SMK – SMAK BOGOR

Formic Acid
Organic Chemistry

By Group 1 :
1. Fadila Rahmat Firmansyah
2. Maulida Azizza Shizen
3. Yusuf Yofany Maryono
FOREWORD
Praise and thanks are given to God Allah SWT, because all of the blessings, we can
finish this paper well and in time. In this paper we will talk about formic acid.

This paper was made in a lot of research in so many sources and helps from so many
parties to finish the challenges and the barriers when finishing the paper. So, we would like to
say thank you to all the party that had helped us in constructing the paper.

We are aware that there are so many basic inadequacies in this paper. So, we all are
inviting the readers to give us critical and comments about this paper that can make us be
better in making paper. All the constructive critics are very welcomed.

We hope this paper can be useful to all of the readers.

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CONTENTS
FOREWORD ...............................................................................................................................................2
PREFACE ....................................................................................................................................................5
CHAPTER I : DEFINITION, ISOMERS AND NOMENCLATURE .......................................................6
Definition ..................................................................................................................................................6
Isomers.....................................................................................................................................................6
Nomenclature ..........................................................................................................................................6
CHAPTER II : PROPERTIES ...................................................................................................................8
Physical Properties .................................................................................................................................8
Chemical Properties ...............................................................................................................................9
1. Decomposition.......................................................................................................................... 10
2. Addition to alkenes .................................................................................................................. 11
3. Formic acid anhydride ............................................................................................................. 11
4. Oxidation with KMnO4 ............................................................................................................. 11
CHAPTER III : QUANTITATIVE AND QUALITATIVE ANALYSIS ................................................... 12
CHAPTER IV : PREPARATION ............................................................................................................ 17
1. Hydrolysis of the methyl formate ............................................................................................... 17
2. Niche chemical routes................................................................................................................. 17
3. Biosynthesis ................................................................................................................................. 18
CHAPTER V : USES IN DAILY LIFE.................................................................................................... 19
Laboratory use ..................................................................................................................................... 19
Medical use........................................................................................................................................... 19
Therapeutic Uses................................................................................................................................. 19
Industrial Uses ..................................................................................................................................... 19
Agricultural Uses .................................................................................................................................. 20
CHAPTER VI : RELATED RESEARCHES .......................................................................................... 21
Formic Acid as Fuel Cell ..................................................................................................................... 21
Formic Acid as Hydrogen Source ..................................................................................................... 21
Hydrogen Generation from Formic Acid and Alcohols Using Homogeneous Catalysts ........... 22
Catalysts for direct formic acid fuel cells .......................................................................................... 22
Formic acid pretreatment enhances immunostaining of cerebral and systemic amyloids. ...... 22
Formic Acid Decomposition on Polycrystalline Platinum and Palladized Platinum Electrodes 23
Bridge-Bonded Formate:  Active Intermediate or Spectator Species in Formic Acid Oxidation
on a Pt Film Electrode? ...................................................................................................................... 24

3
 Morphology and distribution of plaque and related deposits in the brains of Alzheimer's
disease and control cases. An immunohistochemical study using amyloid beta-protein
antibody. ................................................................................................................................................ 25
Effect of Formic Acid and Plant Extracts on Growth, Nutrient Digestibility, Intestine Mucosa
Morphology, and Meat Yield of Broilers ........................................................................................... 25
CHAPTER VII : REFERENCES ........................................................................................................... 27
ATTACHMENT ......................................................................................................................................... 28

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PREFACE
Formic acid (HCO2H), also called methanoic acid, the simplest of the carboxylic acids,
used in processing textiles and leather. Formic acid was first isolated from certain ants and was
named after the Latin formica, meaning “ant.” Formic acid is a commonly occurring intermediate
in cellular metabolism and is excreted in urine as a normal physiological product. Formic acid is
produced as a degradation product of certain amino acids, e.g. methionine, serine and glycine,
as well as of several organic substances such as methanol and acetone.

Formic acid is a weak, colourless, volatile organic acid (H2CO2). Pure formic acid is a
colourless, fuming liquid with a pungent odour; it irritates the mucous membranes and blisters
the skin. It freezes at 8.4 °C (47.1 °F) and boils at 100.7 °C (213.3 °F). It occurs naturally in ants
and in the fruit of the soaptree, and is also formed as a by-product in the atmospheric oxidation
of turpentine. The principal commercial product is sodium formate, which is prepared by the
reaction of carbon monoxide and sodium hydroxide under pressure and heat. Formic acid is
also prepared in the form of its esters by treatment of carbon monoxide with an alcohol such as
methanol (methyl alcohol) in the presence of a catalyst.

Formic acid is not a typical carboxylic acid; it is distinguished by its acid strength, its
failure to form an anhydride, and its reactivity as a reducing agent—a property due to the −CHO
group, which imparts some of the character of an aldehyde. The methyl and ethyl esters of
formic acid are commercially produced. Concentrated sulfuric acid dehydrates formic acid to
carbon monoxide.

