Chapter 18 Carboxylic Acids and their derivatives Part 1- Chemistry free study material by TEACHING CARE online tuition and coaching classes
Chapter 18 Carboxylic Acids and their derivatives Part 1- Chemistry free study material by TEACHING CARE online tuition and coaching classes
Carboxylic Acids
æ ö
Carboxylic acids are the compounds containing the carboxyl functional group ç – C– OH ÷
|
|
ç || ÷
è O ø
The carboxyl group is made up of carbonyl ( C = O) and hydroxyl (–OH) group.
(1) Classification
- Carboxylic acids are classified as monocarboxylic acids, dicarboxylic acids, tricarboxylic acids depending on the number of – COOH groups present in the molecule.
CH2COOH
|
CH 3 COOH
C H 2COOH
|
CH2COOH
C HCOOH
|
CH2COOH
monocarboxylic acid Dicarboxylic acid Tricarboxylic acid
- Monocarboxylic acids of aliphatic series are commonly known as fatty acids such as palmitic acid (C15 H 31 COOH) and stearic acid (C17 H 35 COOH) .
- The general formula for monocarboxylic acids is carbon
Cn H 2n+1 COOH or Cn H 2n O2 . Where n = number of
- The carboxylic acids may be aliphatic or aromatic depending upon whether – COOH group is attached to aliphatic alkyl chain or aryl group
Aliphatic acids
HCOOH
Formic acid
Aromatic acids
COOH
Benzoic acid
CH 3 COOH
Acetic acid
COOH
NO2
m-Nitrobenzoic acid
CH3 –CH COOH
|
CH3
Isobutyric acid
COOH
CH3
o-Toluic acid
(2) Structure :
- The name carboxyl is derived from carbonyl hydroxyl groups are directly linked to each
C = O
and hydroxyl (– OH) because both carbonyl and
- The carboxylic carbon atom and two oxygen atom in carboxylic acid are sp2
1.23 Å
O
R – C
1.36 Å ® |
H
|
R – C – OH
|
1.43Å
Pure p-orbital
R – C = O
|
1.20Å
O – H H R
Delocalized p-electron cloud
- The shorter bond (c – o) and longer bond (c = o) of carboxylic acid than alcohol and ketone is due to delocalization of p
- Nomenclature : The monocarboxylic acids are named according to following
- Common or trivial names : The names of lower members are derived from the Latin or Greek word that indicates the source of the particular The common names have ending –ic acid.
| Formula | Source | Common name |
| HCOOH | Red ant (Latin, ant = Formica) | Formic acid |
| CH3 COOH | Vinegar (Latin; vinegar = Acetum) | Acetic acid |
| C2 H5 COOH | Proton-pion (Greek; Proton = first, Pion = Fat) | Propionic acid |
| C3 H7 COOH | Butter (Latin ; Butter = Butyrum) | Butyric acid |
| C4 H9 COOH | Root of valerian plant | Valeric acid |
- Derived system : Monocarboxylic acids may be named as alkyl derivatives of acetic
CH3CH 2COOH
Methyl acetic acid
CH3 – C H – COOH
|
CH3
Dimethyl acetic acid
- IUPAC system : Acids are named as alkanoic acids (Alkane – e + oic acid). The name is derived by replacing ‘e’ of the corresponding alkane by –oic
HCOOH Methanoic acid (Methane – e + oic acid)
CH3COOH
Ethanoic acid (Ethane – e + oic acid)
In case of substituted acids,
5 4 3 2 1
Br
4 3| 2 1
C H3 – C H – C H – C H 2 COOH; C H3 – C H– C H – COOH;
|
CH3
|
CH3
|
CH3
3,4-Dimethylpentanoic acid
(4) Isomerism
3-Bromo- 2- methyl butanoic acid
CH3
|
(i) Chain isomerism :
CH3 – CH2 – CH 2 – CH 2 – COOH ;
Pentanoic acid
CH3 – CH 2 – C H – COOH
2-methyl butanoic acid
(ii) Position isomerism :
CH3 – C H – CH2 – COOH
|
CH3
3- methyl butanoic acid
; CH3 – CH 2 – C H – COOH
|
CH3
2-methyl butanoic acid
(iii) Functional isomerism :
- Optical isomerism
C2H5
|
CH3 – CH 2 – COOH ;
Propanoic acid
C2H5
|
CH3 COOCH3
Methyl acetate
; HCOOC2 H5
Ethyl formate
CH3 – C– C3 H7
|
COOH
C3 H7 – C– CH3
|
COOH
2-Ethyl-2Methyl Pentanoic Acid
(1) By oxidation of alcohols, aldehydes and ketones
RCH 2 OH ¾¾[O¾} ® RCHO ¾¾[¾O] ® RCOOH
alcohol
K2Cr2O7
K2Cr2O7
Carboxylic acid
RCHO ¾¾[¾O] ® RCOOH
Aldehyde
Ketones and secondary alcohols form acid with fewer carbon atoms.
|
|
R CHOH ¾¾[O¾} ® R C = O ¾¾K C¾r O¾® RCOOH + R¢COOH
R¢CH2
Sec. Alcohol
Ketones
H2SO4
Note : ® Aldehyde can be oxidized to carboxylic acid with mild oxidising agents such as ammonical silver
|
nitrate solution [Ag 2O or Ag(NH3 )+ OH – ]
- Methanoic acid can not be prepared by oxidation
- Ketones can be oxidized under drastic conditions using strong oxidising agent like
K2Cr2O7 .
- Methyl ketones can also be converted to carboxylic acid through the haloform reaction.
