Title Of Experiment
: Carboxylic Acid
B. Date Of Experiment
: Thursday, 10th March 2016 , 01.00 04.00 PM
C. Purpose Of Experiment :
1. To prepare the simplest carboxylic acid in laboratory,
example formic acid
2. To understand the principal of carboxylic acid such as
decarboxylation, oxidation, and esterification.
D. Basic Theory
A carboxylic acid is an organic compound containing the carboxyl group
,-CO2H. the carboxyl group contains a carbonyl group and hydroxyl group. The
interactions of these two groups lead to a chemical reactivity that is unique to
carboxylic acids.
(Fessenden and Fessenden, 2008: 597)
The characteristic functional group of the carboxylic acids is the carboxyl
group,
+CO2
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
(Sutcliffe, 1930: 167)
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The whole CO2H group is removed from the molecule, leaving the
carbonyl group at the
stuff 1 mentioned a
minute ago. This happens either when theres a ketone at the -position.
Formic acid easy to oxidation produce CO2 if formic acid react with
KMnO4. The reaction is:
HCOOH+ 2 MnO4- 3 CO2+ 2 MnO2 (brown)+ 2 OH-+2 H2O
Some of the carboxylic acid
Numbe
r of
Carbon
s
1
2
3
Structure
Trivial Name
Occurrence and
Derivation Name
HCO2H
CH3CO2H
CH3CH2CO2H
formic
acetic
propionic
4
5
CH3(CH2)2CO2H
CH3(CH2)3CO2H
butyric
Valeric
6
7
CH3(CH2)4CO2H
CH3(CH2)5CO2H
Caproic
Enanthic
8
9
CH3(CH2)6CO2H
CH3(CH2)7CO2H
Caprylic
Pelargonic
10
CH3(CH2)8CO2H
capric
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For example:
propan-1-ol
CH3CH2CH2O
97.2
ethanoic
H
CH3COOH
C
118
acid
These are
chosen
for
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2. Oxidation reaction
Because it is already in a high oxidation state, further
oxidation removes the carboxyl carbon as carbon dioxide.
Depending on the reaction conditions, the oxidation state of
the remaining organic structure may be higher, lower or
unchanged. The following reactions are all examples of
decarboxylation (loss of CO2). In the first, bromine replaces the
carboxyl group, so both the carboxyl carbon atom and the
remaining organic moiety are oxidized. Silver salts have also
been used to initiate this transformation, which is known as
the Hunsdiecker reaction. The second reaction is an interesting
bis-decarboxylation, in which the atoms of the organic residue
retain their original oxidation states. Lead tetraacetate will also
oxidize mono-carboxylic acids in a manner similar to reaction
#1.
Finally,
the
third
example
illustrates
the
general
halo
compound
or
an
aliphatic
or
aromatic
hydrocarbon.
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Mechanism of Decarboxylation:
Step 1:
Start at the prot pronation
of the carbonyl, break the
O-H bond and form the p
bond, break the C-C and
make the C=C. Note the
concerted nature of this
reaction and the cyclic
transition state
Step 2:
Tautomerization of the enol of
the carboxylic acid leads to the
acid product (not shown here).
Esters are produced when carboxylic acids are heated with alcohols in
the presence of an acid catalyst. The catalyst is usually concentrated sulphuric
acid. Dry hydrogen chloride gas is used in some cases, but these tend to
involve aromatic esters (ones containing a benzene ring). If you are a UK A
level student you won't have to worry about these.
