ALKANES

Alkanes are saturated hydrocarbon. Molecules are essentially ___________. General formula : ____________ Alkanes are the major fraction of both crude oil and natural gas. NOMENCLATURE a) Naming the Branched Chain Alkanes Examples: Write the IUPAC name for the following alkanes CH3 CH2 CH CH3 | CH3 CH3 | CH3 C CH2 CH CH2 CH3 | | CH3 CH2 CH3 CH3 | CH3 C CH3 CH2 | CH3 CH3 CH2CH3 | | CH3 CH CH2 CH2 CH CH CH3 | CH3 1,1,1-trichloroethane

CH3 | CH3 CH CH2 CH CH3 | CH3

CH3 CH2 CH CH3 CH3 CH2 CH3 | CH3 CH2 | | CH3 CH CH CH3

b) Naming Cycloalkanes

Cycloalkanes are ring structures with the general formula: CnH(2n). Following are basic rules for naming cycloalkanes. 1. Parent Chain a) Use the cycloalkane as the parent chain if it has a greater number of carbons than any alkylsubstituent. b) If an alkyl chain off the cycloalkane has a greater number of carbons, then use the alkyl chain as the parent and the cycloalkane as a cycloalkyl-substituent. 2. Numbering the Cycloalkane a) When numbering the carbons of a cycloalkane, start with a substituted carbon so that the substituted carbons have the lowest numbers (sum). b) When two or more different substituents are present, number according to alphabetical order.

3. Halogen Substituents a) Halogen substituents are treated exactly like alkyl groups
Examples : Give the names for the following cycloalkanes.

PHYSICAL PROPERTIES
Table 2.0 gives the physical properties of some straight-chain of alkanes. Alkane Methane Ethane Propane Butane Pentane Hexane Heptane Octane Nonane Decane Undecane Dodecane Icosane Triacontane Formula Boiling point [C] Melting point [C] Density [gcm3] (at 20C) CH4 C2H6 C3H8 C4H10 C5H12 C6H14 C7H16 C8H18 C9H20 C10H22 C11H24 C12H26 C20H42 C30H62 -162 -89 -42 0 36 69 98 126 151 174 196 216 343 450 -183 -182 -188 -138 -130 -95 -91 -57 -54 -30 -26 -10 37 66 gas gas gas gas 0.626(liquid) 0.659(liquid) 0.684(liquid) 0.703(liquid) 0.718(liquid) 0.730(liquid) 0.740(liquid) 0.749(liquid) solid solid

Tetracontane C40H82 Pentacontane C50H102

525 575

82 91

solid solid

1. Alkanes are __________ in water because the polar molecules are not attracted to the nonpolar alkane molecules. However, its soluble in ____________ solvents such as tetrachloromethane and benzene. 2. Alkanes are _______ ________ than water. The liquid and solid alkanes float on the surface of water. That is why water cannot be used for putting out petrol and oil fires. 3. ___________ of liquid alkanes increase with increasing ________________. 4. Boiling points : a) Alkanes experience inter-molecular _____________________ forces. b) Stronger inter-molecular van der Waals forces give rise to greater boiling points of alkanes. c) There are two determinants for the strength of the van der Waals forces:

the _______________________ surrounding the molecule, which increases with the alkane's molecular weight the ______________of the molecule

d) Under___________________, from CH4 to C4H10 alkanes are gaseous; from C5H12 to C17H36 they are liquids; and after C18H38 they are solids. e) As the boiling point of alkanes is primarily determined by weight, it should not be a surprise that the boiling point has almost a linear relationship with the size (molecular weight) of the molecule. f) As a rule of thumb, the boiling point rises 20 - 30 C for each carbon added to the chain; this rule applies to other homologous series. g) A straight-chain alkane will have a boiling point __________than a branched-chain alkane due to the greater surface area in contact, thus the greater van der Waals forces, between adjacent molecules. For example, compare isobutane (2-methylpropane) and nbutane (butane), which boil at -12 and 0 C, and 2,2-dimethylbutane and 2,3dimethylbutane which boil at 50 and 58 C, respectively. For the latter case, two molecules 2,3-dimethylbutane can "lock" into each other better than the cross-shaped 2,2dimethylbutane, hence the greater van der Waals forces. h) On the other hand, cycloalkanes tend to have higher boiling points than their linear counterparts due to the locked conformations of the molecules, which give a plane of intermolecular contact.

Graph 2.1: Melting (bottom) and boiling (top) points of the first 14 n-alkanes in C.