R – C– CH3 + 3I 2 + 3NaOH ¾¾D ® R – C– OH + CHI 3 + 3NaI + 3H 2 O
|| H2O ||
O O
(2) By Hydrolysis of nitriles, ester, anhydrides and acid chloride
(i) Hydrolysis of nitriles
R – C º N + HOH ¾¾H¾Cl ®éR – C
OH ù ¾¾Rea¾rran¾gem¾e¾nt ® R – C O
¾¾H2¾O ® RCOOH + NH Cl
|
or NaOH ê
NH ú
NH2
HCl 4
|
- Hydrolysis of Esters : RCOOR‘+ HOH ¾¾H¾Cl ® RCOOH+ R‘ OH
Ester
OH –
Acid
Alcohol
(iii) Hydrolysis of Anhydrides :
O
||
CH3 – C
O + HOH ¾¾H+ ¾/ OH¾- ® 2CH COOH
CH3
- C
||
O
Ethanoic anhydride
3
Ethanoic acid
(iv) Hydrolysis of acid chloride and nitro alkane
R – C– Cl + HOH ¾¾H+ ¾/ OH¾- ® RCOOH + HCl
||
O
R – CH 2 – NO2 ¾¾85%¾H2¾SO¾4 ® RCOOH
X
é OHù O
|
|
- Hydrolysis of Trihalogen : R – C X + 3NaOH ® êR – C
OHú ¾¾- H¾2O ® R – C
OH + 3NaX
X
(3) From Grignard Reagent
|
O
ëê OHúû
O = C = O +
d –d +
RMgX
¾¾Dry¾eth¾er ® R – || – OMgX ¾¾H+ ¾/ H2¾O ® RCOOH + Mg(OH)X
Carbon dioxide Grignard reagent
(R = CH3 ,C2 H5 ,(CH3 )2 CH-,(CH3 )3 C –
(4) From Alkene or Hydro-carboxy-addition (koch reaction)
When a mixture of alkene, carbon monoxide and steam is heated under pressure at 350°C in presence of phosphoric acid (H3 PO4 ) monocarboxylic acid is formed.
CH 2 = CH 2 + CO + H 2 O ¾¾H3 P¾O¾4 ® CH 3 CH 2 COOH
500-1000atm
&350°C
Mechanism :
H Å
H H H
|
| | |
OH
|
C= O
|
(i)
C = C
+ H + ®
– C – C–
(ii)
– C – C– ¾¾Cº¾O ®
– C – C
¾¾H2¾O ® – C – C –
| | |
| | –H Å | |
(5) Special Methods
Carbocation
C=O
Å
Acyl cation
Carboxylic acid
- Carboxylation of sodium alkoxide : RONa + CO ® RCOONa ¾¾H¾Cl ® RCOOH
Sod. alkoxide
Sod. salt
Acid
(ii) Action of heat on dicarboxylic acid :
R – CH COOH ¾¾–CO¾2 ® R – CH
COOH
COOH
Substituted malonic acid
heat
2
Monocarboxylic acid
(iii) From Acetoacetic ester :
CH3 CO
CHRCO
OC2 H5 ¾¾Hyd¾roly¾¾sis ®
CH3COOH
OH H
(iv) Oxidation of alkene and alkyne
OH H
- RCH COOH + C H OH
2 2 5
RCH = CHR¢ ¾¾[¾O] ® RCOOH + R¢COOH
Alkene
Hot alkalne
KMnO4
R – C º C – R¢ ¾¾(i)O¾3 ® R – COOH + R¢COOH
Alkyne
(ii)H2O
(v) The Arndt-Eistert Synthesis :
R – C– Cl + CH 2 N 2 ® R – C– CHN 2 ¾¾H2¾O ® R – CH 2 – COOH
|| ||
O O
Ag2O
(vi) From acid amides :
RCONH 2 + H 2 O ¾¾Ac¾id ® RCOOH+ NH 3
Amide
or Alkali
Acid
RCONH 2 +
Amide
HNO2
Nitrous acid
® RCOOH + N 2 + H 2O
Important physical properties of carboxylic acids are described below :
- Physical state : The first three members (upto 3 carbon atoms) are colourless, pungent smelling The next six members are oily liquids having unpleasant smell. The higher members are colourless and odourless waxy solids.
- Solubility : The lower members of the aliphatic carboxylic acid family (upto C4) are highly soluble in The solubility decreases with the increase in the size of the alkyl group. All carboxylic acids are soluble in alcohol, ether and benzene etc.
Note : ® The solubility of lower members of carboxylic acids is due to the formation of hydrogen bonds between the – COOH group and water molecules.
- Acetic acid exists in the solution in dimer form due to intermolecular hydrogen The observed molecular mass of acetic acid is 120 instead of 60.
(3) Melting point
- The melting points of carboxylic acids donot vary smoothly from one member to
- The melting point of the acids having even number of carbon atoms are higher than those containing an odd number immediately above and below
5 0
3 0
1 0
–1 0
–3 0
–5 0
1
3 5 7 9 11
No. of C-atoms/molecule
- The acids with even number of carbon atoms have the – COOH group and the terminal – CH3 group on the opposite side of the carbon
- In the case of odd numbers, the two groups lie on the same side of the
CH3
CH2
CH2
COOH
CH3
CH2
CH2
CH2
COOH
the two terminal groups lie on the opposite sides of the chain
the two terminal groups lie on the same side of the chain
When the terminal groups lie on the opposite sides the molecules fit into each other more closely. More effective packing of the molecule in the lattice. Therefore, results into higher melting point.
- Boiling point : Boiling point of carboxylic acids increase regularly with increase of molecular mass. Boiling points of carboxylic acids are higher than those of alcohols of same molecular mass. This is due to intermolecular hydrogen bonding between two acid
CH3 – C
Hydrogen bonding
O H – O
O – H O
C – CH3
Hydrogen bonding Acetic acid dimer
Among organic compounds, carboxylic acid are the most acidic and ionize in aqueous solution. It is expressed in term of dissociation constant (Ka)
R – COOH+ H 2O
Carboxylic acid
RCOO– +
|
Carboxylate ion
H3O+
Hydronium ion
K = [RCOO– ][H3O+ ]
a [RCOOH]
Note : ® Greater the value of Ka or lesser the value of
- Acidic nature ( Ka ) a 1/molecular weight
pKa
stronger is the acid, i.e.
pKa = – log Ka
HCOOH
- CH3COOH > C2 H5COOH
Ka Value
17.7 ´ 10-5
1.75 ´ 10-5
1.3 ´ 10-5
- The formic acid is strongest of all fatty acids.
- Acetic acid is less weak acid than sulphuric acid due to less degree of
(1) Cause of Acidic Nature
- A molecule of carboxylic acid can be represented as a resonance hybrid of the following
.. ..
|
O: O:
|| | Å
R – C – O..- H « R – C = O..- H
- (II)
- Due to electron deficiency on oxygen atom of the hydroxyl group (Structure II), their is a displacement of electron pair O–H bond toward the oxygen This facilitate the release of hydrogen as proton (H+).
