CHY 32

Activity 6
ALCOHOLS AND PHENOLS
Solubility of Alcohols in Water
• In the case of alcohols, hydrogen bonds occur between the
partially-positive hydrogen atoms and lone pairs on oxygen
atoms of other molecules.
• Small alcohols are completely soluble in water; mixing the two
in any proportion generates a single solution.
• However, solubility decreases as the length of the hydrocarbon
chain in the alcohol increases.
• At four carbon atoms and beyond, the decrease in solubility is
noticeable; a two-layered substance may appear in a test tube
when the two are mixed.
 Alcohol Structure Observation Solubility in H2O at 23 ◦C
(g/100 mL)

Methanol CH3OH Soluble/Miscible infinite

Ethanol CH3CH2OH Soluble/Miscible infinite
Isopropyl alcohol CH3CH(OH)CH3 Soluble/Miscible 10.0
Tert-butyl alcohol (CH3)3COH Soluble/Miscible 10.0
N-Butyl alcohol CH3CH2CH2CH2OH Slightly Miscible 8.0
Benzyl alcohol C6H5CH2OH Slightly Miscible 3.5
From:
https://chem.libretexts.org/Courses/Purdue/Purdue_Chem_26100%3A_Organic_Chemistry_I_(Wenthold)/Chapter_10%3A_Alcohols/10.1_Structure_and_Classification_o
f_Alcohols
• the smaller alcohols - methanol, ethanol, and propanol - dissolve
easily in water. This is because the water is able to form hydrogen
bonds with the hydroxyl group in these molecules, and the combined
energy of formation of these water-alcohol hydrogen bonds is more
than enough to make up for the energy that is lost when the alcohol-
alcohol hydrogen bonds are broken up. When you try butanol,
however, you begin to notice that, as you add more and more to the
water, it starts to form its own layer on top of the water.
• The longer-chain alcohols - pentanol, hexanol, heptanol, and octanol
- are increasingly non-soluble. What is happening here? Clearly, the
same favorable water-alcohol hydrogen bonds are still possible with
these larger alcohols. The difference, of course, is that the larger
alcohols have larger nonpolar, hydrophobic regions in addition to
their hydrophilic hydroxyl group. At about four or five carbons, the
hydrophobic effect begins to overcome the hydrophilic effect, and
water solubility is lost.
 Alcohols and Phenols
Acidity of Alcohols and
Phenols

pH
Ethanol 6
Phenol 5

pH = - log [H+]
• Alcohols are so weakly acidic that, for normal lab purposes, their acidity
can be virtually ignored.

• However, phenol is sufficiently acidic for it to have recognizably acidic

properties - even if it is still a very weak acid. A hydrogen ion can break
away from the -OH group and transfer to a base.
In solution in water,

Phenol can lose a hydrogen ion because the phenoxide ion formed is
stabilized to some extent (pi electron delocalization).
Combustion
• Alcohols are flammable.
• They burn in air because of the presence of a hydrocarbon chain.
They burn to produce carbon dioxide and water.
• This property allows alcohols to be used as a fuel. In countries with
no oil industry ethanol produced by fermentation is used as an
alternative fuel supply to importing oil.
45% Ethanol Blue, sootless flame
95% Ethanol Blue, sootless flame

Chemical equation involved :

CH3CH2OH(aq) + O2(g) CO2(g) + H2O(g)
Lucas Test
• This reaction with the Lucas Reagent (ZnCl2) is a qualitative test for
the different types of alcohols because the rate of the reaction differs
greatly for a primary, secondary and tertiary alcohol.
• Alcohol (R-OH) is converted to alkyl halide (R-X).
• The difference in rates is due to the solubility of the resulting alkyl
halides.
Tertiary Alcohol→ turns cloudy immediately (the alkyl halide is not soluble
in water and precipitates out)
Secondary Alcohol → turns cloudy after 5 minutes (the alkyl halide is
soluble in water)
Primary Alcohol → takes much longer than 5 minutes to turn cloudy (the
alkyl halide is soluble in water)
• Indications of a positive test:
clear solution to cloudy solution
The Lucas test is a test for the ease of replacement of a
hydroxyl group by a halogen atom, according to the reaction:

Order of increasing reactivity with Lucas Reagent:

10 ROH < 20 ROH < 30 ROH
• Since the product (alkyl halide) is insoluble in water, the
solution becomes cloudy and may separate into two layers
when the hydroxyl group is replaced with halogen.

