Chapter 2

Table of Contents
Introduction 1. Alkanes 2. Alkyl Groups 3. Nomenclature of Alkanes 4. Isomerism in Alkanes 5. Physical Properties of Alkanes

Alkanes

6. Chemical Properties of Alkanes 7. Preparation of Alkanes 8. Methane 9. Cycloalkanes

Chapter 2
Warm up

Alkanes

What does hydrocarbon word imply?

Where do you use hydrocarbons in life?

List down common names of hydrocarbons you commonly use.

Chapter 2

Introduction

Hydrocarbons, as the name implies, are compounds whose molecules contain only carbon and hydrogen.

They are extracted from petroleum, natural gas and coal.

Aliphatic Hydrocarbons 1. Saturated Hydrocarbons Alkanes(Parafins) 2. Unsaturated Hydrocarbons Alkenes(Olefins) Alkynes(Acetylenes) 3. Cycloalkanes

Aromatic Hydrocarbons (Benzene compounds)

Chapter 2

Introduction

Chapter 2

Introduction
Petroleum products

Chapter 2

1. Alkanes

Contain C-C and C-H sigma bonds. Known as paraffin, meaning inert. General formula is CnH2n+2, n is number of carbon atoms. First four members have common names, methane, ethane, propane and butane. Names end with ane suffix. In the names latin number + -ane is used, for example penta + ane = pentane -CH2-, methylene, is difference between consecutive alkanes, forming homologous series.

Chapter 2
Section Review Exercise 1

1. Alkanes

What are the main sources of hydrocarbons in nature? Exercise 2 What does saturated hydrocarbon mean? Give examples. Exercise 3 What does unsaturated hydrocarbon mean? Give examples. Exercise 4 What does cyclohydrocarbon mean? Give examples.

Chapter 2
Section Review Exercise 5

1. Alkanes

What are the main substances obtained when crude oil is distillated? Exercise 6 What are the formula and name of the first four members of alkanes? Exercise 7 What are the formula and name of the alkane with 8 carbon atom?

Chapter 2
Section Review Exercise 8

1. Alkanes

Name and write the structural formula of the following alkanes. Exercise 9 What are the molecular and structural formula of the following alkanes? Butane Exercise 10 What are the general properties of alkanes? Octane Decane C5H12 C7H16 C9H20

Chapter 2

1. Alkanes

First 10 Members of Alkanes

Chapter 2

1. Alkanes

Straight chain alkanes take n- in front of name, meaning normal and shows the alkane is unbranched.
H3C C H2 H2 C CH3 H3C C H2 H2 C C H2 H2 C CH3

n-butane

n-hexane

In branched alkanes, if one methyl,-CH3, group is on the second carbon the iso- prefix is added to name.
H3C CH CH3 CH3 H3C CH CH3 H2 C CH3

iso-butane

iso-pentane

Chapter 2

1. Alkanes

Additionally if there are two methyl,-CH3, groups are on the second carbon the neo- prefix is added to name.
CH3 H3C C CH3 CH3 H3C CH3 H 2 C C CH3

CH3

neopentane

neohexane

Example 1 What is the molecular formula of the alkane having the 58 g/mole molecular mass?

Chapter 2
Example 2

1. Alkanes

14.4 g of an alkane, when analyzed, is found to contain 12 g carbon. What is its molecular formula? Example 3 If a 3 g sample of alkane is burned, 5.4 g of water vapor is produced. What is the molecular formula of hydrocarbon? Example 4
When the CO2 gas produced by the combustion 0.2 mol of an alkane is passed into limewater (Ca(OH)2), 40 g of calcium carbonate precipitates. What is the molecular formula of the alkane?

Chapter 2

2. Alkyl Groups

If one hydrogen atom is removed from an alkane, an alkyl group is formed. General formula of alkyl groups is CnH2n+1. Instead of the ane suffix in alkanes, -yl is used for naming of alkyl groups. They are represented as R, meaning radical. A carbon atom in an alkane can be named as primary, secondary or tertiary according to number alkyl groups bonded to it.

Chapter 2
CnH2n+2 Alkane Example 5
H H C H H H

2. Alkyl Groups
CnH2n+1 Alkyl

C H

methane CH4

methyl CH3-

Chapter 2
H R C H R' R C H

2. Alkyl Groups
R' R C

1o

2o

3o

R"

primary

secondary

tertiary

Example 6
H H3C C H CH3 C2H5 C H CH3 C2H5 C

1o

2o

3o

CH3

primary

secondary

tertiary

Chapter 2
Example 7

2. Alkyl Groups

Name the carbon atoms shown in the following molecules as primary, secondary or tertiary.
CH3 CH H3C CH3 C H2 CH3 C H3C

2o

*o 3

*o
1

1o CH3

* C

CH3

H2

Chapter 2

3. Nomenclature of Alkanes

For simple alkanes common names are used.

n-butane

isopentane

tertiary butane

For the branched complex alkanes IUPAC system is used. In the IUPAC system following rules can be used. 1. Determine the longest number of continuous carbon atom chain. This gives the parent name of alkane.