O– Å é O O– ù
R – C
O ¬ H « êR – C
O– « R – C
º R – C
O
1.27 A°ú
|
1.27 A°ú
ëê Resonance hybrid úû
- The resulting carboxylate ion also stabilized by resonance (As negative charge is dispersed on both the oxygen atom). This enhance the stability of carboxylate anion and make it weaker
(2) Effect of substituent on acidic nature
- An electron withdrawing substituent (– I effect) stabilizes the anion by dispersing the negative charge and therefore increases the
G ¬ C
Où–
|
ú
û
G ® C
Où–
|
ú
û
- (II)
- An electron releasing substituent (+ I effect) stabilizes negative charge on the anion resulting in the decrease of stability and thus decreased the acidity of
Electron with drawing nature of halogen : F > Cl > Br > I
Thus, the acidic strength decreases in the order :
FCH 2 COOH > ClCH2 COOH > BrCH 2 COOH > ICH 2 COOH
similarly : CCl3 COOH > CHCl2 COOH > CH 2 ClCOOH > CH3 COOH
- Inductive effect is stronger at a-position than b-position similarly at b-position it is more stronger than at g -position
Example: CH3 – CH2 – C H– COOH > CH3 – C H – CH2 – COOH > C H 2 – CH 2 – CH 2 – COOH
| | |
Cl Cl Cl
- Relative acid strength in organic and inorganic acids
RCOOH > HOH > ROH > HC º CH > NH 3 > RH
(1) Reaction involving removal of proton from –OH group
- Action with blue litmus : All carboxylic acids turn blue litmus
(ii) Reaction with metals :
- Action with alkalies :
2CH3 COOH + 2Na ® 2CH3 COONa+ H 2
Sodium acetate
2CH3 COOH + Zn ® (CH3 COO)2 Zn + H 2
Zinc acetate
CH3 COOH+ NaOH ® CH3 COONa+ H 2 O
Acetic acid
(iv) Action with carbonates and bicarbonates
Sodium acetate
2CH3 COOH + Na2 CO3 ® 2CH3 COONa+ CO2 + H 2 O
Sod. acetate
CH3 COOH + NaHCO3 ® CH3 COONa+ CO2 + H 2 O
Sod. acetate
Note : ® Reaction of carboxylic acid with aqueous sodium carbonates solution produces bricks effervescence. However most phenols do not produce effervescence. Therefore, this reaction may be used to distinguish between carboxylic acids and phenols.
(2) Reaction involving replacement of –OH group
(i) Formation of acid chloride :
CH3 COOH+ PCl5 ® 3CH3 COCl+ POCl3 + HCl
Acetic acid Acetyl chloride
3CH3 COOH+ PCl3 ® 3CH3 COCl+ H3 PO3
Acetic acid Acetyl chloride
CH3 COOH+ SOCl2 ® CH3 COCl+ SO2 + HCl
Acetic acid
(ii) Formation of esters (Esterification)
Acetyl chloride
CH3 CO
Acetic acid
OC2 H5
|
Ethyl alcohol
Conc.H2SO4
D
CH3 COOC2 H5 + H 2 O
Ethyl acetate (Fruity smelling)
- The reaction is shifted to the right by using excess of alcohol or removal of water by
- The reactivity of alcohol towards
tert-alcohol < sec-alcohol < pri-alcohol < methyl alcohol
- The acidic strength of carboxylic plays only a minor
R3 CCOOH < R2 CHCOOH < RCH 2 COOH < CH3 COOH < HCOOH
Mechanism of Esterification : The mechanism of esterification involves the following steps :
Step I : A proton from the protonic acid attacks the carbonyl oxygen of acetic acid.
CH – C O
+ H+ CH – C
O+ – H
CH – C
- OH
3 OH
Acetic acid
3 OH
Protonated acetic acid
3 OH
Step II : The electron rich oxygen atom of the ethyl alcohol attaches itself at positively charged carbon atom.
H OH H
OH | | |
CH3 – C
+ : O -& C2 H5
CH3 – C– O– C2 H5
OH ·· | +
Ethyl alcohol OH
Step III : From the resulting intermediate, a proton shifts to OH group as :
..
: OH H + OH2
|
|
CH – –
|
– C H
Proton transfer CH
|
– – OC H
|
|
|
O C 2 5
|
| + |
OH OH
Step IV : The intermediate obtained in Step III loses a water molecule to form a carbocation.
CH3 – C– OC2 H5
|
OH
+
CH3 – C– OC2 H5 + H 2 O
|
OH
Carbocation
Step V : The carbocation loses a proton to form an ester.
CH3
+
- C– OC2 H5
|
– H+
CH3
- C– OC2 H5
||
O
Ethyl acetate
Note : ® The OH
group for making H2O comes from acid.
- The mechanism is supported by labelling of Isotopic oxygen as :
O
||
CH – – OH +
18 H+
O
|| 18
CH – –
- H O
3 C CH3 CH 2 O H 3 C OC2 H5 2
When methanol is taken in place of ethanol. then reaction is called trans esterification.
(iv) Formation of amides :
CH3 COOH+ NH 3 ¾¾he¾at ® CH3 COONH4 ¾¾D ® CH3 CONH 2 + H 2 O
Acetic acid
Amm. acetate
Acetamide
(v) Formation of acid anhydrides :
CH3COO H CH CO
|
+ ¾¾¾®
O + H 2 O
CH3CO OH
Acetic acid
P2O5
CH3 CO
Acetic anhydride
(vi) Reaction with organo-metallic reagents :
R‘ CH2 MgBr + RCOOH ¾¾eth¾er ® R‘ CH3 + RCOOMgBr
Alkane
- Reaction involving carbonyl (>C = O) group : Reduction :
R – C– OH ¾¾LiA¾lH¾4 ® R – CH 2 – OH
||
O
Carboxylic acid are difficult to reduce either by catalytic hydrogenation or
(4) Reaction involving attack of carboxylic group (– COOH)
O
Na C2 H 5 OH
||
|
- Decarboxylation : R – – OH ¾¾(–C¾O¾2 ) ® R – H
When anhydrous alkali salt of fatty acid is heated with sodalime then :
RCOONa+ NaOH ¾¾Ca¾O ® R – H+ Na 2 CO3
Sodium salt
heat
Alkane
Note : (Exception) q When sodium formate is heated with sodalime H2 is evolved.