• This cloudiness or appearance of a second layer (heterogeneous

mixture) is evidence that a reaction has occurred.

.
• When Lucas reagent (ZnCl2 + conc. HCl) is added to
alcohols, H+ from HCl will protonate the -OH group, so that
the leaving group H2O, being a much weaker nucleophile
than OH-, hence can be substituted by nucleophile Cl-.
• Lucas' reagent offers a polar medium in which SN1
mechanism is favored.
• Therefore, tertiary alcohols react immediately with Lucas
reagent to produce turbidity while secondary alcohols do so in
about five minutes.
Chemical Equations Involved:
ZnCl2
CH3CH2OH CH3CH2Cl + H2O
HCl
10 ROH 10 R-X
CH3 CH3
ZnCl2
CH3 C OH CH3 C Cl + H2O
HCl
CH3 CH3
OH Cl 30 ROH 3O R-X
ZnCl2
CH3CHCH3 CH3CHCH3 + H2O
HCl
20 ROH 20 R-X
 Chemical Formula of the Reagent: ZnCl2/HCl
Color of the Reagent COLORLESS SOLUTION

Sample Observation Rate of Layer

Formation
(fast, faster, fastest)
Ethanol turbid(layer forms after more than 5 min) fast
Isopropyl alcohol turbid (layer forms after 5 min) faster
Tert-butyl alcohol turbid (layer forms immediately) fastest
Reaction of Alcohols with Sodium
• Alcohols react with sodium to form a salt (sodium alkoxide) and
hydrogen gas.
• The reaction is similar but much slower than the reaction of
water and sodium. This is because of the similarities in the
structure of the water molecule and the alkyl (O—H) group in
alcohols.
• Due to the low density of the alcohols the sodium sinks. The
reaction proceeds steadily with the evolution of hydrogen gas
and leaves a colorless solution of the salt. The salt can be
recovered as a white solid by careful evaporation of the
solution.
• If a small piece of sodium is dropped into some ethanol, it reacts
steadily to give off bubbles of hydrogen gas(H2) and leaves a colorless
solution of sodium ethoxide, CH3CH2ONa. Sodium ethoxide is known
as an alkoxide.

• If the solution is evaporated carefully to dryness, the sodium ethoxide

is left as a white solid.
 Chemical Formula of the Reagent: Na metal
Color of the Reagent LUSTROUS GRAY SOLID

Sample Observation Rate of Layer

Formation
(fast, faster, fastest)
Ethanol Bubbling Fastest
Isopropyl alcohol Bubbling Faster
Tert-butyl alcohol No reaction Fast

Order of increasing reactivity with Na metal:

30 ROH < 20 ROH < 10 ROH
• At the lower end of the molecular-mass for this series the destabilization of the
hydroxyl intermediates by the electron-rich hydrocarbon groups (of course absent
in water) also slows the progress of the reaction to some degree.
• The inductive destabilization effect mentioned above also largely controls the
relative acidities of the alcohols, which in turn are directly related to the
reactivity of the alcohol with sodium. The relative acidities of pure solutions of
water and some selected C1 to C3 alcohols goes as:
water > methanol > ethanol > isopropanol
Ferric chloride Test
Ferric Chloride Test
Ferric Chloride test
• Phenols complex with the iron ion
• A test for the presence of phenol and derivatives of phenol
• An intense color ranging from purple to reddish brown to green is
observed.
Chemical Formula of the Reagent: FeCl3
Color of the Reagent: YELLOW SOLUTION

