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Chapter Scopes FHSC1124 Organic Chemistry Alkanes

Chapter 2 IUPAC Nomenclature / naming Physical properties Free-radical reactions Crude oil and cracking Cycloalkanes

Objectives
After this chapter, you will be able to: Name alkanes using IUPAC Draw the correct structure of simple alkanes Draw/write the product of an organic chemical reaction Understand reactions of alkanes and be able to write out the chemical reactions.

Introduction to Alkanes
Simplest members of hydrocarbon family Paraffins Aliphatic compounds open chain / acyclic compounds General formula of alkanes = CnH2n+2 The names of alkanes end with suffix -ane. Saturated hydrocarbon as only have CC & CH single bonds & contain the max. possible number of H per C.

IUPAC Nomenclature
IUPAC International Union of Pure & Applied Chemistry The IUPAC nomenclature system is a set of logical rules devised and used by organic chemists to name the organic compounds. Prefix Parent Suffix What are the How many What family? substituents? carbons?

IUPAC Rules
1. Select the longest continuous C chain as parent chain (use root word for the no. of C) 2. Name each of the branch/substituents as an alkyl / aryl group 3. Number the C chain begin from the end nearest to the branch branch/substituents appear at the lowest no. possible

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IUPAC Rules
4. Name each substituent according to its chemical identity & the no. of the C atom to which it is attached For identical substituent, use the prefix di, tri & write appropriate C no. for each substituent 5. Separate no. from no. by commas (,) & no. from letters by hyphens (-) 6. List the substituents alphabetically by name di, tri. dont count

Base Names
Root No. of Name Carbons (n) Meth 1 Eth 2 Prop 3 But 4 Pent 5 Root Name Hex Hept Oct Non Dec No. of Carbons (n) 6 7 8 9 10

Straight-Chain Alkyl Groups, R

Alkyl group Name (abbreviation) Methyl (Me) CH3 Ethyl (Et) CH2CH3 Propyl (Pr) CH2CH2CH3 Butyl (Bu) CH2CH2CH2CH3 Pentyl CH2CH2CH2CH2CH3 Alkyl groups are named by replacing the ane ending of the parent alkane with an yl ending

Example: Naming Alkanes

PHYSICAL PROPERTIES OF ALKANES

Condensed structural formula
Name Methane Ethane Propane Butane Pentane Hexane Heptane Octane Nonane Decane BP (oC) -161.7 -88.6 -42.2 -0.5 36.1 68.7 98.4 125.6 150.7 174.0 MP (oC) State at 25oC Density -182.6 Gas 0.424 -172.0 Gas 0.546 -187.1 Gas 0.582 -135.0 Gas 0.579 -129.7 Liquid 0.626 -94.0 Liquid 0.659 -90.5 Liquid 0.684 -56.8 Liquid 0.703 -53.7 Liquid 0.718 -29.7 Liquid 0.730

Carbon skeleton
1 2 3 4 5 6

1. Longest continuous C chain is 6 hex 2. All C & H with single bonds ane 3. Parent name: hexane 4. Two methyl groups on 2nd C & 5th C dimethyl 5. Use 2,5-dimethylhexane

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Boiling Points of Alkanes

Alkanes have relatively low bp (e.g.: methane bp~ -161 oC) because: Alkanes are ____________ molecules which held by _____________________________. BP of alkanes increase as number of carbon increase because: As the number of C , molecules get ______, Van der Waals forces become ___________ and more energy needed to break the bond

Comparison of BP: Branched-Chain & Straight-Chain

Isomer pentane 2-methylbutane 2,2-dimethylpropane BP (K) 309.2 301.0 282.6

The more branched the chain, the _______ the boiling point tends to be.

Comparison of BP: Branched-Chain & Straight-Chain

The branched-chain isomer will have a lower bp compared to the straight-chain isomer because: Branched-chain alkanes are short, fat & spherical in shape. Thus this reduces the surface area that is exposed to Van der Waals forces. Less energy needed, bp decreases.

Reaction of Alkanes

Combustion / oxidation of Alkanes

Free Radical Halogenation

1. Combustion / Oxidation of Alkanes

Alkanes burn in excess air or O2, to formed CO2 and H2O CxHy +
y x + O 4 2 4

2. Free Radical Halogenation of Alkanes

Alkanes react with chlorine or bromine: When the mixture is heated at 300 400 oC, OR At room temperature under the influence of UV light which act as catalysts.

xCO2 +
4

y 2

H2O

CH4 + 1 + 4 O2 CO2 + 2 H2O CH4 + 2O2 CO2 + 2H2O

XX + Halogens

light / heat X = Br, Cl

X + HX

Haloalkanes / alkyl halides

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Chlorination of Methane

Mechanism of Halogenation
Chlorination or bromination of alkanes is by a free-radical substitution mechanism. Involved 3 steps: Step 1: Initiation Step 2: Propagation Step 3: Termination

Mechanism of Halogenation: Step 1: Initiation

Heat or UV light cause the weak halogen bond to undergo ____________ cleavage to generate two bromine radicals and starting the chain process.

Mechanism of Halogenation: Step 2: Propagation

(a) Br radical abstracts a H to form HBr and a methyl radical (b) The methyl radical abstracts a Br atom from another molecule of Br2 to form the methyl bromide and another bromine radical, which can then itself undergo reaction 2(a) creating a cycle that can repeat.

Mechanism of Halogenation: Step 2: Propagation

Mechanism of Halogenation: Step 3: Termination

Various reactions between possible pairs of radicals allow the formation of ethane, Br2 or the product, methyl bromide. These reactions remove radicals and do not perpetuate the cycle.

(a)

(b)

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Crude Oil / Petroleum

Alkanes occur naturally in petroleum and natural gas. Petroleum, brownish to black liquid, formed from dead organisms that sank to the bottom shallow seas and were subsequently covered by clay & silt. Pressure heating caused by burial changed these organic matter slowly, after million years, to petroleum. Raw petroleum consists of a mixture of hydrocarbon of various sizes separated by distillation before they used.

Cracking of Alkanes
Cracking involves the _____________ of large alkane molecules into a mixture of smaller-sized alkanes and alkenes.

Cracking of Alkanes

Cracking of Alkanes Catalytic Cracking Thermal/Steam Cracking

Catalytic Cracking
Modern cracking uses zeolites as the _____________. Zeolites = complex aluminosilicates, and are large lattices of aluminium, silicon and oxygen atoms carrying a negative charge. The alkane is brought into contact with the catalyst at a T of about 500 and C moderately low P.

Thermal / Steam Cracking

In thermal cracking, high T (typically in the range of 450 to 750 & P (up to C C) about 70 atm) are used to break the large hydrocarbons into smaller ones. Thermal cracking gives mixtures of products containing high proportions of hydrocarbons with double bonds alkenes.

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Cycloalkanes: Cyclic Structures of Alkanes

Halogenation of Cycloalkanes
The reactions of the cycloalkanes are generally just the same as the alkanes, e.g. free radical substitution, oxidation & halogenation.

+ Br2

Br + HBr

Summary
To learn the naming of alkanes Understand reactions of alkanes and be able to write out the chemical reactions.

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