Chapter 2
CH3 CH H3C C H2 CH3 CH

3. Nomenclature of Alkanes

CH3 C H2

six carbon in the longest chain refers to hexane

2. Number the carbon atoms in the longest chain, starting nearer at the end nearer to the branched.
CH3 CH H3C CH3

C H2

CH

C H2

CH3

Chapter 2

3. Nomenclature of Alkanes

3. Show the position of groups bonded to parent chain, if there are more than one identical groups, use di, -tri or tetra prefixes. Some important groups are F (fluoro), -Cl (chloro), -Br (bromo), I (iodo), -NO2(nitro), -OH (hydroxyl), and NH2(amino)
CH3 CH H3C C H2 CH3 CH C H2 CH3

2, 4-dimethylhexane

Chapter 2

3. Nomenclature of Alkanes

3. When two or more different groups are bonded to the carbon chain, they are ordered alphabetically.
CH3 CH H3C CH C2H5 Cl CH C H2 CH3

4-chloro-3-ethyl-2-methylhexane

Chapter 2
Example 8

3. Nomenclature of Alkanes

Name the following structures.

Isobutane or 2- methylpropane
c. H3C H2 C CH3 C C2H5 H2 C CH3 CH2

3-methylpentane
d. H3C H2 C Br C C3H7 H2 C CH3 CH2

3-ethyl-3-methylhexane

4-bromo-4-ethylheptane

Chapter 2
Example 9

3. Nomenclature of Alkanes

Draw the structures of following alkanes. a. 3-ethyl-2-methylpentane b. 1,3-dibromopropane c. 2,2,3,3-tetramethylbutane d. 2,2,4-trimethylpentane e. 2-chloro-2,3-dimethyl-3-ethylheptane f. 5-ethyl-2-methylheptane

Chapter 2

4. Isomerism in Alkanes

Compounds having same molecular formula but different structural formula are said to be isomers. First three members of alkanes do not have isomers. Physical and chemical properties of isomers are different.
CH3 H3C H2 H2 C C CH3 n-butane H3C C H CH3

2-methylpropane (isobutane)

Example 10 Write the structural formulae and the IUPAC name of possible isomers of hexane, C6H14.

Chapter 2

5. Physical Properties of Alkanes

Alkanes are non polar molecules, only van der waals forces are responsible for the attractions between molecules. C1-C4 are gases, C5-C17 are liquids, and the rest are solids. Bp, Mp, and densities of alkanes increase by the increasing number of carbon atom. They are generally tasteless, odorless and colorless. Branching decreases boiling point. They are insoluble in water, but soluble in organic solvents such as benzene and carbon tetrachloride.

Chapter 2

6. Chemical Properties of Alkanes

Another name for alkanes is paraffin, meaning inert. They are chemically quite unreactive. They do not react with dilute acids (HCl, H2SO4), active metals(Na, K) and strong oxidizing agents(KMnO4, Na2Cr2O4). They only undergo combustion and substitution reaction with halogens. They can be nitrated under high pressure. 1. Combustion Reaction CnH2n+2 + (3n+1)/2 O2 CH4 + 2O2 n CO2 + (n+1) H2O

CO2 + 2H2O

Chapter 2

6. Chemical Properties of Alkanes

2. Substitution Reaction R H + XX
alkane halogen heat hv

RX +
alkyl halide

H X

Halogenetion

CH4

+ Cl2

CH3Cl + HCl
425oC

R H + HONO2
Alkane

RNO2

H 2O

Nitration

nitroalkane

Chapter 2
3. Cracking Reactions

6. Chemical Properties of Alkanes

Higher alkanes are converted into smaller alkanes and alkenes at high temperature. When a catalyst is used in the process, it is known as catalytic cracking. 4. Isomerization Reaction Straight-chain alkanes are converted into branched alkanes.
H3C C H2 H2 C C H2 H2 C CH3 H3C H2 C CH CH3 C H2 CH3

heat AlCl3

n-hexane

isohexane

Chapter 2

6. Chemical Properties of Alkanes

Example 11 When 8.8 g of an alkane is burned completely, 26.4 g of carbon dioxide and 14.4 g of water are produced. What is the molecular formula of the alkane? Example 12 To burn a mixture of 33.6 L of methane and propane gas at STP, 144 g of oxygen gas are required. According to this information, what is the total mass of the original mixture? (H:1, C:12, O:16 ) Example 13 What is the pressure of CO2 gas in 2-L container which is produced from the combustion of 7.2 g of C5H12 at 27oC?

Chapter 2

7. Preparation of Alkanes

Main sources of alkanes are crude oil, natural gas and coal. Many useful alkanes are obtained from fractional distillation of petroleum. 1. Wurtz Synthesis This method was first used by Adolph Wurtz in 1854. Methane cannot be produced in this process. R-X + 2Na + X-R 2CH3-Br + 2Na R-R + 2NaX CH3-CH3 + 2NaBr

Chapter 2
Example 14

7. Preparation of Alkanes

Which alkyl halides can be used to prepare pentane by the Wurtz synthesis.

