensation or addition
polymers based on the method used in synthesizing them. In addition to polymerization,
many molecules are linked together by an addition reaction. The monomer molecules
must be unsaturated, containing multiple bonds that can undergo addition reactions. In
a free radical addition, an initiator is used to prepare an addition polymer. An initiator is
2.2 Introduction 15
a compound that can produce free radicals, and organic compounds with O–O group
(peroxides) are commonly used as initiators. When organic peroxides are heated RO–OR,
the O–O bond breaks and free radical form (species having unpaired electrons). Alkene
monomers would react with the free radical formed and produce another free radical,
which in turn reacts with another monomer molecule and produce another free radical
molecule in a chain reaction. The reaction terminates when a free radical at the end of
the chain reacts with another free radical. In condensation polymerization, many mono-
mer molecules are linked together, and a polymer is formed by a condensation reaction,
where a water molecule is removed by joining two molecules. Examples of condensation
polymers are polyesters and polyamides. The repeating monomer units are joined to-
gether by an ester group in polyesters and by an amide group in polyamides.
H H H H H H H H
C C C C C C C C
H H H H H H H H
Fig. 2.4: Shown is a piece of polyethylene.
H H
H H Catalyst
C C [ C C ]n
H CH 3 H CH 3
Fig. 2.5: Example for addition polymerization of propene into polypropylene.
RO–OR→ RO· + ·OR
H H
C C H H
H CH3 RO C C
H CH3
Propene + ·OR →
H H
H H C C
RO C C H CH3
H CH3
+ Propene →
H H H H
RO C C C C
H
Fig. 2.6: Example for free radical polymerization of propene using organic peroxide.
16 2 Chemical Formulations for Acrylic Matt and Acrylic Gloss Paints
nHOH2C CH2OH + nHOOC COOH
Ethylene glycol Terephthalic acid
O
OCH2 CH2 O C C
Fig. 2.7: Example of polyester Dacron formed
O n from condensation polymerization of ethylene
glycol and terephthalic acid.
The technological and physicomechanical properties of various polymers are de-
pendent on the branching that occurs in the polymer chain compared to a linear poly-
mer. An increased degree of branching in the polymer leads to a decrease in strength
properties. For example, branched polybutadiene, divinyl styrene, and other branched
elastomers exhibit low elasticity and breaking strength.
Polymers are classified based on their composition into homopolymer and copol-
ymer. A homopolymer is a polymer that consists of only one monomer. A copolymer
can be either alternate, random, or block copolymer. An alternate copolymer consists
of alternating monomers ab–ab–ab, a block copolymer consists mainly of two or
more monomer chains combined, aaaaa–bbbbb, and a random copolymer consists of
monomers combined in a random array aa–bb–bb–ab–ba.
The durability of concrete structures can be increased by the application of pro-
tective coatings, such as paints.
Protective coatings can be used for the modernization of older concrete works,
rehabilitation of deteriorated concrete, and for restoration of its original properties.
The chemical composition of the protective coatings determines the film properties.
Its properties can be modified by altering the amounts of additives and pigments. Pig-
ments affect the permeability and strength of the film and control the color and gloss.
Latex paints have 10 times greater water diffusion, and it is less homogenous
than solvent paint films.
When concrete is exposed to the environment, it deteriorates, especially when ex-
posed to aggressive environments: industrial and coastal areas. The performance of
paints depends on the chemical composition of their formulation. The better protec-
tion against water penetration was greater with increasing the amounts of binders
(resin) and decreasing amounts of polyvinyl chloride (PVC) polymer. In case of con-
crete with low compressive strength, paints are shown to be efficient for its protec-
tion, while high-compressive strength concrete paints have smaller importance as it
already has a low permeability. Paints are considered for visual aspects with concrete
of high compressive strength. Ref [30]. Decreasing amounts of PVC in the paint formu-
lation from 75% to 0% showed a decrease in water absorption and an increase in coat-
ing effectiveness from 6% to 91%.
2.3 Experimental 17
2.3 Experimental
The paint is prepared by emulsion polymerization, where soap, free radical catalysts
(potassium persulfate, peroxides), and monomers are emulsified in water. The water-
soluble free radical catalyst is added to induce polymerization.
Natrosol 250-HHBR is used as a nonionic water thickener, a protective colloid, sus-
pending agent, and stabilizer and gives chemical mechanical stability and controls
rheology after, during, and before application.
Water is used as a dispensing solvent for emulsion polymerization.
Sodium bicarbonate is used as a pigment, and it dissolves immediately upon addi-
tion to the reaction mixture; a thick textured effect is the result. If more baking soda
is used, it causes the paint to fluff up and become more textured.
Polyoxyethylene 25 octyl phenol is used as a spermaticide. Octyl phenol polyglycol
ether sulfate sodium salt is used as a surfactant and a buffer in emulsion polymeriza-
tion, copolymerization, and homo-polymerization of monomers, and the sodium salt
is used to main pH 6.5–7.5.
Octylphenol polyglycol ether sulfate sodium salt is used in the emulsion polymeri-
zation of acrylate and methacrylate esters, styrene, and vinyl esters. Sodium salt can
be used in homopolymerization as well as in copolymerization of these monomers;
the sodium salt maintains a pH level ranging from 6.5 to 7.5.
Provichem, sodium vinyl sulfonate is a surfactant in emulsion polymerization; it
produces a copolymer with high water stability.
Butyl acrylate is used as a monomer in copolymerization.
Vinyl acetate is used as the other monomer in homopolymerization or copolymeri-
zation.
Potassium persulfate is used as an initiator for free radical polymerization and is
also known to be used as a bleaching agent.
Tertiary butyl hydrogen peroxide is commonly used as an oxidizing catalyst.
Hydrogen peroxide is known to be used as an initiator in vinyl polymerization in
a homogeneous system.
Sodium formaldehyde sulfoxylate is used in redox-reaction polymerization as a re-
ducing agent and as a release and stripping agent in the textile industry; it is also used in
emulsion polymerization as a reducing agent, and it can be used in combination with all
other oxidizing agents, and the recommended usage would be within the range 0.05–0.2%
for postpolymerization reactions, and it can be dry-stored for 12 months at 25 °C.
Dibutyl phthalate is used in adhesives, printing inks, and lacquers as a plasticizer,
and it can be used with other phthalates for PVC compounds as a secondary plasticizer.
Formalin is used as a preservative in some types of adhesives, such as vinyl, and
it may result as a by-product from some polymerization reactions. Biocide is known to
be a chemical substance that has a controlling effect on any harmful organism by bio-
logical or chemical means.
18
Tab. 2.1: Lists the chemical name, molecular formula, and molecular weight of chemical compounds used in the current acrylic paint formulation.
Chemical Name Percent (%) Used in the Molecular Chemical Structure Molecular Formula
Current Formulation Weight (g/mol)
2 Chemical Formulations for Acrylic Matt and Acrylic Gloss Paints
Water . . HO
Natrosol - HHBR . . N/A CHO
Sodium Bicarbonate . . NaHCO
Polyoxyethylene () . . N/A (C-H-O)mult-CH-O
octyl phenyl ether
Octyl phenol polyglycol ether . Buffer and N/A Octyl phenol polyglycol ether
sulfate sodium salt Surfactant sulfate sodium salt
Provichem . . O CHNaOS
(Sodium vinylsulfonate) O–
S Na+
Buyl acrylate . . O CHO
H2C
Vinyl acetate . . O CHO
Potassium Persulfate . . O
O O–
S K+
O
K+ S O
–O O
Tertiary butyl hgrogen peroxide . . OH CHO
Hydrogen peroxide . . H O HO
H
Sodium formaldehyde . . O Na+ CHNaOS
H S O–
sulfoxylate
(continued)
2.3 Experimental
19
Tab. 2.1 (continued)
20
Chemical Name Percent (%) Used in the Molecular Chemical Structure Molecular Formula
Current Formulation Weight (g/mol)
2 Chemical Formulations for Acrylic Matt and Acrylic Gloss Paints
Di butyl phthalate . . CHO
O O
O
Formaline . . H CHO
Biocide . biocide N/A Biocide
Silquesit A- . . CHOSi
(Vinyltrimethoxysilane) O
O
Si
O
Defoamer . Defoamer N/A Defoamer
Total Percentage N/A N/A N/A
2.4 Discussion 21
Additives are chemical substances added in small amounts to the main ingredient
to improve some chemical or physical properties of the material being synthesized.
Silquesit A-171, vinyltrimethoxysilane, offers silanes and vinyl compounds some func-
tionality by cross-linking organic polymers; the cross-linked Si–O–Si bond formed is
highly resistant to UV light, other chemicals, and exposure to moisture. It can also be
added as a monomer in emulsion polymerization to form modified silane latexes,
functioning as a cross-linker forming stable Si–O–Si bond linkages.
2.4 Discussion
The current formulation consists of the following chemical compounds: 0.4% natrosol
250-HHBR, 44.39% water, 0.14% sodium bicarbonate, 2.0% polyoxyethylene 25 octyl phe-
nol, 2.0% octyl phenol polyglycol ether sulfate sodium salt, 0.5%, provichem, 2.0% butyl
acrylate, 47% vinyl acetate, 0.1258% potassium persulfate, 0.0234% tertiary butyl hydro-
gen peroxide, 0.06% hydrogen peroxide, 0.05% sodium formaldehyde sulfoxylate, 1.0% di
butyl phthalate, 0.1% formaline, 0.05% biocide , 0.1% Silquest A-171, and 0.06% defoamer.
The current acrylic paint formulation consists mainly of 44.39% water as solvent,
49% pre-emulsion monomers (vinyl acetate and butyl acrylate), and 6.61% additives
(natrosol 250-HHBR, sodium bicarbonate, polyoxyethylene 25 octyl phenol, octyl phe-
nol polyglycol ether sulfate sodium salt, Provichem, 2.0% butyl acrylate, potassium
persulfate, tertiary butyl hydrogen peroxide, hydrogen peroxide, sodium formalde-
hyde sulfoxylate, dibutyl phthalate, formaline, biocide, Silquest A-171, and defoamer).
The current percentage of each component in the current formulation provided
are pigments (sodium bicarbonate) 0.14%, extenders (none used), additives 6.4629%,
solvent 44.39%, and binders 49%.
The main pre-emulsion monomer used is of only one type of monomer, and vinyl
acetate and butyl acrylate are only of 2% and is used as additive in the current formu-
lation. The binder formed from the pre-emulsion polymerization of the monomers
used in the formulation would mainly be a homopolymer consisting of vinyl acetate
monomers and some butyl acrylate impurities.
The amount of surfactant used as an additive is 4.5%, which is very high and causes
a lower scrub resistance test for the current formulation. The addition of surfactants
does not always have a positive effect on all properties. The water resistance of the
coating can be decreased with surfactant addition since surfactants can be very water-
soluble and will easily wash out of a coating. This problem of moisture resistance is a
particularly prevalent problem for art conservation as well as problems with adhesion,
loss of optical clarity, and dirt pickup caused by polyether surfactants in contemporary
acrylic emulsion used in artworks bearing acrylic coats. While the type and amount of
surfactant determine what properties will be affected, other chemicals in paint can
alter the overall effect the surfactants may have on the paint. Elasticity has been found
to either increase or decrease in latex paints depending on the amount of TiO2 present.
22 2 Chemical Formulations for Acrylic Matt and Acrylic Gloss Paints
Fig. 2.8: Sheen scrub tester used in the scrub resistance test for the
current acrylic paint formulation.
2.5 Conclusion
In order to improve the quality of the paint and increase its scrub resistance, missing
chemical compounds from the current formulation, pigments, extender, and another
type of pre-emulsion monomer must be added to the formulation. The use of pigments
and extenders in the formulation would form a firm protective layer and prevent the
dissolution of the paint film from the surface and to improve the scrub resistance test of
the acrylic paint, and it is recommended to avoid using copious amounts of surfactants.
The current formulation consists of pigments 0.14% in the form of sodium bicar-
bonate compared to the literature amount 25%. Extender pigments weren’t used in
the current formulation compared to the literature amount 12%, surfactants 4.5%
compared to the literature amount 0–1%, and binders 49% compared to the literature
amount 14%. The current paint scrub resistance test shows that the paint operates
with 60% effectiveness compared to the reference due to missing 40% of the main in-
gredients that make good acrylic paint.
Copious amounts of surfactants 4.5% (2.0% octyl phenol polyglycol ether sulfate
sodium salt, 2.0% octyl phenol polyglycol ether sulfate sodium salt, and 0.5% Provi-
chem) have been causing a low-scrub resistance test of current formulation compared
to the reference. The large amounts of surfactants are used as an additive, 4.5%, has a
negative effect on the formulation, causing a low-scrub resistance test result com-
pared to the reference.
References 23
Chapter Questions
1) What’s the aim of the chapter?
2) What’s the main chemical composition of paints and its function in the formulation?
3) What’s the chemical name for Provichem?
4) What are the chemicals used in the current formulation? Which chemicals are
found to be harmful to the current formulation? And what are the recommended
additives to increase its quality?
5) What’s a crosslinker and its function?
References
[1] http://pscf.com.sa/
[2] The Essential Chemical Industry, 2013, Paints. Retrieved February 9, 2022, from www.essentialchemi
calindustry.org
[3] Dunn Edwards Paints, 2013, What is Paints Made of? Retrieved February 10, 2022, from www.dunned
wards.com.
[4] Wikipedia, January 2022, Surfactants in Paint. Retrieved February 9, 2022, from https://en.wikipedia.
org/
[5] Ebbing and Gammon, 2015, General Chemistry 11th edition, Boston MA, Cengage.
[6] https://coatings.specialchem.com/product/a-ashland-specialtychemical-natrosol-250-hhbr
[7] National Library of Medicine, 2022, Sodium Bicarbonate. Retrieved March 9, 2022, from
https://pubchem.ncbi.nlm.nih.gov.
[8] Haz-Map, “Octoxynol, CAS# 9002-93-1”, Haz-Map (2022, April 22), http://haz-map.com
[9] https://chem.nlm.nih.gov/chemidplus/rn/9002-93-1
[10] JimTrade, “Octylphenol Polyglycol Ether Sulphate Sodium Salt”, Jim Trade (2022, April 22),
https://www.jimtrade.com/
[11] https://www.alfa.com/en/catalog/L15356/
[12] National Library of Medicine, 2022, Butyl Acrylate. Retrieved March 9, 2022, from https://pubchem.
ncbi.nlm.nih.gov.
[13] Wikipedia, January 2022, Vinyl Acetate. Retrieved March 9, 2022, from https://en.wikipedia.org/
[14] National Library of Medicine, 2022, Potassium Persulfate. Retrieved March 9, 2022, from
https://pubchem.ncbi.nlm.nih.gov.
[15] National Library of Medicine, 2022, Tert Butyl Hydroperoxide. Retrieved March 11, 2022, from
https://pubchem.ncbi.nlm.nih.gov.
[16] Nandi U. S., Palit S. R., Hydrogen peroxide as initiator in vinyl polymerization in homogeneous
system. I. Kinetic studies, Journal of Polymer Science, 1955, 17 (83), pp 65–78.
[17] National Library of Medicine, 2022, Sodium Formaldehyde Sulfoxylate. Retrieved March 12, 2022,
fromhttps://pubchem.ncbi.nlm.nih.gov.
[18] https://coatings.specialchem.com/product/a-bruggemannreducing-agent-tp-1648
[19] Wikipedia, January 2022, Dibutyl Phthalate. Retrieved February 11, 2022, from https://en.wikipedia.
org/
[20] Stefano Ciroi, 2017, Formaldehyde in Vinyl Adhesives. Retrieved March 13, 2022, from https://catas.
com/en-GB/news.
[21] Michalak, K. Chojnacka, Biocides, Encyclopedia of Toxicology (Third Edition) 2014, Pages 461–463.
24 2 Chemical Formulations for Acrylic Matt and Acrylic Gloss Paints
[22] National Library of Medicine, 2022, Vinyltrimethoxysilane. Retrieved March 9, 2022, from
https://pubchem.ncbi.nlm.nih.gov.
