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Organic Chemistry (AS)

Alkane (saturated hydrocarbon):

 Combustion (complete and incomplete)
 Free-radical substitution
 Cracking (elimination): alkane → alkene + alkane (no oxygen, high temperature, zeolite
catalyst)

Alkene (unsaturated hydrocarbon):

 Addition (electrophilic addition):
 Hydrogen (H2 (g)): CH2=CH2 + H2 → CH3CH3 (140℃, Ni catalyst)
 Steam (H2O (g)): CH2=CH2 + H2O → CH3CH2OH (330℃, 6MPa, H3PO4)
 Hydrogen Halides (HX (aq)): CH2=CH2 + HBr → CH3CH2Br (conc. HX, r.t.p.)
 Halogens (X2 (aq)): CH2CH2 + Br2 → CH2BrCH2Br (r.t.p.
 Test for the presence of C=C bond (decolourisation of Br2)

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 Oxidation:
 Cold Dilute Acidified Manganate(VII) Solution (KMnO4)

 Hot Concentrated Acidified Manganate(VII) Solution (KMnO4)

 Addition Polymerisation

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Halogenoalkane:
 Subsitution (nucleophilic substitution):
 Aqueous Alkali (OH- (aq)): CH3CH2Br + NaOH → CH3CH2OH + NaBr / CH3CH2Br +
H2O → CH3CH2OH + HBr (Heated under reflux)
 Alcohol produced
 KCN (CN- (in ethanol)): CH3CH2Br + CN- → CH3CH2CN + Br- (heated under reflux)
 Addition of carbon atom
 Nitrile produced
 Ammonia (NH3 (in ethanol)): CH3CH2Br + NH3 → CH3CH2NH2 + HBr (heated)
 Alkylamine produced
 Mechanism:

 Primary Halogenoalkane (SN2): S stands for substitution, N stands for nucleophilic, 2

is the rate of reaction; depends on both conc. of halogenoalkane and hydroxide
ions present.

 Tertiary halogenoalkanes (SN1): two-step mechanism, where a carbocation is

produced, due to the stability of the carbocation – due to the inductive effect of the
alkyl groups attached to the C atom; depends on only the conc. of the
halogenoalkane (slow-step)

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 Secondary halogenoalkane (SN1 and SN2)
 Elimination: CH3CHBrCH3 + NaOH(ethanol) → CH2=CHCH3 + H2O + NaBr
 Ethanolic sodium hydroxide as the reagent
 HBr eliminated from the 2-bromopropane
 Propene produced

Alcohol:
 Hydrogen bonding causes the higher boiling point than expected compared to other
organic molecules with similar relative molecular masses.
 Combustion: C2H5OH + 3O2 → 2CO2 + 3H2O
 Substitution (forming halogenoalkane (nucleophilic substitution)):
 CH3CH2OH + HCL → CH3CH2Cl + H2O
 Chloroalkane produced
 Occur due to the partial positive charge of the C atom bonded to the
hydroxyl group
 Carbon atom open to nucleophilic attack (by the partially negative halogen
atom in the hydrogen halide)
 Dry HCl(g) made in situ: NaCl + H2SO4 → NaHSO4 + HCl
 C2H5OH + SOCl2 → C2H5Cl + HCl(g) + SO2(g)
 Sulfur dichloride oxide as the reagent
 C2H5OH + PCl5 → C2H5Cl +HCl(g) + POCl3
 At room temp.
 Phosphorus halides as the reagent
 Test for hydroxyl group: steamy fumes of HCl observed
 3C2H5OH + PCl3 → 3C2H5Cl + H3PO3
 Requires heating
 Phosphorus (III) chloride as the reagent
 3C2H5OH + Pl3 → 3C2H5l + H3PO3
 Requires heating with the alcohol
 Phosphorus (III) halide made in situ using red phosphorus and bromine or
iodine
 Substitution with sodium metal: C2H5OH + Na → C2H5O-Na+ + H2(g)
 O-H bond in the alcohol breaks instead of C-O
 Sodium alkoxide produced - basic ionic compound (sodium ethoxide in the ex.)
 H2 gas given off
 Esterification: CH3CH2COOH + CH3CH2OH ↔ CH3CH2COOC2H5 + H2O
 Ethyl propanoate produced
 Reagents heated under reflux with a strong acid catalyst (conc. H2SO4)
 Esters produced usually have sweet, fruity smell
 Esters used in artificial flavouring, perfumes and solvents

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 Hydrolysis of Esters:
 With an acid (H2SO4) – catalyst: Reverses the preparation of an ester from an
alcohol and a carboxylic acid.
 Reaction will be reversible and an equilibrium mixture is established.

 With an alkali (NaOH(aq)): fully hydrolysed

 An alcohol and the sodium salt of the carboxylic acid produced

 Dehydration (Elimination): CH3CH2OH → CH2=CH2 + H2O

 Heating required
 Catalyst: Al2O3 (s) - powder or H2SO4
 Alkene produced

 Oxidation (using potassium dichromate(VI) solution, K2Cr2O7, acidified with dilute H2SO4
– Orange Cr2O72-(aq) reduced to green Cr3+(aq), warming of reaction mixture required):
 Tertiary alcohol: No change, remains orange
 Secondary alcohol: Oxidised to form a ketone, turns green

 Primary alcohol: Oxidised to an aldehyde (distillation), where further oxidation

forms carboxylic acid – achieved by reflux with excess acidified potassium
dichromate(VI):

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Nitrile:

 Hydrolysis: CH3CH2CN + HCl + 2H2O → CH3CH2COOH + NH4Cl

 Alkanenitrile to carboxylic acid
 Refluxed with dilute HCl
 Reduced to an amine (NH2): –CN + 4[H]→ –CH2NH2
 Na & ethanol

Carboxylic Acid:
 Dissociation: CH3COOH(aq) ↔ CH3COO-(aq) + H+(aq)
 alkanoate ions produced
 Neutralisation (Alkali): CH3COOH + NaOH → CH3COONa + H2O
 Reactive metals: 2CH3COOH + Mg → (CH3COO)2Mg + H2
 Salt (magnesium ethanoate) and H2(g) produced
 Carbonates: 2CH3COOH + K2CO3 → 2CH3COOK + H2O + CO2
 Salt (potassium ethanoate), H2O and CO2 produced
 Reduction: CH3COOH + 4[H] → CH3CH2OH + H2O
 Reducing agent: LiAlH4 (lithium tetrahydridoaluminate) – dry ether at r.t.p (v.
Reactive)
 Primary alcohol produced

Aldehyde & Ketone:

 Reduction (reducing agents: NaBH4 (sodium tetrahydridoborate) Or LiAlH4 (lithium

tetrahydridoaluminate)):
 Aldehyde + reducing agent → primary alcohol
 CH3CHO + 2[H] → CH3CH2OH
 Ethanal into ethanol
 Ketone + reducing agent → Secondary alcohol
 CH3COCH3 + 2[H] → CH3CH(OH)CH3
 Propanone into propan-2-ol
 (Warming the aldehyde or ketone with an aqueous alkaline solution of sodium
tetrahydridoborate)

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 (Adding lithium tetrahydridoaluminate dissolved in a dry ether, such as diethyl ether, at
r.t.p. As it reacts vigorously with water and a more powerful reducing agent compared to
sodium tetrahydridoborate)
 Nucleophilic addition with HCN (The HCN is generated in situ (in the reaction vessel) by
the reaction of sodium cyanide, NaCN, and dilute sulfuric acid):

 Increases the length of the hydrocarbon chain

 Mechanism of Nucleophilic addition:

Testing for the carbonyl group:

 Tri-iodomethane (Alkaline iodine solution test): Formation of yellow ppt. with methyl
ketones, compounds containing CH3CO- group or secondary alcohol (CH3CH(OH)-) due to
its oxidation into ketone (reagent: alkaline solution of iodine; warmed together with the
substance being tested):

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 Tollen’s reagent: Colourless to silver ‘mirror’ formation for aldehyde
 Fehling’s solution: Clear blue turns to opaque red/orange as ppt. of copper(I) oxide forms
throughout the solution for aldehyde
 2,4-DNPH (2,4-dinitrophenylhydrazine) – condensation reaction: A deep-orange ppt. is
formed when ketone or aldehyde is present

C=C → Electrophilic addition

C=O → Nucleophilic addition

Organic Chemistry (A-level)

Benzene:
 Organic hydrocarbons containing one or more benzene rings are called arenes. In general,
compounds of benzene are known as aryl compounds or aromatic compounds; an example
is chlorobenzene, which is one of the halogenoarenes. The simplest arene is benzene itself
(C6H6)
 Benzene molecule is a planar, perfectly symmetrical molecule
 Each carbon atom in the hexagonal ring is sp2 hybridised sharing:
 one pair of electrons with one of its neighbouring carbon atoms
 one pair of electrons with its other neighbouring carbon atom
 one pair of electrons with a hydrogen atom
 All three are σ (sigma) bonds; leaves one electron to spare contributing to a π (pi) bond –
delocalised
 The π bonding is formed by the overlap of carbon p atomic orbitals, where the lobes form a
ring of delocalised electrons above and below the plane of the carbon atoms.

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 Substitution (Cl & Br) – Electrophilic substitution:

 The Br2 molecule forms a dative (co-ordinate) bond with Iron (III) bromide by
donating a lone pair of electrons from one bromine atom into an empty 3d orbital
in the iron. This draws electrons from the other bromine atom in the Br2 molecule
making it partially positive, creating the electrophile (Br+):

 The Br+ cation and the ‘electron-rich’ benzene ring are attracted to each other, as
the mechanism (electrophilic substitution) shows:

 Mechanism done at r.t.p & FeCl3, AlCl3 and FeBr3 (halogen carriers) catalyst
 Another example:

 When we halogenate alkylarenes, the halogen atom substitutes into the

benzene ring at positions 2 or 4. While in excess chlorine gas, we can form 1-
methyl-2,4,6-trichlorobenzene (2 and 6 positions in substituted arenes are
equivalent)
 The C-X bond in halogenoarenes is stronger than the C-X bond in a
halogenoalkane, as one of the lone pairs on the halogen atom overlaps
slightly with the π bonding system in the benzene ring, hence giving the C-X
bond a partial double bond character
 Free-radical substitution (Cl & Br) into the alkylbenzene side-chain:
 In excess chlorine, eventually all three of the hydrogen atoms will be replaced by
chlorine atoms

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 Nitration – Electrophilic substitution:

 Conc. HNO3 & conc. H2SO4 to create the electrophile – nitronium ion (NO2+ ion):

 Reflux with benzene at 55℃ to make nitrobenzene:

 Mechanism (In stage 1, NO2+ is attracted to the high electron density of the π
bonding system inn benzene; a pair of electrons donated to NO2+, forming a new
covalent bond, disrupting benzene’s ring of electrons (4 π bonding electrons and a
positive charge spread over 5 carbon atoms. In stage 2, C-H bond breaks
heterolytically, H+ ion leaves the system, restoring the full delocalised ring.):

 Further nitration yields 1,3,5-trinitrobenzene

 Alkylation or Acylation (Friedel-Crafts reaction):
 Friedel-Crafts reactions result in the introduction of a side-chain into a benzene
ring, also called alkylation or acylation reactions

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 Mechanism:

 Oxidation of the side-chain:

 Alkylarenes’ alkane side-chain can be oxidised form carboxylic acid.
 Reagent and conditions:
 Reflux, alkaline potassium manganate(VII) then acidified with dilute H2SO4
 Reflux, potassium dichromate(VI) then acidified with dilute H2SO4

Phenol:
 Phenol, C6H5OH, a crystalline solid that melts at 43℃, due to its hydrogen bonding,
however, its non-polar benzene ring causes only a slight solubility in water
 Weakly acidic (however still stronger than water or alcohol):

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 Phenol’s conjugate base (the phenoxide ion, C6H5O-(aq)), has its negative charge
spread over the whole ion as one of the oxygen’s lone pairs overlaps with the
delocalised π bonding system, hence reducing the charge density of the C6H5O -(aq)
compared with OH-(aq) or C2H5O-(aq); therefore H+(aq) ions are less attracted to
the phenoxide than hydroxide or ethoxide ions, making phenoxide less likely to re-
form the undissociated molecules
 Phenol ionises to form a stable negative ion, so the position of equilibrium
lies further to the right-hand side
 Ethanol is the weakest acid due to the electron-donating alkyl group
attached to the oxygen atom in the ethoxide ion, concentrating more
negative charge on the oxygen atom, which more readily accepts H+ ions
(equilibrium lies further to the left-hand side)

 Breaking of OH bond:
 Slightly soluble in water, but dissolves well in alkaline solutions (NaOH):
 Sodium phenoxide salt is soluble in water

 Reacts vigorously with Na(s):

 H2 gas released (effervescence) & Sodium phenoxide salt produced

 Electrophilic Substitution into benzene ring:

 Phenol reacts with electrophiles more readily than benzene
 The overlap of one of the lone pairs of electrons on the oxygen atom in the OH
group with the π bonding system increases the electron density of the benzene ring
in phenol. This makes the benzene ring more open to attack from electron-deficient
electrophiles
 Substitution (Cl & Br) at r.t.p (a white ppt. forms):

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 Nitration with dilute nitric acid at r.t.p:

OR
Carboxylic Acids:

 Neutralisation (Alkali): CH3COOH + NaOH → CH3COONa + H2O

 Carboxylate salt produced (Sodium ethanoate)
 Dissociation:
 CH3COOH(aq) ↔ CH3COO-(aq) + H+(aq)
 Alkanoate ions produced
 Considered as weak acids (equilibrium lies well over to the left-hand side),
however are still stronger than alcohols
 The O-H bond in the carboxylic acid is weakened by the carbonyl group,
C=O:

 Carboxylate ion stabilised by the delocalisation of electrons around the –

COO- group (spreading out the negative charge on the ion), reducing its
charge density, hence less likely to bond with an H +(aq) ion to reform the
undissociated acid molecule:

 Electron-withdrawing groups (halogens) bonded to the carbon atom next to

the –COOH group make the acid stronger:
 Electron-withdrawing groups further weaken the O H bond in the
undissociated acid molecule
 Electron-withdrawing groups extend the delocalisation of the
negative charge on the COO– group of the carboxylate ion (pulling of

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negative charge further from O-), making it less likely to bond with H+
(aq) ions
 E.g. CCl3COOH which has three strongly electronegative Cl atoms all
withdrawing the electrons from the –COOH group, weakening the O-H bond
more than the other acids; once it is broken the resulting anion would be
stabilised more effectively, making it less attractive to the H + (aq) ions
 E.g. CH3COOH is the weakest acid, due to its electron-donating nature:
 It strengthens the O-H bond in the acid’s –COOH group
 It donates negative charge towards the –COO- group of the
carboxylate ion, making it more prone to accept H +

 Oxidation Of HCOOH (methanoic acid):

 Special cases of carboxylic acids which can undergo further oxidation

 Oxidation will occur with strong oxidising agents:
 Reflux with alkaline potassium manganate(VII) then acidified with dilute
H2SO4 (decolourising the purple solution)
 Reflux with potassium dichromate(VI) then acidified with dilute H2SO4
(solution turns from orange to green)

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 Oxidation will occur with milder oxidising agents:
 Fehling’s and Tollen’s – same positive results as test for adehydes

 Oxidation Of (COOH)2 (ethanedioic acid):

 Oxidised by only strong oxidising agents
 The reaction is often used to standardise potassium manganate(VII) solution:
 A standard solution of ethanedioic acid is acidified with dilute sulphuric acid,
warmed and titrated with potassium manganate(VII) solution from the
burette
 Decolourisation of potassium manganate(VII) solution can be observed until
the end-point when a trace of pale pink remains
 An example of an autocatalysis reaction, where Mn2+ (the product) acts as the
catalysis for that reaction

 Nucleophilic substitution, forming acyl chlorides:

 Replacement of carboxylic acid’s –OH with a Cl atom:
 Reagents and conditions:
 Phosphorus(V) chloride (r.t.p.):

 Phosphorus(III) chloride (heating required):

 Sulfur dichloride oxide (r.t.p.):

Acyl Chlorides:

 Acyl chlorides are more reactive than carboxylic acid, hence are more used in compound
synthesis:

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 The carbonyl carbon has electrons drawn away from it by electronegative atoms (O and Cl),
giving it a large partial positive charge, open to nucleophiles:

 Reactions will cause C-Cl bond to break; HCl(g) to be given off as white fumes:
 Where HZ can be water, an alcohol, ammonia or an amine (contains either an
oxygen or nitrogen atom with a lone pair that can be donated – nucleophile)

 Hydrolysis (r.t.p.):
 A lone pair on the oxygen atom in water initiates the attack on the δ+ carbonyl
carbon atom

 Carboxylic acid and HCl(g) forms

 The ease of hydrolysis: acyl chloride > chloroalkane > aryl chloride
 Acyl chloride has a more δ+ carbon compared to chloroalkane, due to the
attachment of an oxygen atom to the chlorine bonded carbon
 Aryl chloride will not undergo hydrolysis due to the overlapping of p orbitals of the
Cl atom to the delocalised p electrons in the benzene ring
 Esterification:
 When acyl chlorides reacts with alcohols or phenol, esters (and HCl) formed
 Reaction will occur more quickly and go to completion compared to that of
carboxylic acid + alcohols:

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 To produce phenyl esters (+ phenol), acyl chlorides must be used, warmed and in
the presence of a base (NR with carboxylic acid); where in the initial reaction,
phenoxide ion (C6H5O-) will form to act as the nucleophile to attack the acyl
chloride:

 Nucleophilic substitution with amines:

 Amines with a lone pair of electrons acts as a nucleophile and attacks the carbonyl
carbon atom in acyl chlorides (reaction is vigorous and a substituted amide
formed):

Amines:

 Three classes of amine: primary (NH2 group bonded to an alkyl or aryl group, e.g.
ethylamine (C2H5NH2) or phenylamine (C6H5NH2)), secondary (two alkyl or aryl groups
attached to an NH group, e.g. dimethylamine (CH3)2NH), tertiary (three alkyl or aryl groups
attached to the same nitrogen atom, e.g. trimethylamine (CH3)3N)
 Ammonia and amines act as bases due to the lone pair of electrons on the nitrogen atom
(donation of the lone pair to a H+ ion, forming a co-ordinate (dative) bond)
 Reaction with dilute acids (HCl in the example):

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 The strength of ammonia and amines as bases depends on the availability of the lone paur
of electrons on their N atom to bond with an H+ ion
 Ethylamine > ammonia due to the ethyl group’s electron-donating nature, releasing
more electrons towards the N atom
 Ammonia > phenylamine due to the overlapping of the p orbitals on the nitrogen
atom with the π bonding system in the benzene ring, causes the lone pair to
delocalise into the benzene ring: benzene ring’s electron-withdrawing nature
 Formation of ethylamine:
 Ammonia (NH3 (in ethanol)) (excess) (hot)+ bromoethane, to avoid formation of
secondary and tertiary amines

 Bromomethane + KCN (potassium cyanide); reduced by adding of hydrogen to the

ethanenitrile (passing of the nitrile vapour and H2(g) over a nickel catalyst / LiAlH4
in dry ether)

 Reduction of amides to amines, by using LiAlH4 in dry ether catalyst

 Formation of phenylamine:
 Reduction of nitrobenzene, by heating nitrobenzene with tin (Sn) and concentrated
hydrochloric acid (separation of phenylamine from reacting mixture using steam
distillation:

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 Electrophilic substitution of Br(aq) into phenylamine:
 A white ppt. forms
 The nitrogen in the –NH2 group has a lone pair of electrons that can be delocalosed
into the benzene ring, increasing the electron density of the ring, hence more prone
to electrophile attacks (reaction similar to that of phenols)

 Diazotisation:
 Used in the synthesis of dyes
 First step (must be kept below 10℃ due to the instability of the diazoniium salt –
decomposes easily giving N2(g) at higher temperatures):

 Phenylamine + nitrous acid (nitric(III) acid) → diazonium salt

 The positive charge on the diazonium ion (C6H5N2+) is on the nitrogen atom
shown with four bonds
 Nitrous acid can be bade using sodium nitrite (sodium nitrate(III)) and dilute
HCl:

 Second step:

 Diazonium ion reacts with an alkaline solution of phenol in a coupling

reaction
 The positively charged diazonium ion acts as an electrophile, substituting
into phenol at the 4 position
 An orange dye – very stable – is formed, called an azo dye, or diazonium dye

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The delocalised π bonding system extends between the two benzene rings
through the NN group
 Using alternative aryl compounds to phenol:

Amino acids:

 The general structure: RCH(NH2)COOH

 Examples of amino acids: glycine (aminoethanoic acid) (R group: H atom) (simplest amino
acid); alanine (2-aminopropanoic acid) (R group: -CH3)

 The R group can be acidic (e.g. containing another –COOH group), basic (e.g. containing
another –NH2 group) or neutral (e.g. where R is an alkyl group)
 Interactions between the molecules within amino acids are possible due to its basic –NH2
group and its acidic –COOH group (forming a zwitterions as it carries two charges):

 Zwitterion creates relatively strong intermolecular force due to their ionic nature (carrying
two charges); they are crystalline solids that are soluble in water
 Solutions of amino acids are amphoteric, buffer solutions:

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 Two amino acids reacted together will create a dipeptide (condensation reaction –
elimination of a small molecule when the reactant molecules join together):

 The amide link between the two amino acids are also called a peptide link
 The dipeptide product still has an –NH2 group and –COOH at its ends, hence the
reaction can continue forming polypeptides and then proteins

Amides:

 Structural formula: CONH2, e.g. CH3CONH2

 Amides are neutral compounds unlike amines, due to the presence of the electron-
withdrawing oxygen atom in the amide group, hence the unavailability of lone pair on the
amide’s nitrogen to donate to electron deficient species, such as H + ions
 Formation of amides:


 Ethanoyl chloride with conc. NH3(aq) producing ethanamide


 Primary amide with an acyl chloride producing a substituted amide
 Excess amines will react with HCl forming a salt (e.g. C2H5NH3+Cl-)
 Both reactions are in r.t.p.; white fumes of HCl forms

 The italic letter N is used in naming substituted amides to denote which alkyl (or
aryl) group or groups are bonded to the nitrogen atom, e.g. N-ethylbutanamide,
C3H7CONHC2H5, the ethyl (C2H5-) group has replaced an H atom in the amide
group. If the H atom on the nitrogen in this molecule is replaced by another alkyl or

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aryl group, two N’s are used in the name, e.g. C3H7CON(C2H5)2 is called N,N-
diethylbutanamide
 Hydrolysis:
 Substituted amides (-CONH-):
 Reflux with, e.g. HCl(aq) or NaOH(aq):

The product of hydrolysis with acid yields a carboxylic acid (R1COOH) and a
primary amine (R2NH2); excess acid in the reaction will react with amine to
form ammonium salt, e.g. R2NH3+Cl- with excess HCl
 The product of hydrolysis with an alkali, the product are sodium salt of the
carboxylic acid (R1COO-Na+) and the primary amine (R2NH2)
 Unsubstituted amide (RCONH2):
 Same reactions and products, except ammonia will be produced instead of
primary amines, and ammonium salts during excess of acid

Page 23
 CIE Chemistry A Level

14 : An introduction to Organic Chemistry

Notes

www.pmt.education
Formulae, functional groups and naming of organic compounds

Naming​ organic compounds is something that you must be comfortable with in order to understand
the rest of organic chemistry. You are required to be able to name organic compounds which have
up to ​6 carbons in a chain​.