HCOONa + NaOH ¾¾Ca¾O ® H 2 + Na 2 CO3
- Heating of calcium salts : (RCOO)2 Ca ¾¾he¾at ® RCOR+ CaCO3
Sodium salt
Ketone
- Electrolysis : (Kolbe’s synthesis) : RCOONa ⇌
RCOO– + Na +
At anode
2RCOO– ® R – R + 2CO2 + 2e –
At cathode
2Na + + 2e – ® 2Na ¾¾2H¾2¾O ® 2NaOH + H 2
2CH 3 COOK+ 2H 2 O ¾¾Elec¾trol¾y¾sis ® CH 3 – CH 3 + 2CO2 + 2KOH + H 2
Potassium acetate Ethane
(iv) Formation of Alkyl halide (Hunsdiecker’s reaction) :
CH 3 COOAg+ Br2 ¾¾he¾at ®
CH 3 Br
- AgBr + CO2
Silver acetate
CCl4
Methyl bromide
Mechanism : Two step process –
|
O O
Step – I :
||
R – C– OAg + Br2
O
¾¾CC¾l4 ® R – || – OBr + AgBr
O
|| || . .
Step – II : (ii)
R – C– OBr + Br2 ® R – C– O+ Br
|
|
O
||
R – C– O ® R+ CO2
. .
R+ Br ® R – Br
Note : ® In Hunsdiecker reaction, one carbon atom less alkyl halide is formed from acid salt.
- Formation of amines (schmidt reaction) :
RCOOH+
Acid
N 3 H
Hydrazoic acid
¾¾H2S¾O4¾(con¾¾c.) ® RNH 2 + CO2 + N 2
Primary amine
In schmidt reaction, one carbon less product is formed.
Mechanism :
O
|| H +
OH
||
- HN
OH
| – H O
O
|| – N
O
|| +
R – C
|
OH
¾ ¾® R – C
|
OH
¾¾¾3 ®
R – C– OH
+
¾¾¾2
® R – C
|
¾¾¾2 ® R – C– N – H
+
H – N – N º N
NH – N º N
|
¾¾¾® R – N = C = O ¾¾H2¾O ® RNH2 + CO2
(vi) Complete reduction :
CH3 COOH+ 6HI ¾¾P ® CH3 CH3 + 2H 2 O + 3I 2
Acetic acid Ethane
In the above reaction, the – COOH group is reduced to a CH3 group.
(5) Reaction involving hydrogen of a-carbon
Halogenation
(i) In presence of U.V. light
H Cl
– | U.V .D |
C – COOH + Cl2 ¾¾¾® – C– COOH + HCl
| |
a -chloro acid
(ii) In presence of Red P and diffused light [Hell Volhard-zelinsky reaction]
Carboxylic acid having an a-hydrogen react with Cl2 or Br2 in the presence of a small amount of red phosphorus to give chloro acetic acid. The reaction is known as Hell Volhard-zelinsky reaction.
CH3 COOH ¾¾Cl2 ¾,red ¾P4 ® ClCH2 COOH ¾¾Cl2 ¾,red¾P4 ® Cl2 CHCOOH ¾¾Cl2¾, red ¾P4 ® Cl3 CCOOH
Acetic acid
Mechanism :
–HCl
Chloro acetic acid
–HCl
Dichloro acetic acid
–HCl
Trichloro acetic acid
Step – I :
R – CH2C
O
O – H
¾¾P+B¾r2 ® R – CH2 – C
(PBr3 )
O enolisation R – CH = C OH Br Br
|
|
.. Br
Step – II :
R – CH = C
O H + Br – Br ¾¾–H¾Br ® R – | – C O
Br
Step – III :
R – C H– C
|
Br
Br
O + RCH – C
Br 2
O ® R – CH – C OH |
Br
O O
OH + R – CH2C Br
Acid bromide (IV)
Second molecule of acid
a -bromocarboxylic acid
Formic Acid or Methanoic acid (HCOOH)
Formic acid is the first member of monocarboxylic acids series. It occurs in the sting of bees, wasps, red ants, stinging nettles. and fruits. In traces it is present in perspiration, urine, blood and in caterpillar’s.
- Methods of preparation : The following methods can be used for its preparation
(i) Oxidation of methyl alcohol or formaldehyde :
CH OH + 1 O
3 2 2
¾¾Pt ® HCHO + H 2 O
HCHO + 1 O
2 2
® HCOOH
CH 3 OH + O2 ® HCOOH + H 2O
Formic acid
- Hydrolysis of hydrocyanic acid : Formic acid is formed by the hydrolysis of HCN with acids or
HCN + 2H 2 O ¾¾H¾Cl ® HCOOH + NH 3 ; HCN + H 2 O ¾¾NaO¾H ® HCOONa + NH 3
- Laboratory preparation : Formic acid is conveniently prepared in the laboratory by heating glycerol
with oxalic acid at 100-120°C. In actual practice, glycerol is first heated at 105 o C and then hydrated oxalic acid is
added and the temperature is raised to 110°C. Glycerol monoxalate is first formed which decomposes into glycerol monoformate and carbon dioxide. When the evolution of carbon dioxide ceases, more of oxalic acid is added. The monoformate gets hydrolysed to formic acid regenerating glycerol which reacts with fresh oxalic acid. Thus, a small quantity of glycerol is sufficient to convert large quantities of oxalic acid into formic acid.
CH2OH HO OC–COOH
CH2OOC COO H
CH2OOCH
CH2OH
| Oxalic acid
– H O |
–CO |
(COOH) 2H O |
CHOH
¾¾¾2¾® CHOH
¾¾¾2 ® CHOH
¾¾¾¾2 ¾2¾® HCOOH+ CHOH
|
CH2OH
Glycerol
|
CH2OH
Glycerol monoxalate
110°C
|
CH2OH
Glycerol monoformate
Formic acid
|
CH2OH
Glycerol
The following procedure is applied for obtaining anhydrous formic acid.
2HCOOH + PbCO3 ® (HCOO)2 Pb+ CO2 + H 2 O ; (HCOO)2 Pb + H 2 S ® Pbs+ 2HCOOH
Lead formate
ppt.
Formic acid
- Industrial preparation : Formic acid is prepared on industrial scale by heating sodium hydroxide with carbon monoxide at 210°C under a pressure of about 10
CO + NaOH ® HCOONa
Sodium formate
Sodium formate thus formed is distilled with sodium hydrogen sulphate, when anhydrous formic acid distils over.