[23] Momentive Solutions for a Sustainable Group, 2022, Silquest A-171 Silane. Retrieved March 12, 2022,
from www.momentive.com.
[24] Encyclopedia Britannica, Inc., 2022, Emulsion Polymerization, Retrieved 10 March 2022, from www.
Britannica.com
[25] Grechanovskii, V. A., Branching in Polymer Chains, Rubber Chemistry and Technology (1972) 45 (3):
519–545.
[26] Charles E. C Jr., 2017, Introduction to Polymers 4th edition,Boca Raton, Taylor & Francis Group.
[27] Swamy, R. N. and Tanikawa, S., ‘An external surface coating to protect concrete and steel from
aggressive environments’, Mater. Struct. 26 (1993) 465–478.
[28] Tyssal, L. A., ‘Industrial paints: Basic principles’, (Pergamon Press Ltd, London 1964).
[29] Uemoto, K. L., Agopyan, V., Ranieri, R. and Quarcioni, V. A.,’Effect of concrete coating systems on
chloride penetration’, in ‘Consec 98: Concrete Under Severe Conditions’, Proceedings of an
International Conference, Norway, (1998) 1321–1330.
[30] Uemoto KL, Agopyan V, Vittorino F. Concrete protection using acrylic latex paints: Effect of the
pigment volume content on water permeability. Materials and Structures. 2001 Apr; 34(3):172–7.
3 Increase Product Quality for a Car-Wash
Shampoo Concentrate
3.1 Overview
The market for vehicle cleaning products in Western Europe approached a value of
$400 million dollars in 2007. Domestic and industrial automated cleaning of vehicles
can include four main steps: prewash, main wash, rinse, and drying, besides the man-
ual cleaning of domestic vehicles. This chapter presents the methods used to improve
the properties of the current car wash shampoo concentrate formulation and increase
its quality. The chapter also presents some new chemical compounds and additives that
would increase the quality of the car wash shampoo concentrate and methods used to
increase the concentration of the current formulation for its use and distribution.
3.2 Introduction
Saka International Group, a leading manufacturer of home care business, laundry,
and car care products by Schnnell, ON, Canada, are looking to improve the chemical
properties of their car wash shampoo. A liter of car wash shampoo concentrate di-
lutes only to 200 L using the current formulation. The formulation consists of the fol-
lowing chemical compounds: 5% linear alkyl benzene sulfonic acid (LABSA), 20%
sodium lauryl ether sulfate (SLES), 5% sodium lauryl sulfate (SLS), 1% sodium hydrox-
ide, 2% betaine, 61.5% water, 3% sodium triphosphate, 2% glycerol, and 0.5% propyl-
ene glycol.
Car maintenance products are classified into the interior and exterior car care
products. Interior car care products are deodorants, grease cleaners, vinyl and plastic
cleaners and polishes, and interior wins screen cleaners, carpet shampoos, and leather
polishes. Interior car care products include tire dressings and cleaners, presoak deter-
gents, car polishes, wash and wax formulations, windscreen cleaners, water-repellents
and drying aids, and wheel rim cleaners. The climate and the season of the year affect
the nature of the soiling of the vehicle and the ease of its removal.
The bodywork of the automobile consists of multiple coatings; each coating pro-
vides a variety of functions. Figure 3.1 shows the coating layers in the bodywork of
modern cars. The paintwork of the vehicle is the external surface to be cleaned.
The base coat is usually water-based polymeric binders, fillers, and pigments. The
inner coating, the electro-deposition paint, and the phosphate-based anticorrosion
layer provide protection to the metal surface. On top of the protective coatings is the
filler layer; it must have an excellent adhesion property to both the top coat and the
base coat. The finishing lacquer must have good impact strength, retain gloss, and it
must be waterproof. Domestic and industrial automated cleaning of vehicles can be
https://doi.org/10.1515/9783111316864-003
26 3 Increase Product Quality for a Car-Wash Shampoo Concentrate
Base Lacquer
12–15μm
Filler Coating 35 μm
Electro-redeposition paint
18–25 μm
Phosphate anti-corrosion layer 2 μm
Metal bodywork
Fig. 3.1: Modern vehicle paintwork structure.
divided into four main steps: pre-wash, main wash, rinse, and drying, besides the
manual cleaning of domestic vehicles. Prewash includes cold degreaser, microemul-
sion, and foam wash. The main wash includes shampoo and microemulsion. Rinse in-
cludes hot/cold wax and rinse aid.
Car shampoos can be either in liquid or powder form. Liquid car shampoos are a
combination of binders, surfactants, and liquids dissolved in water as the main sol-
vent. These products are easy to rinse off, high foaming, biodegradable, made to cut
through grease on the bodywork, and they don’t damage any part of the vehicle sur-
face including the paintwork. Economy car shampoos do not contain builders. Powder
car shampoos are made of a mixture of builders (carbonates, phosphates, or metasili-
cates) and surfactants (fatty alcohol ethoxylates or dodecylbenzene sulfonates) ab-
sorbed into the powder.
The main anionic detergent can be either alkylbenzene sulfonates and/or sodium
lauryl ether sulfates. Sodium lauryl ether sulfate is incorporated into the formulation
used when the denser, richer foam is required. Fatty acid alkanolamides, amine oxide,
or betaine is used in the formulation for viscosity and to stabilize the foam produced.
For greater foam stability and viscosity, amides are added to the formulation. To in-
crease the quantity of the foam produced, betaines and amine oxides are used. Glycerol
ether is used to ease grease removal. Secondary surfactants are used for viscosity and
foam modifications and are also used to enhance spot removal and improve deter-
gency. Binders such as phosphates (0.5–2.5%) are added to improve detergency.
Low hydrophilic-lipophilic balance (HLB) fatty alcohol ethoxylate/hydrotropic sys-
tem replaced the traditional anionic surfactant-based car shampoo as they afford
more effective cleaning performance, decreasing and they have low foam profile.
Sodium citrate is known to be a water softener and a PH adjuster. It is an ingredi-
ent used in most common liquid detergents. It is also used in some food products to
adjust their acidity. It is used in ice cream, gelatin desserts, candy, and jelly. It is also
3.3 Experimental 27
Tab. 3.1: Traditional anionic car wash shampoo formulation.
Chemical Compound % by weight used the formulation
Soudium carbonate (binders)
Sodium metasilicate pentahydrate (binders)
Sodium citrate (water softner)
Glycerol ether (solvent)
Linear alkyl benzene sulphonate (%) detergent
Sodium lauryl ether sulphate (%) Detergent
Coconut diethanolamide (foam producer)
Water
Preservatives/ dyes Q.S.
Tab. 3.2: HLB fatty alcohol ethoxylate/hydrotropic car wash shampoo formulation.
Chemical Compound % by weight used the formulation
Fatty alcohol ethoxylate (low HLB)
Hydrophobe (alkyl glycoside or quaternary -
fatty amine ethoxylate)
TKPP (Tetrapotassium Pyrophosphate)
Detergent builder
Sodium metasilicate
Balance water
used in some pharmaceutical and personal care products such as sunscreens, facial
moisturizers, makeup, baby wipes, soaps, shampoos, and conditioners.
Coconut diethanolamide is used as an emulsifying and foaming agent in personal
care products and in cosmetics. It is extracted from coconut oil. It is also used in hy-
draulic fluids and industrial cooling lubricants.
3.3 Experimental
The chemical composition of the ingredients used in the making of the car-wash
shampoo concentrate is presented in Tab. 3.1.
Linear alkyl benzene sulfonic acid is used as a mercerizing and washing agent in
the textile industry. It is used as an emulsifier and wetting agent in small quantities
with surfactants as it increases the surface area of distempers. Because of its good per-
formance and low-cost linear alkylbenzene sulfonic acid is the largest volume synthetic
anionic detergent. As all surfactants, linear alkylbenzene sulfonic acid has both hydro-
philic and hydrophobic groups. Other examples of commercial anionic surfactants are
alkyl sulfates and alpha-olefin sulfonates. These compounds are produced by sulfona-
tion, and they are nonvolatile compounds. Linear alkylbenzene sulfonic acid consists of
28 3 Increase Product Quality for a Car-Wash Shampoo Concentrate
a phenyl isomer of five to two-position substituents, different alkyl chain lengths con-
sisting of 10–14 carbon atoms (C10–C14), and an aromatic ring sulfonated at the para-
position attached to the linear alkyl chain at any position except position 1, the 1-phenyl
position. The chemical and physical properties of linear alkylbenzene sulfonic acid dif-
fer based on the length of the alkyl chain, giving rise to different formulations and dif-
ferent usage in various applications.
Sodium lauryl ether sulfate is a surfactant, and it is an anionic detergent. It is a
very effective foaming agent, inexpensive, and used in shampoos, toothpastes, and
soaps.
Sodium lauryl sulfate is used in hygiene, cleaning, food, and pharmaceutical
products, and it is an anionic-surfactant. It is widely used as a food additive in the
food industry and as an emulsifier and an ionic solubilizer in the pharmaceutical
industry.
Sodium hydroxide sulfate is a strong base, hygroscopic solid, and soluble in water
and can cause severe burns. It is used in various industries; it is used in the manufac-
ture of drain cleaners, soaps, detergents, textiles, drinking water, pulp, and paper. It
is used as a paint stripper, cleaning agent, relaxer, and in food preparation.
Betaine is a chemical compound occurring in plants, and it is an amino acid; it is
a white solid at room temperature. It is present in living cells, and it is a methylated
nitrogen compound. It is used in the pharmaceutical industry in the preparation of
shampoo and soap as it is a nonionic surfactant. Due to its high surface activity, its
derivatives are used as efficient cleansing agents. It is also used as viscosity modifiers,
foam stabilizers, and detoxifiers. Betaine esters can be used in antiperspirants as it
processes antimicrobial activity.
Water is an inorganic compound that is odorless, tasteless, transparent liquid at
room temperature and acts as a solvent. It is present in 70% of the earth’s surface as
seas and oceans. In the world economy, 70% of water is used in agriculture.
Sodium triphosphate is used as a component of industrial and domestic products
on a large scale.
It is used as a builder and a water softener in commercial detergents. Detergents
are deactivated in water containing high concentrations of Mg2+ and Ca2+, hard water.
It is a chelating agent as it binds tightly to bications and prevents them from interfer-
ing with sulfonate detergent. It is used as an emulsifier to retain moisture, and it is
also used as a preservative in the food industry. It is also used as an anticracking
agent, flame-retardant, anticorrosion pigment, synthetic tanning agent, and masking
agent in the leather industry.
Glycerol is an odorless and nontoxic colorless viscous liquid at room temperature.
Glycerol is hygroscopic in nature and is miscible in water. It is used as a humectant in
pharmaceutical formulations as it improves the ability of the skin to absorb water,
and it is used in the food industry as a sweetener.
Propylene glycol is a colorless viscous liquid at room temperature and has a
faintly sweet taste. It is miscible in a wide variety of solvents including chloroform,
3.3 Experimental 29
acetone, and water. It is a nonirritating substance with low volatility. It is used in var-
ious industries, including food and drug, antifreezes, polymers, and electronic ciga-
rettes. It is used as a humectant in hand sanitizers to prevent skin drying. It is used in
coffee-based drinks, ice creams, whipped dairy products, soda, and liquid sweeteners.
Polypropylene glycol alginate gives rise to a greater increase in foam stability equal to
the amount of neutral polysaccharides.
The current formulation consists of 1% builder in the form of sodium hydrox-
ide, 3% water softener in the form of sodium triphosphate, 32% surfactants in the
form of 5% linear alkyl benzene sulfonic acid, 20% sodium lauryl ether sulfate, and
5% sodium lauryl sulfate and 2.5% solvents in the form of 0.5% propylene glycol and
2% glycerol.
Sodium and potassium hydroxides are known to be used in wheel rim cleaner
formulations as the alloy wheel picks up dirt and grease from the road, and they are
prone to dirt from the abrasive wear of brake shoes. The amount of sodium and po-
tassium hydroxides used in the wheel rim cleaner formulation is 0–15%. It isn’t
known to be used in car wash formulations. Other builders are known to be used in
car wash formulations to soothe out slight imperfections and to remove road grease
and stubborn tar from the bodywork of the vehicle. These builders would be calcium
carbonate, silicones, and lamella aluminum silicates. To increase the quality of the
car wash shampoo formulation, silicone derivative builders are added to the formula-
tion. Silicone derivative builders contribute to the ease of application of the products,
the gloss, and its water-repellency property.
The amount of surfactant used in the current car wash shampoo formulation con-
centrate is 32% (5% linear alkyl benzene sulfonic acid, 20% sodium lauryl ether sulfate,
5% sodium lauryl sulfate, and 2% betaine). To increase the quality of the car wash
shampoo, the amount of surfactants in the formulation must be increased to 37%.
The solvents used in the current formulation: 0.5% propylene glycol and 2.0%
glycerol are both known to be used as humectants in pharmaceutical and personal
care product formulations to improve the ability of the skin to absorb water. These
solvents aren’t known to be used in car wash shampoo formulations. Other solvents
are used in car wash shampoo formulations (4% glycol ether) to aid in the removal of
surface dirt and to act as a carrier for silicates and components of the shampoo. Sol-
vents that are commonly used in car wash shampoo formulations are glycol ethers
such as dipropylene alcohol monomethyl ether to dissolve grease.
The choice of solvent is critical to avoid the stress and cracking of plastics and to
avoid damage to the painted surface. It didn’t recommend the use glycerol or propyl-
ene glycol in the formulation and glycol ether. Also, the amount of solvents used in
the current formulation is low, 2.5%, compared to the amount used, reference 4%. The
amount of solvents used should be increased to 4% to increase the quality of the car
wash shampoo formulation.
For the current formulation to dilute to a greater volume of 500 L and to also
maintain the quality of the car wash shampoo concentrate, the amount of surfactants,
30
Tab. 3.3: Chemical name, molecular formula, and molecular weight of chemical compounds used in the current formulation.
Chemical Name Chemical Structure Molecular Formula Molecular weight Amount Used in the
(g/mol) Current Formulation (%)
3 Increase Product Quality for a Car-Wash Shampoo Concentrate
Linear Alkyl Benzene Sulphonic CH(CH)CHSOH .
Acid (LABSA)
O O
S
HO
Sodium Lauryl Ether Sulphate CH(CH)(OCHCH)nOSONa Variable; typicaly around
(SLES) g/mol
Sodium Lauryl Sulphate (SLS) CHNaSO .
Sodium Hydroxide H Na+ NaOH .
O–
Betaine CH3 O CHNo .
H 3C +
N
O–
H3C
Water .. .. HO . .
(Dihydrogen Monoxide) O
H H
Sodium triphosphate o o o NaPO .
P P P Na+
–o o o o–
o– o– o–
5
Glycerol H CHO .
H C OH
H C OH
H C OH
Propylene Glycol HO CHO . .
OH
3.3 Experimental
31
32 3 Increase Product Quality for a Car-Wash Shampoo Concentrate
builders, foaming agents, and solvents must be increased relative to the amount of
the main solvent used to dissolve its components. The current formulation dilutes to
200 L; in order for the formulation to dilute to double this volume, the amount of the
main solvent used to dissolve its components must be decreased to half, and the
amount of surfactants/builders/foaming agents and solvents must be increased by 1½.
Taking the traditional anionic car wash shampoo formulation as an example, the per-
centage of each chemical compound in the formulations would be 3% sodium carbon-
ate, 4.5% sodium metasilicate pentahydrate, 3% sodium citrate, 6% glycerol ether,
40.0% linear alkyl benzene sulfonate, 15% sodium lauryl ether sulfate, 4.5% coconut
diethanolamide, and 24.0% water as the dissolving solvent.
3.4 Conclusion
To increase the quality of the car wash shampoo-concentrate 2% builders in the form
of sodium carbonate, 3% builders in the form of silicates, and 3% foaming and emulsi-
fying agents in the form of coconut diethanolamide should be included in the formu-
lation. It also recommends the use of another different solvent to dissolve grease and
improve the quality of the car wash shampoo concentrate, 4% glycol ether.
Foaming and emulsifying agent are used to dissolve solvents, builders, and sili-
cates and facilitate the formation of foams. Builders used in car wash shampoo formu-
lations remove road grease and stubborn tar from the bodywork of the vehicle,
smooth out minor surface scratches and slight imperfections, contribute to the gloss,
the water repellency, increase the durability of the overseal, and polish the paint-
work. The choice of builders and solvents is critical to avoid the stress-cracking of
plastics and to avoid damage to the painted surface. Calcium carbonates, silicones, la-
mella aluminum silicates, and poly dimethyl siloxane are known to be used in car
wash shampoo formulations as builders.
It recommends avoiding the use of sodium hydroxide as a builder or the use of
glycerol/propylene glycol as solvents in the car wash shampoo formulation, and the
amount of surfactants must be increased to at least 37%.
Sodium hydroxide is known to be used in wheel rim cleaner formulation as the
alloy wheel pick up dirt and grease from the road not in car wash shampoos; glycerol
and propylene glycol are known to be used as humectants in lotions and personal
care products. Sodium hydroxide, glycerol, and propylene glycol aren’t known to be
used in car wash shampoo formulations.
In order to increase the concentration of the car-wash shampoo concentrate and
make a liter of concentrate dilute to 500 L instead of 200 L, the amount of builders,
solvents, and surfactants must be increased to 1½, and the amount of water must be
decreased to half.
References 33
Chapter Questions
1) What’s the aim of the chapter?
2) What are the types of car wash shampoos and the main difference in their chemi-
cal composition?
3) What’s the main chemical composition of an anionic car was shampoos?
4) What are the chemicals used in the current formulation? What are the methods
used to increase its quality? And what are the recommended additives to increase
its quality?
5) What’s the chemical structure and the main function of glycerol in a car wash
shampoo?
References
[1] http://www.sakagroup.com
[2] Company M., Karsa D. R., Handbook for Cleaning/ Decontamination of Surfaces, Amsterdam, the
Netherlands, Elsevier B.V., 2007.
[3] H.G. Hauthal and G. Wagner (eds.), Household Cleaning, Care and Maintenance Products:
Chemistry, Application, Ecology and Consumer Safety, pub1. Verlag Fur chemische Industrie H
Ziolkowsky GmbH, 2004.
[4] Surfactants Selector; A Guide to the Selection of I&I and Household Product Formulations, Akcros
Chemicals (now part of Akzo Nobel Surface Chemistry AB) 1998.
[5] Further formulation information available from Akzo Nobel Surface Chemistry AB, S 444 85
Stenungsund, Sweden, on request.
[6] Chemicalland21, 2013, Linear Alkylbenzene Sulfonic Acid, Retrieved May 2022, from www.chemical
land21.com/specialtychem/perchem.
[7] Wikipedia the Free Encyclopedia, 2022, Sodium Laureth Sulfate, Retrieved May 2022, from
https://en.wikipedia.org.
[8] Wikipedia the Free Encyclopedia, 2022, Sodium Dodecyl Sulfate, Retrieved May 2022, from
https://en.wikipedia.org.
[9] Wikipedia the Free Encyclopedia, 2022, Sodium Hydroxide, Retrieved May 2022, from
https://en.wikipedia.org.
[10] Wikipedia the Free Encyclopedia, 2022, Trimethylglycine, Retrieved May 2022, from https://en.wikipe
dia.org.
[11] Wikipedia the Free Encyclopedia, 2022, water, Retrieved May 2022, from https://en.wikipedia.org.
[12] Wikipedia the Free Encyclopedia, 2022, Sodium Triphosphate, Retrieved May 2022, from
https://en.wikipedia.org.
[13] Wikipedia the Free Encyclopedia, 2022, Glycerol, Retrieved May 2022, from https://en.wikipedia.org.
[14] Wikipedia the Free Encyclopedia, 2022, Propylene Glycol, Retrieved May 2022, from https://en.
wikipedia.org.
[15] World of Chemicals, 2022, Linear Alkylbenzene Sulfonic Acid, Retrieved May 2022, from
www.worldofchemicals.com.
[16] Valappil K., Lalitha S., Gottumukkala D., Sukumaran R. K., Pandey A., White Biotechnology in
Cosmetics, Industrial Biorefineries & White Biotechnology, 2015, pp. 607–652. ISBN 9780444634535
34 3 Increase Product Quality for a Car-Wash Shampoo Concentrate
[17] “Water Q&A: Why is water the “universal solvent”?”. http://www.usgs.gov. (U.S. Department of the
Interior). Retrieved 15 January 2021.
[18] “CIA – THE WORLD FACTBOOK Geography Geographic overview”. Central Intelligence Agency.
Retrieved 20 December 2008.
[19] Baroni, L.; Cenci, L.; Tettamanti, M.; Berati, M. (2007). ”Evaluating the environmental impact of
various dietary patterns combined with different food production systems”. European Journal of
Clinical Nutrition. 61 (2): 279–286. doi:10.1038/sj.ejcn.1602522. PMID 17035955.
[20] Complexing agents, Environmental and Health Assessment of Substances in Household Detergents
and Cosmetic Detergent Products, Danish Environmental Protection Agency, Accessed 2008-07-15
[21] Schrödter, Klaus; Bettermann, Gerhard; Staffel, Thomas; Wahl, Friedrich; Klein, Thomas; Hofmann,
Thomas (2008). “Phosphoric Acid and Phosphates”. Ullmann’s Encyclopedia of Industrial Chemistry.
doi:10.1002/14356007.a19_465.pub3. ISBN 978-3527306732.
[22] Oxford Dictionaries – English, glycerol – Definition of glycerol in English by Oxford Dictionaries”.
Archived from the original on 21 June 2016. Retrieved 21 February 2022.
[23] Christoph, Ralf; Schmidt, Bernd; Steinberner, Udo; Dilla, Wolfgang; Karinen, Reetta (2006).
“Glycerol”. Ullmann’s Encyclopedia of Industrial Chemistry. doi:10.1002/14356007.a12_477.pub2.
ISBN 3527306730.
[24] Sullivan, Carl J.; Kuenz, Anja; Vorlop, Klaus‐Dieter (2018). “Propanediols”. Ullmann’s Encyclopedia of
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[25] Lohrey, Jackie. ”Ingredients in Hand Sanitizer”. LIVESTRONG.COM. Retrieved 2018-06-11.
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0416.1980.tb03953.x.
[28] PersianUTab, “Sodium citrate in detergents”, www.persianutab.com, 2020. Retrieved May 11, 2022
[29] Contact Dermatitis Institute, “Coconut diethanolamide”, www.contactdermatitisinstitute.com, 2022.
Retrieved May 11, 2022.
4 Modification to an Acrylic Paint Formulation
4.1 Overview
Paints are used to protect and prolong the life of natural and synthetic materials as it
acts as a barrier against environmental conditions. Paints contain extenders, solvents,
pigments, binders, and some additives. The contents of acrylic white matt emulsion
paint are known to be 25% pigments, 12% extender pigments, 5% additives, 44% sol-
vents, and 14% binders.
Binders are matrices and are used to hold the pigment in place. Extenders have
larger pigment particles to improve adhesion, strengthen the film, and save the
binder. Pigments are used to give color and opacity to the paint. A solvent can be ei-
ther an organic solvent or water and is used as a thinner to dissolve paint components
and make them uniform. Additives are commonly used to improve the properties of
the paint.
This chapter briefly shows how to manipulate the chemical and physical proper-
ties of chemical compounds making acrylic matt paint improve its quality. It presents
the chemical compounds that would potentially lower the scrub resistance test. It also
presents the additives and the chemical compounds that would potentially increase
the quality and increase the scrub resistance test for acrylic matt paint.
4.2 Introduction
A polymer production unit in Saudi Arabia, PSCF, is looking to improve its current
formulation of the current acrylic matt paint formulation as the current formulation
shows a low scrub resistance test compared to the reference. The current paint scrub-
resistance test shows that the paint operates with 60% effectiveness compared to the
reference.
The current formulation consisted of 47% vinyl acetate, 0.1258% potassium persul-
fate, 0.0234% tertiary butyl hydrogen peroxide, 0.06% hydrogen peroxide, 0.05% sodium
formaldehyde sulfoxylate, 1.0% di butyl phthalate, 0.1% formaline, 0.05% biocide, 0.1%
Silquest A-171 and 0.06% defoamer, 0.4% Natrosol 250-HHBR, 44.39% water, 0.14% so-
dium bicarbonate, 2.0% polyoxyethylene 25 octyl phenol, 2.0% octyl phenol polyglycol
ether sulfate sodium salt, 0.5%, Provichem, and 2.0% butyl acrylate. Chemical names,
molecular formulas, and molecular weights of all chemical compounds used in making
the current acrylic paint formulation are listed in Tab. 4.1.
An acrylic white matt emulsion paint is known to consist of 25% pigments, 44%
solvents, 12% extender pigments, 5% additives, and 14% binders (Fig. 4.1).
https://doi.org/10.1515/9783111316864-004
36 4 Modification to an Acrylic Paint Formulation
Emulsion White Matt Paint
Composition
12.0% 44.0% 5%
14.0% Binder 25.0% Pigment
Extender Solvent Additives
Fig. 4.1: Chemical composition for a matt white paint.
Tab. 4.1: Chemicals, amounts in percentage, and the role of chemical compounds used in the current
acrylic paint formulation.
Chemical Name Percent (%) Used Molecular Formula Role of Each Chemical
in the Current Compound in Current
Formulation Formulation
Water . HO Solvent
Natrolsol -HHBR . CHO Nonionic water thickener
Sodium Bicarbonate . NaHCO Pigment
Polyoxyethylene () octyle . (C-H-O)mult-CH-O Surfactant and buffer
phenyl ether
Octyl phenol polyglycol . Octylphenol polyglycol Surfactant and buffer
ether sulfate sodium salt ether sulfate sodium salt
Provichem (Sodium . CHNaOS Surfactant
vinylsulfonate)
Buyl acrylate . CHO Monomer in homo or
copolymerizaton (Binder)
Vinyl acetate CHO Monomer in homo or
copolymerization (Binder)
Potassium Persulfate . Initiator
Tertiary butyl hgrogen . CHO Oxidizing catalyst
peroxide
Hydrogen peroxide . HO Initiator
Sodium formaldehyde . CHNaOS Reducing agent
sulfoxylate
DI butyl phthalate . CHO Secondary plasticizer
Formaline . CHO Preservative
Biocide . Biocide Biocide
4.4 Conclusion 37
Tab. 4.1 (continued)
Chemical Name Percent (%) Used Molecular Formula Role of Each Chemical
in the Current Compound in Current
Formulation Formulation
Silquesit A- . CHOSi Crosslinking polymer
(Vinyltrimethoxysilane)
Defoamer . Defoamer Defoamer
Total Percentage N/A N/A
4.3 Detailed Analysis
The current acrylic paint formulation consisted mainly of 44.39% water as a solvent,
49% pre-emulsion monomers (vinyl acetate and butyl acrylate), and 6.61% additives
(Natrosol 250-HHBR, sodium bicarbonate, polyoxyethylene 25 octyl phenol, octyl phe-
nol polyglycol ether sulfate sodium salt, Provichem, 2.0% butyl acrylate, potassium
persulfate, tertiary butyl hydrogen peroxide, hydrogen peroxide, sodium formalde-
hyde sulfoxylate, dibutyl phthalate, formaline, biocide, Silquest A-171, and defoamer).
4.4 Conclusion
The current formulation consists of pigments 0.14% in the form of sodium bicarbon-
ate compared to the literature amount 25%. Extender pigments weren’t used in the
current formulation compared to the literature amount 12%, surfactants 4.5% com-
pared to the literature amount 0–1%, and binders 49% compared to the literature
amount 14%. The copious amounts surfactants are causing a low-scrub resistance test
of the current formulation compared to the reference.
In order to increase the quality of the acrylic paint, pigments, extenders, and an-
other type of pre-emulsion monomer should be included in the formulation to form a
firm protective layer and prevent the dissolution of the paint film from the surface and
improve the scrub resistance test of the acrylic paint. It is recommended to avoid using
copious amounts of surfactants, 4.5% (2.0% octyl phenol polyglycol ether sulfate sodium
salt, 2.0% octyl phenol polyglycol ether sulfate sodium salt, and 0.5% Provichem).
38 4 Modification to an Acrylic Paint Formulation
Chapter Questions
1) What are uses for paints?
2) What’s the role of sodium bicarbonate in the current formulation?
3) What’s the chemical composition for white paint?
4) What are the chemical compounds found to be missing from the current formula-
tion decreasing its quality?
5) What are the chemical compounds mainly found to be causing the low scrub re-
sistance in the current formulation?
References
[1] http://pscf.com.sa/
[2] Izzo, Francesca Caterina; Balliana, Eleonora; Pinton, Federica; Zendri, Elisabetta, “A preliminary
study of the composition of commercial oil, acrylic and vinyl paints and their behavior after
accelerated ageing conditions”, 2014, 353–369. doi:10.6092/ISSN.1973-9494/4753.
[3] Abdel-Wahab H., Gund, M. Chemical Formulations for Acrylic Matt and Acrylic Gloss Paints.
American Journal of Applied and Industrial Chemistry. Vol. 6, No. 1, 2022, pp. 13–19. doi: 10.11648/j.
ajaic.20220601.13
[4] Nandi U. S., Palit S. R., Hydrogen peroxide as initiator in vinyl polymerization in homogeneous
system. I. Kinetic studies, Journal of Polymer Science, 1955, 17 (83), pp 65–78.
[5] I. Michalak, K. Chojnacka, Biocides, Encyclopedia of Toxicology (Third Edition) 2014, Pages 461–463.
5 Modification to a Chemical Formulation
for Optimal Performance
5.1 Overview
In a chemical reaction, the reactant substance changes to a product substance, and
the product substance will have different physical and chemical properties than the
reactant substance. All chemical reactions involve a detectable change: color change,
bubbling, heat evolution, heat absorption, light emission, or formation of a precipi-
tate. Reactions are classified into three main reactions: precipitation reactions, acid-
base reactions, and oxidation-reduction reactions. The counting unit for a number of
atoms, ions, or molecules in a laboratory seize sample is mole, abbreviated mol. A lim-
iting reactant is a reactant that is completely consumed in a chemical reaction; it lim-
its and determines the amount of product formed; the other reactants are called
excess reactants. The quantities of product formed and reactant consumed are re-
stricted by the amount of limiting reactant. This chapter presents the methods used to
increase the quality of a bubble-forming product, increasing the amount of bubbling
per table by using the difference in chemical and physical properties of the chemical
compounds included in the ingredient. The chapter also presents chemical com-
pounds in the ingredient that would be harmful to the quality of the product, and it
also presents new additives that would increase the quality of the product.
5.2 Introduction
Some of the companies in the US are looking to produce kid-safe foaming tablets from
household chemicals that would produce bubbles when placed in the snow. The ingre-
dient included the following chemical compounds: corn starch (pure starch), red beet
powder (betanin), salt (sodium chloride), cream tartar (potassium bitartrate), baking
soda (sodium bicarbonate), vitamin C (citric acid), and drops of water (H2O). The
amount of bubbling was minimal; also, the tablet didn’t hold together and was grainy
and fragile. Since bubbling forms when the fragile tablet is placed in the snow, it is
the evidence of a chemical reaction.
In a chemical reaction, the reactant substance changes to a product substance,
and the product substance will have different physical and chemical properties than
the reactant substance. All chemical reactions involve a detectable change.
A chemical equation is used to describe a chemical reaction. A chemical reaction
is represented by a molecular equation. Reactant species are always listed on the left
side of a chemical equation and the product species are listed on the right side of the
chemical equation and they are separated by an arrow. A chemical reaction can also
be presented by an ionic equation or net ionic equation:
https://doi.org/10.1515/9783111316864-005
40 5 Modification to a Chemical Formulation for Optimal Performance
Reactants ! Products
The reactions are classified into three main reactions: precipitation reactions, acid-
base reactions, and oxidation-reduction reactions. Precipitation reactions would in-
volve the formation of insoluble ionic compound forms from mixing a solution of two
ionic substances. Acid-base reactions involve the reaction of an acid with a base and a
transfer of a proton between reactants is involved. Oxidation-reduction reactions
(redox reactions) involve the transfer of an electron between reactant species.
The reaction that takes place when placing the created tablet in water/ice is an
acid-base reaction. Acid-base reactions are widely known for their ability to produce
bubbling if either reactant is a weak acid or weak base that would produce a gas
product. In an acid-base reaction, acid and base properties neutralize, where the
anion of the acid and the cation of the base combine to form the salt, and the hydrox-
ide anion, OH−, combines with the hydrogen cation, H+, to form water.
The counting unit for a number of atoms, ions, or molecules in a laboratory seize
sample is mole, abbreviated mol. A mole of samples of different substances has differ-
ent masses. For example, 1 mol of 24 mg and 1 mol of 12C. A single 24 mg atom is twice
as massive and has a mass of 24 a.m.u, as a single 12C atom has a mass of 12 a.m.u.
The formula weight of any substance is numerically equal to the molar mass of that
substance. For example, for table salt with the chemical formula NaCl, the formula
weight is 58.5 a.m.u, and its molar mass is 58.5 g/mol. The molar mass of a substance
in gram per mole can be used as a conversion factor to convert the mass of a sub-
stance into moles or moles of a substance into grams.
The relative number of molecules in a reaction is represented by coefficients in a
balanced chemical equation. The relative number of moles and the relative number
of molecules in a reaction are indicated by the coefficients in a balanced chemical
equation.
A limiting reactant is a reactant that is completely consumed in a chemical reac-
tion. It limits and determines the amount of product formed. The other reactants are
called excess reactants. The quantities of product formed and reactant consumed are
restricted by the amount of limiting reactant. If one reactant, the limiting reactant, is
consumed, the reaction stops, and the amount of limiting reactant becomes zero at
the end of the reaction.
Carboxylic acids are the largest category of weak organic acids that contain car-
boxylic groups (−COOH). The generic formula for carboxylic acids is R-COOH, where
R = alkyl group.
The acidic behavior of carboxylic acids is due to the oxygen atom bonded to the
carboxyl group carbon drawing electron density from the hydroxyl bond. It helps sta-
bilize the conjugate base and increases the polarity of the −OH bond. The carboxylate
anion, the conjugate base of acid, has resonance, which spreads the negative charge
over several atoms and contributes to the stability of the anion.
5.2 Introduction 41
.. . . .–
...O.– O O– .O. .
C C
Fig. 5.1: Resonance behavior of carboxylic acids.
Alcohols are compounds that contain one or more hydroxyl or alcohol groups (−OH).
The −OH bonds are polar; bonds and alcohols are more soluble in polar solvents than
hydrocarbons, and OH groups can form hydrogen bonds: Examples of alcohols are 1,2
HO
O
H
ethanediol H and glycerol
O
HO OH
In industry, occasional modification to the formulation of a product is necessary
to improve its quality and performance. In 2021 Chegeni et al. [18] developed a new
formulation for air revitalization tablets using the Taguchi statistical method in
closed atmospheres. The air revitalization tablets are used in closed spaces such as
submarines, underground mines, shelters, and spacecrafts to absorb carbon dioxide,
decrease its concentration, and produce fresh oxygen necessary for life in a closed
space. The initial formulation consisted of various amounts of additives: MnO2 (cata-
lyst), LiOH (CO2 auxiliary absorbent), Cu2Cl (OH)3, and CaSO4. It has been found that
for optimal performance, the greatest amount of oxygen is produced, and the maxi-
mum amount of carbon dioxide adsorbed occurs when using a certain amount of
each chemical compound in the formulation. This optimal formulation consisted of
3 wt% lithium hydroxide, 3 wt% copper oxychloride, 3 wt% calcium sulfate, and 5 wt
% manganese dioxides.
In medicine, modification to the method of delivery of the drug to the organ is
necessary to improve its performance. In 2020, Chen et al. [19] developed an optimal
method to deliver the drug formulation to the pancreas; they used a bubble bursting-
mediated oral drug delivery system that enables concurrent delivery of hydrophilic
and lipophilic chemotherapeutics for treating pancreatic tumors in rats. The optimal
formulation consisted of paclitaxel (PTX; 1 mg) that had been predissolved in capric
acid (18 mg), gemcitabine (GEM; 1 mg), sodium bicarbonate (5 mg), and citric acid (0,
2, 4, 6, or 8 mg) was exposed to a simulated intestinal fluid (SIF; 3 mL, pH 6.4) that
contained bile extract (5 mg/mL). The oral drug delivery system that initiates an ef-
fervescent reaction to form gas-bubble carriers was proposed; these carriers deliver
lipophilic PTX and hydrophilic GEM in the small intestine. The bursting of the bubbles
promotes the absorption of the drugs in the intestines. The study revealed that the
42 5 Modification to a Chemical Formulation for Optimal Performance
orally delivered formulation has no toxic side effects that are associated with the i.v.-
injected formulation. It resulted in an increase in the bioavailability of PTX, and the
oral formulation had a greater impact than the i.v. formulation on tumor-specific stro-
mal depletion, resulting in greater inhibition of tumor growth with no evidence of
metastatic spread. This unique approach of oral chemotherapy has the potential for
use on outpatients, greatly improving the quality of their lives and enhancing thera-
peutic efficacy.
5.3 Experimental
The chemical composition of the ingredients used in the making of the bubble-
producing tablets is presented in Tab. 5.1.
Corn starch is pure starch and is known to be used as a liquid thickener. Red beet
powder is used as a dye that colors the tablet. Table salt is sodium chloride with the
formula NaCl and molar mass of and this salt has a neutral pH, pH = 7. Cream tartar is
potassium bitartrate with formula KC₄H₅O6 and molar mass: 188.177 g/mol. Baking
soda is a weak base with a formula of NaHCO₃ and a molar mass: 84.007 g/mol. Citric
acid is a triprotic acid, a weak organic acid that has the formula of C6H8O7 and a
molar mass: 192.124 g/mol.
Tab. 5.1: Chemical name, molecular formula, and molecular weight of household chemicals in the
ingredients.
Household Chemical Chemical Structure Molecular Molecular
and chemical Name Formula Weight (g/mol)
Corn Starch (Pure Starch) CHO .
OH
O O
HO
OH HO
O O
O
HO
HO O
O
HO
HO
O
Table Salt (Sodium NaCl .
Chloride) Cl– Na Cl–
Na Cl– Na
Cl– Na Cl–
5.3 Experimental 43
Tab. 5.1 (continued)
Household Chemical Chemical Structure Molecular Molecular
and chemical Name Formula Weight (g/mol)
Cream Tartar (Potassium KCHO .
H
Bitartrate) O O
⊕
Na – O H
O
O O
H
Baking Soda (Sodium NaHCO .
Na+ –O OH
Bicarbonate)
C
O
Citric Acid (Vitamin C) CHO .
O OH
O O
HO OH
OH
Water (Dihydrogen HO .
Monoxide ...
.O
H H
Red Beet (Betanin) CHNO .
OH O
HO O
OH O
O N
HO HO OH
N
HO
HO O
Glycerol CHO .
H
H C OH
H C OH
H C OH
The bubbling while creating the tablet using water as a binding agent is due to the
reaction between weak acid (citric acid) and potassium bitartrate with the weak base
(baking soda) to form a salt, water, and carbon dioxide, causing loss of bubbles while
making the tablet.
In order to get the maximum amount of yield, the maximum amount of CO2 per
tablet, intern the greatest amount of bubbling, the number of moles of citric acid to
44 5 Modification to a Chemical Formulation for Optimal Performance
sodium hydrogen carbonate must be 1:3, and the number of moles of sodium bitar-
trate to sodium hydrogen carbonate must be 1:1 according to the balanced chemical
equations.
Vitamin C, citric acid, is a triprotic acid containing three acidic groups and one hy-
droxyl group. The hydroxyl groups (−OH) are alcoholic groups, and they don’t react
with sodium hydrogen carbonate or baking soda, while the acidic groups, carboxylic
group (−COOH), can react with sodium hydrogen carbonate to form a salt, carbon diox-
ide, and water. The bubbling is due to the formation of carbon dioxide as a product.
The molar amount of citric acid and sodium bicarbonate reactants must be 1:3 in
order to produce the maximum amount of bubbling in the formula per tablet:
O OH O
O OH
O O
NaO ONa
HO OH
OH O ONa
+ 3 NaHCO3→ + 3H2O + 3CO2
Citric acid baking soda
Fig. 5.2: Acid-base reaction between citric acid and backing soda.
Using 1 g of vitamin C with formula C6H8O7 in the ingredients, the amount needed for a
reaction to go to completion and produce the maximum amount of carbon dioxide, and
hence the maximum amount of bubbling would be 1.3 g of baking soda as follows:
1 g =192.124 g=mol × 3 NaHCO3 =1 C6 H8 O7 × 84.007 g=mol = 1.312 g of NaHCO3
Cream tartar, potassium bitartrate, is a monoprotic acid containing an acidic group and
two hydroxyl groups. The hydroxyl groups (−OH) are alcoholic groups, and they don’t
react with sodium hydrogen carbonate or baking soda, while the acidic group, carbox-
ylic group (−COOH), can react with sodium hydrogen carbonate to form salt, carbon di-
oxide, and water. The bubbling is due to the formation of carbon dioxide as a product.
Using 1 g of cream tartar, potassium bitartrate with formula KC₄H₅O6 in the ingre-
dients, the amount needed for a reaction to go to completion and produce the maxi-
mum amount of carbon dioxide, and hence the maximum amount of bubbling would
be grams of baking soda as follows:
H
O O
⊕ O OH
Na – O – ⊕
O H O Na
⊕ –
Na O
O O
H + NaHCO3→ OH O + H2O
Fig. 5.3: Acid-base reaction between cream tartar and baking soda.
5.4 Conclusion 45
1 g= 188.17 g=mol × 1 NaHCO3=1 KC4 H5 O6 × 84.007 g=mol = 0.4464 g of NaHCO3 .
The number of grams of sodium hydrogen carbonate needed to completely neutralize
1 g of vitamin C and 1 g of sodium bitartrate must be 1.3117 g +0.4464 g = 1.76 g.
Water as a binding agent causes bubble loss while creating the tablet, and glyc-
erol would act as a better binding agent since sugars would cause bubbling to persist,
and the compounds in the ingredients are inert in glycerol. Sodium chloride reduces
bubble formation, but the amount of base used was insufficient to neutralize both cit-
ric acid and potassium bitartrate in the formula.
Fig. 5.4: Manual tablet press machine.
5.4 Conclusion
For optimal performance, the molar amounts of reactants were calculated to produce
the greatest amount of bubbling per tablet. The bubbling power of the tablets in
water is due to the reaction between vitamin C and cream tartar with baking soda.
Using 1 g of vitamin C and 1 g of sodium bitartrate, 1.76 g of sodium hydrogen carbon-
ate is required to be used as an ingredient to get the maximum amount of yield, the
maximum amount of CO2 in the product, in turn, the maximum amount of bubbling
per tablet in the formula.
46 5 Modification to a Chemical Formulation for Optimal Performance
Sugars can be used to increase the quality of the product. It is recommended to
use a greater number of moles of starch for the tablet to be thicker on snow, and glyc-
erol acts as an ideal chemical binding agent for the ingredient.
Sugars, including glycerol, sugar alcohol, and sucrose, are good additives to cause the
persistence of the bubbling forming ability of the tablet created, and it is not recom-
mended to use sodium chloride in the formulation as it would prevent forming bubbles.
For the tablet to look smoother and for equal distribution of each of the com-
pounds in the ingredient per table, the ingredients must be grinded to powder before
adding the binding agent glycerol.
The tablets have been created using the correct molar amount for each chemical
in the ingredients, and the amount of bubbling has increased significantly; the num-
ber of bubbles formed has doubled using the correct formula.
Chapter Questions
1) What’s the aim of the chapter?
2) What’s the chemical name for cream tartar?
3) What are the chemicals used in the current formulation?
4) What’s the type of reaction occurring when the tablet is placed in aqueous
medium?
5) What’s the molar amount in grams of baking soda required for the optimal per-
formance of the current formulation, 1g of citric acid and a gram of cream tartar?
References
[1] https://en.wikipedia.org/wiki/Acid%E2%80%93base_reaction
[2] https://www.molinstincts.com/formula/Cornstarch-cfml-CT1087471098.html
[3] https://en.wikipedia.org/wiki/Sodium_chloride
[4] https://en.wikipedia.org/wiki/Potassium_bitartrate
[5] https://en.wikipedia.org/wiki/Sodium_bicarbonate
[6] https://pubchem.ncbi.nlm.nih.gov/compound/Citric-acid
[7] https://en.wikipedia.org/wiki/Betanin
[8] Ebbing and Gammon, 2015, General Chemistry, Cengage, P.103
[9] Ebbing and Gammon, 2015, General Chemistry, Cengage, P.108
[10] Ebbing and Gammon, 2015, General Chemistry, Cengage, P.111
[11] Brown, LeMay, Burstein, Murphy, Woodward, Stottzfus, 2017, Chemistry the Central Science,
Pearson, P.93
[12] Brown, LeMay, Burstein, Murphy, Woodward, Stottzfus, 2017, Chemistry the Central Science,
Pearson, P.94–95
[13] https://pubchem.ncbi.nlm.nih.gov/compound/Glycerol
[14] Brown, LeMay, Burstein, Murphy, Woodward, Stottzfus, 2017, Chemistry the Central Science,
Pearson, P. 102.
References 47
[15] Brown, LeMay, Burstein, Murphy, Woodward, Stottzfus, 2017, Chemistry the Central Science,
Pearson, P.106
[16] Brown, LeMay, Burstein, Murphy, Woodward, Stottzfus, 2017, Chemistry the Central Science,
Pearson, P.703
[17] Brown, LeMay, Burstein, Murphy, Woodward, Stottzfus, 2017, Chemistry the Central Science,
Pearson, P.1048
[18] Chegeni A, Babaeipour V, Fathollahi M, Hosseini SG. Development of a new formulation of air
revitalization tablets in closed atmospheres using the Taguchi statistical method. International
Journal of Environmental Science and Technology. 2021:13:1–6.
[19] Chen KH, Miao YB, Shang CY, Huang TY, Yu YT, Yeh CN, Song HL, Chen CT, Mi FL, Lin KJ, Sung HW. A
bubble bursting-mediated oral drug delivery system that enables concurrent delivery of lipophilic
and hydrophilic chemotherapeutics for treating pancreatic tumors in rats. Biomaterials.
2020;255:120157.
6 The Effect of Lack of Oxygen and Excess
Carbon Dioxide Buildup on Joint Diseases
and the Natural Treatments for Some
Joint Diseases
6.1 Overview
The leading cause of disability worldwide is arthritis. Arthritis can be either an auto-
immune joint disease or osteoarthritis (OA). According to the Center for Disease Con-
trol (CDC), by 2040, 80 million US adults will have some form of arthritis. This chapter
presents the effect of the obstructed ability to breathe by a physical block limit or by
prolonged hypoventilation or by a pulmonary condition on hypoxia, hypercapnia,
and blood chemical pH imbalance. Mechanism of alternating blood pH values, meth-
ods of identifying blood chemical pH imbalance, methods of measuring PCO 2 , PO2 , and
blood pH, types of joint diseases caused due to blood chemical pH imbalance, current
medicine prescribed in their treatments, and the natural treatments of such joint dis-
eases are also discussed.
6.2 Introduction and Background
The earth’s atmosphere contains 21% oxygen. A closed space has safe oxygen levels if
readings are between 20.8 and 21%, while a space with readings of less than 19.5% is
oxygen-deficient according to OSHA guidelines. Home air conditioners: split AC, window
AC, and portable AC can’t ventilate your room: they don’t have the capability to bring
the outside air; they only circulate indoor air and cool it. Complex HVAC systems used
inside some hotels, office buildings, big malls, and airports have the feature of ventilat-
ing the indoor area and maintaining freshness, humidity, and oxygen level. Some win-
dow ACs in the US can bring outside air and maintain oxygen levels. Most window ACs
around the globe do not have this feature. Oxygen room level of 19.5–23.5% is considered
safe, and oxygen levels between 14 and 16% and below 19.5% are considered hazardous.