The esterification reaction is both slow and reversible. The equation for
the reaction between an acid RCOOH and an alcohol R'OH (where R and R'
can be the same or different) is:
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So, for example, if you were making ethyl ethanoate from ethanoic acid
and ethanol, the equation would be:
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formal
resemblance to salt formation. Since in this both case the acid react with a
hydroxyl, containing compound and water is one of the products. The entirely
covalent nature of the bonds in an ester, however, give it the usual properties of
organic compound, relatively low boiling point, in solubility in water,
solubility in organic solvents. These properties are in marked contrast to those
of n alkali metal salt of an acid, with contains one electrovalence. (Cason,
1956: 120-121)
Ethyl ethanoate C4H8O2 is an organic compound is a
liquid, colorless and 770C boiling point, refractive index of
1.372, fragrant smell (aroma), volatile. In everyday life ethyl
acetate serves as the smell of food (essence) and solvent
organic compounds. Ethyl ethanoate / ethyl acetate prepared
by esterification reaction of acetic acid with an alcohol
compound in acid and heated atmosphere
Compounds which can be considered to be derived from
a carboxylic acid with hydrogen from group function replacing
hydroxyl with a hydrocarbon group called Esther. Presumably
most common ester is ethyl acetate CH 3CO2CH2CH3, a solvent
commonly used in many solvent. Ethyl acetate and other
esters with carbon ten or less a volatile liquid with bad smell
like fruits
A carboxylic acid ester is a compound contain -CO2R
group with R can be alkyl or aryl-shaped. An ester may be
formed by direct reaction between a carboxylic acid and an
alcohol, a reaction called esterification reaction.
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Tools
Distillation flask
1 piece
Liebig Condenser
1 piece
Test tube
3 pieces
Erlenmeyer flask
1 piece
Bunner
1 piece
Gradauated cylinder 1 piece
Materials
Oxalic acid
2.5 mL
Glycerol
5 grams
Glacial acetic acid
2 mL
Ethanol 96 %
4 mL
Ca(OH)2 Solution
CH3COONa 10 % solution 5mL
KMnO4 1 N solution 3 mL
FeCl3 5 % solution
3 mL
K4Fe(CN)6 1 M solution
Concentrated sulfuric acid 12 mL
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F. Procedural
1) Preparation of formic acids and reactions happen in formic acid
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3)Glacial
Esterification
aceticReaction
acid 2 mLEthanol 96% 28mL
mL of Concentrated sulfuric acid
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Ethanol 96% 2 mL
H2SO4 4 mL
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G. Observation Result
N
o
1
Experiment Procedural
Preparation of Formic Acids and reactions happen in
formic acid
Observation Result
Before :
H2C2O4 (s) = White
Crystal
Glycerol = Colorless
KMnO4 (aq) = Purple
CH3COOH(aq) =
Colorless
Lime water = colorless
Hypothesis/ Reaction
- H2C2O4 (aq) +
14
(CH2)2CH(OH)3
HCOOH(aq) + CO2 (g)
- CO2 (g) + CO(OH)2(aq)
CaCO3(s) + H2O(l)
- 2 HCOOH(aq) + 2
KMnO4 3CO2 (g) +
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Conclusion
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Before :
CH3COONa (aq)=
colorless
FeCl3 5% = Yellow
After :
CH3COONa (aq) + FeCl3
5% = Red
After Heated
CH3COONa (aq) + FeCl3
5% = formed precipitate
and the solution is
colorless after filtered
Residue = brownish Red
Filtrate = Colorless
3CH3COONa
(aq) +
and
3FeCl3(aq)
brown
3CH3COO- +
Fe3+ +
oxidation
3NaCl(s)
NaCl(s) +
K4Fe(CN)6 (aq)
[Na4Fe(CN)6]
+ 4KCl (s)
FeCl3
precipitate and
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Filtrate + K4Fe(CN)6 =
green soft
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reaction.
It
have
yellow.
produce
color
is
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FeCl3 5% comparative =
yellow
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Esterification Reaction
- CH3COOH(aq) +
Before =
CH3COOH glacial =
colorless
Ethanol 96% =
colorless
H2SO4 concetrated =
colorless
C2H5OH(aq)
CH3COOC2H5 +
H2O(l)
C2H5OH(aq) +
H2SO4 (aq)
After
Test tube 1
CH3COOH glacial +
Ethanol 96%+ H2SO4
concetrated = colorless
After Heated
CH3COOH glacial +
Ethanol 96%+ H2SO4
concetrated = colorless
and produce odor like
as rubber
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Test Tube 2
Ethanol 96%+ H2SO4
concetrated = colorless
After heated Ethanol
96%+ H2SO4
concetrated = colorless
And produce odor that
sting
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H. Analysis
1. Preparation of formic acids and reactions happen in formic acids
On the frist experiment aims for Preparation of formic acids and reactions
happen in formic acids . First, Count weight of 5 gram oxalic acid (H2C2O4) white
crystalline and count weight 5 gram glycerol ( colorless and viscous solution) .