Carbons in chain 1 2 3 4 5 6

Prefix meth- eth- prop- but- pent- hex-

There are different ways in which an organic compound can be displayed:

● Molecular formula​ ​- actual number of atoms of each element in a molecule.
● Structural formula​ - shows the structure carbon by carbon with hydrogens and functional
groups attached.
● Skeletal formula ​- only shows the bonds on the carbon skeleton. The carbon and
hydrogen atoms are not shown but any functional groups are. It can be used to simplify
large complicated structures.
● Displayed formula​ - shows how all the atoms are arranged and every bond between them.

Examples of these different types of formula can be seen in the table below.

Table 1 and table 2 ​(A level only)​ show the different types of compounds you are expected to be
able to name.
A ​homologous series​ is a group of compounds with the same ​functional group​, with successive
members differing by -CH​2​.

Table 1: Aliphatic compounds

Homologous Prefix Example Example Example Example Example
series or suffix name molecular structural skeletal displayed
formula formula formula formula

Alkanes -ane Propane C​3​H​8 CH​3​CH​2​CH​3

Alkenes -ene Ethene C​2​H​4 CH​2​CH​2

Halogenoalkanes Fluoro- Chloroethane C​2​H​5​Cl CH​3​CH​2​Cl

Chloro-
Bromo-
Iodo-

Alcohols -ol Ethanol C​2​H​5​O CH​3​CH​2​OH

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 Aldehydes -al Ethanal C​2​H​4​O CH​3​CHO

Ketones -one Propanone C​3​H​6​O CH​3​COCH​3

Carboxylic acids -oic Ethanoic acid C​2​H​4​O​2 CH​3​COOH

acid

Esters Alkyl- Methyl C​3​H​6​O​2 CH​3​COOCH​3

-oate ethanoate

Amines -amine methylamine CH​5​N CH​3​NH​2

Nitriles -nitrile Ethane nitrile C​2​H​3​N CH​3​CN

Table 2: ​(A Level only)

Homologous Prefix or Example name Example Example Example Example
series suffix molecula structural skeletal displayed
r formula formula formula formula

Arenes -benzene methylbenzene C​7​H​8 C​6​H​5​CH​3

Or phenoyl-

Halogenoare Fluoro- bromobenzene C​6​H​5​Br C​6​H​5​Br

nes /Chloro-
/Bromo-
/Iodo-
-benzene

Phenols -phenol Phenol C​6​H​6​O C​6​H​5​OH

Or
-benzenol

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 Acyl -oyl Ethanoyl C​2​H​3​OCl CH​3​COCl
chlorides chloride chloride

Amides -amide Ethanamide C​2​H​5​NO CH​3​CONH​2

Amino acids Amino- Aminoethanoic C​2​H​5​O​2​N H​2​NCH​2​COOH

-oic acid acid

Naming organic compounds

Follow these rules when naming organic compounds:
1. Identify the ​longest carbon chain​ that contains the functional group.
2. Identify the ​functional group​ on the chain. This gives you the suffix or prefix of the
compound.
3. Count along the carbon chain so that the ​functional group has the lowest number​. See
the example below to illustrate this.
4. If there are any ​side chains​, add these as ​prefixes​ (e.g. methyl-) to the beginning of the
name. Do the same if there are other (less important) functional groups. Put these at the
start of the name in ​alphabetical order​.
5. If there are ​two or more identical functional groups​ or side chains use the prefixes di-,
tri- and tetra- before that section of the name.

Example:
1. The longest carbon chain is ​6 carbons
long​ so the prefix is hex-.
2. The most important functional group on
the chain is the ​-OH​ alcohol. The suffix
is therefore -ol.
3. The alcohol is on ​the second carbon​ in
the chain (count from the side closest to
this functional group). The suffix
becomes ​-2-ol.
4. There are ​two side chains​:
An ethyl on the third carbon: 3-ethyl
A methyl on the fifth carbon: 5-methyl
5. Place the prefixes in alphabetical order and add them to the name:
3-ethyl-5-methylhexanol.

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Example 2:
1. This chain is ​symmetrical​ so it does not matter which
way the carbons are numbered. Prefix: but-
2. There are ​two alcohol groups​ on the second and third
carbon: -2,3-diol.
3. There are no other groups so the overall name is:
butan-2,3-diol.

Naming simple aromatic compounds ​(A Level only)

When it comes to naming aromatic compounds, the method to go about it is similar to the one
above. The main difference is the ​benzene ring​ which means you count the carbons in the circle.

Example:
1. There are ​two alcohol groups​ on the benzene. This means the suffix is
-benzenol​, as seen in the table above.
2. Counting from the first alcohol as ‘1’, the second alcohol group is on the
third carbon in the chain. This gives the overall name ​benzene-1,3-diol​.

Example 2:
1. The biggest group on the benzene chain is the ​carboxylic acid ​so start
counting from there. The ​nitro- group​ is on the fourth carbon.
2. The overall name therefore is:
4-nitrobenzoic acid​.

Characteristic organic reactions terminology

The following terms are important in organic chemistry so you must make sure you are familiar with
them:
● Functional group​ - a group of atoms responsible for the characteristic reactions of an
organic compound.
● Homolytic fission​ - the splitting of a covalent bond where each atom retains one electron
from the bonding pair.
● Heterolytic fission​ - the splitting of a covalent bond where one atom retains both electrons
from the bonding pair.
● Free radical​ - an uncharged molecule with an unpaired electron.
● Initiation​ - an initial chemical reaction which triggers further reactions.
● Propagation​ - a secondary reaction where there is no net gain or loss of free radicals.

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 ● Termination​ - the final step in a chain reaction where a reactive intermediate is rendered
inactive.
● Nucleophile​ - a molecule or substance that donates electrons.
● Electrophile​ - a molecule or substance that acts as an electron pair acceptor.
● Addition​ - a reaction where two or more molecules react to form a larger molecule.
● Substitution​ - a reaction where an atom or group is replaced by another atom or group.
● Elimination​ - a reaction in which two substituents are removed from a molecule in a
mechanism with one or two steps.
● Hydrolysis​ - the splitting up of a compound or molecule using water.
● Condensation​ - the formation of a compound with the release of water.
● Oxidation​ - loss of electrons.
● Reduction​ - gain of electrons.

Shapes of organic molecules

Bonding in ethane
The shape of an ethane molecule (seen on the right) is
tetrahedral​ with bond angles of ​109.5​o​.
The bonds between each atom are ​sigma (𝜎) bonds​.
Rotation​ can occur around sigma bonds because they are
formed when two orbitals overlap end-to-end.

Bonding in ethene
Ethene molecules have a ​trigonal planar ​shape with bond
angles of ​120​o​. These molecules contain both sigma and pi
bonds (see diagram). The molecule is planar because there is
restricted rotation​ around the C=C pi (π) bond. Rotation is
restricted around this bond because a pi bond is formed
when orbitals overlap below and above the plane of atoms.

Bonding in benzene ​(A Level only)

Benzene is a ​planar molecule​ with bond angles of ​120​o​. All the
carbon-to-carbon bonds are identical so it has a regular hexagonal
shape. There are C-H and C-C sigma bonds as well as a
delocalised pi system ​above and below the carbon ring. One
electron from each carbon is delocalised into the pi (π) system
which​ contains 6 electrons.

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Isomerism

Structural isomers
Isomers are molecules with the ​same molecular formula​ but a different arrangement of ​atoms in
space​. There are different types of structural isomerism:
● Chain​ isomerism: This occurs when there is branching on the carbon chain.
● Functional group​ isomerism: The functional groups on the carbon chain changes.
● Positional​ isomerism: The basic carbon chain, the backbone, remains the same but the
groups attached to the chain move around and change position.

Structural isomerism Isomer 1 Isomer 2

Chain CH​3​CH​2​CH​2​CH​2​CH​3 C(CH​3​)​4

Functional group CH​3​COCH​3​ (ketone) CH​3​CH​2​CHO (aldehyde)

Position CH​3​CH=CHCH​3 CH​2​=CHCH​2​CH​3

Stereoisomerism
Stereoisomers are molecules with the ​same molecular and structural formula​ but a different
arrangement of ​atoms in space​.

Geometrical (cis-trans)
Geometrical isomerism is a branch of stereoisomerism. It can also be called ​cis-trans or E/Z
isomerism​. This occurs due to a pi bond which ​restricted rotation​ around the C=C double bond.
Since there is restricted rotation around this bond, the ​various groups attached​ to the carbon are
fixed in position ​meaning​ ​different isomers can form. Examples of this type of isomerism are
shown below (see example 1 in ‘Isomerism in alkenes’).

Optical isomerism
Optical isomerism is another branch of stereoisomerism. It occurs when there is a ​chiral centre​,
(explained in more depth in ‘What is a chiral centre?’ on the following page). Optical isomers have
the same molecular and structural formula but they are ​mirror images of one another​.

Isomerism in alkenes
Geometrical isomerism is the type of isomerism that occurs in alkenes because it relies on a C=C
double bond. The ​cis isomer​ has ​both of the highest priority groups on the same end​ (either
both above or below the C=C bond). The ​trans isomer​ the highest priority groups ​diagonally
across​ from each other, on opposite sides of the double bond.
The priority of a group is decided by ​atomic number​. If the attached groups are different but the
first atom joined from each group is the same then you work along each group simultaneously until
you reach an atom with a different atomic mass to decide which has priority. A ​higher atomic
mass means a higher priority​.

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Example 1:
For the isomers below, the highest priority group on the left hand side is the methyl group, CH​3​,
and on the right hand side it is the ethyl group, CH​2​CH​3​.

Example 2:
For the isomers below, the priority group for the left hand side is the chlorine atom since it has a
higher atomic mass than carbon in the methyl group. On the right hand side the groups are similar
so you work along the chain until the chlorine atom which gives priority to the group with chlorine.

What is a chiral centre?

A chiral centre is an ​atom with four different groups bonded ​to it. This arrangement creates
compounds which are ​non-superimposable​ ​mirror images ​of each other. If a compound has a
chiral centre, it will display ​optical isomerism​.
It is possible for compounds to have ​more than one chiral centre​.

Spotting chiral centres:

Chiral centres can be spotted in organic compounds by identifying a ​carbon atom which is
bonded to four different groups​.

Example:
The carbon highlighted in the compound below is a ​chiral centre​ since it has bonded to four
different groups: a hydrogen atom, a methyl group, an alcohol group and an ethyl group.

CH​3​C​H(OH)CH​2​CH​3

This compound displays ​optical isomerism​. The isomers can be drawn in a ​tetrahedral​ shape
with the chiral carbon at the centre. It is easiest to draw these isomers by drawing one then
mirroring​ it on the other side of the page:

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www.pmt.education
 Organic Chemistry - Introduction 1

Basic definitions for organic chemistry

Scope Organic chemistry is a vast subject so is split it into small sections for study. This
is done by studying compounds which behave in a similar way because they have
a particular atom, or group of atoms, (FUNCTIONAL GROUP) in their structure.

Catenation The ability to form bonds between atoms of the same element. Carbon
catenates to form chains and rings, with single, double or triple covalent bonds.

Q.1 • Why does carbon form so many catenated compounds ?

• Why does silicon undergo catenation to a lesser extent than carbon ?

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Homologous
Series A series of organic compounds having the same functional group and each
member differs from the previous by CH2 .

• all share the same general formula

• formulae differ from their neighbours by CH2. (e.g. CH4, C2H6, . . . etc )
• contain the same functional group(s)
• have similar chemical properties
• show a gradual change in physical properties as molar mass increases
• can usually be prepared by similar methods.

Functional
Group A group of atoms responsible for the characteristic reactions of a compound.
• can consist of - one atom — Br
- a group of atoms — OH
- multiple bonds between carbon atoms C=C

• each functional group has its own distinctive properties

H H H H H H H H H H

H C C C C C OH H C C C C C NH 2

H H H H H H H H H H
carbon skeleton functional
carbon skeleton functional group
group

© KNOCKHARDY PUBLISHING 2015

2 Organic Chemistry - Introduction

Some common functional groups

GROUP ENDING GEN. FORMULA / STRUCTURE EXAMPLE

ALKANE - ane RH C C C2H6 ethane

ALKENE - ene C C C2H4 ethene

ALKYNE - yne C C C2H2 ethyne

HALOALKANE halo - RX C − X (X= Cl, Br, I) C2H5Cl chloroethane

ALCOHOL - ol ROH O H C2H5OH ethanol

H
ALDEHYDE -al RCHO C CH3CHO ethanal
O

C
KETONE - one RCOR C O CH3COCH3 propanone
C

O H
CARBOXYLIC - oic acid RCOOH C CH3COOH ethanoic acid
ACID

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O

Cl
ACYL - oyl chloride RCOCl C CH3COCl ethanoyl chloride
CHLORIDE O

NH2
AMIDE - amide RCONH2 C CH3CONH2 ethanamide
O

O R
ESTER - yl - oate RCOOR C CH3COOCH3 methyl ethanoate
O

NITRILE - nitrile RCN C N CH3CN ethanenitrile

AMINE - amine RNH2 C − NH2 CH3NH2 methylamine

+ O
NITRO - nitro RNO2 N CH3NO2 nitromethane
O
-

ETHER - oxy - ane ROR R-O-R C2H5OC2H5 ethoxyethane

The symbol R represents groups of carbon and hydrogen atoms in the rest of the molecule

Q.2 Draw out legitimate structures for each formula and classify the compounds according to the
functional group present. NB Carbon atoms will have four covalent bonds surrounding them,
oxygen atoms two, nitrogen atoms three and hydrogen atoms and halogen atoms just one.

C2H6 C4H10 C4H8 C2H6O C3H6O C2H7N C2H4O2 C2H3N

© KNOCKHARDY PUBLISHING 2015

 Organic Chemistry - Introduction 3

Use of different formulae in organic chemistry

General the simplest algebraic formula for a

member of a homologous series CnH2n+2 for an alkane
CnH2n for an alkene

Molecular shows the exact number of atoms

of each element in a molecule C4H10 for butane

Empirical shows the simplest whole number ratio

of atoms of each element in a molecule C2H5 for butane

Structural the minimal detail that shows the

arrangement of atoms in a molecule CH3CH2CH2CH3 butane
CH3CHOHCH3 propan-2-ol
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H H H H
Displayed shows the relative positioning of atoms
and the number of bonds between them H C C C C H butane

H H H H

Skeletal used to show a simplified organic formula

by removing hydrogen atoms from alkyl
chains, leaving just a carbon skeleton and cyclohexane
associated functional groups.

• each covalent bond is shown by a line cyclohexene

• a carbon atom is at the join of lines
• functional groups are shown OH
• the number of hydrogen atoms on cyclohexanol
each carbon atom is the difference
between the number of lines and 4

OH butan-1-ol

O
Skeletal formulae tend to be used with
larger organic molecules - e.g. thalidomide N

O O N O

© KNOCKHARDY PUBLISHING 2015

4 Organic Chemistry - Introduction

Nomenclature in organic chemistry

Systems A naming system must tell you everything about a structure without ambiguity.
There are two types of naming system commonly found in organic chemistry;

Trivial : based on some property or historical aspect;

the name tells you little about the structure

Systematic : based on an agreed set of rules (I.U.P.A.C);

exact structure can be found from the name (and vice-versa).

Series trivial name systematic name example(s)

paraffin alkane methane, butane
olefin alkene ethene, butene
fatty acid alkanoic (carboxylic) acid ethanoic acid

Compounds trivial name derivation systematic name

acetic acid acetum = vinegar (Lat.) ethanoic acid (CH3COOH)

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Systematic (IUPAC) Nomenclature

STEM Shows the number of carbon atoms in longest chain bearing the functional group
+ (if necessary) a prefix showing the position and identity of any substituents

Nomenclature Apart from the first four, which retain trivial names, Prefix C atoms Alkane
the number of carbons atoms is indicated by a
prefix derived from the Greek numbering system. meth- 1 methane
eth- 2 ethane
prop- 3 propane
• the list of alkanes demonstrate the use of prefixes but- 4 butane
pent- 5 pentane
• the ending is the same as they are all alkanes hex- 6 hexane
hept- 7 heptane
oct- 8 octane
non- 9 nonane
dec- 10 decane

SUFFIX The ending tells you which functional group is present

Nomenclature If any functional groups are present, add relevant ending to the basic stem. The
position of the functional group must be given to avoid any ambiguity.

In many cases the chain of carbon atoms is branched so one must include the ...

Substituents Many compounds have substituents (additional atoms, or groups of atoms)

attached to the chain. Their position is numbered according to a set of rules.

© KNOCKHARDY PUBLISHING 2015

 Organic Chemistry - Introduction 5

NOMENCLATURE - GENERAL RULES

Stem • look for the longest chain of carbon atoms containing the functional group.
• the carbon atoms must be in a continuous row.
• use prefixes as shown on previous page
• ending tells you what type of carbon structure you have; alkanes end in ANE

Side-chain • carbon based substituents are named before the chain name.
• they have the prefix -yl added to the basic stem (e.g. CH3 is methyl).
• Number the principal chain from one end so that the side chain is attached
to a carbon atom with the lowest possible number.

CH3
e.g. 2-methylhexane CH3 CH 2 CH CH 2 CH CH
2 3

If there is more than one side-chain the following rules apply:-

• side-chain names appear in alphabetical order i.e. butyl, ethyl, methyl, propyl.
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• number the principal chain from one end to give the lowest numbers.
• each side-chain is given its own number.
• if identical side-chains appear more than once, prefix with di, tri, tetra etc
• numbers are separated from names by a HYPHEN 2-methylheptane
• numbers are separated from numbers by a COMMA 2,3-dimethylbutane

Example CH 3
CH2 CH3
• longest chain 8 (it is an octane)
CH3 CH2 CH2
• 3,4,6 are the numbers NOT 3,5,6 CH3 CH 2 CH CH2 CH CH CH2 CH3
• order is ethyl, methyl, propyl 6 5 4 3 2 1
NOT 1 2 3 4 5 6

3-ethyl-6-methyl-4-propyloctane

Q.3 Name these alkanes

CH3 CH3

CH2 CH2

CH3 CH CH2 CH3 CH3 CH CH2 CH2 CH2 CH2 CH3

CH3
CH3 CH3 CH2 CH3
CH3 CH CH2 CH2 CH2 CH CH3 CH3 CH CH2 CH2 CH CH2 CH3

© KNOCKHARDY PUBLISHING 2015

6 Organic Chemistry - Introduction

ALKENES / ALCOHOLS

Length In alkenes and alcohols the principal chain is not always the longest chain.

Alkenes It must contain the C=C bond. The name ends in -ENE
Alcohols It must contain the OH group. The name ends in -OL

Position Alkenes Indicated by the lower numbered carbon atom on one end of the
double bond. Count from one end to give lowest number.

CH3 CH CH CH2 CH 3 is pent-2-ene ( NOT pent-3-ene )

Alcohols Count from one end to give lowest number.

CH3 CH 2 CH2 CH CH 3 is pentan-2-ol ( NOT pentan-4-ol )

OH

Side-chain Position is based on the number allocated to the C=C bond or OH group.

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CH3 CH3 OH
CH3 CH2 C CH2 CH3 CH CH CH3

2-methylbut-1-ene 3-methylbutan-2-ol

Q.4 Draw structures for . . . • 4-methylhex-2-ene

• 3,3-dimethyloct-1-ene • 4-ethyl-3-methylhexan-1-ol

Q.5 Name these compounds.