If, while breathing out, not enough carbon dioxide is expelled from the lungs, the
increased carbon dioxide in the blood reduces the blood’s pH and makes the blood
acidic, causing respiratory acidosis. When your ability to breathe is blocked by physi-
cal block limits, another condition or a disease, such as respiratory acidosis, is caused.
Respiratory acidosis can be either acute, chronic, or acute and chronic. The sudden
arrival of CO2 in the lungs is called acute respiratory acidosis. The kidney’s response
to acute respiratory acidosis is so quick that it can happen within minutes. The causes
may include cerebrovascular accidents like strokes, a group of diseases that interfere
with gene’s ability to make muscle and causes steady loss of muscles causing muscu-
https://doi.org/10.1515/9783111316864-006
6.2 Introduction and Background 49
lar dystrophy, voluntary muscles may become weak, or loss of control of them caus-
ing myasthenia gravis, heart attack, a very rare neurological disorder where the im-
mune system attacks itself and can cause problems from trouble eating to full body
paralysis causing Guillain-Barre syndrome and/or block airways.
Chronic respiratory acidosis is more serious, and it happens at a slower rate and at
a lesser degree than acute respiratory acidosis. The lower oxygen rate for the tissues to
be fully supplied in the blood is known as hypoxemia. The conditions may include pul-
monary fibrosis or diseases that happens in the lung tissue/nerve or muscular diseases,
sleep apnea, obesity, and thoracic skeletal defects that cause pecs/rib cage/or sternum to
be shaped in a way that limits lung functioning or breathing, asthma, and a group of
airflow and breathing diseases including diseases like bronchitis and emphysema called
chronic obstructive pulmonary disease (COPD). Common treatments for respiratory aci-
dosis are oxygen tubes, different medications or other treatments to stop smoking, nal-
oxone (for opioid overdose), anti-inflammatory medications to ease any constrictive
swelling, and breathing machines like a continuous positive airway pressure (CPAP) or
BiPAP. To prevent getting respiratory acidolysis in general, lose weight if overweight,
quit smoking, and don’t drink alcohol while taking opioids and strong pain medications.
A 2-year study showed that there is an adverse physical effect on medical staff
when wearing an N95 mask. Wearing an N95 mask resulted in hypercapnia (excessive
CO2 in the blood caused by inadequate respiration) and hypoxemia (lack of oxygen in
the blood) which reduced the ability to make a correct decision and the working effi-
ciency. Dizziness, shortness of breath, and headache were experienced by the medical
staff wearing N95 masks.
If prolonged hypoventilation accompanies respiratory acidosis, the condition be-
comes more severe, and it can cause the patient to have additional symptoms: myoc-
lonus, seizures, and altered mental status. Hypercapnia (excessive amounts of carbon
dioxide in the blood) can be caused by respiratory acidosis leading to cerebral vasodi-
lation. Severe respiratory acidosis may cause papilledema and increased intracranial
pressure increasing the risk of death and herniation. Chronic respiratory acidosis
may cause impaired coordination, polycythemia, memory loss, heart failure, and pul-
monary hypertension.
Dyspnea (difficult respiration) is commonly caused by COPD, interstitial lung dis-
ease, heart failure, asthma, psychogenic problems that are usually linked to anxiety,
and pneumonia. Chest X-rays and computed tomography (CT) images are used by doc-
tors for its diagnosis. Spirometry tests can be used to measure the airflow and the
patient’s lung capacity and to pinpoint the extent and the type of an individual’s
breathing problems. Other tests can be used to directly measure the blood capacity to
carry oxygen and the level of oxygen in the blood. Treatment of dyspnea is dependent
on its cause. If it is caused from having bacterial pneumonia, antibiotics are pre-
scribed. If it is caused from having asthma, bronchodilators and steroids are pre-
scribed, and other medications are also effective (opiates, antianxiety drugs, and
nonsteroidal anti-inflammatory drugs (NSAIDs)). Special breathing techniques, such
50 6 The Effect of Lack of Oxygen and Excess Carbon Dioxide Buildup on Joint Diseases
as breathing muscle strengthening exercises and pursed-lip breathing, can be used if
the cause of dyspnea is caused by COPD. Supplemental oxygen may be prescribed if
tests indicate low levels of oxygen in the blood.
A less well-known side effect of using NSAIDs (drugs) is the degradation of joint
cartilage. Nonsteroidal anti-inflammatory drugs include: ibuprofen, used in some
drugs such as mortin, nuprin, and advil; piroxicam, used in drugs such as feldene;
diclofenac, used in drugs such as voltaren; fenoprofen, used in drugs such as nalfon;
indomethacin used in drugs such as indocin; naproxen used in drugs such as napro-
syn; tolmetin used in drugs such as tolectin; and sulindac used in drugs such as cli-
noril. Other side effects of using nonsteroidal anti-inflammatory drugs are ulcer
formation, dizziness, headaches, and gastrointestinal upset. Clinical studies have
shown that nonsteroidal anti-inflammatory drug usage has caused an acceleration of
OA and increased joint destruction.
Common joint diseases may include bursitis, OA, gout, rheumatoid arthritis (RA),
spondyloarthritis, lupus, and juvenile idiopathic arthritis. Bursitis is caused by the in-
flammation of the small, fluid-filled sacs called bursae around the joints, tendons,
muscles, and bones. Overuse or sudden injury of joints such as the elbow, hip, and
shoulder can lead to flare-ups. Bursitis can sometimes result from bacterial infections.
OA is the wear-and-tear form that increases with age. Adults in their 50s and older
are more likely to develop this kind of chronic and progressive disease. Women are
more vulnerable to OA than men. It is stiffness and pain with movement caused by
break down of cartilages that cushion the joints. The flexibility decreases, and walking
becomes more difficult, especially with knee and hip arthritis. The type of arthritis
that affects the joint connecting the big toe to the rest of the foot is called gout. A
waste product in the blood, uric acid, would exist in excess and forms crystals in the
joints. Flare-ups caused by gout are extremely painful and it would commonly strike
at night. Men are more vulnerable to gout disease, and women become more vulnera-
ble to this disease after menopause.
The autoimmune condition that affects the lining of the joints is called RA. Im-
mune system cells accumulate in large numbers in the joints. The interaction between
joint cells and immune cells causes increased inflammation leading to damage and
destruction of the bone and cartilage. Spondyloarthritis consists of certain other rheu-
matoid diseases, including axial spondylitis, enteropathic arthritis, and psoriatic ar-
thritis. The inflammation in the spine that can eventually lead to spinal fusion or
ankylosing spondylitis is called axial spondylitis. The complication of inflammatory
bowel diseases, like ulcerative colitis, is called enteropathic arthritis. Psoriatic arthri-
tis is associated with the skin condition psoriasis, and it tends to affect the joints of
the hands and feet. The autoimmune condition affects various parts of the body, in-
cluding internal organs, skin, brain, blood, bones, and joints are called lupus. Lupus
can cause an inflammation that triggers arthritis, particularly in the knees, feet,
hands, elbows, and shoulders. The most common chronic joint condition in kids is ju-
venile idiopathic arthritis. The child’s immune system attacks the body’s own healthy
6.3 Review and Discussion 51
tissue, and it is an autoimmune condition. The cause is unknown, and it may alter
children’s normal growth. This inflammation may affect the internal organs, eyes,
muscles, joints, and ligaments.
6.3 Review and Discussion
The amount of oxygen circulating in the blood is the blood oxygen level. The normal
reading using an oximeter is between 95 and 100. Forms of carbon dioxide carried in
the blood are carbaminohemoglobin (CO2 bound to hemoglobin) and chemically modi-
fied bicarbonate (HCO3−). The solubility of CO2 in the blood is 0.07 mL CO2/100 mL
blood/mm Hg which would be almost 5% of the total CO2 content of the blood. The solu-
bility of oxygen in the blood is 0.003 mL O2/100 mL blood/mm Hg, which would be al-
most 2% of the total O2 content of the blood. The solubility of carbon dioxide is 20 times
more soluble in blood than oxygen. According to Henry’s law, the solubility of a gas is
directly proportional to the partial pressure of that gas above the liquid. Increasing the
pressure and decreasing the temperature would lead to an increase in the solubility of
gaseous over a liquid [16]. CO2 gas has a lower ability to diffuse and exit the lungs com-
pared to oxygen gas according to Graham’s law [95]. As it is denser than oxygen gas, the
density of oxygen gas is 1.43 g/L compared to the density of carbon dioxide gas 1.81 g/L.
The body normally maintains CO2 in a range from 38 to 42 mm Hg by balancing its
elimination and production. Ventilation is primarily initiated by the blood pH. The pH
of the blood is mainly regulated by the amount of CO2 in the blood. The body produces
more CO2 than it can eliminate in case of hypoventilation, causing retention of CO2. The
increased CO2 is what leads to an increase in blood acidity due to an increase of hydro-
gen ion concentration, and a slight increase in bicarbonate concentration, and the equi-
librium would shift toward forming more hydrogen ions according to the following
reaction:
CO2 + H2 O ! H2 CO3 ! HCO−3 + H + (6:1)
A buffer system is created from the presence of the flowing molecules: HCO3, CO2, and
H2CO−3 in equilibrium.
In the presence of excess hydroxide ions (OH−), carbonic acid (H2CO3) would
buffer a high pH, and in the presence of excess hydrogen ions (H+), carbonate anion
(HCO−3 ) would buffer a low pH which is the main mechanism behind respiratory acid-
olysis blood pH drop. In respiratory acidolysis, the slight increase in bicarbonate acts
as a buffer for the increase in H+ ions, which helps minimize the drop in pH blood
value. Increased hydrogen ions (H+) would lead to a slight decrease in the buffered
blood pH; blood pH would be below 7.35.
To evaluate patients with suspected respiratory acidosis, serum bicarbonate level
and an arterial blood gas (ABG) are necessary. An elevated bicarbonate level of HCO−3
52 6 The Effect of Lack of Oxygen and Excess Carbon Dioxide Buildup on Joint Diseases
(>30 mmHg), an elevated PCO2 (>45 mmHg), and decreased pH (<7.35) would show on
an ABG test in case of respiratory acidolysis. Respiratory acidosis can be either
chronic or acute based on the relative increase in HCO3− with respect to PCO2. An
HCO–3 will have increased by one mEq/L for every 10 mmHg increase in PCO2 over a
few minutes in case of acute respiratory acidosis. An HCO3− will have increased by
4 mEq/L for every 10 mmHg increase in PCO2 over a time course of days in case of
chronic respiratory acidosis. A mixed respiratory-metabolic disorder may be present
if it doesn’t show either pattern of acute or chronic respiratory acidosis. A drug screen
may also be warranted in a patient who shows unexplained respiratory acidosis.
The cause of respiratory acidosis must be treated once the diagnosis has been
made. The rapid alkalization of the cerebrospinal fluid may lead to seizures; there-
fore, the hypercapnia should be corrected gradually. To help improve ventilation,
pharmacologic therapy may be used. Beta-agonists, anticholinergic drugs, and methyl-
xanthines (bronchodilators) may be used in treating patients with obstructive airway
diseases. In case of patients who overdose on opioid use, naloxone can be prescribed.
Acidolysis can be either respiratory or metabolic in origin, depending on the mea-
sured pCO2. If pCO2 is greater than 40–45, it is known to be due to decreased ventila-
tion, and it is called respiratory acidosis. If the pCO2 is less than 40 since it is not the
cause of the primary acid-base disturbance, it is called metabolic acidosis, and it is
confirmed by a measured decrease in bicarbonate (normal range 21–28 mEq/L).
In alkalosis, the fluids of the body are alkaline; the blood pH is high. When the
blood has too little acid making it basic, the condition is called alkalosis; blood pH
would be higher than the normal pH value of 7.45. There might be no noticeable
symptoms for mild and chronic alkalosis. If there is a rapid pH increase, symptoms
may include confusion, nausea or vomiting, muscle twitching or spasms, numbness of
the hands and feet, and/ or dizziness or lightheadedness.
Alkalosis can be either respiratory or metabolic, depending on pCO2. If pCO2 is
greater than 45 mmHg, it is called metabolic alkalosis, and the measured bicarbonate
is greater than 29 mM. If pCO2 is less than 32 mmHg, it is called respiratory alkalosis,
and the measured bicarbonate is less than 22 mM.
pH H+ Pco2 HCO3–
Normal 7.4 40 mEq/L 40 mm Hg 24 mEq/L
Respiratory acidosis ↓ ↑ ↑↑ ↑
Respiratory alkalosis ↑ ↓ ↓↓ ↓
Metabolic acidosis ↓ ↑ ↓ ↓↓
Fig. 6.1: Types of blood alkalosis and acidosis.
6.3 Review and Discussion 53
A number of diseases, including RA, are caused by alterations in tissue oxygen pres-
sure. In a condition known as hypoxia, low partial pressure of oxygen is involved in
angiogenesis, apoptosis, cartilage degradation, inflammation, oxidative damage, and en-
ergy metabolism. Synovial hypoxia can be linked to pathogenic processes through indi-
rect and direct effects on angiogenesis, oxidative damage, inflammation, cartilage
damage, and bone resorption. Studies show that hypoxia and other promoters lead to
inflammation in RA. The metabolic environment in the synovium is modified by hyp-
oxia, and an autoimmune response is initiated by the presentation of the upregulated
antigenic enzymes in the context of cellular stress. Hypoxia induces an anaerobic glyco-
lytic phenotype in the synovium. Several of the enzymes induced by this metabolic shift
may become antigenic once anaerobic glycolysis is established in the synovium.
The abnormal biomechanics, attendant tissue-derived, and cell-derived factors
cause OA. The progression of OA is related to reactive oxygen species (ROS) and oxida-
tive stress. It is a multifactorial and polygenic joint disease. ROS target the complex
oxidative stress signaling pathways as it regulates chondrocyte senescence and apo-
ptosis, extracellular matrix synthesis and degradation, along with synovial inflamma-
tion and dysfunction of the subchondral bone and intracellular signaling processes.
OA progresses from silent cartilage destruction to painful presentation. Free radicals
mediate and amplify the sequence of joint degeneration in all tissues affected due to
their chemical properties. Free radicals are the crucial factor involved in the inflam-
matory transformation of OA joints and all joint tissues disease development. Both OA
and RA are caused by reduced oxygen levels from increased consumption by inflam-
matory cells such as synoviocytes and the oxygen-reduced delivery to synovial fluid.
Gout is a result of the presence of uric acid crystals building up in the joints. The
production of uric acid in the joints is increased by the presence of excess carbon diox-
ide and the lack of presence of oxygen in the lungs. While sleeping, it produces less
cortisone, an inflammation-suppressant; the reduction of cortisone level might be con-
tributing to gout disease. A person may have as much as a 50% chance of getting gout
disease if they suffer from sleep apnea. Dehydration and loss of water in the body can
contribute to the increase in the concentration of uric acid in joint fluids, enhancing the
formation of uric acid crystals in the joints and causing gout attacks. Gout is a type of
arthritis that is caused by a uric acid concentration increase in the blood; it may cause
debilitation due to uric acid deposits around tendons and joints. It is the most controlla-
ble metabolic disease. Gout is classified into primary and secondary. Primary gout
causes are unknown. There are known genetic defects causing elevated uric acid. The
increase of uric acid in primary gout can be due to the reduced ability to excrete uric
acid found in a smaller group of patients (30%), increased formation of serum uric acid
found in most patients, or both, which is found in a minority of patients.