HCOONa + NaHSO4 ® HCOOH + Na 2 SO4
(2) Physical properties
- It is a colourless pungent smelling
- It melts at 4°C and boils at 100.5°C.
- It is miscible with water, alcohol and It forms azeotropic mixture with water.
- It is strongly corrosive and cause blisterson
- It exists in aqueous solution as a dimer involving hydrogen bonding.
Hydrogen bonding
H – C
O H – O O – H O
C – H
Hydrogen bonding
- Chemical properties : Formic acid is the strongest acid among all the members of the homologous
series. It exhibits some characteristics which are not shown by other members. This unique nature is due to the fact that it contains both aldehyde group and carboxyl group.
H – C
O
O ||
H – C
OH Aldehyde
OH H
O
||
C– OH
Carboxyl
Formic acid
group
group
(i) Acidic properties
- It is a monobasic Its dissociation constant value is 18 × 10–5 at 25°C. It’s acidic properties are due to its ionisation in aqueous solution.
HCOOH
Formic acid
HCOO– + H +
|
Formate ion
- It reacts with carbonates and bicarbonates evolving carbon dioxide. HCOOH + NaHCO3 ® HCOONa + H2O + CO2 2HCOOH + Na2CO3 ® 2HCOONa + H2O + CO2
- It reacts with alkalies to form corresponding The salts of formic acid are termed as formates. Most of
the formates are soluble in water but lead and silver formates are insoluble.
HCOOH + NaOH ® HCOONa + H2O
HCOOH + NH4 OH ® HCOONH4 + H2O
Amm. formate
- Highly electropositive metals evolve hydrogen when react with formic 2HCOOH + 2Na ® 2HCOONa + H 2
- It combines with alcohols to form It is not necessary to use a mineral acid as to catalyse the reaction since the formic acid itself acts as a catalyst.
HCOOH + CH3 OH ⇌ HCOOCH3 + H2O
Methyl formate
- It reacts with PCl5 or SOCl2 to give formyl chloride which is not a stable It decomposes at once into hydrogen chloride and carbon monoxide.
HCOOH + PCl5 ®
HCOCl
Formyl chloride
- POCl3 + HCl
HCOCl ® HCl + CO
- Action of heat : When heated above 160°C, it decomposes to give carbon dioxide and
HCOOH ® CO2 + H2
(iii) Action of heat on formates
- When sodium formate is heated to 360°C. It decomposes to form sodium oxalate and
COONa
2HCOONa ® |
COONa
Sodium oxalate
- H 2
- It does not form a hydrogen when sodium formate is heated with sodalime or its aqueous solution is
HCOONa + NaOH ¾¾Ca¾O ® Na2CO3 + H2
- Formaldehyde is formed when dry calcium formate is
(HCOO)2 Ca ® HCHO + CaCO3
formaldehyde
(iv) Reducing properties
- Like aldehyde formic acid behaves as reducing agents, it is oxidised to an unstable acid, carbonic acid, which decompose into CO2 and H2O
O
||
H – COOH ¾¾[O¾] ® HO – C– OH ® CO2 + H2O
Carbonic acid
- It decolourises acidified KMno4.
2KMnO4 + 3H 2 SO4
[HCOOH + O
® K 2 SO4 + 2MnSO4 + 3H 2 O + 5[O]
® CO2 + H 2O] ´ 5
2KMnO4 + 3H 2 SO4 + 5HCOOH ® K 2 SO4 + 2MnSO4 + 5CO2 + 8H 2 O
- It reduces mercuric chloride to mercurous chloride to mercury black
HCOOH + 2HgCl2 ® Hg2Cl2 + CO2 + 2HCl HCOOH + Hg 2 Cl2 ® CO2 + 2HCl + 2Hg
- It reduces ammonical silver nitrate (Tollen reagents)
HCOOH + Ag 2O ¾¾he¾at ® 2Ag + CO2 + H2O
Silver mirror
- It reduces fehling solution give red precipitate of Cu2O
HCOOH + 2CuO ® Cu2O + CO2 + H2O
(Red ppt.)
- Uses : Formic acid is
- In the laboratory for preparation of carbon
- In the preservation of
- In textile dyeing and
- In leather
- As coagulating agent for rubber
- As an antiseptic and in the treatment of
- In the manufacture of plastics, water proofing
- In electroplating to give proper deposit of
- In the preparation of nickel formate which is used as a catalyst in the hydrogenation of
- As a reducing
- In the manufacture of oxalic
(5) Tests of Formic Acid
- It turns blue litmus
- Its aqueous solution gives effervescences with sodium
- Its neutral solution gives red precipitate with Fehling’s
- Its neutral solution with Tollen’s reagent gives silver mirror or black
- It gives white precipitate with mercuric chloride which changes to
HgCl2 ® Hg2Cl2 ® Hg
White ppt. Grey
Acetic Acid (Ethanoic Acid) (CH3COOH)
Acetic acid is the oldest known fatty acid. It is the chief constituent of vinegar and hence its name (Latin acetum = vinegar)
(1) Preparation
(i) By oxidation of acetaldehyde (Laboratory-preparation) :
CH3 CHO ¾¾Na2¾cr2¾o7 ® CH3 COOH
H2So4 (O)
(ii) By hydrolysis of methyl cyanide with acid :
CH3 CN + 2H2O ¾¾H¾Cl ® CH3 COOH + NH3
O æ O ö
(iii) By Grignard reagent : CH
MgBr + CO
® CH
||
- – OMgBr
H 2O H +
ç || ÷
CH – – OH
3 2 3 C
¾¾¾¾®ç 3 C ÷
ç ÷
è ø
(iv) By hydrolysis of acetyl chloride, acetic anhydride or acetamide and ester
- CH3COOC2 H5 + H2O ¾¾H2S¾O4 (¾con¾) ® CH3COOH + C2 H5OH Ester
- CH3COCl + H2O ¾¾dil.H¾Cl ® CH3COOH + HCl
acetylchloride
|
- (CH3CO) O + H2O ¾¾dil.H¾Cl ® 2CH3COOH
(v) Manufacture of acetic acid
- From ethyl alcohol (Quick vinegar process) : Vinegar is 6-10% aqueous solution of acetic acid. It is obtained by fermentation of liquors containing 12 to 15% ethyl alcohol. Fermentation is done by Bacterium Mycoderma aceti in presence of air at 30-35°C. The process is termed acetous fermentation.