Next, pour boiling stone in the destillation flask functioning for flatten heat to all
parts of the solution. Then entered 5 gram oxalic acid and 5 gram gliserol in the
destillation flask , so that mix become colorless viscous solution and there insoluble
crystall oxalic acid. Add glycerol have function ie as catalyst which accelarate
preparation of formiac acid. And then heated. The Solution change color become
soft yelow and form gas. Gas is formed ran in the lime water for checking
destillation process running with appropiate after while lime water change become
turbid solution . it shows that gas formed is gas CO 2 because gas carbon dioxyde
reacting with lime water can be form CaCO3 , so that lime water become turbid. The
reaction :
CO2 (g) + Ca(OH)2(aq) CaCO3(s) + H2O(l)
After lime water become turbid solution , heating is . and then added 2,5
gram oxalic acid (H2C2O4) into destillation flask . Addition of oxalic acid is made to
add reactants which aims to shift the reaction to the right (product). Due to obtain
yield much, equilibrium should be shifted towards the product. by using one of the
substances in excess perekasi cheap, in this experiment was added oxalic acid. Then
reheated to get distilatnya (formic acid). After some time, formed a colorless
distillate .
Reaction :
H2C2O4 (s)
HO C 4 H 8 OH
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solution become brown and there are black precipitate. This is because the addition
of KMnO4 act as an oxidant.
Then make the compare solution by entering a 1 mL CH 3COOH into a test
tube and then added 1 mL of solution KMnO 4 also the color purple, so the mixture
becomes thick purple solution. From the experimental results, after Destillate drops
of KMnO4 , distillate becomes brown due to the oxidation of formic acid susceptible
when reacted with KMnO4 to produce CO2, then this is the function of KMnO4
which acts as an oxidant. Permanganate that is reduced to Mn 2+ is what causes the
appearance of a brown color.
The Reaction Is :
3HCOOH(aq) + 2KMnO4(aq) 3CO2(g) + MnO2(s) + 2KOH(aq) +
2H2O(l)
While the reaction tube 2 purple solution was concentrated. It showed no
redox reaction occurs, which is characterized by the dont formation of MnO 2
precipitate in the form of brown. From the equation occur, KMnO 4 oxidizes formic
acid. This is due to acetic acid binds with a methyl group on the carboxyl group
while formic acid is only bind H+ so that when reacted with KMnO4 formic acid will
be more easily oxidized to form MnO 2 than acetic acid, then the acetic acid was not
contained precipitate and color of the solution remains purple as KMnO 4. The
reaction equation:
3CH3COOH + 8 KMnO4
2. Acetic Acid Reaction
The second experiment is acetic acid reaction. The purpose of the second
experiment is to understanding the principle of carboxylic reaction (oxidation). In
this experiment 5 mL of sodium acetate (10%) that colorless react with 3 mL of
FeCl3 that yellow, adding FeCl3 is to produce ferric precipitate. But after adding
FeCl3 is not formed precipitate just red color solution. From this reaction produce
red solution. It is caused the solution contain ferric acetate. This is appropriate with
this equation bellow:
3CH3COONa+FeCl3 (CH3COO)3Fe+3NaCl
(Raj, 2009: 28)
After that the solution heating and the solution formed brown precipitate. It cause
after heated the solution (CH3COO)3Fe changed be CH3COOFe(OH)2. This is
appropriate with this equation bellow:
(CH3COO)3Fe+2HOH
Heated
2CH3COOH+CH3COOFe(OH)2
(Basic Ferric acetate)
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+3
Oxidation
So from this experiment can conclude that reaction of acetic acid and FeCl 3 produce
brown precipitate and in reaction that occur is oxidation reaction. It cause the result
of filter is ferro ion.
