Alcohols

Nomenclature & Type ; Polarity of OH & Its Effect on the Physical Properties ; Chemical Properties of Alcohol & Fermentation
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Learning Outcome

Name alcohol compounds with more than one hydroxyl group

Identify a hydroxyl group in an alcohol as primary, secondary or tertiary, given the structural formula
Predict and explain the polarity and solubility of alcohol compounds

Describe how primary and secondary alcohols can distinguished from tertiary alcohols, using the reaction with acidified dichromate solution
Predict the structural formula of dichromate oxidation of primary or secondary alcohol, given its structural formula Describe the conditions and write equations for the hydrolisis of polysaccharides and the production of ethanol by fermentation of glucose
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Alcohols

Hydroxyl compounds are organic compounds containing the OH (hydroxyl) group. -OH group is a functional group for alcohol. They can be broadly divided into two groups:

Alcohols, where the OH group is not directly attached to a benzene ring.

Phenols, where the OH group is attached directly to a benzene ring.

Where R = alkyl group / hydrocarbons, aromatic, cyclic or hydrogen atom OH = active site / functional group

Alcohols

Alcohols have general structural formula ROH. ( R = CnH2n+1)

Hydroxyl group (-OH) group is very polar and is able to form hydrogen bond.

Alcohols are classified as primary, secondary or tertiary depending on the number of R groups (or H atoms) attached to the C atom carrying the OH group.

Nomenclature Alkanol
Step 1 : Find the longest chain that contains hydroxyl group. Step 2 : The e of an alkane is dropped and replaced by ol. Step 3 : Assign the smaller number to carbon having the OH group.

CH3 CH2 CH2 CH2-OH

The longest chain has 4 carbon atoms. Therefore butane Replace e with ol. Therefore butanol Number the carbon atoms.
4 3 2 1

CH3 CH2 CH2 CH2-OH

Therefore butan-1-ol / 1-butanol
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Name the following alcohols :OH CH3 CH2 CH2 CH2

OH CH3 CH2 CH CH3

1-butanol OR butan-1-ol
OH CH3 CH CH2 CH3

2-butanol OR butan-2-ol
OH CH3 C CH3 CH3

2-methyl-1-propanol

2-methyl-2-propanol
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CH3CH2CHCH2CH3 3-pentanol | OH b) CH3CHCH2CH2CH2OH 4-methyl-1-hexanol | CH2CH3 c) CH3CHCH2CHCH2CH2CH3 | | 2-methyl-4-heptanol CH3 OH

a)
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d) CH3CH2CHCH2CH2CH3 | | 3-ethyl-2-hexanol OH CH2CH3

e)

CH3 | HO-CCH2CH2CHCH2CH3 | | 2,5-dimethyl-2-heptanol CH3 CH3

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CH2OHCH2OH 1,2-ethandiol 1,1-propandiol

CH2OHCHCH3CH2OH 2-methyl-1,3-propandiol

CH3C(CH3)2CH2CHOHCH3 4,4-dimethyl-2-pentanol 2-methyl-1,3-butandiol

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Draw the structure below

Methanol
Ethanol Propanol

2-propanol

OR propan-2-ol 3- methyl-1-butanol 3-ethyl-3,5-dimethyl-2-hexanol. 3-methyl-4-heptanol

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Primary, secondary, tertiary

There are three major subsets of alcohols: primary (1), secondary (2) and tertiary (3), based upon the number of carbon atoms the C-OH group's carbon (shown in red) is bonded to. Ethanol is a simple 'primary' alcohol. The simplest secondary alcohol is isopropyl alcohol (propan-2-ol), a simple tertiary alcohol is tert-butyl alcohol (2-methylpropan-2-ol).

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Classification of Alcohols
Primary (1) H R C OH H 1 R attach to C-OH Secondary (2 ) R R C OH H 2 R attach to C-OH Tertiary (3) R R C OH R 3 R attach to C-OH
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Where R = alkyl group or simply refer to C

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Classify the following as 1, 2, or 3 alcohols: OH CH3CH2CH2OH

CH3-CH-CH2CH3 2

OH

CH3-C-CH2CH3 CH3

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Physical Properties
Volatility

Simple aliphatic alcohols are colorless liquids at room temperature. Alcohols containing more than 12 carbons are waxy solids. Larger molecular mass alcohols are non-volatile liquid at room temperature.Molecules are held by more dispersion forces

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 Volatile
Alcohols

liquid.

has very polar hydroxyl group Alcohol molecules are held in clusters by hydrogen bonds (weak 2 interactions) The heat energy at r.t.p. can easily break these weak interactions between alcohol molecules Diagram: liquid methanol

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 Diols and triols are viscous liquids at r.t.p. - molecules have many very polar hydroxyl group - molecules are held by extensive hydrogen bonds - heat at r.t.p is not sufficient to break these many secondary interactions.