Example 15 What is(are) the products of the reaction of 2-chloropropane and 1-bromoethane with excess sodium metal?

Chapter 2

7. Preparation of Alkanes

2. Hydration of Grignard Compounds

R-MgX

H-OH

Grignard Reagent

R-H + Mg(OH)X Alkane

This method was first used by Victor Grignard in 1912. Example 15 Prepare ethane by using Grignard reagent. Solution
CH3CH2Br + Mg
Anhydrous
Ether

CH3CH2MgBr
Ethyl Magnesium Bromide Grignard Reagent

CH3CH2MgBr + H-OH

CH3CH3 + Mg(OH)Br Ethane

Chapter 2
Zn H+

7. Preparation of Alkanes

3. Reduction of Alkyl Halides

Example 16 Prepare propane by using 2-bromopropane. Solution

2CH3CHCH3
Br

Zn H
+

2CH3CH2CH3 + ZnBr2
propane

2-bromopropane

Chapter 2

7. Preparation of Alkanes

4. Heating the Metal Salts of Carboxylic Acids Heat R-COONa + NaOH R-H + Na2CO3 CaO Alkane sodium salt of
a carboxylic acid

Example 17 Prepare methane by using sodium acetate. Solution CH3-COONa + NaOH

Heat
CaO

CH4 + Na2CO3
Methane

Chapter 2

7. Preparation of Alkanes

5. Hydrogenation of Unsaturated Hydrocarbons

+ H2

Pt, Pd or Ni
C H C H

alkene

alkane
H H C H

+ 2H2

Pt, Pd or Ni
C H

alkyne alkane

Chapter 2
Example 17

7. Preparation of Alkanes

5 mol mixture of C3H6 and C3H8 is reacted with 2 mol of H2 gas. What is the total volume of gases at STP when the reaction is completed? Solution In the mixture only C3H6 reacts with H2. C 3H 6 + H 2 C 3H 8 2 mol H2 2 mol C3H6, the mol of C3H8 = 5 2 = 3 mol is unreacted. nT = 2 mol C3H8 produced + 3 mol C3H8 unreacted = 5 mol V= 5x22.4 = 112 L
Ni

Chapter 2

8. Methane

It is found in mines and in natural gas. It is also known as marsh gas and is formed by decomposition of plants in the absence of oxygen. It is colorless and odorless has. It is insoluble in water, but soluble in benzene and gasoline. 10-15% of methane in air may cause an explosion. It is called in mines firedamp explosions. It burns with a light blue flame.

Chapter 2
1500oC CH4 1000oC CH4
2CH4 + O2

8. Methane

C2H2 + H2 C + 2H2
catalyst

2CH3OH

260oC 100 atm

Preparation

Al4C3 + 12H2O

H+

4Al(OH)3 + 3CH4

Chapter 2
CO + 3H2

8. Methane
Ni H2O + CH4

300-400oC

Ni C + 2H2
pressure, heat

CH4

Example 18 What is the percent of a 150 g of Al4C3 sample that produces 67.2 L of CH4 gas when put in water? (Al:27, H:1, C:12)

Chapter 2

9. Cycloalkanes

Alkanes bonded to one another in a ring formation is called cycloalkanes. General formula is CnH2n. Nomenclature of Cycloalkanes Use cyclo- prefix to the names of alkanes.
H2 C H3C CH3 H2 C H2C CH2

propane

cyclopropane

cyclopropane

Chapter 2
H2 C H3C CH3 C H2 CH3

9. Cycloalkanes
H2C H2C CH2 CH2

butane

cyclobutane
Cl

cyclobutane
C2H5

Methylcyclobutane

Chlorocyclopentane

Ethylcyclohexane

If there are more than one substituent in the ring, the ring is numbered starting with the substituent first in the alphabet, and numbered in the direction which gives the lowest number for the second substituent.

Chapter 2
Cl CH3

9. Cycloalkanes
H3C

2
H3C

3 4

2 1

C2H5

1-chloro-2-methylcyclobutane

1-ethyl-3,4-dimethylcyclohexane

If the number of carbon atom in the ring is less than that is in the substituent, then they are named as cycloalkylalkanes.
H2 C H3C CH H2 C C H2 CH3 H3C H2 C C H2 H2 C C H2

1-cyclobutylpentane 3-cyclopropylhexane

Chapter 2

9. Cycloalkanes

Chapter 2

9. Cycloalkanes

Physical Properties Melting point, boiling point and densities of cycloalkanes are different from the alkanes possessing the same number of alkanes. Melting and boiling points increase as the number of carbon atom increases in the ring. Chemical Properties Cycloalkanes with more than 5 carbon atom undergo substitution reaction. Cycloalkanes with 3 or 4 carbon atoms undergo addition reaction.

End of the chapter 2