RA can’t be cured by drugs, but it can be treated as it can/will come back. Treat-
ment of RA includes using medications to slow the progression of the disease. Drugs
including sulfasalazine (azulfidine), methotrexate (trexall), and other biologic drugs
such as etanercept (enbrel), and adalimumab (humira) may be prescribed. Biologic
54 6 The Effect of Lack of Oxygen and Excess Carbon Dioxide Buildup on Joint Diseases
drugs reduce inflammation by targeting the immune system. Short-term treatment
may include low-dose steroids. RA is a multifactorial disease as both environmental
and genetic factors contribute to the disease. Medical therapy is limited in most RA
cases; it fails to address the causes of the disease. As in OA, the use of NSAIDs drugs,
including aspirin, is accompanied by the acceleration of factors that promote the dis-
ease process. Examples of drugs currently in use are hydroxychloroquine, penicilla-
mine, methotrexate, gold therapy, azathioprine, and cyclophosphamide. A diet rich in
vegetables, fiber, and whole foods and low in meat, sugar, saturated fat, and refined
carbohydrates (Western diet) prevents the development of RA disease. Dietary ther-
apy is to follow a vegetarian diet, eliminate food allergies, increase the intake of anti-
oxidants, and alter the intake of fats and oils. Dietary therapy shows tremendous
promise in the treatment of RA. Incomplete digestion may be a major factor in RA.
Gamma-linolenic acid (GLA) acts as a precursor to an anti-inflammatory prostaglan-
dins’ series [1]. Studies show that some patients have responded to GLA treatment
while others didn’t. Fish oil supplementation containing omega-3 fatty acids shows a
better and more positive response than GLA in the treatment of RA. Due to the neu-
tralization of inflammation and support of collagen structure, dietary antioxidants
such as flavonoids are used in the treatment of RA. Patients with RA have low levels
of selenium. Selenium combined with vitamin E had a positive effect in the treatment
of RA. Zinc levels are commonly low in RA patients; treatments with zinc supplements
in the form of sulfates showed a slight therapeutic effect. Patients with RA are defi-
cient in manganese-containing superoxide dismutase (SOD). The injectable form of
the enzyme (antioxidant enzyme SOD (manganese SOD) available in Europe is effec-
tive in the treatment of RA. Oral administration of SOD showed no effect. Patients
with RA are also deficient in vitamin C. Supplements with vitamin C give some anti-
inflammatory action. Pantothenic acid in blood has been shown to be lower in RA pa-
tients. Patients who received 2 g of calcium pantothenate daily showed improvement.
Arthritis patients showed a lower sulfur content in the fingernails. Using injectable
sulfur alleviated pain and swelling. A high dose of niacinamide (900–4,000 mg) has
shown good results in the treatment of both OA and RA. The administration of 500 mg
of pantothenic acid has shown no effect on the treatment of RA.
A vegetarian diet following short-term fasting showed a reduction of RA disease
activity.
Treatment of OA includes prescribing medications called bisphosphonates: risedr-
onate (actonel) and alendronate (fosamax). In most OA cases, drug treatment has
shown to be ineffective, and if the failure of nonsurgical treatment is consistent in at
least three to six months, surgical replacement of large joints, knee replacement, or
hip replacement, is needed.
The therapeutic goal in the natural treatment of OA is to enhance and repair the
collagen matrix and the regeneration of the connective tissues. It is recommended to
lose excess weight, causing increased stress on joints, use a healthy diet rich in complex
carbohydrates and fiber, and minimize and eliminate the consumption of nightshade
6.3 Review and Discussion 55
vegetables. Nightshade vegetables, including potatoes, tomatoes, peppers, tobacco, and
eggplants, are known to contain alkaloids that promote the inflammatory degradation
of the joints and inhibit normal collagen repair. The high intake of antioxidants is
shown to inhibit the progression of the disease and reduce the risk of cartilage loss. As
some people age, they lose their ability to manufacture sufficient levels of glucosamine.
Glucosamine, in the form of glucosamine sulfate drug, is used to incorporate sulfur into
the cartridges and stimulate the manufacture of glucosamineglycans.
Chondroitin sulfate is a drug that is composed of repeating units of derivatives of
glucosamine sulfate attached to sugar molecules and is known to be a less effective
drug than that of glucosamine sulfate due to its low absorption 0–13% compared to
the solubility of glucosamine sulfate which is 90–98%. A high dose of niacinamide
(900–4,000 mg) has shown good results in the treatment of both OA and RA. SOD in-
jections showed a significant effect in the treatment of OA. Vitamin E has the ability
to stimulate the formation of new cartilage components and inhibit the breakdown of
cartilage, and the administration of 600 IU showed significant benefits. Vitamin C is
like vitamin E and protects and enhances cartilage formation. The administration of a
small amount (12.5 mg) of pantothenic acid is effective in relieving symptoms of OA.
Joint degradation is accelerated by the deficiency of one of the vitamins: A, B6, zinc,
copper, and boron, and supplementation at the appropriate level may promote carti-
lage synthesis and repair. Niacinamide in high dosage of 900–4,000 mg per day
showed a promising result for the treatment of OA.
Treatments of gout joint disease include prescribed medications such as allopuri-
nol and febuxostat. Treatment of sleep apnea that would include CPAP machine or
another treatment device to increase oxygen intake while sleeping is used to increase
oxygen level and lower uric acid production and reduce the risk of gout attacks. De-
creasing the concentration of uric acid by drinking fluids would increase blood vol-
ume and lowers the risk of gout attacks. Other lifestyle changes that may lower the
risk of a gout attack include getting regular exercise, eating a plant-based diet that is
low in purines and whole foods, and losing excess weight. The standard medical treat-
ment for the disease is the administration of colchicine, indomethacin, naproxen, fe-
noprofen, or phenylbutazone. The dietary treatment involves fluid intake, low fat,
low purine, and low protein intake, consumption of complex carbohydrates, elimina-
tion of alcohol intake, and achieving the ideal body weight. The natural treatment of
gout disease includes the consumption of nutritional supplements: eicosapentaenioc
acid, vitamin E, folic acid, and amino acids such as alanine, aspartic acid, glutamic
acid, glycine, and niacin, and vitamin C. Eicosapentaenioc acid and omega-3 oils are
found useful in the treatment of gout joint disease. Vitamin E acts as an antioxidant
and inhibits the formation of leukotrienes. Folic acid is known to inhibit the produc-
tion of uric acid by inhibiting the enzyme xanthine oxidase, alanine, aspartic acid,
glutamic acid, and glycine. These amino acids are shown to lower serum uric acid
level by increasing uric acid excretion. Niacin and vitamin C, high doses of vitamin C,
56 6 The Effect of Lack of Oxygen and Excess Carbon Dioxide Buildup on Joint Diseases
and niacin are used in the treatment of gout; niacin competes with uric acid in excre-
tion, and vitamin C increases the formation of uric acid in small groups of people.
6.4 Conclusion
If the ability to breathe is obstructed by a pulmonary condition or by physical block
limits or prolonged hypoventilation, respiratory acidosis is caused. Three main types
of joint diseases are directly related to hypoxia (low levels of oxygen in your body
tissues), hypercapnia (excessive amounts of carbon dioxide in the blood), and blood
pH imbalance: RA, OA, and gout joint diseases.
Both OA and RA are caused by reduced oxygen levels from increased consump-
tion by inflammatory cells such as synoviocytes and the oxygen-reduced delivery to
synovial fluid. RA is directly caused by alterations in tissue oxygen pressure. OA is
directly related to aging, as the ability to synthesize and restore cartilage structure
decreases, and the progression of the disease was found to be directly related to the
presence of ROS and oxidative stress. Gout joint disease is directly caused by the pres-
ence of uric acid crystals building up in the joints, and the crystal buildup is increased
by the presence of excess carbon dioxide.
The natural treatment of both RA and OA includes minimizing the consumption
of nightshade vegetables and eliminating the use of NSAIDs (drugs) as they cause the
degradation of joint cartilages. A high dose of niacinamide (900–4,000 mg) has shown
good results in the treatment of both OA and RA. Vitamin C is, like vitamin E supple-
ments, has shown good results in the treatment of OA and RA and gout joint diseases.
It is recommended to increase oxygen intake while sleeping and increase blood vol-
ume by drinking fluids to lower the risk of a gout attack. It is recommended to lose
excess weight and maintain a healthy body weight in the treatment of both OA and
gout joint diseases.
The dietary treatment of RA includes following a vegetarian diet, eliminating
food allergies, increasing the intake of antioxidants, and altering the intake of fats
and oils. The dietary treatment of OA includes the use of a healthy diet rich in com-
plex carbohydrates and fiber to minimize and eliminate the consumption of night-
shade vegetables and to intake antioxidants. The dietary treatment of gout joint
disease includes fluid intake, low fat, low purine, and low protein intake, consump-
tion of complex carbohydrates, and elimination of alcohol intake.
The natural treatment of gout joint disease includes the administration of nutri-
tional supplements: eicosapentaenioc acid, vitamin E, folic acid, amino acids such as
alanine, aspartic acid, glutamic acid, glycine, and niacin, and vitamin C. The natural
treatment of RA disease includes the administration of some nutritional supplements:
omega-3 fatty acid, selenium combined with vitamin E, vitamin C, niacinamide, and
pantothenic acid. The natural treatment of OA disease includes the administration of
References 57
nutritional supplements: glucosamine sulfate, niacinamide, vitamin E, vitamin C,
small amounts of pantothenic acid, and niacinamide.
Chapter Questions
1) What’s the aim of the chapter?
2) What’s the amount of oxygen in air? What amounts are considered deficient?
3) What kind of diseases are caused by the effect of the obstructed ability to breathe?
4) What’s the main cause of gout joint disease?
5) What’s recommended in the natural treatment of Rheumatoid Arthritis, Osteoar-
thritis, and gout joint diseases?
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7 Enthalpy and Bond Dissociation Energy Values
for Multifluorinated Ethanol and Its Radicals
Using Gaussian M-062x/6-31+g (d,p) Method
at Standard Conditions
O-H BDE in Kcal/mol vs Number of Fluorine atoms in the
molecule
BDE Kcal/mol
Number of Fluorine atoms per molecule
C-H BDE in Kcal/mol vs Number of Fluorine atoms in
the molecule
BDE Kcal/mol
Number of Fluorine atoms per molecule
CF3CH-HOH C-HF2CHFOH CHF2C-HFOH HC-HFCF2OH CF3CF-HOH CF2HCF2O-H
Fig. 7.1: C–H and O–H bond dissociation energy values and its relation to number of fluorine
atoms per molecule.
7.1 Overview
Fluorinated alcohols are used as solvents for proteins, organic compounds, and pepti-
des. They are also known to be used in the organic synthesis industry due to their
strong hydrogen bonding character. Halogenated hydrocarbons are mostly syntheti-
cally produced, and they don’t exist naturally in the environment. Bond dissociation
energy (BDEs) values can be used to explain the reactivity and stability of chemical
https://doi.org/10.1515/9783111316864-007
7.2 Introduction 63
compounds. This chapter presents the methods used to calculate some kinetic and
thermodynamic parameters: standard enthalpy of formation and BDE values for 18
different fluorinated ethanol, tri-fluorinated ethanol, tetra-fluorinated ethanol, and
penta-fluorinated ethanol using the popular ab initio and density functional theory
Gaussian M-062x/6-31+g (d,p) method.
Optimized structures and thermochemical properties of tri-, tetra-, and penta-
fluorinated ethanols and its radicals determined by the Gaussian M-062x/6-31 + g (d,p)
calculation are presented in this chapter. The tabulated literature values for calcu-
lated enthalpies of formation and BDEs for 18 fluorinated ethanol and some radicals
via several series of isodesmic reactions are also included.
7.2 Introduction
Fluorinated alcohols are known to be used in the organic synthesis industry. They have
strong hydrogen bonding donor character, and they are strong nucleophiles that allow
organic reactions to occur without the use of a catalyst. Fluorinated alcohols have been
used as solvents in epoxidation reactions, annulation reactions, nucleophilic substitu-
tion reactions, electrophilic reactions, and the functionalization of multiple bonds.
Fluorinated alcohols are excellent solvents of proteins, peptides, and other or-
ganic compounds due to their physicochemical properties. Fluoro-alcohols, like other
alcohols, can alter lipid bilayer properties and stability, and protein function.
Most halogenated hydrocarbons don’t exist naturally in the environment and are
synthetically produced. The major source of halogenated hydrocarbons in the atmo-
sphere is agriculture. Crop spraying introduces halogenated hydrocarbons to the envi-
ronment entering through adsorption and deposition onto airborne particles or directly
entering the aquatic system. Some halogenated hydrocarbons, PCBs, furans, and dioxins
are by-products of industrial waste that would unintentionally enter the atmosphere.
The onset temperatures for energetic materials in the calorimetric measurements
have been roughly predicted using molecular orbital calculations of BDEs. The stability
and reactivity of chemical compounds can be explained using BDEs values. Standard
enthalpies of formation estimated using semiempirical MO calculations, the MOPAC-
PM7 package, has been used previously to derive BDE values for chemical compounds.
BDEs values for some inorganic compounds, lanthanide selenides, and sulfides
were measured in 2021 using resonant two-photon ionization spectroscopy. The predis-
sociation thresholds were found to be the BDE values for these molecules. The 0 K gas-
eous heat of formation, ΔHf, for each molecule, was also reported using this method.
The amount of energy used to break a mole of the covalently bonded gas mole-
cule to a pair of radicals is the BDE. The units used for the BDE are commonly kilo-
joule per mole. Covalent bonds can be broken heterolytically or homolytically. The
heterolytic breaking of a covalent bond would result in the pair of electrons going to
only one atom, either A or B:
64 7 Enthalpy and Bond Dissociation Energy Values for Multifluorinated Ethanol
C − D ! C + + D: − or C − D ! C: − + D + .
The homolytic breaking of a covalent bond, on the other hand, would result in one elec-
tron staying with each atom, A − B ! A + B . BDE can be calculated for molecules as
the difference in enthalpy of the formation of products and reactants. BDE is a state
function, as it doesn’t depend on the mechanism or pathway of how bonds form or
break. The energy of chemical reactions can be assessed using values for the BDE.
There are some systematic trends for the bond dissociation values; BDE varies with hy-
bridization. For example, sp3-hybridized carbons in hydrocarbons have smaller bond
dissociation values compared to sp2-hybridized carbons. The longer and weaker sp3-
hybridized bond is easier to break compared to the shorter and stronger sp2- and sp-
hybridized bonds (double and triple bonds). Among sp3-hybridized bonds, bond dissoci-
ation values depend on their position, whether it’s on a primary, secondary, or tertiary
carbon. Methane has the strongest C–H bond with the highest bond dissociation values,
following C–H bonds on primary carbons, following C–H bonds on secondary carbons,
and following C–H bonds on tertiary carbons.
Energetics of chemical processes can be assessed using BDEs. Hess’s law has been
used in the past and is currently being used to estimate reaction enthalpies by com-
bining BDEs of bonds formed and BDEs of bonds broken.
The energy change when forming a mole of compound from its component elements
is called the enthalpy of formation, ΔHf. If heat is released when the elements combine to
form the compound, enthalpy of formation would have a negative sign. If heat is ab-
sorbed when the elements combine to form the compound, the enthalpy of formation
would have a positive sign. Values of the enthalpy of formation are dependent upon tem-
perature, pressure, and physical states of reactants and products in the chemical reaction.
Standard enthalpy of formation ΔHfo is the enthalpy of formation at standard condi-
tions: 1 atm pressure, 25 °C, and 1 M aqueous solution concentration. Any element in its
most stable form has a standard enthalpy of formation and has a value of zero. Tabulated
enthalpy of formation values can be used to calculate the standard enthalpy of any reac-
tion whose standard enthalpy of formation values are well known:
X X
ΔHrxn
o
= mΔHfo ðproductsÞ − nΔHfo ðreactantsÞ
The heat involved in chemical or physical change at constant temperature and pressure
is the enthalpy of reaction (H), and its thermodynamic quantity q = ΔH.
Molecules, ions, or atoms containing at least an unpaired electron in the valance
shell are called free radicals. Free radicals are chemically reactive, unstable, and mostly
short-lived. Heat, electrolysis, electrical discharge, and ionizing radiation can generate
free radicals. Free radicals are intermediates in many chemical reactions. Free radicals
are important in atmospheric chemistry, combustion, plasma chemistry, polymerization,
and biochemistry, and they are important in many chemical reactions.