Formic acid is used in leather manufacture to control pH, as well as in acid dyeing. The
principal use of formic acid is as a preservative (E236). It is used as an antibacterial agent in
livestock feed. When sprayed on fresh hay or other silage, it arrests certain decay processes
and causes the feed to retain its nutritive value longer, and so it is widely used to preserve
winter feed for cattle. In the poultry industry, it is sometimes added to feed to kill salmonella
bacteria. As a preservative in fruit juices and pickles it has an antiseptic affect against yeasts.
Some beekeepers use formic acid as a miticide against the Varroa mite. Some formate esters
are artificial flavourings or perfumes.

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CHAPTER I : DEFINITION, ISOMERS AND NOMENCLATURE

Definition
Formic acid also called methanoic acid is the simplest carboxylic acid. Its chemical
formula is HCOOH or HCO2H. It is an important intermediate in chemical synthesis and occurs
naturally, most notably in ant venom. Its name comes from the Latin word for ant, formica,
referring to its early isolation by the distillation of ant bodies.

Formic acid is not a typical carboxylic acid; it is distinguished by its acid strength, its
failure to form an anhydride, and its reactivity as a reducing agent—a property due to the −CHO
group, which imparts some of the character of an aldehyde.

Functionally, it is not only an acid but also an aldehyde; it reacts with alcohols to form
esters as an acid and it is easily oxidized which imparts some of the character of an aldehyde.
Esters, salts, and the anions derived from formic acid are referred to as formates.

Formic acid has other names, they are; Aminic acid, Formylic acid, Hydrogen carboxylic
acid, Hydroxymethanone, Hydroxy(oxo)methane, Metacarbonoic acid, Oxocarbinic acid,
Oxomethanol

Isomers
Isomers are molecules with the same chemical formula but different chemical structures.
In this case, a formic acid doesn’t have isomers or the isomer is the compound itself.

Nomenclature
Formic acid is classified as a carboxylic acid; naming formic acid comes from the
nomenclature of carboxylic acid. IUPAC Names of carboxylic acid is named after the amount of
C atoms with –oic suffix while the Common Names are using the historical name of the acids.

IUPAC Name : Alkanoic acid (Alkane + oic acid)

→ methanoic acid

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 Common Name : History name of acid

Formula Common Name Source IUPAC Name Melting Point Boiling

Point

HCO2H formic acid ants (L. formica) methanoic 8.4 ºC 101 ºC

acid

CH3CO2H acetic acid vinegar (L. acetum) ethanoic acid 16.6 ºC 118 ºC

CH3CH2CO2H propionic acid milk (Gk. protus prion) propanoic -20.8 ºC 141 ºC
acid

CH3(CH2)2CO2H butyric acid butter (L. butyrum) butanoic acid -5.5 ºC 164 ºC

CH3(CH2)3CO2H valeric acid valerian root pentanoic acid -34.5 ºC 186 ºC

CH3(CH2)4CO2H caproic acid goats (L. caper) hexanoic acid -4.0 ºC 205 ºC

CH3(CH2)5CO2H enanthic acid vines (Gk. oenanthe) heptanoic acid -7.5 ºC 223 ºC

CH3(CH2)6CO2H caprylic acid goats (L. caper) octanoic acid 16.3 ºC 239 ºC

CH3(CH2)7CO2H pelargonic acid pelargonium (an herb) nonanoic acid 12.0 ºC 253 ºC

CH3(CH2)8CO2H capric acid goats (L. caper) decanoic acid 31.0 ºC 219 ºC

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CHAPTER II : PROPERTIES

Physical Properties

Molar mass 46.03 g·mol−1

Appearance colorless fuming liquid

Taste Sour

Odor pungent, penetrating

Density 1.220 g/mL

Melting point 8.4 °C (47.1 °F; 281.5 K)

Boiling point 100.8 °C (213.4 °F; 373.9 K)

Flash point 69°C (156°F)

Solubility in miscible
water

Solubility miscible with ether, acetone,ethyl

acetate, glycerol,methanol, ethanol
partially soluble
in benzene,toluene, xylenes

Dissolves to the extent of about 10% in

benzene, toluene, and xylenes, and to
a lesser extent in aliphatic
hydrocarbons.

Stability May deteriorate in normal storage and

cause hazard.

Corrosivity Corrosive to metals

Heat of 20.10 kJ/mol at 25°C

Vaporization

Surface 37.13 mN/m at 25°C

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 Tension

Iconicity 11.05 eVfrom

Odor Water: 1700 mg/L; air 49 uL/L; Odor

Thereshold safety class E. E= less than 10% of
attentive persons can detect TLV
concentration in the air.

log P −0.54

Acidity (pKa) 3.77 [3]

Refractive 1.3714 (20 °C)

index(nD)

Viscosity 1.57 cP at 268 °C

Chemical Properties

XLogP3 -0.2

Hydrogen Bond Donor Count 1

Hydrogen Bond Acceptor Count 2

Rotatable Bond Count 0

46.005479
Exact Mass
g/mol

46.005479
Monoisotopic Mass
g/mol

Topological Polar Surface Area 37.3 A^2

Heavy Atom Count 3

Formal Charge 0

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 Complexity 10.3

Isotope Atom Count 0

Defined Atom Stereocenter Count 0

Undefined Atom Stereocenter Count 0

Defined Bond Stereocenter Count 0

Undefined Bond Stereocenter Count 0

Covalently-Bonded Unit Count 1

Formic acid shares most of the chemical properties of other carboxylic acids. Reflecting
its high acidity, its solutions in alcohols form esters spontaneously. Formic acid shares some of
the reducing properties of aldehydes, reducing solutions of GOLD, silver, and platinum to the
metals.