CH3 CH CH 3
CH3 CH2
CH3 CH OH CH3 CH2 CH CH CH2
CH3 CH2 CH CH2 CH CH3 CH 2 CH2

© KNOCKHARDY PUBLISHING 2015

 Organic Chemistry - Introduction 7

PERCENTAGE YIELD

Yield • the mass of a product obtained in reaction

Percentage • the mass of product obtained expressed as a percentage of what you ought
yield to get assuming complete conversion

Example 1 What mass of salicylic acid will make 5g of aspirin (assuming 100% conversion)?

Aspirin can be made by the reaction between salicylic acid and ethanoic
anhydride. If one mole of each of the reactants is used the masses involved are...

COOH COOH
OH OOC CH3
+ (CH3CO)2O ——> CH3COOH +

Mr = 138 Mr = 102 Mr = 60 Mr = 180

In order to make 180g of aspirin you will need a minimum of 138g of salicylic acid.
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If you only want 5g of aspirin you will need to scale the masses accordingly...

molar scale 138g 102g 60g 180g

divide by 180 138g/180 102g/180 60g/180 1g

multiply by 5 5 x 138g/180 5 x 102g/180 5 x 60g/180 5g

3.833g salicylic acid will produce 5g of aspirin

Example 2 When an experiment was carried out using 3.833g of salicylic acid, only 3.75g
of aspirin was produced. What is the percentage yield of aspirin?

If there is a 100% yield then... 3.833g salicylic acid ——> 5g of aspirin

If 3.75g of aspirin is made, the percentage yield = 3.75g / 5g x 100 = 75%

Q.6 The equation for the synthesis of N-ethyl ethanamide from ethylamine and ethanoyl chloride is
CH3COCl + C2H5NH2 ——> CH3CONHC2H5 + HCl
• What mass of ethanoyl chloride is required to make 3g of N-ethyl ethanamide?
• If only 1.8g are produced, what is the percentage yield?

Q.7 Ethyl ethanoate can be synthesised from ethanoyl chloride and ethanol.
CH3COCl + C2H5OH ——> CH3COOC2H5 + HCl
• What mass of ethanoyl chloride will react with 2.3g of ethanol?
• If only 1g of ethyl ethanoate is produced, what is the percentage yield from 2.3g of ethanol?

© KNOCKHARDY PUBLISHING 2015

8 Organic Chemistry - Introduction

ATOM ECONOMY

Background • in most reactions you only want to make one of the resulting products
• atom economy is a measure of how much of the products are useful

ATOM ECONOMY = MOLECULAR MASS OF DESIRED PRODUCT x 100

SUM OF MOLECULAR MASSES OF ALL PRODUCTS

Example 1 Calculate the atom economy for the formation of 1,2-dichloroethane, C2H4Cl2
C2H4 + Cl2 ——> C2H4Cl2
Mr 28 71 99

atom economy = molecular mass of C2H4Cl2 x 100 = 99 x 100 = 100%

molecular mass of all products 99

Example 2 Calculate the atom economy for the formation of nitrobenzene, C6H5NO2

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C6H6 + HNO3 ——> C6H5NO2 + H2O
Mr 78 63 123 18

atom economy = molecular mass of C6H5NO2 x 100 = 123 x 100 = 87.2%

molecular mass of all products 141

Notes • addition reactions will have 100% atom economy

• substitution reactions will have less than 100% atom economy
• elimination reactions will have less than 100% atom economy
• high atom economy = fewer waste materials
• reactions may have a high yield but a low atom economy

Q.8 Calculate the atom economy of the following reactions (required product is in bold);

• CH3COCl + C2H5NH2 ——> CH3CONHC2H5 + HCl

• C2H5Cl + NaOH ——> C2H5OH + NaCl
• C2H5Cl + NaOH ——> C2H4 + H2O + NaCl

© KNOCKHARDY PUBLISHING 2015

 Organic Chemistry - Introduction 9

Elucidation of the structures of organic compounds - a brief summary

Introduction Traditionally, working out the identity was a long-winded process but, with the use
of modern analytical instruments, the process is much quicker.
ELEMENTAL COMPOSITION PERCENTAGE COMPOSITION EMPIRICAL FORMULA

STRUCTURAL FORMULA MOLECULAR FORMULA MOLECULAR MASS

Elemental
composition The presence of carbon and hydrogen can be proved by letting the compound undergo
combustion. Carbon is converted to carbon dioxide and hydrogen to water. Other
elements can also be identified.

Percentage
composition The percentage composition by mass is found by dividing the mass of an element present
by the mass of the compound present, then multiplying by 100. Elemental mass of C and
H can be found by allowing the substance to undergo complete combustion.

• mass of carbon = 12/44 of the mass of CO2 produced

• mass of hydrogen = 2/18 of the mass of H2O produced
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Empirical
formula Gives the simplest ratio of elements present in the substance. It can be calculated by
dividing the mass or percentage mass of each element present by its molar mass and
finding the simplest ratio between the answers. Empirical formula is converted to the
molecular formula using molecular mass.

Molecular
mass Nowadays mass spectrometry is used. The position of the last m/z signal is due to the
molecular ion and gives the molecular mass. The fragmentation pattern also gives
information about the compound.

Molecular
formula The molecular formula is an exact multiple of the empirical formula. Comparing the
molecular mass with the empirical mass allows one to find the true formula.

if the empirical formula is CH (relative mass = 13) and the molecular mass is 78
the molecular formula will be 78/13 or 6 times the empirical formula i.e. C6H6 .

Structural
formula Because of the complexity of organic molecules, there can be more than one structure for
a given molecular formula. To work out the structure, one can carry out different tests...

Chemical Use chemical reactions to identify the functional group(s) present.

Spectroscopy IR detects bond types due to absorbance of i.r. radiation

NMR gives information about the position and relative
numbers of hydrogen atoms present in a molecule

Confirmation By comparison of spectra and melting point or boiling point.

© KNOCKHARDY PUBLISHING 2015

 Hybridisation 1

HYBRIDISATION IN CARBON

What happens?
2p 2p
2 2
2s 2s

1 1s 1 1s

The electronic configuration of If you provide energy you can promote

a carbon atom is 1s22s22p2 (lift) one of the s electrons into a p orbital.
The configuration is now 1s22s12p3

The process is favourable because of the arrangement of electrons;

four unpaired means less repulsion and therefore more stability.

sp3
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The four orbitals (an s and three p’s) combine or HYBRIDISE

to give four new orbitals. All four orbitals are equivalent.

In ALKANES, the four sp3 orbitals repel each other into

a tetrahedral arrangement.

sp2

Only three orbitals (an s and two p’s)

HYBRIDISE to give three new orbitals. All
three orbitals are equivalent. The remaining
2p orbital is unchanged.

In ALKENES, the three sp2 orbitals repel

each other into a planar arrangement and the
2p orbital lies at right angles to them
2 Hybridisation

Bond formation
in alkanes • Covalent bonds are formed by overlap of orbitals
• Each sp3 orbital from carbon overlaps with a hydrogen s orbital
• The resulting bond C-C bond is called a SIGMA (σ) bond
• The four σ bonds repel each other to give a tetrahedral shape

s orbital
of hydrogen

4 sp3 orbitals in carbon

Bond formation
in alkenes • An sp2 orbital from each carbon overlaps to form a single C-C bond

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The resulting bond is called a SIGMA (σ) bond.

The two 2p orbitals also overlap to form a

second bond. This is known as a PI (Π) bond.

For maximum overlap and hence the

strongest bond, the 2p orbitals are in line.

This gives rise to the PLANAR

arrangement around C=C bonds.
This gives RESTRICTED ROTATION.

To complete the structure of ethene, the

remaining sp2 orbitals overlap with four
hydrogen 1s orbitals to form four C-H bonds.
 Alkanes 1

ALKANES
General • a homologous series with general formula CnH2n+2 - non-cyclic only
• saturated hydrocarbons - all carbon-carbon bonding is single
• aliphatic - C atoms are in straight chains, branches or non-aromatic rings
• C-C and C-H bonds are called sigma (σ) bonds; formed by overlap of orbitals
• σ bonds can rotate freely
• bonds are spaced tetrahedrally about carbon atoms.

Isomerism • the first example of structural isomerism occurs with C4H10

• two structural isomers exist
CH 3
CH3 CH 2 CH2 CH3 CH3 CH CH3

butane 2-methylpropane

Q.1 Structural
Draw out and nameisomers haveisomers
the structural different
of Cphysical
5H12 and Cproperties
6H14.

Physical properties of alkanes

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Boiling point • increases as they get more carbon atoms in their formula
• the more atoms there are the greater the induced dipole-dipole interactions
• greater intermolecular force = more energy needed to separate the molecules
• the more energy required, the higher the boiling point

CH4 (-161°C) C2H6 (-88°C) C3H8 (-42°C) C4H10 (-0.5°C)

difference gets less - mass is increasing by a smaller percentage each time

• straight chains have larger surface areas giving greater molecular interaction
• branched molecules are more compact and have less intermolecular attraction
• the lower the intermolecular forces, the lower the boiling point

“The greater the branching, the lower the boiling point ”

CH 3
CH3 CH 2 CH2 CH3 CH3 CH CH3

b.p. - 0.5°C b.p. ______ °C

Q.2 Arrange the isomers of C5H12 in ascending boiling point order .

Melting point A general increase with molecular mass BUT not as regular as for boiling point.

Solubility Are non-polar so are immiscible with water but soluble in most organic solvents.

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2 Alkanes

CHEMICAL PROPERTIES OF ALKANES

Introduction • fairly unreactive - their old family name, paraffin, means little reactivity
• consist of relatively strong, almost non-polar covalent bonds
• have no real sites that will encourage substances to attack them

Combustion • alkanes make useful fuels - especially the lower members of the series
• combine with oxygen in an exothermic reaction

complete combustion CH4(g) + 2O2(g) ——> CO2(g) + 2H2O(l)

incomplete combustion CH4(g) + 1½O2(g) ——> CO(g) + 2H2O(l)

• the greater the number of carbon atoms, the more energy produced but...
• the greater the amount of oxygen needed for complete combustion.

Handy tip When balancing equations involving complete combustion, every carbon in the

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original hydrocarbon gives a carbon dioxide and every two hydrogens give a water
molecule. Put these numbers into the equation, count up the O and H atoms on
the RHS of the equation then balance the oxygen molecules on the LHS.

Q.3 • Write out the equation for the complete combustion of

butane

hexane

decane

• List uses of methane .............................................................................

propane .............................................................................
butane .............................................................................

Q.4 • Discuss the dangers of being over reliant on fossil fuels for providing energy.

• What alternative fuels are available?

• List any problems associated with an increase of CO2 in the atmosphere.

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 Alkanes 3

Pollution Processes involving combustion give rise to a variety of pollutants ...

power stations SO2 emissions produce acid rain
internal combustion engines CO, NOx and unburnt hydrocarbons

Q.5 What does the formula NOx stand for ?

Q.6 Why are the following classed as pollutants ?

• CO
PLATINUM, PALLADIUM, RHODIUM

• NOx

• unburnt hydrocarbons
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Removal SO2 react effluent gases with a suitable basic compound (e.g. CaO)
CO and NOx pass exhaust gases through a catalytic converter

Catalytic
converters In the catalytic converter ... CO is converted to CO2
NOx are converted to N2
Unburnt hydrocarbons to CO2 and H2O

e.g. 2NO + 2CO ——> N2 + 2CO2

• catalysts are made of finely divided rare metals

• leaded petrol must not pass through the catalyst as the lead deposits on the
catalyst’s surface and “poisons” it, thus blocking sites for reactions to take place.

Q.7 • Which metals are used in catalytic converters ?

• Why is the catalyst used in a finely divided form ?

© KNOCKHARDY PUBLISHING 2015

4 Alkanes

Breaking covalent bonds

There are three ways to split the shared pair of electrons in an unsymmetrical covalent bond.

UNEQUAL SPLITTING

X Y
+
+ Y
-
X

}
produce IONS

known as HETEROLYSIS or

X Y
-+ + HETEROLYTIC FISSION
X Y

EQUAL SPLITTING

X Y X + Y produces RADICALS

known as HOMOLYSIS or

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HOMOLYTIC FISSION

If several bonds are present the weakest bond is usually broken first.

• energy to break bonds can come from a variety of sources such as heat and light

• in the reaction between methane and chlorine either can be used but in the laboratory
a source of UV light (or sunlight) is favoured.

Q.8 Look up the strengths of the following bonds (in kJ mol -1)

348
C-C ................. 412
C-H ................. 242
Cl-Cl .................

Which of the bonds is most likely to break first ? Cl-Cl

...............

Free
Radicals • reactive species (atoms or groups) possessing an unpaired electron
• formed by homolytic fission (homolysis) of covalent bonds
• formed during the reaction between chlorine and methane
• formed during thermal cracking

© KNOCKHARDY PUBLISHING 2015

 Alkanes 5

Chlorination of methane

Reagents chlorine and methane

Conditions UV light or sunlight - heat could be used as an alternative energy source

Equation(s) CH4(g) + Cl2(g) ——> HCl(g) + CH3Cl(g) chloromethane

CH3Cl(g) + Cl2(g) ——> HCl(g) + CH2Cl2(l) dichloromethane

CH2Cl2(l) + Cl2(g) ——> HCl(g) + CHCl3(l) trichloromethane

CHCl3(l) + Cl2(g) ——> HCl(g) + CCl4(l) tetrachloromethane

Mixture • free radicals are very reactive as they are trying to pair up their unpaired electron
• if there is sufficient chlorine, every hydrogen will eventually be replaced.

Mechanism Mechanisms portray what chemists think is actually going on in the reaction,
whereas an equation tells you the ratio of products and reactants. The
chlorination of methane proceeds via a mechanism known as FREE RADICAL
SUBSTITUTION. It gets its name because the methane is attacked by free
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radicals resulting in a hydrogen atom being substituted by a chlorine atom.

The process is an example of a chain reaction. Notice how, in the propagation

step, one chlorine radical is produced for every one used up.

Steps Initiation Cl2 ——> 2Cl• radicals created

Propagation Cl• + CH4 ——> CH3• + HCl radicals used and

Cl2 + CH3• ——> CH3Cl + Cl• then re-generated

Termination Cl• + Cl• ——> Cl2 radicals removed

Cl• + CH3• ——> CH3Cl
CH3• + CH3• ——> C2H6

Q.9 Write out the two propagation steps involved in the conversion of CH3Cl into CH2Cl2.

Four chlorinated compounds can be produced from chlorine. State how many
different chlorinated compounds can be made from...

(i) ethane (ii) propane

© KNOCKHARDY PUBLISHING 2015

6 Alkanes

CRACKING

Process • involves the breaking of C-C (and C-H) bonds in alkanes

• converts heavy fractions into smaller, higher value products such as alkenes

• two types THERMAL Free radical mechanism

CATALYTIC Carbocation (carbonium ion) mechanism

THERMAL • HIGH PRESSURE ... 7000 kPa

• HIGH TEMPERATURE ... 400°C to 900°C
• FREE RADICAL MECHANISM
• HOMOLYTIC FISSION
• PRODUCES MOSTLY ALKENES e.g. ETHENE for making polymers / ethanol
• PRODUCES HYDROGEN used in the Haber Process / margarine manufacture

Examples Bonds can be broken anywhere by C-C bond fission or C-H bond fission

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H H H H H H H H H H H H
C-H
H C C C C H H C C C C H + H H C C C C + H2
fission H
H H H H H H H H H

A C-H bond breaks to The hydrogen radical abstracts another an alkene and
give a hydrogen radical hydrogen leaving two unpaired electrons on hydrogen are formed
and a butyl radical. adjacent carbon atoms. These join together to
form a second bond between the atoms.

C-C H H H H H H H H H H
fission +
H H
H C C C C H H C C C C H H C C H + C C
H H
H H H H H H H H H H

C-C bond breaks to One ethyl radical abstracts a hydrogen from the other, an alkene and an
give two ethyl radicals. thus forming ethane. The unpaired electrons on alkane are formed
adjacent carbons join together to form a second bond.

CATALYTIC • SLIGHT PRESSURE

• HIGH TEMPERATURE ... 450°C
• ZEOLITE (Crystalline aluminosilicates; clay like substances) CATALYST
• CARBOCATION (carbonium ion) MECHANISM
• HETEROLYTIC FISSION
• MAKES BRANCHED / CYCLIC ALKANES & AROMATIC HYDROCARBONS
• MOTOR FUELS ARE A PRODUCT

© KNOCKHARDY PUBLISHING 2015

 Alkanes 7

The Petrochemical Industry

Crude Oil In the past, most important organic chemicals were derived from coal. Nowadays,
natural gas and crude petroleum provide an alternative source.

• the composition of crude petroleum varies according to its source

• it is a dark coloured, viscous liquid
• consists mostly of alkanes with up to 40 carbon atoms +water, sulphur and sand
• can be split up into fractions by fractional distillation
• distillation separates the compounds according to their boiling point
• at each level a mixture of compounds in a similar boiling range is taken off
• rough fractions can then be distilled further to obtain narrower boiling ranges
• some fractions are more important - usually the lower boiling point ones
• high boiling fractions may be broken down into useful lower ones - CRACKING

Approximate C’s per Name of Use(s)

boiling range / °C molecule fraction

< 25 1-4 LPG (Liquefied Calor Gas

Petroleum Gas) Camping Gas
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40-100 6 - 12 GASOLINE Petrol

100-150 7 - 14 NAPHTHA Petrochemicals

150-200 11 - 15 KEROSINE Aviation Fuel

220-350 15 - 19 GAS OIL Central Heating Fuel

> 350 20 - 30 LUBRICATING OIL Lubrication Oil

> 400 30 - 40 FUEL OIL Power Station Fuel

Ship Fuel

> 400 40 - 50 WAX, GREASE Candles, Grease

for bearings

> 400 > 50 BITUMEN Road and roofing

surfaces

Q.10 Not all fractions are of equal importance. Why is this? What is done to get a
greater amount of the more useful products?

© KNOCKHARDY PUBLISHING 2015

 Alkenes 1

ALKENES
Structure • form a homologous series of general formula CnH2n - non cyclic alkenes only
• contain a carbon-carbon double bond somewhere in their structure
• unsaturated hydrocarbons - can still have atoms added to their formula

Naming • select the longest chain of C atoms containing the double bond; end in ENE

• number the chain starting from the end nearer the double bond;
use a number to indicate the FIRST carbon in the double bond.

• prefix with substituents. Side chain positions are based on the number allocated
to the first carbon in the double bond.

• if cis-trans isomerism exists, prefix with cis or trans

e.g. CH3 - CH = CH - CH2 - CH(CH3) - CH3 is called 5-methylhex-2-ene

ISOMERISM Two types of isomerism are found in alkenes.

Structural due to • different positions for the double bond but-1-ene and but-2-ene
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• branching. but-1-ene and 2-methylpropene

E/Z • due to restricted rotation of the carbon-carbon double bond

• single bonds can rotate so the groups around them are not ‘frozen’ in position
• double bonds can’t rotate freely, thus “freezing” groups on either side of C=C
• not all alkenes exhibit this type of isomerism
• if there are two H’s and two non-hydrogen groups attached to each carbon
it is called cis-trans isomerism

H CH2 CH3 CH 3 CH3 CH3 H

C C C C C C
H H H H CH3 H

but-1-ene (Z) cis but-2-ene 2-methylpropene

Z higher priority groups CH 3 H Priority of atoms / groups

on the same side of
the C=C bond. C C I > Br > Cl > F > C > H
E higher priority groups H CH 3
on opposite sides. C3H7 > C2H5 > CH3 > H
(E) trans but-2-ene

STRUCTURAL ISOMERS but-1-ene, but-2-ene and 2-methylpropene

E/Z or CIS-TRANS ISOMERS cis (Z) and trans (E) but-2-ene

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2 Alkenes

Q.1 Draw the structures of all the structural isomers of alkenes of formula C6 H12.
Name them and indicate those which exhibit E/Z (cis-trans) isomerism.

PHYSICAL PROPERTIES

Boiling
point • increases with molecular mass/size - increased induced dipole-dipole attractions
• for isomers the greater the degree of branching, the lower the boiling point

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• the lower members of the series are gases at rtp - cyclohexene is a liquid.

Solubility • non polar so they are insoluble in water but soluble in organic solvents.

CHEMICAL PROPERTIES

Theory • spacial arrangement around the C=C is planar

• the bond angles are 120°

Three of the four electrons of carbon sp2 hybridised and

the remaining electron exists in a 2p orbital at right-angles
to the three sp2 orbitals.

[ For more information, see notes on hybridisation ]

The 2p orbitals overlap to form a new pi (π) orbital; it exists

above and below the plane of the carbon-carbon bond.

• the main reaction of alkenes is ELECTROPHILIC ADDITION

• electrophiles are electron pair acceptors
• electrophiles are attracted to the electron rich carbon-carbon double bond.

© KNOCKHARDY PUBLISHING 2015

 Alkenes 3

ELECTROPHILIC ADDITION REACTIONS OF ALKENES

Addition
of HBr Reagent Hydrogen bromide; it is electrophilic because the H is slightly positive
Condition Room temperature.
Equation C2H4(g) + HBr(g) ———> C2H5Br(l) bromoethane
Mechanism

δ+ δ−
H Br
H H H H
H H
C C H C C H H C C H
H H
H H Br
Br

Step 1 As the HBr nears the alkene, one of the carbon-carbon bonds breaks and the
pair of electrons attaches to the slightly positive H end of H-Br. This is an example
of HETEROLYTIC FISSION. The HBr bond breaks to form a bromide ion.
A carbocation (positively charged carbon species) is formed.
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Step 2 The bromide ion behaves as a nucleophile and attacks the carbocation.