CH3 CH2OH+ O2 ¾¾Myc¾ode¾rma¾ac¾eti ® CH3 COOH+ H2O
Ethyl alcohol
Bacteria
Acetic acid
It is a slow process and takes about 8 to 10 days for completion. In this process, the following precautions are necessary:
- The concentration of the ethyl alcohol should not be more than 15%, otherwise the bacteria becomes
- The supply of air should be With less air the oxidation takes place only upto acetaldehyde stage while with excess of air, the acid is oxidised to CO2 and water.
- The flow of alcohol is so regulated that temperature does not exceed 35°C which is the optimum temperature for bacterial
Acetic acid can be obtained from vinegar with the help of lime. The calcium acetate crystallised from the solution is distilled with concentrated sulphuric acid when pure acetic acid distils over.
- From acetylene : Acetylene is first converted into acetaldehyde by passing through 40% sulphuric acid at 60°C in presence of 1% HgSO4 (catalyst).
CH º CH+ H2O ¾¾H2S¾O4 ¾(d¾il.) ® CH3 CHO
Acetylene
HgSO4
Acetaldehyde
The acetaldehyde is oxidised to acetic acid by passing a mixture of acetaldehyde vapour and air over manganous acetate at 70°C.
2CH3 CHO + O2 ¾¾Man¾gan¾ous¾ace¾ta¾te ® 2CH3 COOH
70°C
Note : ® Acetylene required for this purpose is obtained by action of water on calcium carbide.
CaC2 + 2H2O ® Ca(OH)2 + C2 H2
The yield is very good and the strength of acid prepared is 97%. The method is also quite cheap.
- By the action of CO on methyl alcohol : Methyl alcohol and carbon monoxide react together under a pressure of 30 atmospheres and 200°C in presence of a catalyst cobalt octacarbonyl, Co2(CO)8 to form acetic
CH3 OH + CO ¾¾Co2¾(CO¾)8 ® CH3 COOH
Methyl alcohol
(2) Physical properties
30atm200°C
Acetic acid
- At ordinary temperature, acetic acid is a colourless, corrosive liquid with a sharp pungent odour of It has a sour taste.
- Below 5°C, it solidifies as an icy mass, hence it is named glacial acetic acid.
- It boils at 118° The high boiling point of acetic acid in comparison to alkanes, alkyl halides or alcohols of nearly same molecular masses is due to more stronger hydrogen bonding between acid molecules. This also explains dimer formation of acetic acid in vapour state.
- It is miscible with water, alcohol and ether in all
- It is good solvent for phosphorus, sulphur, iodine and many organic
- Chemical properties : Acetic acid is a typical member of fatty acids. It shows all the general characteristics of monocarboxylic
Reaction chart of Acetic acid
|
Na CH3COONa
Sodium acetate
CH3COONa
CH COONa+H O+CO
3 2 2
CH COOC H
3 2 5
CH COOH
Ethyl acetate
CH3COCl
Acetyl chloride
(CH3CO)2O
Acetic anhydride
CH CONH
3
Acetic acid
3 2
Acetamide
CH3CH2OH
Ethyl alcohol
CH4
Methane
CH COCH
- Uses : It is used,
heat
3 3
Acetone
CH3CHO
Acetaldehyde
CH3NH2
Methyl amine
CH3–CH3
Ethane
CH2ClCOOH
Chloroacetic acid
Cl2 P
CHCl2COOH
Dichloro acetic acid
Cl2 P
CCl3COOH
Trichloro acetic acid
- As a solvent and a laboratory
- As vinegar for table purpose and for manufacturing
- In coagulation of rubber
- For making various organic compounds such as acetone, acetic anhydride, acetyl chloride, acetamide and
- For making various useful metallic acetates, such as:
- Basic copper acetate which is used for making green
- Al, Fe and Cr acetates which are used as mordants in
- Lead tetra-acetate which is a good oxidising
- Basic lead acetate which is used in the manufacture of white
- Aluminium acetate which is used in the manufacture of water-proof
- Alkali acetates which are used as
(5) Tests
- Its aqueous solution turns blue litmus
- Its aqueous solution gives effervescences with sodium
- The neutral solution of the acetic acid gives a wine red colour with neutral ferric chloride
- When heated with ethyl alcohol in presence of a small amount of concentrated sulphuric acid, it forms ethyl acetate which has fruity
- Acetic acid does not show reducing properties like formic acid, e., it does not reduce Tollen’s reagent, Fehling’s solution and mercuric chloride.
Comparison of Formic Acid and Acetic Acid
| Property | Formic acid | Acetic acid |
| 1. Acidic nature,
(i) With electro- positive metals
(ii) With bases
(iii) With carbonates and bicarbonates
2. Ester formation
3. Reaction with PCl5
4. Heating of ammonium salt |
Forms salts, Hydrogen is evolved. HCOOH + Na ® HCOONa + 1 H 2 2 Forms salts. HCOOH + NaOH ® HCOONa + H 2O Forms salts. Carbon dioxide is evolved. HCOOH + NaHCO3 ® HCOONa + H 2 O + CO2
Forms esters when treated with alcohols. HCOOH + C2 H5 OH ® HCOOC2 H5 + H 2 O
Forms formyl chloride which decomposes into CO and HCl. HCOOH + PCl5 ® HCOCl(HCl + CO) + POCl3 + HCl
Forms formamide. HCOONH4 ® HCONH 2 + H 2O |
Forms salts. Hydrogen is evolved. CH3 COOH + Na ® CH3 COONa + 1 H 2 2 Forms salts. CH3 COOH + NaOH ® CH3 COONa + H 2O Forms salts. Carbon dioxide is evolved. CH3COOH + NaHCO3 ®
CH 3COONa + H 2O + CO2 Forms esters when treated with alcohols. CH 3 COOH + C2 H5 OH ¾¾H2S¾O4¾(co¾n¾c.) ®
CH 3 COOC2 H5 + H 2 O Forms acetyl chloride which is a stable compound. CH 3COOH + PCl5 ® CH 3 COCl + POCl3 + HCl Forms acetamide. CH 3 COONH4 ® CH 3 CONH 2 + H 2 O |
- Heating alone it decomposes into CO2 and H2
HCOOH ® CO2 + H 2
Unaffected
- Heating with H2SO4
Decomposed into CO and H2O
Unaffected
- Reaction with Cl2 in presence of red P
8 Action of heat on salts,
Unaffected Forms mono, di or trichloro acetic acids.