1. Decomposition

Heat and especially acids cause formic acid to decompose to carbon monoxide (CO) and
water (dehydration). Treatment of formic acid with sulfuric acid is a convenient laboratory source
of CO.

In the presence of platinum, it decomposes with a release of hydrogen and carbon dioxide.

CH2O2 → H2 + CO2

Soluble ruthenium catalysts are also effective. Carbon monoxide free hydrogen has been
generated in a very wide pressure range (1–600 bar). Formic acid has even been considered as
a material for hydrogen storage. The co-product of this decomposition, carbon dioxide, can be
rehydrogenated back to formic acid in a second step. Formic acid contains 53 g L−1 hydrogen
at room temperature and atmospheric pressure, which is three and a half times as much as
compressed hydrogen gas can attain at 350 bar pressure (14.7 g L−1). Pure formic acid is a
liquid with a flash point of +69 °C, much higher than that of gasoline (–40 °C) or ethanol (+13
°C).

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2. Addition to alkenes

Formic acid is unique among the carboxylic acids in its ability to participate in addition
reactions with alkenes. Formic acids and alkenes readily react to form formate esters. In the
presence of certain acids, including sulfuric and hydrofluoric acids, however, a variant of the
Koch reaction occurs instead, and formic acid adds to the alkene to produce a larger carboxylic
acid.

3. Formic acid anhydride

An unstable formic anhydride, H(C=O)−O−(C=O)H, can be obtained by dehydration of
formic acid with N,N'-Dicyclohexylcarbodiimide in ether at low temperature.
4. Oxidation with KMnO4
Formic acid can have oxidation reaction with strong oxidizer such as KMnO4
3HCOOH + 4MnO4- → 3CO2 + 2MnO2 + 2OH- + 2H2O

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CHAPTER III : QUANTITATIVE AND QUALITATIVE ANALYSIS
I. Determination of Formic-acid and Acetic Acid Concentrations Formed during
Hydrothermal Treatment of Birch Wood and Its Relation to Colour, Strength and
Hardness
Formation of benzyl esters from acetic and formic acids during heat treatment of
birch at 160–200°C has been studied by gas chromatography. High concentrations of
formic and acetic acids formed by the wood itself during hydrothermal treatment were
found. The concentrations of acids increased with both treatment time and temperature.
The maximum formic- and acetic acid concentrations found at 180°C and after 4 h of
treatment performed in this work were 1.1 and 7.2%, based on dry-weight wood,
respectively. The treated wood material was characterised by mechanical testing
[bending tests perpendicular to the grain, modulus of rupture, modulus of elasticity,
Brinell hardness, impact bending and colour measurements (CIE colour space)]. The
experiments, where high concentration of acids was formed, showed severe losses in
mass and mechanical strength. Indications of possible enhanced mechanical properties
for the treated, compared with untreated birch wood were found around 180–200°C at
short treatment times.
II. Standard Test Method for Formic Acid in Glacial Acetic Acid
This test method is useful for determining the formic acid content of glacial acetic
acid by chemical means. Low molecular weight organic acids (such as acetic and
propionic), aldehydes (including formaldehyde and acetaldehyde), ketones, and alcohols
(including methyl alcohol) do not interfere with the test. Formic acid (and other reducing
substances) may be present as a result of contamination during storage, distribution,
and manufacture. This test method may be used in assessing compliance with a
specification.
This test method covers the determination of the formic acid (and other reducing
substances) content of glacial acetic acid by oxidation with lead tetraacetate. For
purposes of determining conformance of an observed or a calculated value using this
test method to relevant specifications, test result(s) shall be rounded off “to the nearest
unit” in the last right-hand digit used in expressing the specification limit, in accordance
with the rounding-off method of Practice E29. The values stated in SI units are to be
regarded as standard. No other units of measurement are included in this standard. For
hazard information and guidance, see the supplier's Material Safety Data Sheets. This
standard does not purport to address all of the safety concerns, if any, associated with
its use. It is the responsibility of the user of this standard to establish appropriate safety
and health practices and determine the applicability of regulatory limitations prior to use.
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III. Analysis of Formic Acid, Acetic Acid and Propionic Acid in Biodiesel Fuel
To reduce the burden of automotive fuels on the environment, attempts are being
made to use substances derived from biomass as fuel. Of these, fatty acid methyl esters
(FAME) from methyl esterification of vegetable oil or other oils are attracting particular
interest as biodiesel fuel (BDF). In addition, there is a trend to use biodiesel fuel blended
with diesel oil (BDF blended diesel oil) in normal diesel vehicles. Therefore, new items
added to the test standards and the corresponding testing procedures are being
investigated to ensure stable quality. The formic acid, acetic acid and propionic acid
were analyzed in BDF blended diesel oil using ion chromatography.

IV.An Enzymatic Method For the Determination of Formic Acid

A specific spectrophotometric method for the determination of formic acid is
described in which an enzyme preparation from lyophilized cells of Clostridium
cylindrosporum is used. The method is based on the enzymatic conversion of formic
acid to lo-formyltetrahydrofolic acid, and the spectrophotometric determination of 5, lo-
methenyltetrahydrofolic acid, which is formed by the action of acid on the enzymatic
product. Formic acid may be determined directly in biological samples containing from
0.02 to 0.2 lcmole per ml. The preparation is homogeneous by sedimentation, diffusion,
and electrophoretic analysis. The crystalline enzyme is free from adenylate kinase
activity and can be used for the quantitative estimation of ATP as well as THF and formic
acid.