Overall there has been addition of HBr across the double bond.

Addition
of H2SO4 Reagent Concentrated sulphuric acid (85%).
Conditions 0°C
Equation C2H4(g) + H2SO4(conc) ——> C2H5OSO2OH(aq)
ethyl hydrogensulphate
Mechanism
H H H H
H H
C C H C C H H C C H
H H
δ+ δ−
H H OSO2OH
H OSO2OH
OSO2OH

Importance Hydrolysis - the product is made into ethanol by boiling with water.

C2H5OSO2OH(aq) + H2O(l) ——> H2SO4(aq) + C2H5OH(g) ethanol

Industrially Phosphoric acid (H3PO4) and steam are used

Ethanol can also be made by FERMENTATION SEE ALCOHOLS

© KNOCKHARDY PUBLISHING 2015

4 Alkenes

Addition
of Br2 Reagent Bromine. (Neat liquid or dissolved in tetrachloromethane, CCl4 )
Condition Room temperature. No catalyst or UV light required !
Equation C2H4(g) + Br2(g) ——> CH2BrCH2Br(l) 1,2 - dibromoethane

Mechanism
δ+ δ−
Br Br
H H H H
H H
C C H C C H H C C H
H H
Br Br Br
Br

It is surprising that bromine should act as an electrophile as it is non-polar.

Explanation ... Br

• as a bromine molecule approaches an alkene, electrons Br

in the pi bond of the alkene repel the electron pair in the
bromine-bromine bond thus inducing a dipole. π
C C
π

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Importance The addition of bromine dissolved in tetrachloromethane (CCl4) or water (known as
bromine water) is used as a test for unsaturation. If the reddish-brown colour is
removed from the bromine solution, the substance possesses a double C=C bond.

Electrophilic addition to propene

Problem • addition of HBr to propene gives two isomeric brominated compounds

• HBr is unsymmetrical and can add in two ways
• products are not formed to the same extent
• problem doesn't arise in ethene because it is symmetrical.

H H H H H H

Mechanism H C C C H H C C C H

δ+ δ− H H H Br H
H Br A Br
CH3 H
C C
H H B
H H H H H H

H C C C H H C C C H

H H H H Br
Br

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 Alkenes 5

Markownikoff’s Rule

Background The Russian scientist, Markownikoff, investigated the products of the addition of
hydrogen halides to alkenes. He found that, when two products were formed, one
was formed in a larger quantity. His original rule was based only on this reaction.
The up-to-date version of Markownikoff’s Rule uses carbocation stability as a
criterion for predicting the products.

It states that “In electrophilic addition to alkenes the major product

is formed via the more stable carbocation (carbonium ion) .“

In the above reaction, path A involves a 2° carbocation, path B a 1° carbocation.

As the 2° ion is more stable, the major product (i.e. 2-bromopropane) is formed via
that route.

H H C C
Carbocations /
Carbonium ions H C+ C C+ C C+ C C+
H H H C
methyl primary secondary tertiary

1° 2° 3°
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least stable methyl < 1° < 2° < 3° most stable

Theory Build up of charge in one place leads to instability. However, if it can be spread
around or neutralised in some way, the stability is increased. Alkyl groups are
electron releasing and can “push” electrons towards the carbocations thus
reducing the charge density.

Q.2 Draw the structures of the product(s) formed when HBr reacts with each of the
isomers of C4H8. If two products are formed, state which is the major product.

Q.3 Outline the mechanism for the reaction between propene and conc. H2SO4 .
Which alcohols are produced by hydrolysing the products ?

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6 Alkenes

OTHER ADDITION REACTIONS

Direct
Hydration Reagent steam (330°C) Bond enthalpies (kJ mol-1)

Conditions High Pressure (6MPa) O-H 463 H-Br 366

Catalyst - phosphoric acid
Product alcohol
Equation C2H4(g) + H2O(g) C2H5OH(g) ethanol
Use ethanol manufacture

Note O-H bonds are more polar than H-Br bonds yet the addition of H2O
requires a catalyst. An explanation is that O-H bonds are stronger so
more energy is needed to break them.

Hydrogenation Reagent hydrogen

Conditions nickel catalyst - finely divided
Product alkanes

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Equation C2H4(g) + H2(g) ——> C2H6(g) ethane
Use margarine manufacture

POLYMERISATION

Process • during polymerisation, an alkene undergoes an addition reaction with itself

• all the atoms in the original alkenes are used to form the polymer
• long hydrocarbon chains are formed
H H H H H H H H H H H H H H H H

C C C C C C C C C C C C C C C C

H H H H H H H H H H H H H H H H

• the equation shows the original monomer and the repeating unit in the polymer

H H
H H
n C C C C
H H
H H
n
ethene poly(ethene)
MONOMER POLYMER

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 Alkenes 7

POLYMERS

Preparation Many are prepared by a free radical process involving high pressure, high
temperature and a catalyst. The catalyst is usually a substance (an organic
peroxide) which readily breaks up to form radicals which initiate a chain reaction.

Another famous type of catalyst is a Ziegler-Natta catalyst (named after the

scientists who developed it). Such catalysts are based on the compound TiCl4.

Properties
Physical Can be varied by changing the reaction conditions (pressure, temperature etc).

Chemical Chemical properties are based on the functional groups within their structure.

e.g. poly(ethene) is typical; it is fairly inert as it is basically a very large alkane.

This means it is resistant to chemical attack and non-biodegradable.

Problems Although polymers derived from alkenes are invaluable to modern society, their
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disposal creates widespread problems.

• they are unreactive to most chemicals and bacteria (non-biodegradable)

• if they are just discarded they add to the landfill problem

recycling • high cost of collection and re-processing

• the different types of polymer have to be separated

burn waste • saves on landfill sites and produces energy

• toxic fumes (HCl) can be removed by ‘scrubbing’ from burning
chlorinated polymers such as poly(chloroethene)

feedstock • use the waste for the production of useful organic compounds
• new technology can convert waste into hydrocarbons
• hydrocarbons can then be turned back into polymers

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8 Alkenes

Q.4 Complete the details showing the formation and use of different polymers.

Polymer Formula of monomer Formula of polymer Use(s)

poly(ethene) n CH2=CH2 ——> — (CH2 — CH2)n —

poly(propene)

poly(chloroethene)

poly(phenylethene)

poly(tetrafluoroethene)

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poly(ethenyl ethanoate)

Q.5 Identify the monomer units in the following addition polymers.

© KNOCKHARDY PUBLISHING 2015

CIE Chemistry A Level

15 : Hydrocarbons
Notes

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Alkanes

Reactivity of alkanes
Alkanes are generally ​unreactive​. This is because alkanes are largely made up of ​C-C ​and ​C-H
covalent bonds which require a lot of energy to break.

Alkanes are also ​‘non polar’​ because there is only a very ​small difference in electronegativity
of the carbon and hydrogen atoms. This means alkanes are also generally not very reactive with
polar reagents​.

Combustion of alkanes
Complete combustion​ occurs in ​excess oxygen​. Complete combustion of alkanes produces
water and carbon dioxide. Examples of balanced combustion equations:

C​3​H​8​ + 5O​2​ → 3CO​2​ + 4H​2​O

2C​6​H​14​ + 19O​2​ → 12CO​2​ + 14H​2​O

Incomplete combustion​ of alkanes occurs when there is ​insufficient oxygen​. This leads to the
formation of water and various other products including, ​carbon particulates​, C, ​carbon
monoxide​, CO, and some ​carbon dioxide​, CO​2​. Examples of these reactions:

2C​3​H​8​ + 7O​2​ → 6CO + 8H​2​O

2C​2​H​6​ + 3O​2​ → 4C + 6H​2​O
4CH​4​ + 5O​2​ → 2CO + 8H​2​O + 2C

Substitution of alkanes
Alkanes can undergo ​substitution reactions with halogens​. This reaction only occurs in the
presence of ​ultraviolet light​.

A substitution takes place when a hydrogen atom is replaced by a halogen atom from a halogen
molecule (Cl​2 or
​ Br​2​). When this reaction takes place, a halogenoalkane is produced.
For example:
CH​4​ + Br​2​ → CH​3​Br + HBr
CH​3​CH​3​ + Cl​2​ → CH​3​CH​2​Cl + HCl

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Free radical substitution
When the substitution reaction above takes place, the mechanism is called ​free radical
substitution​. This mechanism requires a ​free radical​ (a particle with an​ unpaired electron​). A
free radical is denoted by having a dot next to the chemical symbol, e.g. Cl⠂. there are three
stages to free radical substitution: initiation, propagation and termination.

Example: The reaction of methane with chlorine

Initiation​ - ​Free radicals are produced. UV light is required to split the covalent bond in Cl​2​ and
form two chlorine atoms each with an unpaired electron (free radicals):
Cl​2​ → 2Cl⠂
Propagation​ - The free radicals are used up and recreated in chain reactions:
Cl⠂+ CH​4​ → CH​3​⠂+ HCl
A methyl radical, CH​3​⠂, is produced which reacts with Cl​2​ to produce more radicals.
CH​3​⠂+ Cl​2​ → CH​3​Cl + Cl⠂
These reactions continually occur in a chain until the termination stage.
Termination​ - All the free radicals are completely used up. When two radicals react, they form a
covalent bond. Several termination reactions can take place:
Cl⠂+ CH​3​⠂ → CH​3​Cl
Cl⠂+ Cl⠂→ Cl​2
CH​3​⠂+ CH​3​⠂→ C​2​H​6

Crude oil
Crude oil is ​unrefined petroleum​ found in the ground. It contains a ​mixture of hydrocarbons​.
Crude oil isn’t very useful unless it is ​separated​ into the different hydrocarbon fractions by
fractional distillation.

The process of ​fractional distillation​:

1. The crude oil is vaporised.
2. The crude oil vapours are placed into the fractionating column. The column has a
temperature gradient where it is hotter at the bottom and cooler at the top.
3. The vapours rise up the column. Different hydrocarbon vapours have different boiling points
so they condense at different temperatures. The separated liquid hydrocarbons leave the
column.
4. The largest hydrocarbons have higher boiling points, so they are rarely vaporised. They run
off the bottom as a sticky residue.

Crude oil is a source of ​aliphatic and aromatic hydrocarbons​. Aliphatic hydrocarbons are
straight chain hydrocarbons (e.g. alkanes and alkenes). Aromatic hydrocarbons contain at least
one benzene ring.

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Cracking
Shorter alkane chains​ are ​more in demand​ than the heavier fractions. Large fractions can be
cracked (broken down) into smaller alkanes and alkenes.
There are two types of cracking:

Thermal cracking
● High temperatures (around 1000​o​C).
● High pressures (around 70 atm)
● Produces lots of alkenes

Catalytic cracking
● Zeolite catalyst
● Slight pressure
● High temperature (around 450​o​C)
● Produces mostly aromatic hydrocarbons and motor fuels

Examples of cracking
C​10​H​22​ → C​5​H​12​ + C​5​H​10
C​15​H​32​ → 2C​2​H​4​ + C​3​H​6​ + C​8​H​18
Decane → ethene + octane

Alkenes
Alkenes are ​unsaturated​ hydrocarbons. This means they contain at least one ​C=C ​double bond.

Chemistry of alkenes

Addition
Alkenes undergo addition reactions because they contain at least one C=C double bond. This is
when​ two compounds combine to form a larger compound​.
Alkenes can undergo addition with different compounds:
- Halogens
- Hydrogen halides
- Hydrogen
- Water (in the form of steam)

Addition with halogens:

When alkenes react with halogens, covalent bonds form between the halogen atoms and the
corbons on either side of the double bond, producing a di-halogenoalkane. The mechanism is
called electrophilic addition and can be seen in ‘Electrophilic addition’ on the following page.
Addition with hydrogen halides:
A hydrogen halide is polar due to the difference in electronegativity between hydrogen and the
much more electronegative halogen atom. This polarity means both the hydrogen and the halide
bond to carbon atoms in the alkene, forming a halogenoalkane.

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Addition with hydrogen:
Alkenes undergo hydrogenation when they react with hydrogen. The C=C double bond opens up to
form covalent bonds with the new hydrogen atoms. The reaction requires excess hydrogen, a
temperature of around 150​o​C and a nickel catalyst.
CH​2​CH​2​ + H​2​ → CH​3​CH​3
Addition with steam:
Alkenes are hydrated when they react with steam to form alcohols. This requires an acid catalyst
such as phosphorus acid or sulfuric acid.
CH​2​CH​2​ + H​2​O → CH​3​CH​2​OH
When steam reacts with propene, according to Markovnikov’s rule of addition, the OH group joins
to the carbon atom in the double bond which is directly bonded to the most carbons atoms. This
can be seen in the equation below:
CH​3​CHCH​2​ + H​2​O → CH​3​C(OH)CH​3
Using Markovnikov’s rule, propan-2-ol is the major product and propan-1-ol is the minor product.
The reaction will mostly produce propan-2-ol.

Oxidation
Cold, dilute acidified manganate(VII) ions
Potassium manganate(VII) contains manganate(VII) ions meaning it is a strong oxidising agent.
Manganate(VII) ions can oxidise alkenes to form diols (alkane with two alcohol groups). For this
reaction to take place, the manganate ions must be cold, dilute and acidified.
In the reaction below, [O] denotes the oxidising agent:
CH​2​CH​2​ + H​2​O + [O] → CH​2​(OH)CH​2​(OH)

During this reaction, the purple solution will decolourise.

Hot, concentrated acidified manganate(VII) ions

When an alkene reacts with hot, concentrated, acidified manganate(VII) ions the C=C double bond,
ruptures. The manganate(VII) ions oxidise the alkene by breaking the C=C bond and replacing it
with a C=O double bond on each new molecule. Further reactions then take place, depending on
the groups attached to the carbons:

- If both the R groups in the product are alkyl groups then a ​ketone​ will form. Ketones are not
easily oxidised so ​no further oxidation​ takes place.
- If a product has one alkyl group and one hydrogen then an ​aldehyde​ will be produced.
Aldehydes are ​easily oxidised​ to carboxylic acids meaning that the final product will be a
carboxylic acid​.
- If both R groups in the product are hydrogen atoms, methanal will be formed. This is
oxidised to ​methanoic acid ​which is then oxidised to form ​water and carbon dioxide​.

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Polymerisation
Alkenes​ can undergo ​addition polymerisation.​ In this reaction, many ​alkene monomers​ join
together to form a ​polymer.​ Alkenes are able to react and form polymers because their ​C=C
double bonds can open up​, allowing the carbons to join together. The polymers produced are
saturated because they do not contain any carbon-carbon double bonds. Further details about
addition polymerisation can be seen through the examples of ​poly(ethene) ​and ​PVC​ in
‘Characteristics of addition polymerisation’.

Electrophilic addition
Mechanism for Br​2​ and ethene

The ​electron dense double bond​ in ethene causes an ​uneven distribution of electrons in Br​2​.
This causes a difference in charge between the two bromine atoms (dipoles form). The electron
pair in the double bond attracts the ​Br​δ+​, forming a covalent bond between carbon and a bromine
atom. This produces a positively charged ​carbocation intermediate​ which attracts the ​negatively
charged bromide ion​. Dibromoethane is produced.

Mechanism for HBr and propene

Hydrogen bromide​ is ​polar​ due to the difference in the electronegativities of hydrogen and
bromine. The ​electron pair​ in the double bond attracts ​Hδ+​
​ , forming a covalent bond between
carbon and hydrogen. This produces a positively charged ​carbocation intermediate​ which
attracts the negatively charged bromide ion. According to ​Markovnikov’s rule​, the hydrogen joins
to the carbon atom which is bonded to the most hydrogen atoms. The bromide ion bonds to the
carbon atom which is joined to the most carbon atoms. This is why ​2-bromopropane ​forms more
often than 1-bromopropane.

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Inductive effects of alkyl groups
When a hydrogen halide bonds to an ​unsymmetrical alkene​, there are two possible products. The
quantities of each product produced depends on how ​stable​ the ​carbocation intermediate​ is.
Carbocations with ​more alkyl groups are more stable​. This is because alkyl groups have a
positive inductive effect​ on the carbon atom and feed electrons towards the positive charge. The
more stable carbocation
is more likely to form so
there will be higher
quantities of this
product. It is often
referred to as the ​major
product.

Characteristics of addition polymerisation

Addition polymers​ are very ​unreactive​. This is because the polyalkene chains are ​saturated​ and
the main carbon chain is ​non-polar.

The chains are held together by ​van der Waals ​forces since there is generally no polarity in the
main carbon chain. Polymers made up of ​straight chains are strong and rigid​ because the
chains are able to ​lie closer​ together and so there are more points of contact and stronger ​van der
Waals forces​. Polymers made up of branched chains are usually weaker by comparison

Poly(ethene)
Poly(ethene) is produced from the addition polymerisation of ​ethene​. During this reaction, lots of
ethene monomers​ join together to produce one long chain polymer product.

For the equation above, the ​‘n’​ denotes a ​large number of units​ reacting together to form a chain
with this unit length.

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Poly(chloroethene) (PVC)
Poly(chloroethene), otherwise known as PVC, is produced from the addition polymerisation of
chloroethene​. Chloroethene is the ​monomer​ which forms the polymer poly(chloroethene).

Repeat units
Repeat units are the ​section of polymer which repeats ​throughout the whole chain. They can be
easily drawn as they look the same except that the double carbon-carbon bond is drawn as a
single bond and single bonds are drawn coming out the sides of each carbon atom:

Repeat unit of poly(ethene): Repeat unit of PVC:

Disposal of polymers
Polymers produced by addition polymerisation cause problems when it comes to disposal. This is
because they are ​not biodegradable​.
This means many polymers have to be ​incinerated​ or put into ​landfill​, both of which have issues
associated with them.
Landfill​ takes up a lot of land which could otherwise be used as ​habitats for wildlife​. It is also
unattractive​.
Incineration​ of polymers ​release harmful gases like carbon dioxide and HCl ​(if the polymer
contains chlorine) during combustion. However, the incineration of polymers produces a lot of
energy which can be used to generate electricity.

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Hydrocarbons as fuels

Combustion of alkanes
Alkanes make ​good fuels​ because they release ​huge amounts of energy​ when burnt. They are
also relatively readily ​available​, they ​burn cleanly​ in excess oxygen and are ​easy to transport​.
Alkanes are used as fuels in industry, cars and in the home.

However, the combustion of alkanes produces a ​variety of pollutants​.

Carbon monoxide
When a hydrocarbon is combusted in a limited supply of oxygen, ​incomplete combustion​ occurs
which can produce carbon monoxide. For example:
2C​5​H​12​ + 11O​2​ → 10CO + 12H​2​O
Carbon monoxide is a ​toxic colourless and odourless gas​. It binds haemoglobin molecules in
red blood cells (to the same sites as oxygen),​ preventing oxygen being transported​ around the
body. This can ​kill​ people if they too much is inhaled.

Oxides of nitrogen
Oxides of nitrogen are formed when nitrogen and oxygen react in a ​car engine​ due to the high
pressure and temperature. Oxides of nitrogen react with unburnt hydrocarbons to produce ​ground
level ozone​ (see ‘Unburnt hydrocarbons’ below).
Oxides of nitrogen can lead to ​acid rain​. This occurs when nitrogen oxides react with oxygen and
water vapour in clouds. Acid rain causes various problems, including:
- Acidification of lakes ​and ​rivers​ (kills aquatic life)
- Destruction of ​vegetation​.
- Damage to ​limestone buildings​.

Oxides of nitrogen can be removed from car exhaust fumes with ​catalytic converters​. Catalytic
converters contain a ceramic honeycomb structure which is coated in a thin layer of metal catalysts
like ​rhodium​ and ​platinum​. This creates a ​larger surface area​ of metal. Catalytic converters
catalyse the reaction between carbon monoxide with nitrogen monoxide (harmful gases) to
produce nitrogen and carbon dioxide.
2NO + 2CO → N​2​ + 2CO​2

Unburnt hydrocarbons
Unburnt hydrocarbons are released when ​engines don’t completely burn all the fuel molecules​.
These hydrocarbons and oxides of nitrogen react in the​ presence of sunlight​ to form O​3​, ​ground
level ozone​. This is an ​irritant​ to people’s eyes and causes ​respiratory problems​. It can
ultimately cause ​lung damage​.

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Greenhouse gases
Greenhouse gases include ​carbon dioxide​, ​methane​ and ​water vapour​.

The greenhouse effect

● Electromagnetic radiation​ from the sun passes through the Earth’s atmosphere.
● The Earth ​absorbs some radiation​ and warms up.
● Heat is radiated from the Earth as ​infrared radiation.
● Some of the ​infrared radiation is absorbed by greenhouse gases​ in the atmosphere
which warms the atmosphere.

Infra-red spectroscopy to monitor air pollution

Infra-red spectroscopy ​identifies particular bonds ​within​ ​molecules. Different polluting gases
contain different bonds so they will have a ​different infra-red spectrum​. This can be used to
identify which gases are in the air. It is then possible to measure the ​concentration of each
pollutant​. This can be recorded over a period of time to monitor the changes in air pollution.

Arenes ​(A Level only)

Arenes are aromatic hydrocarbons.

Substitution
Aromatic hydrocarbons, such as benzene, are able to undergo ​electrophilic substitution​.
Benzene’s ​delocalised electron system​ makes it a very ​stable​ molecule. Benzene is highly
attractive to electrophiles​ because of the high electron density in the benzene ring. Electrophiles
can be a positive ion or a positive end of a polar molecule. When the reaction takes place, the
delocalised electron system remains in the compound and one of the ​hydrogen atoms swaps
places with the electrophile​. Various different types of substitution reactions can take place:

Substitution with chlorine

The reaction of benzene with chlorine requires an ​aluminium chloride catalyst​.
C​6​H​6​ + Cl​2​ → C​6​H​5​Cl + HCl
The mechanism for the electrophilic substitution reaction:

Stage 1: The aluminium chloride catalyst generates the electrophile from chlorine.
Cl​2​ + AlCl​3​ → AlCl​4​-​ + Cl​+
Stage 2: The electrophile reacts with the benzene molecule.

Stage 3: The hydrogen ion reacts with the AlCl​4​-​, reforming the AlCl​3​ catalyst.
AlCl​4​-​ + H​+​ → AlCl​3​ + HCl

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Substitution - nitration
The reaction of benzene to form nitrobenzene requires a mixture of ​concentrated nitric acid and
concentrated sulfuric acid to generate the electrophile​.

Stage 1: The electrophile is generated from concentrated nitric acid and concentrated sulfuric acid.
H​2​SO​4​+ HNO​3​ → H​2​O + NO​2​+​ + HSO​4​-
Stage 2: The NO​2​+​ electrophile reacts with the benzene molecule in electrophilic substitution.

Stage 3: The hydrogen ion reacts with the HSO​4​-​, reforming the H​2​SO​4​ catalyst.
H​+​ + HSO​4​-​ → H​2​SO​4

Acylation
Acylation of benzene involves the ​substitution of an acyl group​. This reaction takes place when
benzene is reacted with ​ethanoyl chloride​ in the presence of an ​aluminium chloride catalyst.
Stage 1: The electrophile is generated from ethanoyl chloride and aluminium chloride.
CH​3​COCl + AlCl​3​ → AlCl​4​-​ + CH​3​CO​+
Stage 2: The CH​3​CO​+​ electrophile reacts with the benzene molecule.
CH​3​CO​+​ + C​6​H​6​ → C​6​H​5​COCH​3​ + H​+
Stage 3: The aluminium chloride catalyst is regenerated.
H​+​ + AlCl​4​-​ → AlCl​3​ + HCl
Alkylation
Alkylation of benzene involves the ​substitution of an alkyl group​. The reaction occurs in the
same way as the acylation reaction takes place above. It requires a ​halogenoalkane ​as a reactant
as they contain a ​polar bond​ between the carbon and halogen.

Stage 1: CH​3​Cl + AlCl​3​ → AlCl​4​-​ + CH​3​+

Stage 2: CH​3​+​ + C​6​H​6​ → C​6​H​5​CH​3​ + H​+
Stage 3: H​+​ + AlCl​4​-​ → AlCl​3​ + HCl

Complete oxidation of side chains

If an alkyl group is attached to benzene, it can be easily oxidised to form benzoic acid. They can be
oxidised using the oxidising agent, ​potassium manganate(VII)​.

Hydrogenation
Hydrogenation takes place when ​hydrogen atoms are added all around the benzene ring​,
removing the delocalised electron system. A ​cycloalkane​ is formed as the product. The reaction is

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carried out with hydrogen, in the presence of a ​nickel catalyst​. A temperature around ​150​o​C​ is
required.

Difference in reactivity between chlorobenzene and chloroalkane

Chlorobenzene is much less reactive than chloroalkane.​ This is because the C-Cl bond in
chlorobenzene is much stronger than in an halogenoalkane.​ The aromatic C-Cl bond is stronger
due to one of the lone pairs on the chlorine atom interacting with the delocalised electron system,
strengthening the bond. For reactions, like nucleophilic substitution, the C-Cl bond would require
breaking. Since the chlorobenzene bond requires more energy to break, chlorobenzene is less
reactive.

Halogenation ​(A Level only)

When a halogen reacts with methylbenzene, two possible reactions can take place depending on
the conditions. The halogen can bond to the benzene ring or the methyl group.

Substitution in the benzene ring

This reaction happens in the presence of ​aluminium chloride​ and in the ​absence of UV light.

Substitution in the methyl group

This reaction happens in the ​presence of UV light​, without a catalyst.

The reaction can ​continue to undergo substitution​ so that all the hydrogen atoms on the methyl
group are replaced by chlorine atoms, forming C​6​H​5​CCl​3​.

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 Halogenoalkanes 1

HALOALKANES (HALOGENOALKANES)
Structure Contain the functional group C-X where X is a halogen (F, Cl, Br or I)

Types Haloalkanes - halogen is attached to an aliphatic skeleton - alkyl group

Haloarenes - halogen is attached directly to a benzene (aromatic) ring

Classification Classified according to what is attached to the functional group.

H H C C
H C X C C X C C X C C X
H H H C
methyl primary secondary tertiary

1° 2° 3°

Names Based on the original alkane with a prefix indicating halogens and their position.
Knockhardy Publishing

CH3CH2CH2Cl 1-chloropropane CH2ClCHClCH3 1,2-dichloropropane

CH3CHClCH3 2-chloropropane CH3CBr(CH3)CH3 2-bromo-2-methylpropane

Q.1 Draw and name all the structural isomers of C3H6Br2, C4H9Cl and C5H11Br.

Q.2 Classify the structural isomers of C4H9Cl and C5H11Br as 1°, 2° or 3°.

Physical properties

Boiling
points • boiling point increases with mass
• for isomeric compounds the greater the branching, the lower the boiling point

Solubility • haloalkanes are soluble in organic solvents but insoluble in water - they
are not polar enough and don’t exhibit hydrogen bonding.

© KNOCKHARDY PUBLISHING 2015

2 Halogenoalkanes

NUCLEOPHILIC SUBSTITUTION REACTIONS

Theory • halogens have a greater electronegativity than carbon δ+ δ−

• a dipole is induced in the C-X bond and it becomes polar C Br
• the carbon is thus open to attack by nucleophiles polarity in a C-Br bond

Nucleophiles • examples are OH¯, CN¯, NH3 and H2O

• possess at least one LONE PAIR of electrons
• are attracted to the slightly positive (electron deficient) carbon

Basic
mechanism • the nucleophile uses its lone pair to provide the electrons for a new bond
• as carbon can only have 8 electrons in its outer shell a halide ion is displaced
• the result is substitution following attack by a nucleophile
• the mechanism is therefore known as - NUCLEOPHILIC SUBSTITUTION

Nu:-

Knockhardy Publishing
H H H H
-

: :
H C C Br H C C Nu + : Br:

H H H H

Rate of
reaction • the rate of reaction depends on the strength not the polarity of the C-X bond

C-I 238 kJmol-1

........... least polar
276 kJmol-1 WEAKEST BOND
C-Br ...........
338 EASIEST TO BREAK
C-Cl ........... kJmol-1 FASTEST REACTION
484 kJmol-1 most polar
C-F ...........

Practical
investigation The time taken for a precipitate of silver halide is measured. The faster the
precipitate forms, the faster the hydrolysis and the weaker the C-X bond.

• warm equal amounts of each haloalkane in a water bath

• add a solution of ethanol, water and aqueous silver nitrate to each
• record the time it takes for a precipitate to appear

AgCl - white AgBr - cream AgI - yellow (AgF is soluble)

© KNOCKHARDY PUBLISHING 2015

 Halogenoalkanes 3

ˆNaOH Reagent AQUEOUS sodium (or potassium) hydroxide

Conditions Reflux in aqueous solution (SOLVENT IS IMPORTANT)
Product Alcohol
Nucleophile hydroxide ion (OH¯)

Equation e.g. C2H5Br(l) + NaOH(aq) ——> C2H5OH(l) + NaBr(aq)

Mechanism

-
: :

HO: H H H H
-

: :

: :
H C C Br H C C OH + : Br:

H H H H

WARNING It is important to quote the solvent when answering questions.

Elimination takes place when ethanol is the solvent.

This reaction (and the one with water) is sometimes known as HYDROLYSIS
Knockhardy Publishing

H2O • A similar reaction to the above but SLOWER because...

a) the liquids are immiscible - less chance of molecules colliding
b) water is a poor nucleophile

• faster reaction in an alcohol/water mixture; miscible = more collisions

Equation e.g. C2H5Br(l) + H2O(l) ——> C2H5OH(aq/alc) + HBr(aq)

AgNO3 Used to identify the halide in a haloalkane - see above

(aq/alc)

Q.3 Write equations for the reactions of hot, aqueous NaOH with...

a) CH3CH2CH2 Br

b) CH3CHBrCH2CH3

c) (CH3)3CBr

Advanced This form of nucleophilic substitution discussed so far is known as SN2; it is a bimolecular
work process. An alternative method involves the initial breaking of the C-X bond to form a
carbocation, or carbonium ion, (a unimolecular process - SN1 mechanism), which is then
attacked by the nucleophile. SN1 is favoured for tertiary haloalkanes where there is steric
hindrance to the attack and a more stable tertiary, 3°, carbocation intermediate is formed.

© KNOCKHARDY PUBLISHING 2015

4 Halogenoalkanes

KCN Reagent Aqueous, alcoholic potassium (or sodium) cyanide

Conditions Reflux in aqueous, alcoholic solution
Product Nitrile (cyanide)
Nucleophile cyanide ion (CN¯)

Equation C2H5Br + KCN(aq/alc) ——> C2H5CN + KBr

Mechanism

N C :- H H H H
-

: :
H C C Br H C C CN + : Br:

H H H H

Importance extends the carbon chain by one carbon atom as the CN

group can then be converted to carboxylic acids or amines

Hydrolysis C2H5CN + 2H2O ——> C2H5COOH + NH3

Reduction C2H5CN + 4[H] ——> C2H5CH2NH2

Knockhardy Publishing
NH3 Reagent Aqueous, alcoholic ammonia (in EXCESS)
Conditions Reflux in aqueous, alcoholic solution under pressure
Product Amine (or its salt due to a reaction with the acid produced)
Nucleophile Ammonia (NH3)

Equation C2H5Br + NH3 (aq/alc) ——> C2H5NH2 + HBr

HBr + NH3(aq/alc) ——> NH4Br

C2H5Br + 2NH3(aq/alc) ——> C2H5NH2 + NH4Br

Mechanism

H
H N:
H H H H H H
H H
+ -
: :

H C C Br H C C N H + : Br: H C C N H2 + HBr
H
H H H H H H

Why the excess ammonia?

The second ammonia molecule ensures the removal of HBr which would lead to
the formation of a salt.

A large excess of ammonia ensures further substitution doesn’t take place

© KNOCKHARDY PUBLISHING 2015

 Halogenoalkanes 5

Problem The amine produced is also a nucleophile (lone pair on the N) and can attack
another molecule of haloalkane to produce a 2° amine. This in turn is a
nucleophile and can react further producing a 3° amine and, eventually an ionic
quarternary ammonium salt.

C2H5NH2 + C2H5Br —> HBr + (C2H5)2NH diethylamine, a 2° amine

(C2H5)2NH + C2H5Br —> HBr + (C2H5)3N triethylamine, a 3° amine

(C2H5)3N + C2H5Br —> (C2H5)4N+ Br¯ tetraethylammonium bromide,

(a 4° salt)

OTHER REACTIONS OF HALOALKANES

Friedel Crafts
alkylation substitutes an alkyl (e.g. methyl, ethyl) group onto a benzene ring

reagents a haloalkane (RX) and anhydrous aluminium chloride AlCl3

conditions room temperature; dry inert solvent (ether)
Knockhardy Publishing

mechanism electrophilic substitution

electrophile a carbocation ion R+ (e.g. CH3+)
AlCl3
equation C2H5Br + C6H6 ——> C6H5C2H5 + HBr

see notes on benzene

Preparation of haloalkanes - Summary

(details can be found in other sections)

From

alkanes CH4 + Cl2 —> CH3Cl + HCl Free radical substitution / UV light

alkenes C2H4 + HBr —> C2H5Br Electrophilic addition / no catalyst or UV

alcohols C2H5OH + HBr —> C2H5Br + H2O Protonation of alcohol with acid catalyst

© KNOCKHARDY PUBLISHING 2015

6 Halogenoalkanes

USES OF HALOALKANES

Synthetic The reactivity of the C-X bond means that haloalkanes play an important part in
synthetic organic chemistry. The halogen can be replaced by a variety of groups
via a nucleophilic substitution mechanism.

During the manufacture of ibuprofen, substitution of a bromine atom takes place.

Monomers chloroethene CH2 = CHCl tetrafluoroethene CF2 = CF2

Polymers poly(chloroethene) PVC —(CH2 — CHCl)n— packaging

poly(tetrafluoroethene) PTFE —(CF2 — CF2)n— non-stick surfaces

CFC’s dichlorofluoromethane CHFCl2 refrigerant

trichlorofluoromethane CF3Cl aerosol propellant
blowing agent

bromochlorodifluoromethane CBrClF2 fire extinguishers

CCl2FCClF2 dry cleaning solvent

Knockhardy Publishing
degreasing agent

All the above were chosen because of their... • low reactivity

• volatility
• non-toxicity

PROBLEMS WITH CFC’s

Ozone layer • CFC’s have been blamed for environmental damage by thinning the ozone layer
• Ozone absorbs a lot of harmful UV radiation
• CFC’s break up in the atmosphere to form free radicals
CF2Cl2 ——> •CF2Cl + •Cl

• free radicals catalyse ozone decomposition e.g. •Cl + O3 ——> •ClO + O2

•ClO + O ——> •Cl + O2
• overall 2O3 ——> 3O2

Solution • CFC’s were designed by chemists to help people

• chemists now synthesise alternatives to CFC’s to protect the environment
such as hydrocarbons and HCFC’s
• CO2 can be use as an alternative blowing agent
• this will allow the reversal of the ozone layer problem

© KNOCKHARDY PUBLISHING 2015

 Halogenoalkanes 7

ELIMINATION REACTIONS OF HALOALKANES

Problem The products of reactions between haloalkanes and OH¯ are influenced by the
solvent. Both mechanisms take place simultaneously but the choice of solvent
favours one route.

Solvent Product Action of OH¯ Mechanism

WATER ALCOHOL NUCLEOPHILE SUBSTITUTION

ALCOHOL ALKENE BASE ELIMINATION

Reaction Reagent Alcoholic sodium (or potassium) hydroxide

Conditions Reflux in alcoholic solution
Product Alkene
Mechanism Elimination

Equation C3H7Br + NaOH(alc) ——> C3H6 + H2O + NaBr

Mechanism
Knockhardy Publishing

HO:-
: :

H H H H
δ+ δ− -

:
CH3 C C Br C C + H2O + : Br:

:
CH3 H
H H

• the OH¯ ion acts as a base and picks up a proton

• the proton comes from a carbon atom next to the one bonded to the halogen
• the electron pair left moves to form a second bond between the carbon atoms
• the halide ion is displaced
• overall there is ELIMINATION of HBr.

Q.4 What organic products are formed when concurrent substitution and elimination
takes place with CH3CHBrCH3 ?

Complication The OH¯ removes a proton from a carbon atom adjacent the C bearing the
halogen. If there had been another carbon atom on the other side of the C-X, its
hydrogen(s) would also be open to attack. If the haloalkane is unsymmetrical
(e.g. 2-bromobutane) a mixture of isomeric alkene products is obtained.

Q.5 What organic products do you get with alcoholic NaOH and CH3CHBrCH2CH3 ?
Explain your answers with a mechanism.

© KNOCKHARDY PUBLISHING 2015

 Alcohols 1

ALCOHOLS

Aliphatic • general formula CnH2n+1OH - provided there are no rings

• named as substituted alkanes by removing the final -e and adding -ol
• for isomers the position of the OH is given a number - propan-1-ol / propan-2-ol

Aromatic • the OH must be attached directly to a benzene ring; known as phenols

• an OH on a side chain of a benzene ring behaves as a typical aliphatic alcohol.

OH CH3 CH2OH
OH
Q.1 Which of the structures is/are
classified as phenols?

Structures • alcohols are classified according to the environment of the OH functional group
• chemical behaviour, especially with oxidation, often depends on the structure

H H C C
H C OH C C OH C C OH C C OH
H H H C
methyl primary secondary tertiary
Knockhardy Publishing

1° 2° 3°

Physical properties
Boiling point Increases with molecular size due to higher induced dipole-dipole interactions.
Alcohols have higher boiling points than similar molecular mass alkanes due to
the added presence of inter-molecular hydrogen bonding. More energy is
required to separate the molecules.
C
Mr bp / °C C
ethanol C2H5OH 46 +78 O
O H
propane C3H8 44 -42
H
intermolecular hydrogen
bonding in alcohols
Boiling point also increases for “straight” chain isomers.
Greater branching = lower inter-molecular forces.

bp / °C
butan-1-ol CH3CH2CH2CH2OH 118
butan-2-ol CH3CH2CH(OH)CH3 100
2-methylpropan-2-ol (CH3)3COH 83

H
Solubility Low molecular mass alcohols are miscible with water C
O
due to hydrogen bonding between the two molecules. O H
H
Alcohols are themselves very good solvents, being able
intermolecular hydrogen
to dissolve a large number of organic molecules.
bonding with water

© KNOCKHARDY PUBLISHING 2015

2 Alcohols

PREPARATION OF ALCOHOLS

Laboratory • from haloalkanes - reflux with aqueous sodium or potassium hydroxide.

• from aldehydes - reduction with sodium tetrahydridoborate(III) - NaBH4.
• from alkenes - acid catalysed hydration using conc. sulphuric acid.

Industrial Fermentation
Reagent(s) GLUCOSE - from hydrolysis of starch
Conditions yeast
warm but no higher than 37°C
Equation C6H12O6 ——> 2 C2H5OH + 2 CO2

Direct hydration
Reagent(s) ETHENE - from cracking of fractions from distilled crude oil
Conditions • catalyst - phosphoric acid
• high temperature and pressure

Knockhardy Publishing
Equation C2H4 + H2O C2H5OH

Q.2 List some advantages and disadvantages of the two major industrial methods.

Fermentation advantage(s) • CHEAP EQUIPMENT

• MADE FROM RENEWABLE RESOURCES - SUGARS

disadvantage(s) • SLOW REACTION

• IMPURE PRODUCT
• BATCH PROCESS - EXPENSIVE ON MANPOWER

Hydration advantage(s) • FAST REACTION

• CONTINUOUS PROCESS - CHEAPER MANPOWER
• PURE PRODUCT

disadvantage(s) • MADE FROM A NON-RENEWABLE RESOURCE - OIL

• EXPENSIVE EQUIPMENT

Uses ethanol •
•
•

methanol • fuel, added to petrol to improve combustion properties

• solvent
• a feedstock for important industrial processes

© KNOCKHARDY PUBLISHING 2015

 Alcohols 3

CHEMICAL PROPERTIES

General Lone pairs on the oxygen atom makes alcohols Lewis Bases (lone pair donors).
They can use a lone pair to • pick up protons
• behave as nucleophiles.

Elimination Reagent conc. sulphuric acid (H2SO4) or conc. phosphoric acid (H3PO4)
Conditions reflux 180°C
Product alkene
Equation e.g. C2H5OH(l) ———> CH2 = CH2(g) + H2O(l)
Mechanism

H H H H H H
H H
HO HO
H C C H C C H2O H C C H C C H
H H H H
H H H H H

Step 1 protonation of the alcohol using a lone pair on oxygen

Step 2 loss of a water molecule to generate a carbocation
Step 3 loss of a proton (H+) to give the alkene
Knockhardy Publishing

H H
Note 1 There must be a hydrogen atom on a carbon HO
atom adjacent the carbon with the OH on it C C

H H

Note 2 Alcohols with the OH in the middle of a chain

H H
have two ways of losing water. In Step 3 of the
mechanism, a proton can be lost from either side C C C
H
of the carbocation. This can give a mixture of H H

alkenes from unsymmetrical alcohols

Elimination
Method 2 Conditions Pass vapour over a heated catalyst of pumice or aluminium oxide

Q.3 Butan-2-ol reacts with concentrated sulphuric acid to give THREE isomeric alkenes.
What are they and how are they formed?

© KNOCKHARDY PUBLISHING 2015

4 Alcohols

Oxidation of Alcohols

Provides a way of differentiating between primary, secondary and tertiary alcohols.

Reagents include acidified potassium dichromate(VI) or potassium manganate(VII)

Primary Easily oxidised to aldehydes and then to carboxylic acids.

e.g. CH3CH2OH(l) + [O] ——> CH3CHO(l) + H2O(l)

then CH3CHO(l) + [O] ——> CH3COOH(l)

• it is essential to distil off the aldehyde before it gets oxidised to the acid
• the alcohol is dripped into a warm solution of acidified K2Cr2O7
• the aldehyde has a low boiling point - no hydrogen bonding - it distils off
• if it didn’t distil off it would be oxidised to the equivalent carboxylic acid
• to oxidise an alcohol straight to the acid you would reflux the mixture

Knockhardy Publishing
DISTILLATION REFLUXING
gives an gives a
ALDEHYDE CARBOXYLIC ACID

compound formula intermolecular bonding boiling point

ETHANOL C2H5OH HYDROGEN BONDING 78°C
ETHANAL CH3CHO PERMANENT DIPOLE-DIPOLE 23°C
ETHANOIC ACID CH3COOH HYDROGEN BONDING 118°C

Secondary Easily oxidised to ketones

e.g. CH3CHOHCH3(l) + [O] ——> CH3COCH3(l) + H2O(l)

N.B. On prolonged treatment with a powerful oxidising agent they can be further
oxidised to a mixture of acids with fewer carbon atoms than the original alcohol.

Tertiary Not oxidised under these conditions. They do break down with vigorous oxidation

© KNOCKHARDY PUBLISHING 2015

 Alcohols 5

Combustion Alcohols make useful fuels

e.g. C2H5OH(l) + 3O2(g) ——> 2CO2(g) + 3H2O(l)

• have high enthalpies of combustion

• do not contain sulphur so there is less pollution
• can be obtained from renewable resources

Bromination Reagent(s) either conc. hydrobromic acid HBr(aq)

or sodium (or potassium) bromide and conc. sulphuric acid
Conditions reflux
Product haloalkane
Equation e.g. C2H5OH(l) + conc. HBr(aq) ——> C2H5Br(l) + H2O(l)

Mechanism The mechanism starts off in a similar way to the dehydration

(protonation of the alcohol and loss of water) but the carbocation (carbonium ion)
is attacked by a nucleophilic bromide ion in step 3.
Knockhardy Publishing

Step 1 protonation of the alcohol using a lone pair on oxygen

Step 2 loss of a water molecule to generate a carbocation (carbonium ion)
Step 3 a bromide ion behaves as a nucleophile and attacks the carbocation

Esterification Reagent(s) carboxylic acid + strong acid catalyst (e.g conc. H2SO4 )
Conditions reflux
Product ester
Equation e.g. CH3CH2OH(l) + CH3COOH(l) CH3COOC2H5(l) + H2O(l)
ethanol ethanoic acid ethyl ethanoate

An advantage of concentrated H2SO4 is that it is also a dehydrating agent and

removes water as it is formed causing the equilibrium to move to the right and thus
increasing the yield of ester.

Q.4 Name these esters; HCOOC2H5

CH3CH2COOCH3

Complete the equations;

+ HCOOC2H5 + H2O

CH3CH2CH2OH + CH3CH2COOH +

© KNOCKHARDY PUBLISHING 2015

6 Alcohols

IDENTIFYING ALCOHOLS USING INFRA RED SPECTROSCOPY

BOND COMPOUND ABSORBANCE RANGE

O-H alcohols broad 3200 cm-1 to 3600 cm-1
O-H carboxylic acids medium to broad 2500 cm-1 to 3500 cm-1
C=O ketones, aldehydes strong and sharp 1600 cm-1 to 1750 cm-1
esters and acids

Differentiation Compound O-H C=O

ALCOHOL YES NO
ALDEHYDE / KETONE NO YES
CARBOXYLIC ACID YES YES
ESTER NO YES

ALCOHOL 2.5 3 4 5
Wavelength (microns)
6 7 8 9 10 12 15

.00 .00

O-H absorption
.10 .10

.20 .20
Absorbance

Knockhardy Publishing
.40 .40

.80 .80

4000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600
-1
Frequency , cm

Wavelength (microns)

ALDEHYDE .00
2.5 3 4 5 6 7 8 9 10 12 15

.00

C=O absorption .10 .10

.20 .20
Absorbance

.40 .40

.80 .80

4000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600
-1
Frequency , cm

CARBOXYLIC ACID 2.5 3 4 5

Wavelength (microns)
6 7 8 9 10 12 15

O-H absorption .00 .00

C=O absorption .10 .10

.20 .20
Absorbance

.40 .40

.80 .80

4000 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600
-1
Frequency , cm

© KNOCKHARDY PUBLISHING 2015

 INDUSTRIAL PREPARATION OF ETHANOL - SUMMARY

FERMENTATION

Reagent(s) GLUCOSE - from hydrolysis of starch

Conditions yeast
warm but no higher than 37°C

Equation C6H12O6 ——> 2 C2H5OH + 2 CO2

• LOW ENERGY PROCESS

• USES RENEWABLE RESOURCES - PLANTS
• SIMPLE EQUIPMENT

• SLOW
• PRODUCES IMPURE ETHANOL
• BATCH PROCESS
Knockhardy Publishing

HYDRATION OF ETHENE

Reagent(s) ETHENE - from cracking of fractions from distilled crude oil

Conditions catalyst - phosphoric acid

high temperature and pressure

Equation C2H4 + H2O ——> C2H5OH

• FAST

✔ •
•
PURE ETHANOL PRODUCED
CONTINUOUS PROCESS

• HIGH ENERGY PROCESS

✘ •
•
EXPENSIVE PLANT REQUIRED
USES NON-RENEWABLE FOSSIL FUELS TO MAKE ETHENE

USES • ALCOHOLIC DRINKS

• SOLVENT - industrial alcohol / methylated spirits (methanol is added)
• FUEL - used as a petrol substitute in countries with limited oil reserves

© KNOCKHARDY PUBLISHING 2015

8 Alcohols

BIOFUELS

What are
they? Liquid fuels made from plant material and recycled elements of the food chain
• biodiesel diesel alternative
• bioethanol petrol additive / substitute

Biodiesel
What is it? Biodiesel is an alternative fuel which can be made from waste vegetable oil or
from oil produced from seeds. It can be used in any diesel engine, either neat or
mixed with petroleum diesel.

It is a green fuel, does not contribute to the carbon dioxide (CO2) burden and
produces drastically reduced engine emissions. It is non-toxic and biodegradable.

Advantages • renewable - derived from sugar beet, rape seed

• dramatically reduces emissions
• carbon neutral

Knockhardy Publishing
• biodegradable
• non-toxic
• fuel & exhaust emissions are less unpleasant
• can be used directly in unmodified diesel engine
• high flashpoint - safer to store & transport
• simple to make
• used neat or blended in any ratio with petroleum diesel

Disadvantages • poor availability - very few outlets & manufacturers

• more expensive to produce
• poorly made biodiesel can cause engine problems

Future problems • there isn’t enough food waste to produce large amounts of biodiesel
• crops grown for biodiesel use land for food crops
• a suitable climate is needed to grow most crops
• some countries have limited water resources

Q.5 Is it sensible, in a world that is short of food, that land should be turned over to
the production of biofuels? What are your ideas?

© KNOCKHARDY PUBLISHING 2015

 Carbonyl compounds 1

CARBONYL COMPOUNDS - Aldehydes and Ketones

Structure • carbonyl groups consists of a carbon-oxygen double bond

• the bond is polar due to the difference in electronegativity C O
• aldehydes / ketones differ in what is attached to the carbon

ALDEHYDES - at least one H attached to the carbonyl group

H C HCHO
C=O or C=O CH3CHO
H H C6H5CHO

KETONES - two carbons attached to the carbonyl group

C CH3COCH3
C=O C2H5COCH3
C C6H5COCH3
Knockhardy Publishing

Bonding • the carbonyl carbon is sp2 hybridised and three sigma (σ) bonds are planar
• the unhybridised 2p orbital of carbon is at 90° to these
• it overlaps with a 2p orbital of oxygen to form a pi (π) bond
• as oxygen is more electronegative than carbon, the bond is polar

C O C O

Naming • aldehydes end in AL

• ketones end in ONE
• pick the longest chain of carbon atoms which includes the C=O
• substituent positions are based on the carbon with the O attached

CH3CH2CH2CH2CH2CHO CH3COCH2CH2CH2CH3
hexanal hexan-2-one

Q.1 Draw structures for, and name, all the carbonyl compounds with molecular formulae;
a) C4H8O b) C5H10O c) C6H12O

© KNOCKHARDY SCIENCE 2015

2 Carbonyl compounds

Formation of carbonyl compounds from alcohols

Aldehydes • Oxidation of primary (1°) alcohols - risk of oxidation to acids

eg CH3CH2OH(l) + [O] —> CH3CHO(l) + H2O(l)

ethanol ethanal

however, this can happen CH3CHO(l) + [O] —> CH3COOH(l)

ethanal ethanoic acid

• it is essential to distil off the aldehyde before it gets oxidised to the acid
• the alcohol is dripped into a warm solution of acidified K2Cr2O7 ( Cr2O72- / H+)
• the orange Cr2O72- [dichromate(VI)] is reduced to the green Cr3+
• the aldehyde has a low boiling point - no hydrogen bonding - it distils off
• if it didn’t distil off it would be oxidised to the equivalent carboxylic acid
• to oxidise an alcohol straight to the acid you would reflux the mixture

DISTILLATION REFLUXING

Knockhardy Publishing
gives an gives a
ALDEHYDE CARBOXYLIC ACID

Ketones • Oxidation of secondary (2°) alcohols.

eg CH3CHOHCH3(l) + [O] —> CH3COCH3(l) + H2O(l)

propan-2-ol propanone

Q.2 Which alcohol would you use to make the following?

• C2H5CHO

• C2H5COCH3

• hexanal

• 3-methylhexan-2-one

• 3-methylpentanal
 Carbonyl compounds 3

CHEMICAL PROPERTIES OF CARBONYL COMPOUNDS

OXIDATION • provides a way of differentiating between aldehydes and ketones

• mild oxidising agents are best
• aldehydes are easier to oxidise
• powerful oxidising agents oxidise ketones to carboxylic acid mixtures

ALDEHYDES easily oxidised to acids e.g. RCHO(l) + [O] ——> RCOOH(l)

CH3CHO(l) + [O] ——> CH3COOH(l)

KETONES only oxidised under vigorous conditions to acids with fewer carbons.

e.g. C2H5COCH2CH3(l) + 3 [O] ——> C2H5COOH(l) + CH3COOH(l)

Q.3 What product (if any) is formed when the following undergo mild oxidation?
Knockhardy Publishing

• C2H5CHO

• C2H5COCH3

• hexanal

• 3-methylhexan-2-one

• 3-methylpentanal

• cyclohexanone

© KNOCKHARDY SCIENCE 2015

4 Carbonyl compounds

IDENTIFYING A CARBONYL COMPOUND

Methods • characteristically strong peak at 1400-1600 cm-1 in the infra red spectrum or
• formation of orange crystalline precipitate with 2,4-dinitrophenylhydrazine

BUT to narrow it down to an aldehyde or ketone you must do a second test

Differentiation • to distinguish an aldehyde from a ketone you need a mild oxidising agent ...

Tollens’ Reagent • ammoniacal silver nitrate solution

• contains the diammine silver(I) ion - [Ag(NH3)2 ]+
• acts as a mild oxidising agent and will oxidise aldehydes but not ketones
• the silver(I) ion is reduced to silver Ag+(aq) + e¯ —> Ag(s)
• the test is known as THE SILVER MIRROR TEST

Q.4 Which of the following produce an orange precipitate with 2,4-dinitrophenylhydrazine?

Knockhardy Publishing
• C2H5OH • 3-methylhexan-2-one

• C2H5COCH3 • cyclohexanol

• hexanal • 3-methylpentan-1-ol

Q.5 Which of the following produce a silver mirror with Tollens’ reagent?

• C2H5CHO • 3-methylhexan-2-one

• C2H5COCH3 • cyclohexanone

• hexanal • 3-methylpentanal

Fehling’s Solution • contains copper(II) ions complexed with tartrate ions

• on warming, it will oxidise aliphatic (but not aromatic) aldehydes
• copper(II) is reduced to a red precipitate of copper(I) oxide, Cu2O
• Tollens’ reagent is better as it works with all aldehydes.

Ketones do not react with Tollens’ Reagent or Fehling’s Solution.

 Carbonyl compounds 5

NUCLEOPHILIC ADDITION REACTIONS

Mechanism • occurs with both aldehydes and ketones

• involves addition to the polar C=O double bond
• attack is by nucleophiles at the positive carbon centre
• alkenes are non-polar and are attacked by electrophiles

Bond Polarity Attacked by Result

Carbonyl C=O Polar Nucleophiles Addition

Alkene C=C Non-polar Electrophiles Addition

REDUCTION Reagent sodium tetrahydridoborate(III) (sodium borohydride), NaBH4

Conditions aqueous or alcoholic solution
Mechanism Nucleophilic addition (also reduction as it is addition of H¯)
Nucleophile H¯ (hydride ion)

Product(s) Aldehydes REDUCED to primary (1°) alcohols

Knockhardy Publishing

Ketones REDUCED to secondary (2°) alcohols

Equation(s) CH3CHO + 2[H] ——> CH3CH2OH

CH3COCH3 + 2[H] ——> CH3CHOHCH3

H O H
H H H
C O CH 3 C O CH 3 C OH + HO
CH 3 H H

H H+ can be used in the mechanism instead of H2O

:- in this case, OH¯ will not be a product

Step 1 H¯ is a nucleophile and attacks the Cδ+

An electron pair from the C=C moves onto O making it -ive

Step 2 A lone pair on oxygen removes a proton from water

Overall, there is addition of hydrogen (reduction)

Q.6 Draw a diagram to indicate

the bonding in NaBH4.

© KNOCKHARDY SCIENCE 2015

6 Carbonyl compounds

Alternative
Method Reagent hydrogen
Conditions catalyst - nickel or platinum
Reaction type Hydrogenation, reduction (NOT NUCLEOPHILIC ADITION)

Equation(s) CH3CHO + H2 ——> CH3CH2OH

CH3COCH3 + H2 ——> CH3CHOHCH3

Note Hydrogen also reduces C=C bonds

e.g. CH2 = CHCHO + 2H2 ——> CH3CH2CH2OH

Q.7 Why are C=C double bonds NOT reduced when NaBH4 is used?

Knockhardy Publishing
Q.8 Draw structures of the organic products formed when the following are reduced using...
NaBH4 H2

CH2 = CHCH2 CHO

OH

O
 Carbonyl compounds 7

HCN Reagent potassium cyanide (HAZARDOUS) - followed by dilute acid

Conditions reflux
Nucleophile cyanide ion CN¯
Product(s) hydroxynitrile (cyanohydrin)

Equation CH3CHO + HCN ——> CH3CH(OH)CN

2-hydroxypropanenitrile

Mechanism Nucleophilic addition

H
+
H H H
C O CH 3 C O CH 3 C OH
CH 3 C C
_
N N
N—
—C
—

Step 1 CN¯ acts as a nucleophile and attacks the slightly positive C

One of the C=O bonds breaks; a pair of electrons goes onto the O

Step 2 A pair of electrons is used to form a bond with H+

Knockhardy Publishing

Overall, there has been addition of HCN

Notes • HCN is a weak acid ; HCN H+ + CN¯ v. few CN¯ ions produced
• the reagent used is KCN (or NaCN) as more nucleophilic CN¯ is produced
• watch out for the possibility of optical isomerism in hydroxynitriles

_
N—
—C
— N N
CN¯ attacks C C
from above H
C O C C
H O H OH
CH3
H
+
CH3 CH3

+
CH3 H O H CH3 H OH
H C C
CN¯ attacks C O
from below CH3 C C
_
N—
—
— C N N

This is an excellent method for adding an extra C atom to a chain;

the CN group can then be converted to carboxylic acids or amines

Hydrolysis (dilute acid) C2H5CN + 2H2O ——> C2H5COOH + NH3

Reduction (H2 / Ni cat.) C2H5CN + 4[H] ——> C2H5CH2NH2

© KNOCKHARDY SCIENCE 2015

8 Carbonyl compounds

2,4-DINITROPHENYLHYDRAZINE NH NH
2
C6H3(NO2)2NHNH2 NO2

Theory • reacts with carbonyl compounds (aldehydes and ketones)

NO2
• used as a simple test for aldehydes and ketones
• makes orange crystalline derivatives - 2,4-dinitrophenylhydrazones
• derivatives have sharp, well-defined melting points
• also used to characterise (identify) carbonyl compounds.

Identification A simple way of characterising a compound (finding out what it is) is to measure

• the melting point of a solid • the boiling point of a liquid

The following structural isomers have similar boiling points because of similar van
der Waals forces and dipole-dipole interactions. They would be impossible to
identify with any precision using boiling point determination.

Knockhardy Publishing
CHO CHO CHO
isomeric Cl
chlorophenylmethanals
Cl
Cl

Boiling point of compound 213°C 214°C 214°C

Melting point of 2,4-dnph derivative 209°C 248°C 265°C

By forming the 2,4-dinitrophenylhydrazone derivatives and taking the melting point

of the purified, crystalline product, it is easy to identify the original compound.

CH 3
Typical NH2 NH C N NH
equation NO2 H
NO2
+ CH CHO H2O +
3

NO2 NO2

Mechanism ADDITION-ELIMINATION
 Carbonyl compounds 9

Q.9 Write out equations for the reactions between HCN and...

• C2H5CHO + HCN ——>

• CH3COCH3 + HCN ——>

• hexanal + HCN ——>

Indicate which reactions give rise to optically active organic compounds?

Why is the addition of HCN such a useful reaction?

Knockhardy Publishing

Q.10 Suggest a method for differentiating between the following. What would be seen?

• C2H5CHO and C2H5COCH3

• C3H7COCH3 and C2H5COC2H5

• hexanal and hexanone

© KNOCKHARDY SCIENCE 2015

CIE Chemistry A Level

18 : Carbonyl Compounds
Notes

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Aldehydes and Ketones

Aldehydes​ and ​ketones​ both contain the carbonyl group,

C=O.
The​ position​ of the ​carbonyl​ group in the carbon chain is
different​ in aldehydes and ketones.

The carbonyl group is at the end of the carbon chain in

aldehydes and in the middle in ketones. The suffix for
aldehydes is ​-al​ and the suffix for ketones is ​-one​.

Formation of aldehydes and ketones

Aldehydes and ketones are formed when alcohols are
oxidised​ using ​acidified potassium dichromate(VI)
(Cr​2​O​7​2-​/H​+​).

Aldehydes are formed from ​primary​ alcohols, whereas ketones are formed from ​secondary
alcohols.

Primary alcohols
Primary​ alcohols can be ​partially oxidised​ to ​aldehydes​.
CH​3​CH​2​OH + [O] → CH​3​CHO + H​2​O
If the aldehyde undergoes ​further oxidation​, ​carboxylic acids ​are produced.
CH​3​CHO + [O] → CH​3​COOH + H​2​O
The full oxidation reaction can be written as:
CH​3​CH​2​OH + 2[O] → CH​3​COOH + 2H​2​O
If you are only collecting the aldehyde, carry out the reaction with excess alcohol and distill off the
aldehyde as soon as it forms to prevent further oxidation.

Secondary alcohols
Secondary​ alcohols are oxidised to ​ketones​. No further oxidation can take place.
CH​3​C(OH)HCH​3​ + [O] → CH​3​COCH​3​ + H​2​O

Reduction of aldehydes and ketones

A ​reducing agent​ can be used to reverse the reactions above and convert aldehydes and ketones
back to primary and secondary alcohols.
Typically LiAlH​4 or
​ NaBH​4​ (dissolved in water with methanol) are used as reducing agents for this
reaction.

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Reduction of aldehydes
RCHO + 2[H] →RCH​2​OH
For example, the reduction of ​ethanal to ethanol​:

Reduction of ketones
R​1​COR​2​ + 2[H] →RC(OH)HR​2

For example, the reduction of ​propanone to propanal​:

Reaction with HCN and KCN or NaCN

Hydrogen cyanide reacts with aldehydes and ketones to produce ​hydroxynitrile compounds​ by
removing the C=O double bond. The reaction is called ​nucleophilic addition​ (see the mechanism
on the following page).

Naming:
When naming a hydroxynitrile, the ​carbon in the nitrile group (C≡N) ​is referred to as the​ first
carbon​ so the position of groups (including the alcohol group) is counted from there. In the
equations below, the product of the first reaction is ​2-hydroxypropanenitrile​ and the product of
the second reaction is ​2-hydroxy-2-methylpropanenitrile​.

HCN is a very ​poisonous gas. ​Often ​KCN​ or ​NaCN​ are used with acid instead to form HCN in
situ.

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Nucleophilic addition reactions
When aldehydes and ketones react with HCN to form ​hydroxynitriles​, a​ nucleophilic addition
reaction occurs.

A nucleophile is an​ electron pair donor​.

The mechanism:
The ​carbonyl bond​ (C=O) is ​highly polar​. The negative​ cyanide ion​ acts as a ​nucleophile​ and
attacks the slightly positive carbon atom. The C=O bond breaks, leaving only a ​single bond
between the ​carbon and oxygen ​atoms.
The negatively charged oxygen then bonds to a ​hydrogen ion​ (from HCN or any added acid).

Detecting carbonyl compound

The carbonyl group can be detected using 2,4-dinitrophenylhydrazine (2,4-DNPH).
When 2,4-DNPH is added to a solution of aldehyde or ketone, a ​yellow/ orange precipitate​ is
produced. The formation of this coloured precipitate indicates the presence of a​ C=O carbonyl
group​.

Distinguishing between aldehydes and ketones

Simple tests can be carried out to detect whether a compound is an aldehyde or a ketone.
Ketones​ are ​not easily oxidised​ whereas ​aldehydes​ are ​easily oxidised​ to carboxylic acids.

After identifying a solution as a carbonyl using 2,4-DNPH, certain reactions can be carried out
using ​oxidising agents​. A ​positive result​ indicates that an ​aldehyde​ is present while a ​negative
result​ suggests a ​ketone ​is present.

Acidified potassium dichromate(VI)

Aldehyde​ - orange solution turns green.
Ketone​ - no visible change / solution remains orange.

Tollen’s reagent
Aldehyde​ - silver mirror forms on the walls of the test tube.
Ketone​ - no visible change.

Fehling’s reagent
Aldehyde​ - blue solution gives a brick red precipitate.
Ketone​ - no visible change / solution remains blue.

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Deducing the presence of CH​3​CO- group
A CH​3​CO- group can be detected using ​alkaline aqueous iodine,​ I​2​.
Iodine​ is added to the carbonyl, followed by ​sodium hydroxide​ (to make the solution alkaline). If
the CH​3​CO- group is present, a ​yellow precipitate​ of ​tri-iodomethane​ (CHI​3​) will form.
CH​3​COR + 3I​2​ + 4NaOH → RCOONa + CHI​3​ + 3NaI + 3H​2​O

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 Carboxylic acids 1

CARBOXYLIC ACIDS

Structure • contain the carboxyl functional group COOH O

• includes a carbonyl (C=O) group and CH 3 C
a hydroxyl (O-H) group O H
• the bonds are in a planar arrangement
• are isomeric with esters :- RCOOR’

Q.1 Draw structures for, and name, all carboxylic acids with formula :-
CH2O2 C2H4O2 C3H6O2 C4H8O2 C5H10O2
Knockhardy Publishing

Nomenclature Remove e from the equivalent alkane and add . . . OIC ACID .

e.g. CH3COOH is called ethanoic acid as it is derived from ethane.

Many carboxylic acids are still known under their trivial names, some having been
called after characteristic properties or origin.

Formula name (trivial name) origin of name

HCOOH methanoic acid formic acid latin for ant
CH3COOH ethanoic acid acetic acid latin for vinegar
C6H5COOH benzenecarboxylic acid benzoic acid from benzene

© KNOCKHARDY SCIENCE 2015

2 Carboxylic acids

Physical properties

Solubility • acids are very soluble in organic solvents

• soluble in water is due to hydrogen bonding
• small ones dissolve readily in cold water
• as mass increases, the solubility decreases
• benzoic acid is fairly insoluble in cold but soluble in hot water

δ−
δ+
O δ− δ+ δ−
δ+
CH3 C H δ+
O H O
δ− δ+ δ− δ+
O H O CH3 C δ− δ+ δ−
C CH3
δ+
H O H O
Intermolecular hydrogen bonding In non-polar solvents, molecules dimerize
between ethanoic acid and water due to intermolecular hydrogen bonding.

Boiling point • increases as size increases - increased induced dipole-dipole interactions

Knockhardy Publishing
• carboxylic acids have high boiling points for their relative mass
• arises from inter-molecular hydrogen bonding due to the polar O—H bonds
• additional inter-molecular attractions = more energy to separate the molecules

The effect of hydrogen bonding on the boiling point of compounds of similar mass

Compound Formula Mr b. pt. (°C) Comments

butane C4H10 58 -0.5 induced dipole-dipole interaction

propanal C2H5CHO 58 49 + permanent dipole-dipole

propan-1-ol C3H7OH 60 97 + hydrogen bonding

ethanoic acid CH3COOH 60 118 + hydrogen bonding

Preparation • Oxidation of aldehydes RCHO + [O] —> RCOOH

• Hydrolysis of esters RCOOR + H2O RCOOH + ROH
• Hydrolysis of acyl chlorides RCOCl + H2O —> RCOOH + HCl
• Hydrolysis of nitriles RCN + 2 H2O —> RCOOH + NH3
• Hydrolysis of amides RCONH2 + H2O —> RCOOH + NH3

© KNOCKHARDY SCIENCE 2015

 Carboxylic acids 3

CHEMICAL PROPERTIES

Acidity • weak monobasic acids RCOOH + H2O(l) RCOO¯(aq) + H3O+(aq)

They act as typical acids in the following reactions with...

Carbonates • Produce a salt and carbon dioxide

• 2 RCOOH + Na2CO3(s) —> 2 RCOO¯ Na+(aq) + CO2(g) + H2O(l)

ANALYTICAL USE
Carboxylic acids are strong enough acids to liberate CO2 from carbonates.
Phenols are also acidic but not are not strong enough to liberate CO2

Alkalis • form salts with alkalis RCOOH + NaOH(aq) —> RCOO¯Na+(aq) + H2O(l)
soluble

• the acid can be liberated from its salt by treatment with a stronger acid.
Knockhardy Publishing

e.g. RCOO¯ Na+(aq) + HCl(aq) —> RCOOH + NaCl(aq)

Practical use Conversion of an acid to its water soluble salt followed

by acidification of the salt to restore the acid is often
used to separate acids from a mixture.

Metals • Products: a salt and hydrogen

2RCOOH + Mg(s) —> (RCOO¯)2Mg2+(aq) + H2(g)

Metal • Products: a salt and water

oxides
2RCOOH + MgO(s) —> (RCOO¯)2Mg2+(aq) + H2O(l)

Chlorination Reagent(s) thionyl chloride SOCl2

Conditions dry conditions
Product acyl chloride
Equation CH3COOH + SOCl2 —> CH3COCl + SO2 + HCl

Use Acyl chlorides are reactive and useful in synthesis

© KNOCKHARDY SCIENCE 2015

4 Carboxylic acids

Esterification Involves the reaction of a carboxylic acid with an alcohol. A reversible reaction.

Reagent(s) Alcohol + acid catalyst (eg conc. H2SO4)

Conditions Reflux
Equation CH3COOH + CH3OH CH3COOCH3 + H2O
ethanoic acid methanol methyl ethanoate
This is an example of equilibrium. Concentrated sulphuric acid not only makes
an excellent catalyst but also removes water which will, according to Le Chatelier’s
Principle, move the equilibrium to the right and produce a bigger yield of ester.

Q.2 State the compounds needed to synthesise the following three esters;

propyl ethanoate

ethyl propanoate

HCOOC2H5

Knockhardy Publishing
ESTERS - RCOOR’
O
Structure Substitute an organic group for the H in acids
CH3 C
Nomenclature first part from alcohol, second part from acid O CH3
e.g. methyl ethanoate CH3COOCH3 ACID ALCOHOL

Q.3 Draw structures for, and name, all esters of formula C4H8O2 and C5H10O2.
From which acid and alcohol are each derived?

© KNOCKHARDY SCIENCE 2015

 Carboxylic acids 5

Synthesis From carboxylic acids slow, equilibrium process

acyl chlorides faster, but more care must be taken

Properties • colourless liquids which are insoluble in water

• unreactive

REACTIONS Esters are unreactive compared with acids and acyl chlorides.

Hydrolysis CH3COOCH3 + H2O CH3COOH + CH3OH reflux in acid soln.

CH3COOCH3 + NaOH ——> CH3COO¯ Na+ + CH3OH reflux in alkali

very soluble in water

In the presence of alkali, the carboxylic acid reacts to form a soluble sodium salt;
addition of dilute hydrochloric acid will liberate the carboxylic acid
Knockhardy Publishing

USES Despite being fairly chemically unreactive substances, esters are useful as ...
• solvents eg

• plasticisers eg

• “fruity” food flavouring eg

Q.4 Consult a suitable text book to find some esters with characteristic smells.

© KNOCKHARDY SCIENCE 2015

6 Carboxylic acids

DERIVATIVES OF CARBOXYLIC ACIDS

ACYL (ACID) CHLORIDES - RCOCl δ−

δ+
O polarity of bonds
Nomenclature Named from corresponding acid CH 3 C in acyl chlorides
- remove -ic add -yl chloride δ−
Cl
CH3COCl ethanoyl (acetyl) chloride
C6H5COCl benzene carbonyl (benzoyl) chloride

Preparation Involves replacing the OH of a carboxylic acid with a Cl atom

Method 1 Reagent(s) thionyl chloride SOCl2

Conditions dry conditions
Equation CH3COOH + SOCl2 —> CH3COCl + SO2 + HCl

Method 2 Reagent(s) phosphorus(V) chloride PCl5

Knockhardy Publishing
Conditions dry conditions
Equation CH3COOH + PCl5 —> CH3COCl + POCl3 + HCl

Chemical
Properties • colourless liquids which fume in moist air
• attacked at the positive carbon centre by nucleophiles
• nucleophiles include water, alcohols, ammonia and amines
• undergo addition-elimination reactions
• MUCH MORE REACTIVE THAN CARBOXYLIC ACIDS AND ACID ANHYDRIDES

Water Product(s) carboxylic acid + HCl (fume in moist air / strong acidic solution formed)
Conditions cold water
Equation CH3COCl(l) + H2O(l) —> CH3COOH(aq) + HCl(aq)
Mechanism addition-elimination

H
Cl Cl +
H O O
C O CH3 C O C O CH3 C HCl
CH3 + CH3 OH
H O
H Cl
H O
H

© KNOCKHARDY SCIENCE 2015

 Carboxylic acids 7

Alcohols Product(s) ester + hydrogen chloride

Conditions reflux in dry (anhydrous) conditions
Equation CH3COCl(l) + CH3OH(l) —> CH3COOCH3(l) + HCl(g)

Mechanism addition-elimination
CH3
Cl Cl +
H O O
C O CH3 C O C O CH3 C HCl
CH3 + CH3 O CH3
H O
Cl
H O CH3
CH3

Amines Product(s) N-substituted amide + hydrogen chloride

Conditions anhydrous
Equation CH3COCl(l) + C2H5NH2(aq) —> CH3CONHC2H5(s) + HCl(g)
or CH3COCl(l) + 2C2H5NH2(aq) —> CH3CONHC2H5(l) + C2H5NH3Cl(s)

Mechanism addition-elimination
Knockhardy Publishing

H
Cl Cl +
R N H O
C O CH3 C O C O CH3 C HCl
CH3 + CH3 NH
H N H
H Cl R
R
R N
H

Ammonia Product(s) Amide + hydrogen chloride

Conditions Low temperature and excess ammonia. Vigorous reaction.
Equation CH3COCl(l) + NH3(aq) —> CH3CONH2(s) + HCl(g)
or CH3COCl(l) + 2NH3(aq) —> CH3CONH2(s) + NH4Cl(s)

Mechanism addition-elimination
H
Cl Cl +
H N H O
C O CH3 C O C O CH3 C HCl
CH3 + CH3 NH2
H N H
H H Cl
H N
H

Q.5 State the reagents used to synthesise...

C6H5CON(CH3)2
C3H7COOCH3
C2H5COOH

© KNOCKHARDY SCIENCE 2015

 CIE Chemistry A-Level
Topic 14 - An Introduction to Organic
Chemistry
Flashcards

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This work by https://bit.ly/pmt-edu-cc CC BY-NC-ND 4.0

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What is a functional group?

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What is a functional group?

The group of atoms responsible for the

characteristic reactions of a compound.

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What is a homologous series?

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What is a homologous series?

A series of organic compounds with the

same functional group with successive
members differing by -CH2.

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What is an alkane? Include the general
formula

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What is an alkane? Include the general formula

A saturated hydrocarbon with general

formula CnH2n+2.
Suffix: -ane.

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State the molecular, displayed and
skeletal formulae of butane

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State the molecular, displayed and skeletal formulae
of butane
Molecular: C4H10

Displayed:

Skeletal:

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What is an alkene? Include the general
formula

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What is an alkene? Include the general formula

An unsaturated hydrocarbon with the

general formula CnH2n.
Suffix: -ene.

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Write the molecular, displayed and
skeletal formulae of but-2-ene

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Write the molecular and skeletal formulae of
but-2-ene
Molecular: C4H8

Skeletal:

The number 2 in but-2-ene signifies that the double bond is between the
2nd and 3rd carbon.

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What is an arene?
(A level only)

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What is an arene? (A level only)

● An aromatic hydrocarbon.
● Aromatic means that it contains a
benzene ring.
● Prefix: phenoyl- OR suffix: -benzene.
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What is a halogenoalkane?

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What is a halogenoalkane?
An alkane where a hydrogen atom has
been replaced by a halogen atom.
Prefix: fluoro-/ chloro-/ bromo-/ iodo-.

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 Write the molecular, displayed and
skeletal formulae of 1-chloropropane.

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Write the molecular, displayed and skeletal formulae
of 1-chloropropane
Molecular: C3H7Cl
Displayed: The ‘1’ refers to the
carbon the halogen
atom is bonded to.
Skeletal:

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What is a halogenoarene?
(A level only)

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What is a halogenoarene? (A level only)
● An aromatic hydrocarbon whereby one or more hydrogen
atoms bonded to the aromatic ring are replaced by a
halogen atom.
● E.g. Chlorobenzene:

Naming: [fluoro-/ chloro-/ bromo-/ iodo-] - benzene

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What is an alcohol? Include the general
formula

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What is an alcohol? Include the general formula
An organic compound with a lone hydroxyl group
(-OH) attached to an alkyl group. The general
formula is CnH2n+1OH.
Suffix: -ol.

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Write the molecular and skeletal
formulae of propan-2-ol

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Write the molecular and skeletal formulae of
propan-2-ol
Molecular: C3H8O

The ‘2’ refers to

the position of the
Skeletal: hydroxyl group.

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How are alcohols classified?

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How are alcohols classified?
(R group - any alkyl chain)

● Primary, 1° - The carbon bonded to the hydroxyl group is

bonded to one R group only.
● Secondary, 2° - The carbon bonded to the hydroxyl group
is bonded to two R groups.
● Tertiary, 3° - The carbon bonded to the hydroxyl group is
bonded to three R groups.
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What is a phenol?
(A level only)

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What is a phenol? (A level only)

A phenyl group (-C6H5) bonded

to a hydroxyl group (-OH).
Phenol = C6H5OH.
Suffix: -phenol / -benzenol.
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What is an aldehyde? Draw the
functional group

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What is an aldehyde? Draw the functional group

An organic compound with the -CHO

functional group.
Suffix: -al.

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What is a ketone? Draw the functional
group

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What is a ketone? Draw the functional group

An organic compound with the RCOR functional

group.
Suffix: -one.
E.g. propanone, more commonly known as
acetone.
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What is a carboxylic acid? Draw the
functional group

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What is a carboxylic acid? Draw the functional group

An organic compound with the -COOH

functional group.
Suffix: -oic acid.

E.g. ethanoic acid, a key component of vinegar.

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What is an ester? Draw the functional
group

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What is an ester? Draw the functional group

An organic compound commonly formed

from a condensation reaction between
alcohol and carboxylic acid functional
groups.

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Name the ester shown below

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Name the ester shown below
This part of the molecule is
derived from the alcohol,
This part of the
methanol.
molecule is
derived from the
carboxylic acid,
ethanoic acid.

Methyl ethanoate

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What is an acyl chloride? Draw the
functional group
(A level only)

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What is an acyl chloride? Draw the functional group
(A level only)
A carboxylic acid derivative where
the -OH group in -COOH has
been replaced with a chlorine
atom to form a -COCl group.
Suffix: -oyl chloride.
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What is a primary amine? Draw the
functional group

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What is a primary amine? Draw the functional group
● An amine is a derivative of
ammonia.
● In a primary amine, one
hydrogen atom in ammonia is
substituted with an alkyl group.
● Suffix: -amine.
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What is a nitrile? Draw the displayed
formula of ethanenitrile

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What is a nitrile? Draw the displayed formula of
ethanenitrile
● An organic compound with a -CN
functional group.
● Prefix: cyano- OR suffix: -nitrile.
● Ethanenitrile:
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What is an amide?
(A level only)

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What is an amide? (A level only)

Formed from the condensation

reaction between a carboxylic
acid and an amine functional
group.
Suffix: -amide
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What is an amino acid?
(A level only)

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What is an amino acid? (A level only)
● An organic compound that
has both a carboxylic acid and
amine functional group.
● In an alpha-amino acid, both
groups are attached to the
same carbon atom.
● Naming: Amino- -oic acid.

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What is an aliphatic hydrocarbon?

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What is an aliphatic hydrocarbon?

A compound containing only carbon and

hydrogen atoms in which the carbon
atoms are arranged in a linear or
branched structure.
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What is benzene?

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What is benzene?

Benzene is an aromatic hydrocarbon/

arene.
Molecular formula: C6H6

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Describe how to name an organic
compound.

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Describe how to name an organic compound
● Identify the longest carbon chain that contains the functional
group (this is the stem).
● Identify the functional group (this is the prefix / suffix).
● Count the number of carbon atoms so that the functional group
has the lowest number.
● Add any side chains or less important functional as prefixes (in
alphabetical order).
● If there are 2 or more identical groups, use the prefixes di-/ tri-/
tetra- before that part of the name.
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Draw and name the different structural
isomers of dimethylbenzene
(A level only)

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Draw and name the different structural isomers of
dimethylbenzene (A level only)

1,2-Dimethylbenzene 1,3-Dimethylbenzene 1,4-Dimethylbenzene

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Draw and name the structural isomers of
the aliphatic hydrocarbon C5H12

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Draw and name the structural isomers of the
aliphatic hydrocarbon C5H12

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What is the molecular formula of the
compound below?

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What is the molecular formula of the compound
below?

C 4H 6O 2

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What is homolytic fission?

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What is homolytic fission?
A covalent bond breaks. Each bonding atom
receives an electron from the bonding pair, forming
two radicals (highly reactive, neutral species).

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What is heterolytic fission?

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What is heterolytic fission?
A covalent bond breaks. One bonding atom receives
both electrons from the bonding pair.

Jürgen Martens, CC BY-SA 3.0

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What is a free radical?

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What is a free radical?

A highly reactive neutral species with an

unpaired electron.

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What are the three steps in a free radical
substitution mechanism?

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What are the three steps in a free radical substitution
mechanism?

1. Initiation
2. Propagation
3. Termination

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What is an electrophile?

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What is an electrophile?

An electron pair acceptor

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What is an nucleophile?

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What is an nucleophile?

An electron pair donor

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What is an addition reaction?

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What is an addition reaction?

An addition reaction is a reaction where

two reactants react to form one product.
The atom economy is 100%.

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What is a substitution reaction?

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What is a substitution reaction?

A substitution reaction is a reaction

where an atom/ group is replaced by
another atom/ group.
Atom economy is less than 100%.

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What is an elimination reaction?

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What is an elimination reaction?

● An elimination reaction is a reaction where 2

substituents are removed from a molecule.
● E.g. a dehydration reaction (a molecule of
water is produced).

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What is a hydrolysis reaction?

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What is a hydrolysis reaction?

The splitting of a compound/ molecule

using water.

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What is a condensation reaction?

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What is a condensation reaction?

The formation of a compound with the

release of water.

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What is oxidation?

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What is oxidation?

Loss of electrons / increase in oxidation

number.

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What is reduction?

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What is reduction?

Gain of electrons / decrease in oxidation

number.

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In organic redox reactions, how can
oxidising and reducing agents be
represented?

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In organic redox reactions, how can oxidising and
reducing agents be represented?

● Oxidising reagents: [O]

● Reducing reagents: [H]

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What is electron repulsion theory?

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What is electron repulsion theory?

● Electron pairs are areas of negative charge

that repel each other.
● Lone pairs of electrons offer more repulsion
than bonding pairs.

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Describe the shape and bond angles of
ethene

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Describe the shape and bond angles of ethene

● Bond shape: Trigonal Planar

● Bond angle: 120°

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Describe the shape and bond angles in
ethane

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Describe the shape and bond angles in ethane

● Bond shape: Tetrahedral

● Bond angle: 109.5°

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Explain the bond shape and angle in an
ethane molecule.

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Explain the bond shape and angle in an ethane
molecule.
● Both carbon atoms promote an electron from the 2s orbital to the 2p
orbital to form four identical sp3 hybrid orbitals.
● These sp3 orbitals arrange themselves as far apart as possible from each
other.
● Each carbon atom then forms sigma bonds with the three hydrogen
atoms. A sigma bond also forms between the two carbon atoms when the
sp3 orbitals overlap end-to-end.
● There are 4 bonding pairs of electrons which causes a tetrahedral bond
shape and a bond angle of 109.5°.
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Explain the bond shape and angle in an
ethene molecule.

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Explain the bond shape and angle in an ethene molecule.

● Both carbon atoms promote an electron from the 2s orbital to the 2p orbital
to form three identical sp2 hybrid orbitals. (The other 2p orbital is
unchanged).
● The three sp2 orbitals arrange themselves as far apart as possible from
each other.
● 2 sp2 orbitals forms a sigma bond with a hydrogen. A sigma bond forms
between the carbon atoms when the sp2 orbitals overlap end-to-end,
followed by a pi bond when the p-orbitals overlap sideways.
● There are 3 areas of electron density, creating a trigonal planar shape and
a bond angle of 120°.
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Describe the shape and bond angle of
benzene
(A level only)

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Describe the shape and bond angle of benzene
(A level only)

Planar, 120°

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Describe the bonding in benzene
(A level only)

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Describe the bonding in benzene (A level only)
Delocalised structure of benzene:
● Each carbon atom uses two electrons form sigma
bonds with the adjacent carbon atoms. One electron
is used to form a sigma bond with a hydrogen atom.
● The remaining electron on each carbon atom is
delocalised to form a delocalised 𝛑 system (an area
of electron density).
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Predict the shape and bond angle
around carbon in RCOOH

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Predict the shape and bond angle around carbon in
RCOOH
● 3 areas of electron density like ethene
● Bond shape: Trigonal planar
● Bond angle: 120°

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What is structural isomerism?

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What is structural isomerism?

Compounds with the same molecular

formula but different structural formulae.

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What are the 3 divisions of structural
isomerism?

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What are the 3 divisions of structural isomerism?

1. Positional
2. Chain
3. Functional group

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Why are propan-1-ol and propan-2-ol
structural isomers?

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Why are propan-1-ol and propan-2-ol structural
isomers?
Positional isomerism
The position of the functional group has
changed.

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Why are pentane and 2-methylbutane
structural isomers?