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Physical Properties

Alcohol vs alkane, alkene

Alcohol vs poly-hydroxyl alcohol

Alcohol vs water

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Alcohol vs alkane, alkene

Melting and boiling point

Alcohol has low boiling point Alcohols have higher BP/MP compare to alkanes with similar molar mass

Alcohols has very polar hydroxyl group, while alkanes are non-polar molecules alcohol molecules are held by stronger hydrogen bonds compare to weaker dispersion forces between alkane molecules Therefore require different amount of HE to break during boiling/melting

The order of boiling points of isomeric alcohols is: 1 > 2 > 3

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Physical Properties
Solubility in water

Lower alcohols are soluble in water because they form hydrogen bonds with water molecules (polar molecule).

Small molecular mass alcohols are soluble in H2O

Has a very polar hydroxyl group, able to form hydrogen bonds with very polar water molecules

Diagram: ethanol in water

Solubility of alcohols in water decreases with increasing carbon atoms.

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 Thus, alcohol with a long carbon backbone is immiscible with water because it is less polar (or more hydrogen-like).
As size grows bigger, the bigger the alkyl group, non-polarity of the big alkyl group will outweigh the very polar hydrogen group, formation weak dispersion force among themselves more favorable than hydrogen bonds with very polar water.

Larger molecular mass alcohols are less soluble in water, more soluble in organic solvent (eg. petrol) - The non-polar long hydrocarbon chain outweigh the very polar hydroxyl group. - Molecules prefer to form dispersion forces

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Diols and triols are very soluble in water

- many very polar hydroxyl groups, able to form extensive hydrogen bonds with very polar H2O

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Physical Properties

E.g. methanol, ethanol and 1-propanol are miscible in water in all proportions; whereas the solubilities of 1-butanol, 1-pentanol and 1-hexanol at 25C are 8.0 g, 2.7 g and 0.6 g in 100 g of water respectively.
All alcohols are miscible with most organic solvents, and the simpler ones are themselves useful organic solvents.

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Alcohol Dissolves in Water: The -OH group on alcohol is polar and mixes with the polar water through the formation of hydrogen bonds. A wide variety of solutions are in this category such as sugar in water, alcohol in water, acetic and hydrochloric acids.

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Physical Properties
Colourless, neutral, alcoholic odour.

Low boiling point about 78C but higher than alkane with similar RMM due to presence of hydrogen bond in alcohol. Volatile evaporate easily Low density lighter than water Solubility simple covalent compound is very soluble in water because of the presence of OH group.

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Example : Menthol (Terpene alcohol)

Pleasant, minty odour. Low melting point. Cause a refreshing, cooling sensation. Products contain menthol :Throat sprays, cough drops, cigaretters of mentholated type, pre-electric shave preparation and aftershave lotions, toothpastes and mouthwashes.

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Chemical properties

Classification of alcohol => either 1, 2 or 3

Dichromate test is used to determine if a particular organic compound contain hydroxyl group or not.

Preparation of ethanol (edible alcohol) is from the fermentation of glucose.

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Oxidation (Redox reaction)

Oxidizing Reagent: acidified potassium dichromate (K2Cr2O7)

acidified potassium permanganate (KMnO4)

Condition: heat or reflux Observation:

orange solution K2Cr2O7 turns green (due to formation of Cr3+ ions) purple solution KMnO4 decolorised (due to formation of Mn2+ ions)

The oxidising agent will be reduce. Cr2O72- Cr3+ MnO4- Mn2+ Orange green purple colouless
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Oxidation

1 alcohols (primary alcohols) are oxidized to aldehydes and then to carboxylic acids.
Primary alcohols can be oxidized under controlled condition by using weak oxidising agent to give an aldehyde 2 alcohols (secondary alcohols) are oxidised to ketones. 3 alcohols (tertiary alcohols) are not oxidised.