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 V. An Improved Ion Chromatography Method For Analysis Of Acetic And Formic Acid
Vapours
A rapid and sensitive ion chromatographic method was developed to quantify
acetic and formic acid vapours from samples collected by MDTs. During analysis, anion
separation was achieved with an AS11-HC anion exchange column equipped with an
AG11-HC guard column, using 4 mM NaOH as the eluent at 1.5 mL/min. The detection
limits were 0.24 ng for acetate and 0.21 ng for formate, among the lowest reported to-
date. For the analysis of the MDTs, we used calibration standards with concentrations
between 5 and 40 μg/mL, and MilliQ water as a zero standard. The presented method
achieves baseline separation of both acetate and formate in 4.5 min. This IC method
provides elution times up to 5.2 min faster and 2 to 60-fold lower detection limits than
methods reported previously. While the method was developed to analyze acid vapours,
it can also be applied to the analysis of aqueous and water-soluble samples containing
acetate and formate. This method was successfully used to quantify acetic and formic
acid vapours in the μg/m3 range collected by MDT passive samplers in museum
environments. We determined that the acid levels within the storage cabinets in the
Natural History Museum of Los Angeles County are higher than recommended,
contributing to the efflorescence that has been observed on calcareous objects stored in
the cabinets. As a result of this study, steps will be taken to mitigate these acid levels,
which may include replacing the wooden trays with a less reactive material.
VI. Determination of Formic Acid, Acetic Acid and Propionic Acid Contents in FAME -
Blended Diesel Fuels – Water Extraction – Ion Chromatography Method –
Fatty acid methyl esters used for diesel fuels. They are produced from vegetable
oils, animal fats and other fatty oils through methyl-esterification and purification
processes. A sample is mixed with water and shaken to extract formic, acetic and
propionic acids into the water. The separated aqueous phase is injected into an ion
chromatograph to separate and elute each component, of which a chromatogram
corresponding to each acid ion is recorded. The concentration of each acid component
is determined by comparing with a pre-determined calibration curve.
VII. Determination of Formic Acid in Acetic Acid for Industrial Use by Agilent 7820A GC
The Agilent 7820A GC coupled with a μTCD provides a simple method for
analysis of formic acid in acetic acid. Use of a capillary column ensures good separation
of impurities and acetic acid in both high concentrations and low concentrations.
VIII. Sample Preparation Examples:
(a) Determination of formic acid in wine.
For red wine, add 100 mg of charcoal to 5 mL of sample in a polypropylene
tube. Mix by inversion for 1 min and then filter the suspension through
Whatman GF/A glass fibre filter paper. For white wine, analyse the sample
14
 with no prior pre-treatment. Typically, no dilution is required and a sample
volume of 0.1 mL is satisfactory.
(b) Determination of formic acid in fruit juice.
For strongly coloured juices, add 100 mg of charcoal to 5 mL of sample in a
polypropylene tube. Mix by inversion for 1 min andthen filter the suspension
through Whatman GF/A glass fibre filterpaper. Adjust strongly acidic juices to
pH 7-8 using 1 M potassium hydroxide. Typically, no dilution is required and
a sample volume of 0.1 mL is satisfactory.
(c) Determination of formic acid in vinegar.
Add 50 mL of vinegar to a 200 mL beaker and adjust to pH 7-8 with 1 M
potassium hydroxide. Quantitatively transfer to a 100 mL volumetric flask and
adjust to the mark with distilled water. Typically, no further dilution is required
and a sample volume of 0.2 mL is satisfactory.
(d) Determination of formic acid in pickles.
Separate liquid from solid by filtration. Store the solution at 4°C for 20 min to
obtain separation of fat (if necessary). Filter an aliquot of the aqueous layer,
discarding the first few mL. Dilute an aliquot of the filtrate according to the
dilution table, if necessary. Typically, no dilution is required and a sample
volume of 0.1 mL is satisfactory.
(e) Determination of formic acid in fruit and vegetable products.
Homogenise approx. 50 g of fruit or vegetable with 100 mL of water using an
electric blender. Stir the mixture for approx. 15 min and quantitatively transfer
to a 250 mL volumetric flask and adjust to the mark with distilled water. Mix
well. Typically, no dilution is required and a sample volume of 0.2 mL is
satisfactory.
(f) Determination of formic acid in fish and meat products.
Accurately weigh approx. 5 g of representative homogenised sample into a
50 mL beaker. Add 20 mL perchloric acid solution (1 M) and, using a
Polytron® homogeniser or similar, homogenise for 10 min. Adjust the pH to
approx. 8 with 2 M potassium hydroxide solution. Quantitatively transfer the
mixture to a 100 mL volumetric flask and adjust to the mark with distilled
water, ensuring the fatty layer is “above” the mark and that the aqueous layer
is “at” the mark. Filter the solution through Whatman No. 1 (9 cm) filter paper.
Discard the first few mL and use the clear or slightly turbid solution for the
assay. For calculation of the amount of formic acid, take the volume
displacement factor of 0.98 into account. Typically, no dilution is required and
a sample volume of 0.5 mL is satisfactory.
(g) Determination of formic acid in bakery goods.
15
 Accurately weigh 5 g of homogenised or milled sample into a 100 mL
volumetric flask. Add approx. 75 mL of distilled water and extract at 20-25°C
for 15 min. Fill to the mark with distilled water and filter the solution through
Whatman No. 1 (9 cm) filter paper. Typically, no dilution is required and a
sample volume of 0.2 mL is satisfactory.
(h) Determination of formic acid in honey.
Weigh approx. 10 g of honey into a 100 mL volumetric flask. Fill to the mark
with distilled water and mix thoroughly. Use the solution directly in the assay.
Typically, no dilution is required and a sample volume of 0.2 mL is
satisfactory.
(i) Determination of formic acid in jam.
Accurately weigh approx. 20 g of homogenised sample into a 100 mL beaker.
Add approx. 20 mL of hot water (~ 60°C) and mix. Then add 2 mL of Carrez I
solution and 2 mL of Carrez II solution. Mix after each addition. Neutralise the
sample with 4 mL of 100 mM NaOH. Cool the solution to 20-25°C,
quantitatively transfer to a 100 mL volumetric flask and fill to mark with
distilled water. Mix thoroughly and filter through Whatman No. 1 (9 cm) filter
paper. Typically, no dilution is required and a sample volume of 0.2 mL is
satisfactory.
(j) Determination of formic acid in protein containing samples.
Add 40 mL of 30 mM trichloroacetic acid to 20 g of proteincontaining sample
and stir the mixture for 1 min. Neutralise the solution with 1 M potassium
hydroxide and quantitatively transfer the mixture to a 100 mL volumetric flask.
Fill to mark with distilled water and filter an aliquot through Whatman No. 1 (9
cm) filter paper. Use the clear solution, diluted if necessary, in the assay.
Typically, no dilution is required and a sample volume of 0.1 mL is