- Calcium salt Forms
(HCOO)2 Ca ® HCHO + CaCO3
Forms acetone.
(CH COO) Ca ® CH COCH + CaCO
3 2 3 3 3
- Sodium salt Forms sodium Unaffected.
- Sodium salt with soda-lime
Forms sodium carbonate and H2.
HCOONa + NaOH ¾¾Ca¾O ® Na2 CO3 + H 2
Forms sodium carbonate and methane.
CH 3 COONa + NaOH ¾¾Ca¾O ®
- Electrolysis of sodium or potassium salt
- On heating with P2O5
- Reducing
CH 4 + Na2 CO3
It evolves hydrogen. It forms ethane.
Unaffected Forms acetic anhydride.
2CH 3 COOH ¾¾P2O¾5 ®(CH 3 CO)2 O + H 2 O
nature,
- Tollen’s reagent
- Fehling’s solution
- Mercuric chloride
Gives silver mirror or black precipitate.
HCOOH + Ag 2 O ® 2Ag + CO2 + H 2 O
Gives red precipitate
HCOOH + 2CuO ® Cu2 O + CO2 + H 2 O
Forms a white ppt. which changes to greyish black.
HgCl 2 ® Hg 2Cl 2 ® 2Hg
Unaffected.
Unaffected. Unaffected.
- Acidified KMnO4
- Acid (neutral solution) + NaHSO3 +
Sodium nitroprusside.
Decolourises Unaffected.
Greenish blue colour. Unaffected.
- Acid (neutral solution) + neutral ferric
Red colour which changes to brown ppt. on heating.
Wine red colour.
Interconversions
- Ascent of series : Conversion of formic acid into acetic
HCOOH ¾¾Ca(¾OH¾)2 ®(HCOO)2 Ca ¾¾he¾at ®
HCHO
¾¾CH¾3 M¾gB¾r ® CH 3 CH 2 OMgBr ¾¾H2¾O ® CH 3 CH 2 OH
Formic acid
Calcium formate
Formaldehyde
Addition product
H + Ethyl alcohol
¾¾[¾O] ® CH 3 CHO ¾¾[¾O] ® CH 3 COOH
HCHO
¾¾H2 ¾Ni ® CH3OH
Acetaldehyde
¾¾H¾I ® CH3 I ¾¾KC¾N(A¾l¾c.) ® CH3CN ¾¾H2¾O ® CH3COOH
Acetic acid
Formaldehyde
Methyl alcohol
Methyl iodide
Methyl H +
cyanide
Acetic acid
Arndt-Eistert homologation : This is a convenient method of converting an acid, RCOOH to RCH2COOH.
RCOOH ¾¾SO¾CL¾2 ® RCOCl ¾¾CH¾2 N¾2 ® RCOCHN 2 ¾¾EtO¾H ® RCH 2 COOC2 H5 ¾¾Hyd¾rol¾y¾sis ® RCH 2 COOH
Ag2O
- Descent of series : Conversion of acetic acid into formic
¾¾N3¾H ® CH 3 NH 2 ¾¾NaN¾O2¾H¾Cl ® CH 3 OH
¾¾[¾O] ®
HCHO
¾¾[¾O] ® HCOOH
H2SO4
Methyl amine
Methyl alcohol
Formaldehyde
Formic acid
CH 3 COOH ¾¾NH¾3 ® CH 3 COONH 4 ¾¾he¾at ® CH 3 CONH 2 ¾¾Br2¾KO¾¾H ® CH 3 NH 2
Acetic acid
Amm. acetate
Acetamide
Methyl amine
¾¾NaO¾H ® CH3COONa ¾¾Sod¾alim¾e ® CH4
¾¾C¾l2 ® CH3Cl ¾¾AgO¾H ® CH3OH
¾¾[¾O] ®
HCHO
¾¾[¾O] ® HCOOH
Sodium acetate
heat
Methane hv
Methyl chloride
Methyl alcohol Na2Cr2O7 + H2SO4 Formaldehyde
Formic acid
(CH3CO)2O
Acetic anhydride
Conversion of Acetic acid into other organic compound
CH3 – CH3
Cl2 hv
CH3 – CH2Cl
Ethyl chloride
AgOH CH3 – CH2OH
Ethyl alcohol
[O] CH3 – CHO
Acetaldehyde
Ethane
CH3CH2NH2
Ethyl amine
CH CH CH NH
[H] CH CH CN H2O
CH3CH2COOH
3 2 2 2
LiAlH 3 2
H+ Propionic acid
Sodalime
n-Propyl amine
Cl
4
AgOH
[O]
[O]
NaOH
|
CH4
hv CH3 Cl
CH3OH
Methyl alcohol
HCHO
Formaldehyde
HCOOH
Formic acid
Methane
Methyl chloride
COOH
|
COOH
Oxalic acid
|
H2SO4
COONa
|
COONa
Sodium oxalate
heat
HCOONa
Sodium formate
|
Ca(OH)2 (CH COO) Ca
heat CH COCH
H2/Ni CH CHOHCH
Alc.KOH CH CH= CH
3 2 3 3 3 3 3 2
Calcium acetate
Acetone
I2 + NaOH
CHI3
Iodoform
CH3CONH2
Acetamide
Isopropyl alcohol
HC ≡ CH
acetylene
Br2/KOH CH3NH2
Methyl amine
Propene 500°C Cl2
ClCH2CH= CH2
Allyl chloride
CH3COCl
Acetyl chloride
NH3
C2H5OH
CH3CN
|
Methyl cyanide
CH3COOC2H5
Ethyl acetate
[H]
LiAlH4
CH3CH2NH2
Ethyl amine
Rosenmund’s reduction
CH3CHO
Acetaldehyde
HCN CH CH OH
|
CN
H2O H+
CH3CHOHCOOH
Lactic acid
Cyanohydrin
The acids containing two carboxylic groups are called dicarboxylic acids.
The saturated dicarboxylic acid are represented by the general formula Cn H 2n (COOH)2 where n = 0, 1, 2, 3 etc.