Sample Structure Color with FeCl3 (+)/(-) Rxn

ethanol CH3CH2OH yellow solution(color other -
than violet)
phenol VIOLET solution +

Resorcinol VIOLET/DARK solution +

H
O O
H

HO

Salicylic acid HO VIOLET/DARK solution +

O
Chemical Equation Involved:

H
OH O
FeCl3 FeCl3

phenol violet
Ferric Phenoxide
Oxidation of Alcohols
• Alcohols can be oxidized by a variety of oxidizing agents. Oxidation can
be done by using oxidizing agents such as acidified potassium
dichromate (VI), acidified potassium manganate (VII)... ...or atmospheric
oxygen.
• Remember, oxidation is a process involving the gain of oxygen, loss of
hydrogen or loss of electrons.
• Oxidation of alcohols is oxidation in terms of hydrogen transfer. The
alcohol is oxidized by loss of hydrogen.
Oxidation of Alcohols
Oxidation with Chromic Acid
• The oxidation of the alcohol to an aldehyde is indicated by the color
change of the dichromate solution as it is reduced from the
color of Cr2O72− to the green of chromium(III) ions (Cr3+).
Chemical Formula of the Reagent: K2Cr2O7/dil. H2SO4
Color of the Reagent: ORANGE SOLUTION

Sample Description of the Sample with (+)/(-) Rxn

K2Cr2O7/dil. H2SO4
Ethanol GREEN solution(Immediate) +
Isopropyl alcohol GREEN solution(>5 min.) +
Tert-butyl alcohol Yellow/Orange solution -
Oxidation of ethanol
• Primary alcohols can be oxidized to aldehydes.
• In this reaction ethanol is oxidized to ethanal by removing two hydrogen
atoms.

In this reaction the ethanol is oxidized to ethanal by removing two hydrogen atoms. Ethanal can be further oxidized into
ethanoic acid, a carboxylic acid.
CH3CHO CH3COOH
Oxidation of isopropyl alcohol/propan-2-ol (2-
propanol)
• Secondary alcohols are oxidized to ketones.
• In this reaction propan-2-ol is oxidized to propan-2-one by
removing two hydrogen atoms.
 Oxidation of Tert-butyl alcohol
• Tertiary alcohols aren't oxidized by acidified sodium or potassium
dichromate(VI) solution.
• There is no reaction whatsoever.
• If you look at what is happening with primary and secondary alcohols,
you will see that the oxidizing agent is removing the hydrogen from
the -OH group, and a hydrogen from the carbon atom attached to the
-OH.

• Tertiary alcohols don't have a hydrogen atom attached to that carbon.

Esters are derived from carboxylic acids. A carboxylic acid
contains the -COOH group, and in an ester the hydrogen in this
group is replaced by a hydrocarbon group of some kind.

Ethyl acetate

CH3 OCH2CH3
Esterification of Glacial Acetic Acid
Ethyl acetate
• clear colorless liquid with sweet fruity odor
• widely used as a solvent for paint, varnishes cleaning mixtures,
perfumes and decaffeinating coffee beans
O
Heat
CH3CH2OH + CH3COOH CH3 OCH2CH3 + H2O
Ethanol Ethanoic acid Ethyl ethanoate
vinegar-like odor plastic balloon-like odor
 Density Solubility in water
H2O 1.0 g/mL
Ethyl acetate 8.3 g/mL
Ethyl acetate 0.90 g/mL
Reference
• Allen, Frank; Kennard. Olga; Watson, David G.; Brammer, Lee;
Orpen, Guy; Taylor, Robin (1987).J. Chem Soc. Perkin Trans
II,,S1-S19.
• Clark, Jim(2003). https://chemguide.co.uk/organicprops/alcohol.
Accessed on September 12, 2018.
• Schore, Neil E. and Vollhardt, K. Peter C.(2007). Organic
Chemistry: Structure and Function. New York: Bleyer, Brennan,.