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CHAPTER IV : PREPARATION
1. Hydrolysis of the methyl formate

When methanol and carbon monoxide are combined in the presence of a strong base, the
acid derivative methyl formate results, according to the chemical equation:

CH3OH + CO → HCO2CH3
In industry, this reaction is performed in the liquid phase at elevated pressure. Typical
reaction conditions are 80 °C and 40 atm. The most widely used base is sodium
methoxide. Hydrolysis of the methyl formate produces formic acid:
HCO2CH3 + H2O → HCO2H + CH3OH

Efficient hydrolysis of methyl formate requires a large excess of water. Some routes proceed
indirectly by first treating the methyl formate with ammonia to give formamide, which is then
hydrolyzed with sulfuric acid:

HCO2CH3 + NH3 → HC(O)NH2 + CH3OH

2 HC(O)NH2 + 2H2O + H2SO4 → 2HCO2H + (NH4)2SO4

A disadvantage of this approach is the need to dispose of the ammonium sulfate byproduct.
This problem has led some manufacturers to develop energy-efficient methods of separating
formic acid from the large excess amount of water used in direct hydrolysis. In one of these
processes (used by BASF) the formic acid is removed from the water via liquid-liquid
extraction with an organic base.

2. Niche chemical routes

 By-product of acetic acid production
A significant amount of formic acid is produced as a byproduct in the
manufacture of other chemicals. At one time, acetic acid was produced on a large scale
by oxidation of alkanes, by a process that cogenerates significant formic acid. This
oxidative route to acetic acid is declining in importance, so that the aforementioned
dedicated routes to formic acid have become more important.
 Hydrogenation of carbon dioxide
The catalytic hydrogenation of CO2 to formic acid has long been studied. This
reaction can be conducted homogeneously.
 Oxidation of biomass
Formic acid can also be obtained by aqueous catalytic partial oxidation of wet
biomass (OxFA process). A Keggin-typepolyoxometalate (H5PV2Mo10O40) is used as the
homogeneous catalyst to convert sugars, wood, waste paper or cyanobacteria to formic
acid and CO2 as the sole byproduct. Yields of up to 53% formic acid can be achieved.

17
  Laboratory methods
In the laboratory, formic acid can be obtained by heating oxalic
acid in glycerol and extraction by steam distillation. Glycerol acts as a catalyst, as the
reaction proceeds through a glyceryl oxalate intermediary. If the reaction mixture is
heated to higher temperatures, allyl alcohol results. The net reaction is thus:
C2O4H2 → CO2H2 + CO2
Another illustrative method involves the reaction between lead
formate and hydrogen sulfide, driven by the formation of lead sulfide.
Pb(HCOO)2 + H2S → 2HCOOH + PbS

3. Biosynthesis
Formic acid occurs widely in nature as its conjugate base formate. This anion is
produced by reduction of carbon dioxide, catalyzed by the enzyme formate dehydrogenase.
Anassay for formic acid in body fluids, designed for determination of formate after methanol
poisoning, is based on the reaction of formate with bacterial formate dehydrogenase.
Formic acid can be made by the action of sulfuric acid upon sodium formate, which is
produced from carbon monoxide and sodium hydroxide.

Formic acid is also prepared in the form of its esters by treatment of carbon monoxide
such as methanol (methyl alcohol) in the presence of a catalyst.

18
CHAPTER V : USES IN DAILY LIFE
Formic acid is an efficient and environmentally friendly organic acid for many
applications. These are the applications of formic acid in several fields;

Laboratory use

Formic acid is a source for a formyl group for example in the formylation of methylaniline
to N-methylformanilide in toluene. In synthetic organic chemistry, formic acid is often used as a
source of hydride ion. The Eschweiler-Clarke reaction and the Leuckart-Wallach reaction are
examples of this application. It, or more commonly its azeotrope withtriethylamine, is also used
as a source of hydrogen in transfer hydrogenation. Like acetic acid and trifluoroacetic acid,
formic acid is commonly used as a volatile pH modifier in HPLC and capillary electrophoresis.
As mentioned below, formic acid may serve as a convenient source of carbon monoxide by
being readily decomposed by concentrated sulfuric acid.

CH2O2(l) + H2SO4(l) → H2SO4(l) + H2O(l) + CO(g)

Medical use
Formic acid has been shown to be an effective treatment against warts and is marketed
for that purpose by Meda AB under the trade name Vårtfri (="Wart free") in Sweden and
Endwarts internationally.

Therapeutic Uses
Medication (vet): appears to prevent candida growth in partridges exposed to candida
after receiving treated feed (20 mL of 6% solution/100 g feed for 1 week and then 2% soln).
Similarly, a 15% solution can be used to control an outbreak of candida albicans.

Industrial Uses
One of the most common industrial uses of formic acid is in the production of leather.
Because it is so acidic, formic acid has proven itself to be perfect for use in this fashion.
Although formic acid is most frequently used in leather production, other industries currently use
formic acid in the process of dyeing and finishing textiles. It is also commonly used as a
coagulant in many rubber manufacturing processes. In addition to its use in the leather, textile
and rubber industries, derivatives of formic acid have recently been developed to help fight
slippery road conditions in countries such as Austria and Switzerland. These countries, which
fight bitter winters and very dangerous roads, are now using formates, which are the salts that
are derived from formic acid. Not only are these formates more effective than traditional salt
treatments, they are also more environmentally friendly. In the production of epoxidized soy
bean oil formic acid is used in combination with hydrogen peroxide as oxidizing agent.
19
 In oil field applications it helps to dissolve calcium carbonate. Potassium formate, a salt
of formic acid, also helps with well drilling and completion in the oil field industry. Furthermore,
potassium formate is environmentally friendly and at the same time a highly efficient deicing
agent for roads and airport runways. As it is readily biodegradable, it protects the environment.
The pharmaceutical industry uses formic acid in the production of various active pharmaceutical
ingredients.

Formic acid is also a powerful descaler as well as a valuable biocide in many cleaning
applications under the Protectol FM brand. It is also used to adjust pH values in flue gas
desulfurization, latex coagulation and other applications. Formic acid can serve as a hydride
donor in various chemical processes.

And when used properly, formates can greatly increase the gripping ability of otherwise
slick surfaces, as well as promote the removal of these surfaces with machines and other
technologies

Agricultural Uses
Agriculture accounts for a very high percentage of formic acid use worldwide. Because of its
natural antibacterial properties, formic acid has achieved very high use as both an antibacterial
preservative and pesticide. In this industry, it is most commonly used as a food additive, and is
frequently added to animal feed and silage. When it is used in silage, it serves a dual function.
In addition to providing a certain level of antibacterial support, formic acid actually allows silage
to begin fermentation at a lower temperature, greatly reducing the overall time that it takes to
produce while increasing the nutritional value of the finished product.

20
CHAPTER VI : RELATED RESEARCHES

Formic Acid as Fuel Cell

Polymer electrolyte membrane-based direct formic acid fuel cells (DFAFC) have been
investigated for about a decade, and are now becoming an important area of portable power
system research. DFAFCs have the advantages of high electromotive force (theoretical open
circuit potential 1.48 V), limited fuel crossover, and reasonable power densities at low
temperatures. This paper provides a review of recent advances in DFAFCs, mainly focussing on
the anodic catalysts for the electro-oxidation of formic acid. The fundamental DFAFC chemistry,
formic acid crossover through Nafion membranes, and DFAFC configuration development are
also presented.

Formic Acid as Hydrogen Source

Formic acid has recently been suggested as a promising hydrogen storage material. The
basic concept is briefly discussed and the recent advances in the development of formic acid
dehydrogenation catalysts are shown. Both the state of research for heterogeneous and for
homogeneous catalyst systems are reviewed in detail and an outlook on necessary
development steps is presented. Formic acid is considered as one of the most promising
materials for hydrogen storage today. There are a number of highly active and robust
homogeneous catalysts that selectively decompose formic acid to H2 and CO2 near to room
temperature. Although the activity and selectivity of heterogeneous catalysts have not yet
reached the level of homogeneous systems, this gap is closing.

21
Hydrogen Generation from Formic Acid and Alcohols Using Homogeneous Catalysts

This tutorial review describes recent progress in the development of homogeneous

catalytic methodology for the direct generation of hydrogen gas from formic acid and alcohols.

Catalysts for direct formic acid fuel cells

Previous work has demonstrated that formic acid fuel cells show interesting properties
for micro power generation. In this paper the effects of the anode catalyst composition on fuel
cell performance is investigated. In particular, the performance of Pt, Pt/Pd and Pt/Ru catalysts
for direct formic acid fuel cells is investigated and their effect on cell power density output at 30
°C are compared. It is found that the open cell potential varies significantly with the catalyst
composition. The Pt/Pd catalyst shows an open cell potential of 0.91 V compared to 0.71 V with
pure platinum and 0.59 V with Pt/Ru. The current at a cell potential of 0.5 V is 62 mA/cm2 with
Pt/Pd compared to 33 mA/cm2 with pure platinum and 38 mA/cm2 with Pt/Ru. Interestingly, the
Pt/Ru catalyst gives the most power at low voltage 70 mW/cm2 at 0.26 V, compared to 43
mW/cm2 for pure platinum and 41 mW/cm2 for Pt/Pd. All of the catalysts showed stable
operation during several hour tests. Analysis of the data indicates that the addition of palladium
enhances the rate of formic acid electrooxidation via a direct reaction mechanism, while
ruthenium additions suppress the direct pathway and enhance electrooxidation via a reactive
CO intermediate.

Formic acid pretreatment enhances immunostaining of cerebral and systemic amyloids.

The purpose of this study was to design a method by which immunoperoxidase staining
can be applied to formalin-fixed, paraffin-embedded tissue sections to demonstrate amyloid
deposits in cerebral and systemic amyloidotic tissues. We used anti-prion protein, anti-beta-
protein, anti-amyloid A, and anti-prealbumin antisera. The tissue sections were first treated with
100% formic acid for 5, 20, or 60 minutes and the unlabeled immunoperoxidase method (biotin-
streptavidin system reagents) was used. This formic acid pretreatment enhanced
immunoreactivity of the amyloid deposits which reacted positively with specific antiserum. The
specificity of the immunostainings was well preserved. This method can also be used to
demonstrate interspecies cross-reactivity, by using anti-human amyloid A and anti-scrapie
hamster prion protein antisera, which stained negatively or faintly with amyloid deposits of

22
heterogenous species. The technique is expected to reveal the buried epitopes of amyloid
deposits in tissue sections.

Formic Acid Decomposition on Polycrystalline Platinum and Palladized Platinum

Electrodes
This is a comprehensive study in which a formic acid decomposition reaction is
examined as a probe of catalytic properties of polycrystalline platinum and palladized platinum
electrodes. The electrode potential varies in a broad range, and the reaction is carried out in
perchloric acid and sulfuric acid solutions containing different concentrations of HCOOH.
Analytical methods used to access the decomposition reaction are chronoamperometry and
cyclic voltammetry. At very short times, we prove that only a negligible amount of surface CO is
formed, and the CO unaffected decomposition reaction, leading to CO2 formation, can be
interrogated. Surprisingly, the decomposition reaction displays Tafel behavior only in a very
narrow potential range. This observation, made with both clean Pt and Pt/Pd electrodes,
suggests that water−surface interactions, and/or (bi)sulfate−surface interactions, increase with
increasing electrode potential and create a steric/electronic barrier for the decomposition of
formic acid (and methanol, J. Phys. Chem. 1994, 98, 5074). We therefore offer a pessimistic
view about platinum as a universal material for heterogeneous catalysis applications involving
rearrangements of organic molecules. Such rearrangements may only be fulfilled with a low
electrochemical driving force, at least at room temperature, but at higher potentials, the
electrode becomes deactivated due to the unique attributes of the double layer structure on the
platinum electrode. We have also found that the deceleration of formic acid oxidation (to CO2) is
primarily due to CO chemisorption only at potentials overlapping with those from the hydrogen
adsorption range, or not too positive from this range. At more positive potentials, the decay in
formic acid decomposition is neither due to CO formation nor to solution mass transfer
limitations. The presence of interfacial CO2 (J. Electroanal. Chem. 1994, 376, 151) or
adsorption of formic acid and/or formate anion, could account for the decay. Finally, a detailed
analysis of kinetic isotherms involved in the two pathways, CO2 formation and CO
chemisorption, is made and the mechanism of formic acid decomposition on platinum is
discussed. The electrolyte anion effects involved in formic acid oxidation in HClO4 and in
H2SO4 solutions are also presented.

23
Bridge-Bonded Formate:  Active Intermediate or Spectator Species in Formic Acid
Oxidation on a Pt Film Electrode?
We present and discuss the results of an in situ IR study on the mechanism and kinetics
of formic acid oxidation on a Pt film/Si electrode, performed in an attenuated total reflection
(ATR) flow cell configuration under controlled mass transport conditions, which specifically
aimed at elucidating the role of the adsorbed bridge-bonded formates in this reaction.
Potentiodynamic measurements show a complex interplay between formation and
desorption/oxidation of COad and formate species and the total Faradaic current. The notably
faster increase of the Faradaic current compared to the coverage of bridge-bonded formate in
transient measurements at constant potential, but with different formic acid concentrations,
reveals that adsorbed formate decomposition is not rate-limiting in the dominant reaction
pathway. If being reactive intermediate at all, the contribution of formate
adsorption/decomposition to the reaction current decreases with increasing formic acid
concentration, accounting for at most 15% for 0.2 M DCOOH at 0.7 VRHE. The rapid build-
up/removal of the formate adlayer and its similarity with acetate or (bi-)sulfate
adsorption/desorption indicate that the formate adlayer coverage is dominated by a fast
dynamic adsorption−desorption equilibrium with the electrolyte, and that formate desorption is
much faster than its decomposition. The results corroborate the proposal of a triple pathway
reaction

mechanism including an indirect pathway, a formate pathway, and a dominant direct pathway,
as presented previously (Chen, Y. X.; et al. Angew. Chem. Int. Ed. 2006, 45, 981), in which
adsorbed formates act as a site-blocking spectator in the dominant pathway rather than as an
active intermediate.