7.3 Experimental and Data 65
In 2016 Wang studied the thermodynamic properties of fluorinated methanol using
CBS-QB3, M06-2X, WB97X, W1U, M06, B3LYP, CBS-APNO, and G4 calculations. A small
standard deviation suggests good error cancellation of work reactions and accuracy.
Small values for standard deviations were obtained in calculations using the M06-2x/6-
31+g (d,p) Gaussian method; it is an accurate method to calculate the enthalpy of fluori-
nated alcohols; it shows the second smallest standard deviation after the CBS-QB3
method of calculation. The enthalpy of fluorinated methanol was studied in the past.
Halogenated compounds have low reactivity, are highly stable, and are used in in-
dustry. They are of concern to the environment due to their persistence in the environ-
ment and their widespread use. Their thermochemical properties must be studied in
order to understand the reduction and oxidation reactions involving these molecules.
7.3 Experimental and Data
7.3.1 Computational Method
The Global-hybrid meta-generalized gradient approximation (GGA) density functional
approximation, GGA, DFT Gaussian M-062x/6-31+g (d,p) method of calculation has
been used to initially analyze frequencies, optimized structures, and thermo energies
of the molecules studied. In the GGA, the density functional depends on the down and
up spin densities and the reduced gradient. In the meta-GGA, the function also de-
pends on the up and down spin kinetic energy densities. A hybrid GGA is a combina-
tion of GGA with the Hartree-Fock exchange. The hybrid meta-GGA is a combination
of meta-GGA with the Hartree-Fock exchange.
7.3.2 Isodesmic and Isogyric Reaction
A series of isodesmic reactions and composite calculations were employed to calculate
the enthalpy of the formation of tri-, tetra-, and penta-fluorinated ethanol. Calculations
were performed using Gaussian 16 program. All reported calculations of enthalpy of
formation are for standard conditions of 1 atm pressure and 298 K. The Gaussian M-
062x/6-31+g (d,p) level of calculation has been used for this study as this method of cal-
culation was successfully employed in the past when applied to fluoro hydrocarbon 6
with small reported standard deviation values.
The standard deviation is calculated using the following formula:
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
1X N
σ= ðxi − μÞ2
N i=1
66 7 Enthalpy and Bond Dissociation Energy Values for Multifluorinated Ethanol
where Xi is the mean; the average of the numbers, µ is the actual numbers to be calcu-
lated the standard deviation of, and
1X N
ðxi − μÞ2 is the variance.
N i=1
The Gaussian M-062x/6-31+g (d,p) method of calculation used to calculate the enthalpy
of formation of tri-, tetra-, and penta-fluorinated ethanols and its radicals are pre-
sented. Work reactions and reference species used to calculate the enthalpy of forma-
tion of fluorinated ethanol using this method are also presented. The number of each
type of bond must be conserved in each isodesmic reaction to cancel any systematic
error in the molecular orbital calculations using this method. By careful choice of the
isodesmic reactions, all enthalpies of formation calculations are allowed to obtain ac-
curacy close to experimental values. The ΔHf298K° values of all reference species but
the fluoroethanols are known; the ΔHf298°K of the target species fluoro-ethanols is ob-
tained from this data, and the calculated ΔHrxn, 298°. ΔHf298°K calculated using two dif-
ferent reference molecules are within ±(0–0.60 kcal mol−1).
7.3.3 Reference Species
Table 7.1 lists the standard enthalpy of formation for the reference species used in iso-
desmic reactions with their uncertainties. Table 7.2 provides all calculated standard
enthalpy of formation values, Δf Hð298Þ for tri-, tetra-, and penta-fluorinated ethanol
and its radicals.
Tab. 7.1: Reference species in the isodesmic reactions standard enthalpy of formation values (kcal mol−1).
Species ΔfH° () Species ΔfH° ()
CHF –. ± . CHOOH –. ± .
–. ± . CHCHOOH –. ± .
CHCHF –. ± . CHCHCHOOH –. ± .
•
CHCHCHF –. ± . CHOO . ± .
•
CHF –. ± . CHCHOO –. ± .
•
–. ± . CHCHCHOO –. ± .
CHCHF –. ± . CH –. ± .
CHCHCHF –. ± . CHCH –. ± .
CHF –. ± . CHCHCH –. ± .
–. ± . CHCHCHCH –. ± .
7.3 Experimental and Data 67
Tab. 7.1 (continued)
Species ΔfH° () Species ΔfH° ()
•
CHCF –. ± . a
CHO . ± . c
CHCHCF –. ± .a CHCHO• –.d
CH• . ± .c OH . ± .c
CHCH• . ± .c CHOH –. ± .c
CHCHCH• . ± .gj CHCHOH –. ± .i
.i
H .c HOO• .cj
O .c HOOH –. ± .fj
–.i
CF –. CHFCHF –.
CFCHCHF –. CFCHF –.
7.3.4 Standard Enthalpies
Isodesmic work reactions from M-062x/6-31+g (d,p) method of calculation utilized to
perform the calculation of standard enthalpy of formations for tri-, tetra-, and penta-
fluorinated ethanols and some radicals are presented in Tab. 7.2. Reference species
and their standard enthalpy of formation, along with their uncertainties, have been
used in all isodesmic work reactions (Tab. 7.1). The calculated sum of thermal enthal-
pies using the Gaussian M06-2x/6-31+g (d,p) level of theory for all target fluorinated
ethanols, their radicals, and reference species has also been used. The standard en-
thalpy of formation in kcal mol−1 for all reference species is listed in Tab. 7.1. Standard
deviation values are listed for all calculated Gaussian M06-2x/6-31+g (d,p) standard en-
thalpy of formations values. The calculated Gaussian M06-2x/6-31+g (d,p) standard en-
thalpy of formation for tri-, tetra-, and penta-fluorinated ethanol and some radicals
are listed in Tab. 7.2.
68 7 Enthalpy and Bond Dissociation Energy Values for Multifluorinated Ethanol
Tab. 7.2: Isodesmic reactions used in calculating the standard enthalpy of formation, ΔH rxn for tri-, tetra-,
and penta-fluorinated ethanols and its radicals using the Gaussian M06-2x/6-31+g (d,p) level of theory.
Isodesmic Reactions ΔH° Rxn () ΔH° Rxn () ΔfH° () Error
Target Specie Hartrees Kcal/mole kcal mol– kcal
mol–
CFCHOH + CH = CHCHOH + CHF . . –. ±.
–. –. –.
–.
–. –. –.
CFCHOH + CHCH = CHCHOH + –. –. –. ±.
CHCF
–. –. –.
–.
–. –. –.
Reported ΔfH° () kcal mol– –.
±.
Standard Deviation over rxns .
kcal mol–
CFCH•OH + CHCH = CHCHO• + . . –. ± .
CHCF
–. –. –.
–.
–. –. –.
CFCH•OH + CH = CHCHO• + CHF . . –. ±.
–. –. –.
–.
–. –. –.
Reported ΔfH° () kcal mol– –.±.
Standard Deviation over rxns .
kcal mol–
CFCHO• +CHCHCH= CHCHO• + –. –. –. ±.
CHCHCF
–. –. –.
–.
–. –. –.
CFCHO• + CH = CHCHO• + CHF –. –. –. ±.
–. –. –.
–.
–. –. –.
7.3 Experimental and Data 69
Tab. 7.2 (continued)
Isodesmic Reactions ΔH° Rxn () ΔH° Rxn () ΔfH° () Error
Target Specie Hartrees Kcal/mole kcal mol– kcal
mol–
Reported ΔfH° () kcal mol– –.±.
Standard Deviation over rxns .
kcal mol–
CHFCHFOH + CHCH = CHCHOH –. –. –. ±.
+ CHCF
–. –. –.
–.
–. –. –.
CHFCHFOH + CH = CHCHOH . . –. ±.
+ CHF
–. –. –.
–.
–. –. –.
Reported ΔfH° () kcal mol– –.±.
Standard Deviation over rxns .
kcal mol–
C•FCHFOH + CH = CHCHO• . . –. ±.
+CHF
–. –. –.
–.
–. –. –.
C•FCHFOH + CHCH = CHCHO• + –. –. –. ±.
CHCF
–. –. –.
–.
–. –. –.
Reported ΔfH° () kcal mol– –.
±.
Standard Deviation over rxns .
kcal mol–
CHFC•FOH + CHCH = CHCHO• + –. –. –. ±,
CHCF
–. –. –.
–.
–. –. –.
70 7 Enthalpy and Bond Dissociation Energy Values for Multifluorinated Ethanol
Tab. 7.2 (continued)
Isodesmic Reactions ΔH° Rxn () ΔH° Rxn () ΔfH° () Error
Target Specie Hartrees Kcal/mole kcal mol– kcal
mol–
CHFC•FOH + CHCHCH = CHCHO• + –. –. –. ±.
CHCHCF
–. –. –.
–.
–. –. –.
Reported ΔfH° () kcal mol– –.±.
Standard Deviation over rxns .
kcal mol–
CHFCHFO• + CH = CHCHO• + CHF –. –. –. ±.
–. –. –.
–.
–. –.
–.
CHFCHFO• + CHCHCH = CHCHO• + –. –. –. ±.
CHCHCF
–. –.–.
–.
–. –. –.
Reported ΔfH° () kcal mol– –.±.
Standard Deviation over rxns .
kcal mol–
CHFCFOH + CH = CHCHOH + CHF . . –. ±.
–. –. –.
–.
–. –. –.
CHFCFOH +CHCH = CHCHOH –. –. –. ±.
+ CHCF
–. –. –.
–.
–. –. –.
Reported ΔfH° () kcal mol– –.±.
Standard Deviation over rxns .
kcal mol–
C•HFCFOH + CH = CHCHO•+ CHF . . –. ±.
–. –. –.
–.
–. –. –.
7.3 Experimental and Data 71
Tab. 7.2 (continued)
Isodesmic Reactions ΔH° Rxn () ΔH° Rxn () ΔfH° () Error
Target Specie Hartrees Kcal/mole kcal mol– kcal
mol–
C•HFCFOH + CHCH = CHCHO•+ –. –. –. ±.
CHCF
–. –. –.
–.
–. –. –.
Reported ΔfH° () kcal mol– –.±.
Standard Deviation over rxns .
kcal mol–
CHFCFO• + CH = CHCHO• +CHF –. –. –. ±.
–. –. –.
–.
–. –. –.
CHFCFO• + CHCH = CHCHO•+ –. –. –. ±.
CHCF
–. –. –.
–.
–. –. –.
Reported ΔfH° () kcal mol– –.±.
Standard Deviation over rxns .
kcal mol–
CFCFHOH + CH = CHCHOH+ CF . . –. ±.
–. –. –.
–.
–. –. –.
CFCFHOH + CHCH = CHCHOH + . . –. ±.
CHFCHF
–. –. –.
–.
–. –. –.
Reported ΔfH° () kcal mol– –.±.
Standard Deviation over rxns .
kcal mol–
CFC•FOH + CH = CHCHO•+ CF . . –. ±.
–. –. –.
–.
–. –. –.
72 7 Enthalpy and Bond Dissociation Energy Values for Multifluorinated Ethanol
Tab. 7.2 (continued)
Isodesmic Reactions ΔH° Rxn () ΔH° Rxn () ΔfH° () Error
Target Specie Hartrees Kcal/mole kcal mol– kcal
mol–
CFC•FOH + CHCH = CHCHO• . . –. ±.
+ CHFCHF
–. – . –.
–.
–. –. –.
Reported ΔfH° () kcal mol– –.±.
Standard Deviation over rxns .
kcal mol–
CFCFHO• + CH = CHCHO•+ CF –. –. –. ±.
–. –. –.
–.
–. –. –.
CFCFHO• + CHCH = CHCHO• + . . –. ±.
CHFCHF
–. –. –.
–.
–. –. –.
Reported ΔfH° () kcal mol– –.±.
Standard Deviation over rxns .
kcal mol–
CFHCFOH + CH = CHCHOH+ CF . . –. ±.
–. – . –.
–.
–. –. –.
CFHCFOH + CHCH = CHCHOH+ . . –. ±.
CHFCHF
–. –. –.
–.
–. –. –.
Reported ΔfH° () kcal mol– –.±.
Standard Deviation over rxns .
kcal mol–
C•FCFOH + CH = CHCHO• + CF –.E– –. –. ±.
–. –. –.
–.
–. –. –.
7.3 Experimental and Data 73
Tab. 7.2 (continued)
Isodesmic Reactions ΔH° Rxn () ΔH° Rxn () ΔfH° () Error
Target Specie Hartrees Kcal/mole kcal mol– kcal
mol–
C•FCFOH + CHCH = CHCHO• + . . –. ±.
CHFCHF
–. –. –.
–.
–. –. –.
Reported ΔfH° () kcal mol– –.±.
Standard Deviation over rxns .
kcal mol–
CFHCFO• + CH = CHCHO• + CF –. –. –. ±.
–.–. –.
–.
–. –. –.
CFHCFO• + CHCH = CHCHO• + . . –. ±.
CHFCHF
–. –. –.
–.
–. –. –.
Reported ΔfH° () kcal mol– –.±.
Standard Deviation over rxns .
kcal mol–
CFCFOH + CHCHCH= CHCHOH . . –. ±.
+CFCHCHF
–. –.–.
–.
–. –. –.
CFCFOH + CHCH = CHCHOH+ . . –. ±.
CFCHF
–. –. –.
–.
–. –. –.
CFCFOH + CH = CFOH+ CHCHF –. –. –. ±.
–. –.
–.–.
–. –. –.
74 7 Enthalpy and Bond Dissociation Energy Values for Multifluorinated Ethanol
Tab. 7.2 (continued)
Isodesmic Reactions ΔH° Rxn () ΔH° Rxn () ΔfH° () Error
Target Specie Hartrees Kcal/mole kcal mol– kcal
mol–
Reported ΔfH° () kcal mol– –.±.
Standard Deviation over rxns .
kcal mol–
CFCFO• + CH = CHFO• + CHCF –. –. –. ±.
–. –. –.
–.
–. –. –.
CFCFO• + CHCHCH = CHCHO• –. –. –. ±.
+CFCHCHF
–. –. –.
–.
–. –. –.
CFCFO• + CHCH = CHCHO•+ . . –. ±.
CFCHF
–. –. –.
–.
–. –. –.
Reported ΔfH° () kcal mol– –.±.
Standard Deviation over rxns .
kcal mol–
Hartrees, kcal mole-1
✶
SD Standard Deviation kcal mol-1
Errors reported avg of sum of uncertainties in rxn’s reference species
7.3.5 Bond Energies
The calculated BDE values in kcal/mol for methyl C–H, ethyl C–H, and hydroxyl O–H
bonds are listed in Tab. 7.3.
The difference in BDEs of products and reactants for hemolysis is called the BDE.
The BDE values don’t depend on the pathway by which it occurs; it doesn’t depend on
how bonds are formed or on how bonds break. Therefore, BDEs are state functions.
Energetics of chemical processes can be assessed using BDE values.
7.3 Experimental and Data 75
Tab. 7.3: Bond dissociation energy (BDE) of tri-, tetra-, and penta-fluorinated ethanols using Gaussian
M-062x/6-31 + g (d,p) method of calculation.
✶
Reactions Bond Dissociation Energya (Kcal mol-) Error
Kcal mol–
CFCH–HOH .± . ± .
CFCH–HOH = H• + CFCH• OH
–. ±. . –.±.
CFCHO–H .±. ±.
CFCHO–H = H• + CFCHO•
–. ±. . –.±.
C–HFCHFOH .±. ±.
C–HFCHFOH = H• + C• FCHFOH
–.±. . –. ±.
CHFC–HFOH .±. ±.
CHFC–HFOH = H• + CHFC• FOH
–.±. . –.±.
CHFCHFO–H .±. ±.
CHFCHFO–H = H• + CHFCHFO•
–.±. . –.±.
HC–HFCFOH .±. ±.