HO – C– (CH 2 )n – C– OH or HOOC(CH 2 )n COOH
|| ||
O O
According to IUPAC system, the suffix-dioic acid is added to the name of parent alkane, i.e. Alkane dioxic acid.
| Formula | Common name | IUPAC name |
| HOOCCOOH | Oxalic acid | Ethanedioic acid |
| HOOCCH2COOH | Malonic acid | 1-3 Propanedioic |
| acid | ||
| HOOCCH2CH2 | Succinic acid | 1,4-Butanedioic acid |
| COOH | ||
| HOOC(CH2)3COOH | Glutaric acid | 1,5-Pentanedioic acid |
| HOOC(CH2)4 COOH | Adipic acid | 1,6-Hexanedioic acid |
Oxalic Acid or Ethanedioic Acid
COOH
|
COOH
or (COOH)2
or (C2 H 2 O4 )
Oxalic acid is first member of dicarboxylic series.
It occurs as potassium hydrogen oxalate in the wood sorel, rhubarb and other plants of oxalis group and as calcium oxalate in plants of rumex family.
It is found in the form of calcium oxalate in stony deposits in kidneys and bladdar in human body. Oxalic acid present in tomatoes.
(1) Methods of Preparation
(i) By oxidation of ethylene glycol with acidified potassium dichromate
CH2OH+ 4[O] ¾¾K C¾r O¾® COOH + 2H O
| 2 2 7 | 2
CH2OH
Glycol
H2SO4
COOH
(ii) By hydrolysis of cyanogen with conc. hydrochloric acid :
CN
|
| + 4 H CN
O ¾¾2(H¾C¾l) ® COOH+ 2NH Cl COOH
(iii)
|
|
By heating sodium or potassium in a current of carbon dioxide at 360°C
2Na + 2CO
¾¾he¾at ®
COONa
2 |
COONa
Sodium oxalate
(iv) Laboratory preparation :
C12 H
22 O11
+ 18[O] ¾¾HN¾O¾3 ®
COOH
6 | + 5H 2O
Sucrose
V2O5
COOH
Oxalic acid
(v) Industrial method :
2HCOONa ¾¾360¾°¾C ® COONa + H
|
|
Sod. formate
COONa
Sod. oxalate
Sodium formate is obtained by passing carbon monoxide over fine powdered of sodium hydroxide.
CO + NaOH ¾¾200¾°¾C ® HCOONa
8-10atm
The sodium oxalate thus formed is dissolved in water and calcium hydroxide is added. The precipitate of calcium oxalate is formed which is separated by filtration. It is decomposed with calculated quantity of dilute sulphuric acid.
COONa
|
COONa
- Ca(OH)2 ®
COO
|
COO
Calcium oxalate
Ca + 2NaOH
COO
|
COO
COOH
Ca + H 2SO4 (dil.) ® | +
COOH
Oxalic acid (soluble)
CaSO4
Calcium sulphate (insoluble)
(2) Physical Properties
- It is a colourless crystalline It consists of two molecules of water as water of crystallisation.
- The hydrated form has the melting point 101.5°C while the anhydrous form melts at 190°C.
- It is soluble in water and alcohol but insoluble in
- It is poisonous in It affects the central nervous system.
(3) Chemical Properties
- Action of heat : It becomes
(COOH)2 2H2O ¾¾100¾–10¾5°¾C ®(COOH)2 + 2H2O
Hydrated oxalic acid
Anhydrous oxalic acid
- At 200°C, (COOH)2 + HCOOH+ CO2
Formic acid
On further heating, formic acid also decomposes.
HCOOH ® CO2 + H 2
- Heating with H2SO4
COOH
|
COOH
¾¾H2S¾O¾4 ® CO + CO2 + H 2 O
(conc.)
(ii) Acidic nature
Salt formation
COOH
KOH
COOK
KOH
COOK
| +
COOH
Oxalic acid
® |
COOK
Acid pot. oxalate
¾¾¾® |
COOK
Pot. oxalate
COOH
|
COOH
- 2NaHCO3 ®
COONa
|
COONa
Sod. oxalate
+ 2CO2 + 2H 2O
COOH
|
COOH
COONa
- Na 2 CO3 ® |
COONa
- H 2 O + CO2
(iii) Esterification
COOH
C H OH
COOC2 H5
C H OH
COOC2 H5
|
COOH
¾¾2 ¾5 ¾® |
COOH
Ethyl hydrogen oxalate
¾¾2 ¾5 ¾® |
COOC2 H5
Ethyl oxalate
(iv) Reaction with PCl5 :
COOH
|
COOH
COCl
+ 2PCl5 ® |
COCl
Oxalyl chloride
- 2POCl3 + 2HCl
(v) Reaction with ammonia
COOH
COONH4
NH COONH4
|
COOH
- NH3 ®
|
COOH
Acid ammonium oxalate
¾¾¾3 ® |
COONH4
Amm. oxalate
– H2O heat – 2H2O heat
CONH2
|
COOH
Oxamic acid
CONH2
|
CONH2
Oxamide
- Oxidation : When oxalic acid is warmed with acidified
KMnO4 .
2KMnO4 + 3H 2 SO4 ® K 2 SO4 + 2MnSO4 + 3H 2 O + 5[O]
éCOOH
ê|
ëCOOH
+ [O] ® 2CO + H Où ´ 5
|
û
2KMnO4
Pot. permanganate (Purple)
COOH
+ 3H2SO4 + 5 |
COOH
Oxalic acid
® K2SO4 + 2MnSO4 + 10CO2 + 8H2O
Colourless
Note : ® Oxalic acid decolourises the acidic
(vii) Reaction with ethylene glycol
KMnO4 solution.
O= CH2
|
O= CH2
heat
–H2O
O=C
| O=C
O
CH2
| CH2
O
Oxalic acid Ethylene glycol
- Reduction : COOH+ 4 H ¾¾Z¾n ® CH2OH + H O
Ethylene oxalate
|
COOH
H2SO4
| 2
COOH
Glycolic acid
It can also be reduced electrolytically using lead cathode into glycolic acid and glyoxalic acid.
COOH
2 |
CH2OH
¾¾Elec¾tro¾lytic¾red¾uct¾io¾n ® | +
COOH
|
- 2H2O
COOH
6[H]
COOH
Glycolic acid
CHO
Glyoxalic acid
admin
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