24
Morphology and distribution of plaque and related deposits in the brains of Alzheimer's
disease and control cases. An immunohistochemical study using amyloid beta-protein
antibody.
A monoclonal antibody (4D12/2/6) to a synthetic peptide consisting of residues 8-17 of
the amyloid beta-protein of Alzheimer's disease was used in an immunohistochemical study to
investigate the localization of beta-protein immunoreactivity in neuritic plaques in the brains of
20 cases with Alzheimer's disease and a similar number of nonAlzheimer controls. The
morphology and distribution of immunoreactive plaque-like lesions and the sensitivity of
immunostaining were assessed both with and without formic acid pretreatment of the sections,
and these results were compared with those obtained using conventional Congo red and silver
impregnation staining methods. Congo red and immunostaining without formic acid
pretreatment mainly stained the core deposits of amyloid in compact plaques, whereas the
silver stain could also detect numerous diffuse plaques. Immunostaining with formic acid
pretreatment was the most sensitive technique, and this revealed many additional
immunoreactive lesions which were impossible or difficult to detect with the other staining
methods. These additional lesions included variable sized areas of faint granular staining with
little evidence of amyloid deposition or degenerating neurites that are presumed to be very early
stages in plaque development. Far fewer immunoreactive lesions were observed in the
nonAlzheimer controls. It is concluded that an abundant presence of anti-beta-protein
immunoreactive plaque lesions throughout the cortex and subcortical gray matter structures is
typical of Alzheimer's disease even when only moderate numbers of plaques can be detected
by Congo red or silver stain. This immunostaining procedure with a specific monoclonal
antibody for beta-protein may be very useful for the postmortem diagnosis of Alzheimer's
disease.

Effect of Formic Acid and Plant Extracts on Growth, Nutrient Digestibility, Intestine
Mucosa Morphology, and Meat Yield of Broilers
The effect of formic acid and 2 plant extracts on performance traits, apparent ileal
digestibility (AID), intestine mucosa morphology, and meat yield of broilers was studied in a 49-d
experiment. There were 6 treatments: a negative control diet without additives (control); 10 ppm
of avilamycin; 5,000 of formic acid; 10,000 ppm of formic acid; 200 ppm of plant extract based
on a blend of oregano, cinnamon, and pepper essential oil; and 5,000 ppm of hydroalcoholic
plant extract from sage, thyme, and rosemary leaves. A total of 312 Ross chicks were
distributed into 24 groups of 13 in each, comprising 4 replicates per treatment. The performance
data revealed significantly better FCR in all the supplemented diets except for the 5,000 ppm of
hydroalcoholic plant extract diet. All additives improved AID of nutrients. Both acidifier inclusion
levels improved villus height, and the group fed the 10,000 ppm of formic acid diet also had the
25
greatest crypt depth; however, villus surface area was not influenced. Meat yield was not
affected. It was concluded that the diets with 5,000 and 10,000 ppm of formic acid, and with 200
ppm of plant extract based on a blend of oregano, cinnamon, and pepper essential oils were
similar to avilamycin and were beneficial for improving growth traits and nutrient AID.
Furthermore, a positive effect of formic acid on intestine mucosa was observed. This experiment
involved a small sample, so the additives that showed beneficial effects should be further
studied in commercial farms.

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CHAPTER VII : REFERENCES

http://en.wikipedia.org/wiki/Formic_acid

http://pubchem.ncbi.nlm.nih.gov/compound/formic_acid#section=Use-and-Manufacturing

http://www.sciencedirect.com/science/article/pii/S0378775308006332

http://pubs.rsc.org/en/content/articlelanding/2010/cs/b904495g/unauth#!divAbstract

http://pubs.rsc.org/en/content/articlelanding/2012/ee/c2ee21928j#!divAbstract

http://acidpedia.org/formic_acid/

http://www.chemspider.com/Chemical-Structure.278.html

http://chemwiki.ucdavis.edu/Organic_Chemistry/Carboxylic_Acids/Nomenclature_of_Carboxylic
_Acids

http://product-finder.basf.com/group/corporate/product-finder/en/brand/FORMIC_ACID

http://www.ilmukimia.org/2013/11/asam-semut.html

http://www.chemicalland21.com/industrialchem/organic/formic%20acid.htm

http://www.britannica.com/EBchecked/topic/213843/formic-acid-HCO2H

http://pubs.acs.org/doi/abs/10.1021/la060928q

http://europepmc.org/abstract/med/2642985

http://japr.oxfordjournals.org/content/16/4/555.short

http://pubs.acs.org/doi/abs/10.1021/jp992297x

http://europepmc.org/abstract/med/2441141

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