This is because tertiary alcohols do not have any hydrogen atom to be removed from the carbon atom to which OH group is attached.
Thus, oxidation is used to distinguish primary, secondary and tertiary alcohols.
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Dichromate / permanganate Test

Reagent: H+/MnO4- or H+/Cr2O72- solution Condition: warm in water bath, To test the presence of 1 & 2 hydroxyl group in an organic compound Describe the test: 1. Add 1 mL of organic compound into a clean clean test tube, follow by 1 mL of H+/Cr2O72- solution. 2. Warm the mixtures in the water bath 3. Observation: If theres colour change from orange to green means the organic compound contain either 1 & 2 hydroxyl group.
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Oxidation of 1 Alcohols
[O] [O]

Primary alcohol
OH CH3 C H H Ethanol

aldehyde

carboxylic acid

O O [O] [O] CH3 C H CH3 C OH

Ethanal

Ethanoic acid
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Oxidation of 2 Alcohols
[O]

Secondary alcohol OH
[O]

CH3 C H
CH3 Propanol

Ketone O CH3 C
CH3 Propanone

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Oxidation of 3 Alcohols
[O]

Tertiary alcohol OH
[O]

No reaction

CH3 C CH3
CH3 Propanol

no reaction

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H+ / MnO42-

H+ / MnO42-

H+ / MnO42-

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Write a notated equation for ROH with H+ / Cr2O72 Oxidation half Equation CnH2n+1OH CnH2nO + 2H+ + 2e Reduction

Half equation Cr2O72- + 6e- + 14H+ 2Cr3+ + 7H2O

Overall equation 3CnH2n+1OH + Cr2O72- + 8H+ 3CnH2nO + 2Cr3+ + 7H2O

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Preparation

Preparation of any alcohol in the industry is through hydration reaction from alkenes.
Preparation of ethanol (making of alcoholic beverages) through fermentation reaction. Converts simple sugars (fructose or glucose) in aqueous solution into ethanol using yeast with the absence of oxygen (anaerobic process)

C6H12O6 2 CH3CH2OH + 2 CO2

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Preration of alcohols

Hydration of alkenes
Hydration

of alkenes in the presence of a catalyst is used for the preparation of ethanol and other alcohols.

cracking hydration Pt at 200C-300C H20 with diluted H2SO4 Petroleum ------------> alkanes --------------> alkenes -------------> alcohol (a mixture of alkanes) R-R R=R

Fractional distillation

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Industrial sources of alcohols

Fermentation: a method used for ethanol

The fermentation method is used to make alcoholic drinks. Fruits juices such as grape juice contain glucose. When yeast is added, the sugar ferments to form wine (a solution of ethanol) and carbon dioxide.

Carbohydrates (starch)
yeast

(amylase)

complex sugars Yeast

(invertase)

simple sugars Yeast (zymase) CH3CH2OH + CO2

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The hydrolysis & fermentation reactions :

Hydrolysis of polysaccharides disaccharides

(C6H5O5)n + nH2O nC12H22O11

Hydrolysis of disaccharides monosaccharides

C12H22O11 + H2O 2C6H12O6

Fermantation: a method used for ethanol yeast Simple sugars ----------->CH3CH2OH + CO2 yeast C6H12O6 --------------> 2 CH3CH2OH + 2 CO2
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Reaction Product
This reaction produces a dilute aqueous solution of ethanol with concentration of 15% maximum.

Reaction stops at 15% ethanol, because yeast is killed. Higher concentration of ethanol are obtained by fractional distillation.

Could increase ethanol concentration via distillation process (to get purer and more concentrated ethanol).

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Fractional Distillation

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Factors that affect the production of ethanol by fermentation

Conditions required:
1.Optimum 2.Yeast 3.Dilute

temperature of 30C

to provide zymase enzyme aqueous solution acidic condition

4.Slightly 5.In

the absence of oxygen

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 During distillation process, the boiling point of ethanol is around 90 94 C, why the boiling point of ethanol is not at 78 C?
- Ethanol, very polar molecules, will form strong H-bonds with very polar water molecules, the heat energy at 78 C is not sufficient to break all these H-bonds. - Only with higher HE (at around 9094 C), most of the H-bonds can be broken. - Ethanol will still be distilled out with some H2O molecules.

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Uses of Ethanol

alcohol is also widely used as ethanol Solvent in stains and polishes, in the manufacture of dyestuffs, perfumes and drugs. Alcoholic beverages Methanol Solvent and fuel additive

2-propanol Solvent, body rubs, an antiseptic

1,2-ethandiol antifreeze
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Product type of alcohols

Beer 3.2-9% Wine 12% Brandy 40-45% Whiskey 45-55% Rum -45%

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http://www.history-science-technology.com/Notes/Notes%207.htm
http://dl.clackamas.cc.or.us/ch106-03/nomencla.htm http://dl.clackamas.cc.or.us/ch106-03/clasific.htm http://www.chemguide.co.uk/organicprops/alcohols/background.html http://www.chemguide.co.uk/organicprops/alcohols/oxidation.html

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