5. Melting point: a. The melting points of the alkanes follow a similar trend to boiling points for the same reason. That is, the ________the molecule the ______ the melting point. b. There is one significant difference between boiling points and melting points. Solids have more rigid and fixed structure than liquids. This rigid structure requires energy to break down. c. The melting points of branched-chain alkanes can be either higher or lower than those of the corresponding straight-chain alkanes, again depending on the ability of the alkane in question to packing well in the solid phase: This is particularly true for isoalkanes (2-methyl isomers), which often have melting points higher than those of the linear analogues. 6. Alkanes ________ conduct electricity, nor are they substantially polarized by an electric field.
7. Molecular geometry : The molecular structure of the alkanes directly affects their physical and chemical characteristics. It is derived from ______________________ of carbon, which has four valence electrons. 3 The carbon atoms in alkanes are always sp hybridized. These orbitals, which have identical energies, are arranged spatially in the form of a tetrahedron, the angle is 109.47 between them. CHEMICAL PREPARATION OF ALKANES a) Catalytic Hydrogenation of alkenes CnH2n + H2 CnH2n+2

A mixture of the alkene and hydrogen is passed over finely divided __________________ or ________ catalyst. Nickel is the least active of these catalysts and requires an elevated temperature and pressure, whereas platinum and palladium function adequately at ordinary temperature and pressures.

b) Decarboxylation of sodium salts of carboxylic acid. Alkanes can be prepared by heating the anhydrous sodium carboxylate salt with soda lime (a mixture of sodium hydroxide and calcium hydroxide). This reaction is termed decarboxylation because the carboxyl group of __________ is being removed and replaced by a hydrogen atom. RCOONa+ + NaOH RH + NaCO3

This method gives a good yield of methane but higher members of the series are obtained in much lower yield, probably because of thermal decomposition of the longer carbon chains. c) Kolbes method : Electrolysis of a concentrated aqueous solution of the sodium salt of a carboxylic acid, for example, sodium ethanoate. Cathode : Anode:

d) Wurtz reaction: The Wurtz reaction, named after Charles-Adolphe Wurtz, is a coupling reaction in organic chemistry, organometallic chemistry and recently inorganic main group polymers, whereby two __________are reacted with _________to form a new carbon-carbon bond:

2R-X + 2Na R-R + 2Na+X

Other metals have also been used to effect the Wurtz coupling, among them silver, zinc, iron, activated copper, indium and a mixture of manganese and copper chloride. The related reaction dealing with aryl halides is called the Wurtz-Fittig reaction. Mechanism The reaction consists of a halogen-metal exchange involving the _______species R (in a similar fashion to the formation of a Grignard reagent) and then the carboncarbon bond formation in a ______________________reaction. One electron from the metal is transferred to the halogen to produce a metal halide and an alkyl radical. R-X + M R + M+X The alkyl radical then accepts an electron from another metal atom to form an alkyl anion and the metal becomes cationic. This intermediate has been isolated in a several cases. R + M RM+ The nucleophilic carbon of the alkyl anion then displaces the halide in an SN2 reaction, forming a new carbon-carbon covalent bond. RM+ + R-X R-R + M+X

CHEMICAL PROPERTIES 1. Alkanes are relatively _______ compounds. This is because the carbon-hydrogen bond is only slightly polarised. Consequently, alkanes are not readily attacked by common chemical reagents which are usually highly polar compounds. 2. Molecules of alkanes also have _____________ electrons to offer sites for attack by acids. 3. The effects of common reagents on alkanes are listed in the table 2.2 below. Reagent Effect on alkanes Air ( or oxygen ) No effect at room conditions. Burns when heated. Concentrated sulphuric acid No effect cold or hot. Two immiscible layers observed. Aqueous sodium hydroxide No effect cold or hot. Two immiscible layers observed. Aqueous potassium manganate (VII) No effect KMnO4, acidified with dilute H2SO4 No effect cold or hot. No decolourisation of purple KMnO4 even on heating. Two immiscible layers observed. HCl (aq) No effect cold or hot. Two immiscible layers observed. Bromine No effect in the dark. Bromine slowly decolourised in sunlight Chlorine No effect in the dark. Reaction occurs in sunlight.

COMBUSTION OF ALKANES 1. Alkanes do not react with air at room temperature, but when heated, they burned readily to give ____________ and ___________ in an ____________ reaction. Example:

2. Liquid and solid alkanes need to vaporised first before they burn. 3. If the supply of air limited, the combustion of alkanes is ___________, producing _________ and carbon (in the form of soot) along with partially oxidised hydrocarbons. Example:

4. Carbon monoxide is a poisonous gas which bonds to the iron of haemoglobin in the blood in preference to oxygen which could result in death. HALOGENATION 1. Due to chemical inertness, alkanes do not readily react with halogens in the dark at room temperature. 2. However, in the presence of ________________ or at a temperature _____________, halogen atoms will __________ hydrogen atoms in alkanes to form haloalkanes. 3. Since, the reaction takes place in light, it is called ______________ reaction. 4. Chlorination of methane ( when chlorine is mixed with methane and exposed to sunlight), the ________________ colour of chlorine fades and steamy acidic fumes of hydrogen chloride is evolved. The mechanism of chlorination of methane : Free radical substituition a) The mechanism consists of three steps ; __________________, ___________ and _________________. Step 1 : Initiation (i) This steps involved the ______________ ______________ ____________ of the Cl Cl bond in the chlorine ,molecule. (ii) The energy required for homolytic fission comes from the light absorbed. (iii) As the two chlorine atoms in the bond are identical, the bond will break homolytically,i.e. one electron goes to each chlorine producing two chlorine atoms, each with one unpaired electron and is known as free radical. Step 1:

(iv) It is easier to break Cl Cl bond (+242 kJmol-1) than the C H bond ( +435 the kJmol-1). Thus, in this step, only chlorine radicals are produced although both the chlorine and methane molecules are exposed to sunlight. Step II : Chain Propagation (i) The chlorine radical formed is very reactive. It is reactive enough to break the C H bond when it attacks the methane molecule, producing hydrogen chloride, HCl, and a methyl free radical. Step 2 :

(ii) The methyl free radical can react with a chlorine molecule to produce chloromethane, CH3Cl, and a new chlorine free radical. Step 3:

(iii) These two steps, 2 and 3, enable the reaction to continue. In step 2, a chlorine free radical is used up. Meanwhile, in step 3, a new chlorine free radical is produced which allows repetition of step 2. (iv) Steps 2 and 3 constitute a chain reaction and are called ___________________ steps. Step III : Chain termination (i) Thousands of molecules of chloromethane are formed for every photon of light absorbed. The yield is due to the chain reaction step 2 and 3. (ii) The reason why the yield is not higher is that free radicals can combine with each other and bring the chain to an end- termination steps. (iii) The possible reactions that may terminate the chain are as follows:

(iv) These or any other termination steps will remove the free radicals and bring the chain to a stop. Bromination of methane Similar to chlorination. Reaction : methane gas is bubbled into a solution of bromine tetrachloromethane. Observations : no reaction in the dark. The brown solution of bromine water is ______________ in the presence of light. CRUDE OIL 1. The main source of alkane is from underground deposites of crude oil and natural gas. 2. Crude oil is a complex mixture of alkanes and other hydrocarbons. 3. The complex mixture is separated into fractions in the oil refinery . This is done by ________ ______________. 4. This technique relies on the difference in boiling points of the different fractions in the crude oil. Each fraction contains hydrocarbons which boil in a common range of boiling points. 5. Fractional Distillation of Crude Oil. (a) Crude oil is heated in a furnace until it vaporises. The crude oil vapour enters a tall fractionating column and cools. The lower the boiling point, the higher the tray the vapour condenses the column. (b) A fractional distillation column is designed to separate crude oil into following fractions: (c) Table 2.3 gives a summary of the crude oil fractions and their uses.

Fraction Petroleum gas Gasoline Naphtha Kerosene Diesel oil Lubricating oil Fuel oil Bitumen

Number of carbon 14 56 6 10 1014 14 19 19 35 Above 20 Above 35

Boiling range (oC) Under 30 40 180 100 -200 160 230 250 -340 340 500 340 500 Above 500

Uses Gas for cooking and burning stoves Fuel oil Used by the petrochemical industry as the source of a number of useful chemicals Jet fuel Fuel oil for diesel engines like trains, buses, lorries Lubricant to reduce engine wear Fuel oil for ships, heating plants, power stations Used to tar roars and to waterproof roofs and pipes

6. After the distillation, the different hydrocarbon fractions are treated in a variety of ways : (a) Desulphurisation, to remove sulphur (b) Vacuum distillation, to separate less volatile components such as lubricating oils from the residue. (c) Cracking, to produce more petrol and alkenes. CRACKING 1. Cracking is the breaking down of a higher molecular mass alkane to lower molecular mass alkanes and alkenes. 2. The purpose of cracking is to produce high demand hydrocarbons like (a) Petrol (b) Alkenes, as feedstock to produce a wide range of organic compounds including polymers 3. There are 2 types of cracking: Thermal Cracking (a) Involves heating the naphthalene fraction with steam at high temperature and pressure. (b) As bond breaking (homolytic fission) is a random process, a variety of products including unbranched alkanes and alkenes, hydrogen and a small fraction of branched and cyclic hydrocarbons are produced. (c) Example:

Catalytic Cracking (a) Involves heating the oil fraction with catalyst. (b) A mixture of the vaporised fraction and a zeolite catalyst are reacted at low temperatures of about 450oC using slight pressure. (c) This process forms a higher fraction of branched and cyclic alkanescompared to that of thermal cracking. (d) Example: