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ACID-BASE PROPERTY AND

SOLUBILITY OF
ORGANIC COMPOUNDS

Mario A. Tan, Ph.D.


Department of Chemistry, College of Science
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Objectives
to describe the structural features common to compounds that
belong to a specific functional grouping

to be able to differentiate each component of a given mixture of


organic functionality based on solubility and acid-base properties
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Physical Properties
can be determined without changing the chemical identity of a substance
examples are physical color, odor, physical state, solubility and density

Acids and Bases


Brnsted-Lowry Lewis

Acids Proton donor Electron pair acceptor

Bases Proton acceptor Electron pair donor


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Acid-Base properties
Acids Bases
sour in taste taste bitter and feel soapy
increase H+ concentration increase OH- concentration

Organic acids and bases are weak in nature and dont


ionize completely in H2O.

Acid-Base properties of organic compounds


organic acids and bases are weak in nature and dont ionize completely in H2O

organic compounds acid base behavior can be obtained by solubility


comparison in aqueous acids and aqueous bases
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Solubility of Organic Compounds

The solubility of an organic compound is related to its


structure.

Commonly used solvents in determining solubility:


water, concentrated H2SO4, and 5% aqueous solutions of
NaOH, NaHCO3, and HCl
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Polar Covalent Molecules


Polar covalent molecules are soluble in water.
Water can break the weaker dipole-dipole forces
between polar solutes and form new stronger hydrogen
bonds between the polar solute and water.
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Polar Covalent Molecules


As the carbon chain increases while having the same type
and number of polar group, water solubility decreases.

Organic compounds with polar groups, such as alcohols, with


one to three carbon atoms are soluble in water. Meanwhile,
similar compounds with five carbons or more are insoluble in
water.

As the number of polar groups is increased relative to the


increase in carbon chain, water solubility increases.
Example: hexan-1-ol is insoluble in water while
glucose is highly soluble in water
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Non-Polar Covalent Molecules


Alkyl halides (haloalkanes) are generally insoluble in
water. They are weakly polar compounds and cannot form
hydrogen bonds with water.

In addition to alkyl halides, other compounds that are


insoluble in water can be further classified into acidic,
basic, neutral, or inert based on their reactivity.

Solvents used for further classification: 5% aqueous


solutions of NaOH and HCl, and concentrated H2SO4.
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Acidic Organic Compounds


Compounds with acidic hydrogens will dissolve in
NaOH.

Compounds with acidic hydrogens are: carboxylic acids,


sulfonic acids, phenols, thiophenols, mercaptans (or thiols),
1 and 2 nitro-compounds, oximes, and imides.

The strength of the acidity of the organic acid is


determined by its solubility in 5% NaHCO3 (a base
weaker than NaOH).

Strong organic acids are soluble in 5% NaHCO3.


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Acidic Organic Compounds


Compounds weaker than carboxylic acids, such as
phenols, are insoluble in 5% NaHCO3.

The presence of electron-withdrawing groups like


halogens and nitro groups increase the acidity of phenols.
Example: 2,4-dinitrophenol and 2,4,6-
trichlorophenol are soluble in 5% NaHCO3
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Basic Organic Compounds


Basic organic compounds form water-soluble salts
when mixed with HCl.

Amines are the most important organic bases. Their


lone pairs are available for bonding with a hydrogen ion.

The strength of the organic base depends on the


availability of the non-bonding electrons, and the relative
stability of the amine and its conjugate acid.
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Basic Organic Compounds


If the electron pair of the nitrogen is highly available, the
compound (amine) is strongly basic.

The availability of the non-bonding electron pairs


depends on the groups attached on the nitrogen. Electron-
withdrawing groups make the electron pair less available,
thus decreasing the basicity of the amine.

Di- and tri- arylamines, arylamines with electron-


withdrawing groups, and simple monosubstituted amides
are some examples of nitrogen containing compounds that
are insoluble in 5% HCl.
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Neutral Organic Compounds


Compounds that contain oxygen, such as aldehydes, ketones,
alcohols, ethers, esters, and anhydrides, are insoluble in 5%
HCl.

The electron pairs of oxygen are not readily available for


bonding with a free proton because oxygen has a greater
attraction for its electrons due to its electronegativity. Since 5%
HCl is an aqueous solution, the proton released by HCl is being
captured by water molecules instead of the solute molecules.

Increasing the acidity of the solvent would increase the


solubility of the oxygen-bearing compound in the acidic solvent.
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Reference Standards

Cyclohexane Phenol Benzoic acid Amyl acetate Ethanol Ethylamine

Hydrochloric acid (HCl)


strong acid because it can be completely dissociated with water
Sodium hydroxide (NaOH)
strong metallic base which reacts with strong acids to form water and its
corresponding salts
Sodium bicarbonate (NaHCO3)
white crystalline solid which when treated with acids decomposes to
water and CO2
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Physical Properties
Amyl acetate
physical state
Cyclohexane
Ethylamine
5 drops or color
Ethanol microspatula
Benzoic acid
odor
Phenol

Solubility/Miscibility Test
1. Amyl acetate
+ 1 mL 1M HCl
1 2 3 4 5 6
2. Cyclhexane Observe
and record
3. Ethylamine the
solubility of
4. Ethanol each
+ 1 mL 1M NaOH compound
1 2 3 4 5 6
5. Benzoic acid

6. Phenol
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Physical Properties Miscibility


Organic
Sample Physical With 1M
Odor, Color With 1M HCl*
State NaOH*

Before
After heating:
heating:

Amyl acetate Liquid immiscible immiscible


Banana-like Banana-like ___
odor; odor;
Colorless. Colorless.

Cyclohexane Liquid Gasoline-like odor ; Colorless immiscible immiscible

Ethylamine Liquid Ammonia-like odor; Colorless miscible miscible

With
Ethanol Liquid Alcohol-like odor; Colorless miscible miscible
NaHCO3*

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Benzoic Acid Solid Odorless; White, fine powder insoluble soluble
With effervescence

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Phenol Liquid Formalin-like odor; Light red immiscible miscible Without
effervescence
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Amyl Acetate
neutral compound
ester molecules cannot hydrogen-bond to each other
immiscible in both HCl and NaOH
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Cyclohexane
neutral compound
cannot form H bonds because of its non-polarity
immiscible in both HCl and NaOH
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Ethanol
can form H-bond
considered neutral compound but may act as acid or base
can dissolve in both polar and non-polar substances
miscible with HCl and NaOH
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Ethylamine
can form H-bond
act as a base
basicity depends on the availability of the lone pair of electrons of N and on
the electronic properties of the substituents
miscible with HCl and NaOH
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Benzoic acid
can form H-bond
act as an acid
soluble in NaOH
insoluble in HCl and forms effervescence with NaHCO3
Reaction of Benzoic acid with NaOH
C6H5COOH + NaOH C6H5COO-Na+ + H2O
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Phenol
can form H-bond
slightly acidic
miscible in NaOH
immiscible in HCl and does not form effervescence with NaHCO3
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A B C D E F G H

Gives only a C=O stretch at 1735 cm-1


Gives a broad signal at 3200 3500 cm-1
Gives a medium sharp peak at 1602 cm-1
Gives a medium peak at 2254 cm-1
A saturated hydrocarbon
A bicyclic amine
Phenolic compounds
Aromatic compounds
Capable of H-bonding
Soluble in water
Soluble in 1M NaOH
Soluble in HCl
Has a nitrile functionality
Most inert compound
Soluble in 1M NaHCO3
Forms sodium salt with sodium bases
Hydrolyzes in basic condition
Forms a hydrochloride salt
MOST soluble compound in pentane
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Two acid-soluble compounds A&B with molecular


formula, C4H9N, were subjected for IR analysis.
Compound A showed a singlet peak at 3250 cm-1 while
compound B showed IR peaks at 1599 cm-1 and doublet
peaks at 3287 cm-1. Draw the structure of compound A
and B.

Why are they soluble in acid?