3. Esterificarion Reaction
In this experiment aims to understand the principle - the principle of a
carboxylic acid reaction is an esterification reaction. First, set up two test tubes. In
the first test tube, put 2 mL of glacial CH 3COOH in the form of a colorless solution.
Then added 2 mL of 96% ethanol in the form of a colorless solution, and then added
8 mL of concentrated H2SO4 in the form of a colorless solution. So that the mixture
became a colorless. The function of add concentrated H 2SO4 is a catalyst, which is
to reduce the activation energy of the reaction so as to accelerate the formation of
ester (esterification). Then the reaction tube is sealed using aluminum foil. It is
intended that the compounds do not evaporate when heated
In the second test tube, inserted 2 mL of ethanol 96% in the form of a
colorless solution. Then added 4 mL of concentrated H2SO4 in the form of a
colorless solution. So that the mixture became a colorless solution. The function of
add concentrated H2SO4 is a catalyst. Then the reaction tube is sealed using
aluminum foil. It is intended that the compounds do not evaporate when heated.
After that the two tubes are heated to cause odor. Heating function is to accelerate
the esterification reaction or accelerate the formation of esters. After a while, inhaled
the smell, the tube 1 produces fragrant smell like Rubber. Reaction :
CH3COOH(aq) + C2H5OH(aq)
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I.
Coclusion
From explanation above can conclude:
1. Formic acid can produce from decarboxylation of H2C2O4 with use catalyst
glycerol and the other product is CO2 and the function of KMnO4 is as oxidator.
2. Reaction of acetic acid and FeCl3 produce brown precipitate and in reaction
that occur is oxidation reaction. It cause the result of filter is ferro ion. It can
detect because when the filter react with K4Fe(CN)6 the color is soft green, its
different with FeCl3 5% that have color is yellow.
3. If glacial acetic acid react with ethanol and sulfuric acid occur esterification
reaction. It can known by the odor. The odor is like rubber. But ethanol react
with sulfuric acid is not occur esterification reaction and the odor is sting.
J.
Referencess
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Cason, James. 1956. Essential Principle of organic Chemistry. USA: Prentice hall,
Inc
Fessenden, Ralp J., Fessenden, Joans.1982.Organic Chemistry 3rd Edistion, 2nd
Volume. Jakarta: Erlangga
Raj, Gurdeep. 2009. Advanced Practical Inorganic Chemistry. Delhi: Goal
Publishing House
Sutcliffe, Arthur. 1930. Practical Chemistry for Advanced Students. London: John
Murray
Tim Dosen Kimia Organik. 2016. Penuntun Praktikum Kimia Organik I. Surabaya:
Jurusan Kimia FMIPA UNESA
West, Augustus. P. 1920. Experimental Organic Chemistry. New York: World Book
Company
K. Attachment
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Answer
1. Reactions
a) Preparation and Reaction of Formic Acid
H2C2O4(aq) 150 C
HCOOH (aq) + CO2 (g)
Oxalic acid
formic acid
(CH2)CH(OH)3
CO2(g) + Ca(OH)2 (aq) CaCO3(s) + H2O(l)
Hydrated lime
2 HCOOH (aq) + 2KMnO4(aq) 3CO2(g) + MnO2(s) +
2KOH + 2H2O(l)
CH3COOH(l) + KMnO4(aq)
3NaCl(s)
NaCl(s) + K4Fe(CN)6 (aq) [Na4Fe(CN)6] + 4KCl (s)
c) Esterification Reaction
CH3COOH(aq) + C2H5OH(aq)
H2SO4
+ H2O(l)
C2H5OH(aq) + H2SO4 (aq)
CH3COOC2H5
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Stage 2 :
Stage 3 :
Stage 4 :
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Stage 5 :
In
general,
the
primary
alcohol
at
low
to
produce
esters,
whereas
at
high
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