HC–HFCFOH = H• + C• HFCFOH
–.±. . –.±.
CHFCFO–H .±. ±.
CHFCFO–H= H• + CHFCFO•
–.±. . –.±.
CFCF–HOH .±. ±.
CFCF–HOH= H• + CFCF• OH
–.±. . –.±.
CFCFHO–H .±. ±.
CFCFHO–H= H• + CFCFHO•
–.±. . –.±.
CF–HCFOH .±. ±.
CF–HCFOH= H• + CF• CFOH
–.±. . –.±.
CFHCFO–H .±. ±.
CFHCFO–H= H• + CFHCFO•
–.±. . –.±.
CFCFO–H .±. ±.
CFCFO–H= H• + CFCFO•
–.±. . –.±.
✶
Errors reported avg of sum of uncertainties in rxn’s reference specie
76 7 Enthalpy and Bond Dissociation Energy Values for Multifluorinated Ethanol
7.4 Optimized Structures
The GaussView software has been utilized along with Gaussian output files to provide
a picture of the Gaussian M06-2x/6-31 + g (d,p) optimized structure for each molecule
in this chapter (Tab. 7.4).
Tab. 7.4: Optimized geometries for target tri-,
tetra-, and penta-fluorinated ethanols and
their related radicals calculated by Gaussian
M06-2x/6-31 + g (d,p) level of theory.
CF3CH2OH
H O
C H
F
H
C
F F
CF3CH•OH
C
O
F
C H
F F
CF3CH2O•
O
F C
H
C
F
F
7.4 Optimized Structures 77
Tab. 7.4 (continued)
CHF2CHFOH
F F
H
F C C O
H H
C•F2CHFOH
F
C
O
H
F C
CHF2C•FOH
F
O
C H
F
C
H
F
CHF2CHFO•
H
O
F
C
C
H
F
F
78 7 Enthalpy and Bond Dissociation Energy Values for Multifluorinated Ethanol
Tab. 7.4 (continued)
CH2FCF2OH
F
F
H C
C
O
H
F H
C•HFCF2OH
F
F
H C
C
F
O
CH2FCF2O•
F
C
H F
C
F
H
CF3CFHOH
H O
F H
C
F C
F
F
7.4 Optimized Structures 79
Tab. 7.4 (continued)
CF3CF•OH
H
O
C
F
F
C
F
CF3CFHO•
F
F
C O
C
F
F H
CF2HCF2OH
F
F
F
C
C
H O
F H
C•F2CF2OH
H
F
O
C
C
F
F
F
80 7 Enthalpy and Bond Dissociation Energy Values for Multifluorinated Ethanol
Tab. 7.4 (continued)
CF2HCF2O•
F O
C C F
H
F F
CF3CF2OH
F
O
C H
F F
F
F
CF3CF2O•
F F
C O
F C
F F
7.5 Cartesian Coordinates
The Cartesian coordinates for target tri-, tetra-, and penta-fluorinated ethanols and their
related radicals at the Gaussian M-062x/6-31 + g (d,p) level of theory are listed in Tab. 7.5.
7.5 Cartesian Coordinates 81
Tab. 7.5: Cartesian coordinates in angstroms for target fluorinated ethanol and their
related radical’s geometries at the M-062x/6-31+g (d,p) level of theory.
Molecule Cartesian Coordinates
CFCHOH
CFC•HOH
CFCHO•
CHFCHFOH
C•FCHFOH
82 7 Enthalpy and Bond Dissociation Energy Values for Multifluorinated Ethanol
Tab. 7.5 (continued)
Molecule Cartesian Coordinates
CHFC•FOH
CHFCHFO•
CHFCFOH
C•HFCFOH
CHFCFO•
7.5 Cartesian Coordinates 83
Tab. 7.5 (continued)
Molecule Cartesian Coordinates
CFCFHOH
CFC•FOH
CFCFHO•
CFHCFOH
84 7 Enthalpy and Bond Dissociation Energy Values for Multifluorinated Ethanol
Tab. 7.5 (continued)
Molecule Cartesian Coordinates
C•FCFOH
CFHCFO•
CFCFOH
CFCFO•
References 85
7.6 Conclusion
The ab initio and Global-hybrid meta-GGA density function method, Gaussian M06-2x/6-
31 + g (d,p), used to calculate thermodynamic properties of 18 tri-, tetra-, and penta-
fluorinated ethanols and their related radicals are presented. Calculated standard en-
thalpy of formation at the Gaussian M06-2x/6-31 + g (d,p) using multiple work reactions
are also presented; work reactions were employed for cancellation of calculation errors
(Tab. 7.2).
The calculated thermochemical properties: the O–H, secondary methyl C–H, and
ethyl C–H BDEs, and standard enthalpy of formation (298 K) values for tri-, tetra-, and
penta-fluorinated ethanols and their related radicals: CH3CH2–xFxOH, CH3–xFxCH2–
xFxOH, and CH2–xFxCH2OH are tabulated in Tab. 7.3.
The C–H BDEs ranged from 98.6 to 104.9 kcal mol−1 on the secondary ethyl carbons
and from 103.3 to 106.7 kcal mol−1 on the primary methyl carbons. The O–H bond ener-
gies range from 110.7 to 118.9 kcal mol−1. The calculated O–H bond energies increased
by intruding more fluorine atoms into either methyl or ethyl carbons.
Chapter Questions
1) What’s the aim of the chapter?
2) What are the uses for fluorinated alcohols?
3) List names and formulas of the fluorinated alcohols discussed in this chapter?
4) What’s the method used in calculating thermodynamic properties discussed in
the chapter?
5) What is the name and structure of the fluorinated found to have the highest stan-
dard enthalpy of formation? And which is found to have the highest C–H and O–H
bond dissociation energy values?
References
[1] An X., Xiao J., Fluorinated Alcohols: Magic Reaction Medium and Promoters for Organic Synthesis.
The Chemical record, a journal of the chemical society of Japan. 2020, 20(2): 142–161.
[2] Zhang M., Peyear T., Patmanidis I.,Greathouse D.V., Marrink S.J., Andersen O.S., and Ingólfsson
H.I. Fluorinated Alcohols’ Effects on Lipid Bilayer Properties. Biophysical Journal. 2018, 115(4):
679–689.
[3] J. P. Ducrotoy, K.Mazik. Chemical Introductions to the Systems: Point Source Pollution (Persistent
Chemicals). Treatise on Estuarine and Coastal Science. 2011, Volume 8: 71–111
[4] Bao G, Abe RY, Akutsu Y. Bond dissociation energy and thermal stability of energetic materials.
Journal of Thermal Analysis and Calorimetry. 2021 Mar;143(5):3439–45.
[5] Sorensen JJ, Tieu E, Morse MD. Bond dissociation energies of lanthanide sulfides and selenides. The
Journal of Chemical Physics. 2021 Mar 28;154(12):124307.
86 7 Enthalpy and Bond Dissociation Energy Values for Multifluorinated Ethanol
[6] https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Organic_Chemistry_(McMurry)/06%
3A_An_Overview_of_Organic_Reactions/6.08%
3A_Describing_a_Reaction__Bond__Dissociation_Energies.
[7] https://chem.libretexts.org/Courses/Heartland_Community_College/HCC%3A_Chem_161/5%3A_Ther
mochemistry/5.7%3A_Enthalpy_of_Formation
[8] Gammon, Ebbing, General Chemistry 11th edition, Boston MA, Cengage Learning, 2017, pp 608–610.
https://en.wikipedia.org/wiki/Radical_(chemistry)
[9] Wang H., Castillo A., Bozzelli J.W., Thermochemical properties enthalpy, entropy, and heat capacity
of C1-4 fluorinated hydrocarbons. J. Phys. Chem. 2015.
[10] Schneider, W. F.; Wallington, T. J. Ab Initio Investigation of the Heats of Formation of Several
Trifluoromethyl Compounds. J. Phys. Chem. 1993, 97, 12783−12788.
[11] Expanding The Limits of Computational Chemistry, 2015–2019, Density Function Method, 7/24/2020, ‘
https://gaussian.com/dft/.
[12] Wang, H.; Castillo, Á.; Bozzelli, J. W. Thermochemical Properties Enthalpy, Entropy, and Heat
Capacity of C1−C4 Fluorinated Hydrocarbons: Fluorocarbon Group Additivity. J. Phys. Chem. A 2015,
119, 8202−8215.
[13] Math is Fun Advanced, 2017, Standard Deviation and Variance, 12/2019,{https://www.mathsisfun.com/
data/standard-deviation.html
[14] Wang H., Bozzelli J. W., Thermochemical properties and Bond Dissociation Energy for Fluorinated
Methanol and fluorinated methyl hydroperoxides,J. Phys. Chem. 2016.
[15] Ruscic, B., Active Thermochemical Tables: Sequential Bond Dissociation Enthalpy of Methane,
Ethane, and Methanol and related Thermochemistry. J. Phys. Chem. A 2015, 119, 7810–7837.
[16] Burke, S. M.; Simmie, J. M.; Curran, H. J. Critical Evaluation of Thermochemical Properties of C1−C4
Species: Updated Group Contributions to Estimate Thermochemical Properties. J. Phys. Chem. Ref.
Data 2015, 44, 013101.
[17] Chase, M. W. J. NIST-JANAF Thermochemical Tables. J. Phys. Chem. Ref. Data. 1998, Monograph 9,
1–1951.
[18] Luo, X.; Fleming, P. R.; Rizzo, T. R. Vibrational Overtone Spectroscopy of the 4 νOH+νOH′
Combination Level of HOOH via Sequential Local Mode −local Mode Excitation. J. Chem. Phys. 1992,
96, 5659−5667.
[19] Bodi, A., Kercher, J. P., Bond, C., Meteesatien, P., Sztáray, B., Baer, T., Photoion Photoelectron
Coincidence Spectroscopy of Primary Amines RCH2NH2 (R = H, CH3, C2H5, C3H7, i-C3H7): Alkylamine
and Alkyl Radical Heats of Formation by Isodesmic Reaction Networks, 2006, J. Phys. Chem. A,
doi: 10.1021/jp064739s
[20] C3H7): Alkylamine and Alkyl Radical Heats of Formation by Isodesmic Reaction Networks. J. Phys.
Chem. A 2006, 110, 13425−13433.
[21] Wang, H.; Bozzelli, J. W. Thermochemical Properties (ΔHf (298 K), S (298 K), C p(T)) and Bond
Dissociation Energies for C1−C4 Normal Hydroperoxides and Peroxy Radicals. J. Chem. Eng. Data
2016, 61, 1836−1849.
[22] Csontos, J.; Rolik, Z.; Das, S.; Kallay, M. High-Accuracy Thermochemistry of Atmospherically
Important Fluorinated and Chlorinated Methane Derivatives. J. Phys. Chem. A 2010, 114,
13093−13103.
[23] Gronert, S., J. Org. Chem. 2006, 13, 1209.
Disclaimer
Chapter 1: This chapter is another version of the article published by the same au-
thor(s) in the following journal: International Journal of Innovation Scientific Research
and Review, 4: 2404–2408, 2022.
Chapter 2: This chapter is another version of the article published by the same au-
thor(s) in the following journal: American Journal of Applied and Industrial Chemistry,
6: 13–19, 2022.
Chapter 3: This chapter is another version of the article published by the same au-
thor(s) in the following journal: American Journal of Applied and Industrial Chemistry,
6(2): 31–35, 2022.
Chapter 4: This chapter is another version of the article published by the same au-
thor(s) in the following journal: Journal of Pharmaceutics and Pharmacology Research,
5(8), 2022.
Chapter 5: This chapter is another version of the article published by the same au-
thor(s) in the following journal: Journal of Chemistry, Education Research, and Prac-
tice, 5: 127–130, 2021.
Chapter 6: This chapter is another version of the article published by the same au-
thor(s) in the following journal: Journal of Pharmacognosy and Phytochemistry, 11(4):
295–302, 2022.
Chapter 7: This chapter is another version of the article published by the same au-
thor(s) in the following journal: American Journal of Physical Chemistry, 11: 32–44,
2022.
https://doi.org/10.1515/9783111316864-008
Appendix: The Periodic Table of Elements
All known elements that make all existing chemical compounds with varying chemi-
cal and physical properties discussed in detail in most chapters are arranged by their
atomic numbers and listed in the periodic table. The atomic number is the number of
protons in the nucleus. The periodic table is the best tool in science, as many chemical
and physical properties can be known based on their position in the periodic table.
Periodic tables can be obtained using the internet; a good source of information
would be https://ptable.com/#Properties. Most periodic tables contain the atomic mass
of each element, which is the number of neutrons and protons in each nucleus.
Table 1 lists atomic masses for most elements on the periodic table. Some elements
have atomic masses that are known very precisely, to the accuracy of several decimal
places; other elements, like radioactive elements, have atomic masses that aren’t
known precisely; and elements with existing isotopes have varying atomic masses de-
pending on how isotopes are isolated.
https://doi.org/10.1515/9783111316864-009
90 Appendix: The Periodic Table of Elements
Appendix: The Periodic Table of Elements 91
Table 1: Common information of elements of the periodic table.
92 Appendix: The Periodic Table of Elements
Table 1 (continued)
Appendix: The Periodic Table of Elements 93
Table 1 (continued)
94 Appendix: The Periodic Table of Elements
Table 1 (continued)
Source: Adapted from Pure and Applied Chemistry 78, no. 11 (2005): 2051–66. © IUPAC (International Union
of Pure and Applied Chemistry).
Index
Buyl acrylate 18, 36 Red Beet 43
Biocide 20, 36
Betaine 30, 43 Sodium chlorite 5
Baking Soda 43 Sodium benzoate 6
Sodium Bi carbonate 18, 36
Castor oil 5 Sodium vinylsulfonate 18, 36
Citric acid 6 Sodium formaldehyde sulfoxylate 19, 36
Corn Starch 42 Silquesit A-171 20, 37
Cream Tartar 43 Sodium Lauryl Ether Sulphate (SLES) 30
Citric Acid 43 Sodium Lauryl Sulphate (SLS) 30
Sodium Hydroxide 30
Distilled water 5, 30, 43 Sodium triphosphate 31
Di butyl phthalate 20, 36 Sodium Chloride 42
Defoamer 20, 37 Sodium Bicarbonate 43
Formaline 20, 36 Tetrasodium EDTA 7
Tertiary butyl hydrogen peroxide 19, 36
Glycerol 31, 43 Table Salt 42
2,2,2, trifluoroethanol 68
Hydrogen peroxide 19, 36 2,2,2, trifluoro 1-yl ethanol 68
2,2,2, trifluoro ethoxy radical 68
Lemon Juice 6 1,2,2, trifluoroethanol 69
Lemongrass oil 7 1,2,2, trifluoro 1-yl ethanol 69, 70
Linear Alkyl Benzene Sulphonic Acid (LABSA) 30 1,2,2, trifluoro 2-yl ethanol 69
1,2,2, trifluoro ethoxy radical 70
Natrosol 250 HHBR 18, 36 1,1,2, trifluoroethanol 70
1,1,2, trifluoro 2-yl ethanol 70, 71
Octyl phenol polyglycol ether sulfate sodium 1,1,2, trifluoro ethoxy radical 71
salt 18, 36 1,2,2,2 tetrafluoro-ethanol 71
1,2,2,2 tetrafluoro 1-yl ethanol 71, 72
Peppermint Oil 6 1,2,2,2 tetrafluoro ethoxy radical 72
Polyoxyethylene Octylphenyl ether 18, 36 1,1,2,2 tetrafluoro-ethanol 72
Provichem 18, 36 1,1,2,2 tetrafluoro 2-yl ethanol 72, 73
Potassium Persulfate 19, 36 1,1,2,2 tetrafluoro ethoxy radical 72
Propylene Glycol 31
Pure Starch 42 Vinyl acetate 19, 36
Potassium Bitartrate 43 Vinyltrimethoxysilane 20, 37
1,1,2,2,2 pentafluoro-ethanol 73 Vitamin C 43
1,1,2,2,2 pentafluoro- ethoxy radical 74
https://doi.org/10.1515/9783111316864-010
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