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Why are pentane and 2-methylbutane structural
isomers?
Chain isomerism
Branching changes the structural formula of a
compound.

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Why are propanal and propanone
structural isomers?

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Why are propanal and propanone structural
isomers?
Functional group isomerism
The functional group has changed
(molecular formula stays the same).

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What is stereoisomerism?

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What is stereoisomerism?

Compounds with the same molecular

and structural formulae but a different
arrangement of atoms in space.

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What causes geometrical (cis-trans)
stereoisomerism?

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What causes geometrical (cis-trans)
stereoisomerism? What do cis and trans mean?
Cause by the limited rotation around the
carbon-carbon pi bond. Aany groups
bonded to the carbon are fixed in
position.
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How do you determine whether an
stereoisomer is cis or trans?

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How do you determine whether an stereoisomer is
cis or trans?
● In trans (or E) isomers, high priority groups are
on opposite sides of the C=C (above and
below).
● In cis (or Z) isomers, high priority groups are on
the same side of the C=C (above or below).
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How can you identify the highest priority
group?

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How can you identify the highest priority group?
● For molecules where only single atoms are attached to the carbons in the
C=C, the highest priority group has the highest atomic mass.
● For non-complex small groups such as -CH3, look at the atomic mass of
the atom attached directly to the C=C (in -CH3 this would be the carbon
atom- ignore the hydrogen atoms). The one with the greatest atomic
mass is the high priority group.
● For more complex groups (i.e. CH3CH2Cl), don’t just observe the atomic
mass of the carbon as it is directly attached to the C=C, look at what the
carbon is directly attached to etc.

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Draw the cis and trans isomers of
2-chloropent-2-ene

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Draw the cis and trans isomers of 2-chloropent-2-ene

trans-2-Chloropent-2-ene cis-2-chloropent-2-ene

The high priority groups are on The high priority groups are
opposite sides of C=C. on the same side of C=C.
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What causes optical isomerism? What
are optical isomers?

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What causes optical isomerism? What are optical
isomers?
● Optical isomerism is a type of
stereoisomerism found in molecules that
contain a chiral centre.
● Optical isomers or enantiomers are
non-superimposable, mirror images of each
other.
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What is a chiral centre?

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What is a chiral centre?

In organic chemistry, a chiral centre is in

the form of a carbon atom bonded to four
different groups. Compounds may
contain more than 1 chiral centre.
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Draw diagrams to show the optical
isomers of butan-2-ol. Why can
butan-2-ol form optical isomers?

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Draw diagrams to show the optical isomers of
butan-2-ol. Why can butan-2-ol form optical
isomers?
Optical isomers:

The central carbon in the diagrams is chiral because it is attached

to four different groups: -OH, -CH3, -H, and -CH2CH3. The two
isomers are non-superimposable mirror images of each other.
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Identify the chiral centre in the molecule
below

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Identify the chiral centre in the molecule below
This carbon is chiral as it is
bonded to 4 different groups:
-H, -OH, -COOH, -CH2COOH

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CIE Chemistry A-Level
Topic 15 - Hydrocarbons
Flashcards

PMT Education is licensed under https://bit.ly/pmt-cc

This work by https://bit.ly/pmt-edu-cc CC BY-NC-ND 4.0

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Why are alkanes generally unreactive?

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Why are alkanes generally unreactive?

● C-C and C-H bonds have a fairly high bond

enthalpy and therefore require a lot of energy
to overcome.
● The difference in electronegativities of C and
H is so small, making it very resistant to
reactions with polar reagents.
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Write the chemical equation for the
complete combustion of ethane

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Write the chemical equation for the complete
combustion of ethane

C2H6 + 3½O2 → 2CO2 + 3H2O

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 Write an overall equation for the
substitution reaction of ethane with
chlorine. Include any conditions.

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Write an overall equation for the substitution reaction
of ethane with chlorine. Include any conditions.

UV light
C2H6 + Cl2 → C2H5Cl + HCl

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What are the three steps of free radical
substitution?

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What are the three steps of free radical substitution?

1. Initiation
2. Propagation
3. Termination

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Write the mechanism for the free radical
substitution of ethane with chlorine

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Write the mechanism for the free radical substitution of
ethane with chlorine
Initiation: Cl2 → 2Cl•

Propagation: C2H6 + •Cl → •C2H5 + HCl

•C2H5 + Cl2 → C2H5Cl + •Cl

Termination: •Cl + •Cl → Cl2

•C2H5 + •Cl → C2H5Cl

•C2H5 + •C2H5 → C4H10

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What is crude oil a source of?

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What is crude oil a source of?

Aliphatic and aromatic alkanes

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What is cracking?

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What is cracking?

The process in which complex organic

molecules are broken down into smaller
organic molecules, such as simple
alkanes.

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Why is cracking used?

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Why is cracking used?

To obtain more useful and smaller

alkanes and alkenes

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What are the conditions and reagents for
the hydrogenation of alkenes. Write an
equation for the hydration of ethene

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What are the conditions and reagents for the
hydrogenation of alkenes. Write an equation for the
hydration of ethene
● Hydrogen gas
● Nickel catalyst
● 150℃
C 2H 4 + H 2 → C 2H 6
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What are the conditions and reagents for
the hydration of alkenes? Write an
equation for the hydration of ethene

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What are the conditions and reagents for the
hydration of alkenes? Write an equation for the
hydration of ethene
● Steam
● H3PO4 catalyst
● 300℃ degrees
● 60-70 atm
C2H4 + H2O → C2H5OH
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What are the conditions for the reactions
between alkenes and halogens? Write
an equation for the reaction between
ethene and bromine

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What are the conditions for the reactions between
alkenes and halogens? Write an equation for the
reaction between ethene and bromine
● Room temperature
C2H4 + Br2 → C2H4Br2

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What are the conditions for the reactions
between alkenes and hydrogen halides?
Write an equation for the reaction
between ethene and hydrogen bromide

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What are the conditions for the reactions between
alkenes and hydrogen halides? Write an equation for
the reaction between ethene and hydrogen bromide
● Room temperature
C2H4 + HBr → C2H5Br

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What is Markovnikov’s rule?

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What is Markovnikov’s rule?

In the electrophilic addition of a hydrogen

halide to an asymmetric alkene, the
hydrogen atom will bond to the carbon
that is already bonded to the most
hydrogens.
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Draw the mechanism for the electrophilic
addition reaction between ethene and
bromine

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Draw the mechanism for the electrophilic addition
reaction between ethene and bromine

This leaves a (positive)

carbocation that is attracted
The electron dense carbon-carbon double
to the negative bromide ion
bond induces a dipole in the Br2 molecule.
The 𝜋 bond breaks and a carbon atom forms and hence forms a covalent
a bond with a bromine atom. bond with it.
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Draw the mechanism for the electrophilic
addition reaction between propene and
hydrogen bromide (forming the minor
product)

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Draw the mechanism for the electrophilic addition
reaction between propene and hydrogen bromide
(forming the minor product)

Br is more
electronegative than H. This leaves a (positive)
carbocation that is attracted
The electron dense C=C double bond is attracted to
to the negative bromide ion
the slightly positive hydrogen, causing the 𝜋 bond to
break and a covalent bond to form between the and hence forms a covalent
carbon and hydrogen atom. bond with it.
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How are carbocations classified?

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How are carbocations classified?

Primary Secondary Tertiary

Carbocation is bonded Carbocation is bonded Carbocation is bonded

to one alkyl group. to two alkyl groups. to three alkyl groups.

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What is the trend in carbocation stability?

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What is the trend in carbocation stability?

Primary → Secondary → Tertiary

Stability increases →

The more alkyl groups attached to the carbocation, the

more the positive charge is spread out, increasing stability.

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In terms of carbocation stability, what will
be the major product in the addition
reaction between a hydrogen halide and
an unsymmetrical alkene?

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In terms of carbocation stability, what will be the
major product in the addition reaction between a
hydrogen halide and an unsymmetrical alkene?
The major product will be the one whose
carbocation intermediate has the greater
stability i.e. a secondary carbocation is more
likely to form than a primary carbocation.
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How can alkenes be oxidised to form a
diol? Write an equation for the oxidation
of ethene

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How can alkenes be oxidised to form a diol? Write
an equation for the oxidation of ethene
● Manganate(VII) ions are a strong oxidising agent.
● When cold, dilute and acidified, the ions
experience a colour change from purple to
colourless as they are reduced.
C2H4 + H2O + [O] → (CH2OH)2
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 What happens when an alkene is
oxidised with hot, concentrated acidified
potassium manganate solution?

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What happens when an alkene is oxidised with hot, concentrated acidified
potassium manganate solution?

The C=C double bond is broken and replaced with 2 x

C=O bonds (forming 2 carbonyl compounds):

What occurs next is based on whether the R groups are

alkyl groups or hydrogen atoms
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After an alkene has been oxidised using
hot, concentrated H+/Cr2O72-, both R
groups of one of the products are alkyl
groups. What happens to this product?

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After an alkene has been oxidised using hot, concentrated
H+/Cr2O72-, both R groups of one of the products are alkyl
groups. What happens to this product?
● The alkene was split into a ketone (where both
R groups are alkyl groups) and another
carbonyl
● Ketones cannot be oxidised further so
no further reaction occurs.
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After an alkene has been oxidised using
hot, concentrated H+/Cr2O72-, one of the
products has the following R groups: an
alkyl chain and a hydrogen atom. What
happens to this product?

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After an alkene has been oxidised using hot,
concentrated H+/Cr2O72-, one of the products has the
following R groups: an alkyl chain and a hydrogen atom.
What happens to this product?
● The alkene was split into an aldehyde (with an alkyl group and
a hydrogen atom as the R groups) and another carbonyl
● The aldehyde is further oxidised to form a carboxylic acid:

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After an alkene has been oxidised using
hot, concentrated H+/Cr2O72-, both R
groups of one of the products are
hydrogen atoms. What happens to this
product?

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After an alkene has been oxidised using hot,
concentrated H+/Cr2O72-, both R groups of one of the
products are hydrogen atoms. What happens to this
product?
● The alkene was oxidised to form methanal (with 2 hydrogen
atoms as R groups) and another carbonyl
● Methanal will be completely oxidised to form carbon dioxide
and water:

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What is addition polymerisation?

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What is addition polymerisation?

The joining together of unsaturated

alkene monomers to form a polymer. No
other products are formed (atom
economy is 100%).

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How do alkenes undergo addition
polymerisation?

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How do alkenes undergo addition polymerisation?

The 𝛑 bond breaks and each electron

goes towards forming a 𝝈 bond with an
adjacent monomer unit.

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Deduce the repeat unit of the addition
polymer formed from the monomer
below

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Deduce the repeat unit of the addition polymer formed
from the monomer below

● Turn the double C=C into a single C-C.

● Add and extend bonds out from the sides of the carbon
atoms.
● Add in square brackets around the molecule.
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Identify the monomer that formed the
addition polymer below

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Identify the monomer that formed the addition polymer
below

Propene

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Why are polymers difficult to dispose of?

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Why are polymers difficult to dispose of?

● They are non-biodegradable.

● The combustion of polymers can often form
harmful compounds (such as HCl for
chlorinated polymers)

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Why are alkanes suitable for use as
fuels?

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Why are alkanes suitable for use as fuels?

High standard enthalpy changes of

combustion (releases a lot of energy
upon combustion)

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What are the problems with carbon
monoxide?

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What are the problems with carbon monoxide?

● Carbon monoxide is poisonous.

● It irreversibly binds to haemoglobin, reducing the
amount of oxygen that can be carried in the blood.
● Cells may become deoxygenated, leading to cell death.
● If too much CO is inhaled, this could lead to death.

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Why are atmospheric oxides of nitrogen
pollutants?

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Why are atmospheric oxides of nitrogen pollutants?

● Nitrogen monoxide can react with

chemicals that cause acid rain.
● Nitrogen dioxide can also contribute to
photochemical smog.

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Describe how a catalytic converter works

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Describe how a catalytic converter works
● Nitrogen monoxide is formed in car engines:
N2(g) + O2(g) → 2NO(g)
● A catalytic converter removes a majority of NO so it
isn’t released into the atmosphere:
2NO(g) + 2CO(g) → N2(g) + CO2(g)
● A ceramic honeycomb structure is coated in a thin
layer of metal catalysts (such as platinum and
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 What are the environmental
consequences of unburnt hydrocarbons?

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What are the environmental consequences of
unburnt hydrocarbons?

Hydrocarbons in the atmosphere can

absorb infrared radiation, causing the
greenhouse effect.

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 What are the environmental
consequences of the emission of
greenhouse gases?

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What are the environmental consequences of the emission of
greenhouse gases?
Greenhouse gases cause the greenhouse effect which contributes to climate
change:

● Electromagnetic radiation from the sun passes through the atmosphere.

Some radiation is absorbed by Earth so temperature increases.
● Heat is radiated from the Earth as infrared radiation which is absorbed by
greenhouse gases in the atmosphere. This causes the bonds in these
molecules to vibrate before this energy is re-emitted.
● As a result, the atmosphere warms up even further, contributing to global
warming.
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How is infrared spectroscopy used to
monitor air pollution?

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How is infrared spectroscopy used to monitor air
pollution?
● IR spectroscopy identifies particular bonds in a
molecule.
● Different pollutants will have different patterns of
absorption as they contain different bonds.
● It is also possible to measure the concentration of
each pollutant.
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Describe the halogenation of benzene
(A level only)

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Describe the halogenation of benzene (A level only)

● E.g. Bromination:
● Benzene only reacts with bromine if a hydrogen
carrier, FeBr3 or AlBr3, is present.
● This forms bromobenzene and hydrogen bromide:
● C6H6 + Br2 → C6H5Br + HBr

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What is the role of the halogen carrier in
the halogenation of benzene?
(A level only)

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What is the role of the halogen carrier in the
halogenation of benzene? (A level only)
● To generate the electrophile:
● Br2 + FeBr3 → FeBr4- + Br+
● FeBr4- then reacts with the proton expelled from
the intermediate to regenerate the halogen
carrier:
● FeBr4- + H+ → FeBr3 + HBr
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Draw and name the mechanism for the
bromination of benzene (A level only)

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Draw and name the mechanism for the bromination of
benzene (A level only)
Electrophilic substitution.

The Br+ ion accepts a pair of The intermediate is so unstable that it

electrons from the ring of breaks down, releasing a hydrogen ion.
delocalisation. This forms the product, bromobenzene.
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How does benzene undergo nitration?
(A level only)

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How does benzene undergo nitration? (A level only)
Benzene reacts with conc. nitric acid at a
temperature of 50℃ - 60℃ with a conc.
sulfuric acid catalyst to from nitrobenzene
and water:
C6H6 + HNO3 → C6H5NO2 + H2O
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How does sulfuric acid act as a catalyst
in the nitration of benzene?
(A level only)

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How does sulfuric acid act as a catalyst in the
nitration of benzene? (A level only)
● Generation of electrophile:
● H2SO4 + HNO3 → NO2+ + HSO4- + H2O
● Sulfuric acid is regenerated when the
hydrogensulfate ion reacts with the proton that
is expelled from the intermediate:
● HSO4- + H+ → H2SO4
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Draw and name the mechanism for the
nitration of benzene (A level only)

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Draw and name the mechanism for the nitration of
benzene (A level only)
Electrophilic substitution

The NO2+ ion accepts a pair of The intermediate is so unstable that it

electrons from the delocalised breaks down, releasing a hydrogen ion.
pi system. This forms the product, nitrobenzene.

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 How does benzene undergo an
alkylation reaction? Write an equation for
the reaction between benzene and
chloroethane (A level only)

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How does benzene undergo an alkylation reaction?
Write an equation for the reaction between benzene
and chloroethane (A level only)
React benzene with a haloalkane in the
presence of a halogen carrier (e.g. AlCl3):
C6H6 + C2H5Cl → C6H5(C2H5)+ HCl

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How does the halogen carrier generate
the electrophile when benzene reacts
with a haloalkane?

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How does the halogen carrier generate the
electrophile when benzene reacts with a haloalkane?

● Halogen carrier reacts with haloalkane to generate

electrophile:
● AlCl3 + C2H5Cl → AlCl4- + C2H5+
● AlCl4- reacts with the proton expelled from the
intermediate to regenerate the halogen carrier:
● AlCl4- + H+ → AlCl3 + HCl
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How does benzene undergo an acylation
reaction? Write an equation for the
reaction between benzene and ethanoyl
chloride (A level only)

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How does benzene undergo an acylation reaction?
Write an equation for the reaction between benzene
and ethanoyl chloride (A level only)
Reflux benzene with an acyl chloride in
the presence of a halogen carrier (i.e.
AlCl3):
C6H6 + CH3COCl → C6H5COCH3+ HCl
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How does the halogen carrier generate
the electrophile when benzene reacts
with an acyl chloride? (A level only)

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How does the halogen carrier generate the
electrophile when benzene reacts with an acyl
chloride? (A level only)
● Halogen carrier reacts with acyl chloride to generate
electrophile:
● AlCl3 + CH3COCl → AlCl4- + CH3CO+
● AlCl4- reacts with the proton expelled from the
intermediate to regenerate the halogen carrier:
● AlCl4- + H+ → AlCl3 + HCl
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 How does benzene undergo addition
reactions with hydrogen? (A level only)

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How does benzene undergo addition reactions with
hydrogen? (A level only)
C6H6 + 3H2 → C6H12
● Nickel catalyst
● Heated to around 150℃
● High pressure
● These conditions are required because this reaction has a
high activation energy.
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How is the side chain of methylbenzene
completely oxidised to give benzoic
acid? (A level only)

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How is the side chain of methylbenzene completely
oxidised to give benzoic acid? (A level only)
● Alkyl groups attached to a benzene ring are
oxidised fairly easily when heated under reflux with
alkaline potassium manganate solution.
● Purple solution → Dark brown precipitate of MnO2
● Dilute sulfuric acid is then added.
● Overall, methylbenzene is oxidised to benzoic acid.
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How does the ring of delocalisation affect
the reactions of benzene? (A level only)

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How does the ring of delocalisation affect the
reactions of benzene? (A level only)
● Electron density is relatively low so there is weak attraction to
electrophiles.
● This means benzene is unable to undergo electrophilic addition
reactions and will slowly undergo electrophilic substitution
reactions.
● If benzene was to undergo addition reactions it would
permanently break the delocalisation- energetics would be
against this happening.
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Compare the reactivity of chlorobenzene
to chloroalkanes (A level only)

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Compare the reactivity of chlorobenzene to
chloroalkanes (A level only)
● The C-Cl bond in chlorobenzene is stronger than expected.
One of the lone pairs on the chlorine atom interacts with the
delocalised ring electrons, strengthening the bond.
● This means the bond is harder to break and hence requires
more energy to overcome.
● This means chlorobenzene is less reactive than
chloroalkanes.

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How can you tell whether a substitution
reaction by a halogen will occur in the
benzene ring or on the side chain?
(A level only)

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How can you tell whether a substitution reaction by a
halogen will occur in the benzene ring or on the side
chain? (A level only)
For the substitution by a halogen:
● If UV light is present and a catalyst is absent:
substitution takes place on the side chain.
● If a catalyst is present and UV light is absent:
substitution takes place in the ring.
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CIE Chemistry A-Level
Topic 16 - Halogen Derivatives
Flashcards

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This work by https://bit.ly/pmt-edu-cc CC BY-NC-ND 4.0

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What are halogenoalkanes?

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What are halogenoalkanes?

Halogenoalkanes are organic

compounds where the hydrogen atom on
an alkane has been replaced by a
halogen.
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How do halogenoalkanes undergo
hydrolysis reactions?

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How do halogenoalkanes undergo hydrolysis
reactions?

CH3CH2Br + H2O → CH3CH2OH + HBr

- Reaction is fairly slow.
- Resulting solution can be tested with
AgNO3 to determine the halogen present.
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 How do halogenoalkanes undergo a
nucleophilic substitution reaction to form
a nitrile?

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How do halogenoalkanes undergo a nucleophilic
substitution reaction to form a nitrile?

CH3CH2Br + KCN → CH3CH2CN + KBr

- Heat under reflux.
- Ethanol is used as the solvent.

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How do halogenoalkanes react with
ammonia to form a primary amine?

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How do halogenoalkanes react with ammonia to
form a primary amine?
First the halogenoalkane reacts with ammonia to form an alkyl
ammonium salt:

● CH3CH2Br + NH3 → CH3CH2NH3Br

If the ammonia is in excess, the salt reacts to form a primary

amine:

● CH3CH2NH3Br + NH3 → CH3CH2NH2 + NH4Br

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How does 2-bromopropane react to form
an alkene?

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How does 2-bromopropane react to form an alkene?

Elimination reaction:
Reflux with KOH in ethanol (or conc. NaOH
solution).
CH3CHBrCH3 + KOH → CH2=CHCH3 + KBr + H2O

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Describe the SN1 nucleophilic
substitution mechanism

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Describe the SN1 nucleophilic substitution
mechanism
E.g. (CH3)3CCl + OH- → (CH3)3COH + Cl-

In the first stage, the halogenoalkane ionises to form the

carbocation intermediate (CH3)3C+ and Cl-.

The (CH3)3C+ intermediate then immediately reacts with

the hydroxide ion to form the product.

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What does the SN1 mechanism look
like?

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What does the SN1 mechanism look like?

Step 1

Step 2

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Describe the SN2 nucleophilic
substitution mechanism

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Describe the SN2 nucleophilic substitution mechanism
E.g. CH3CH2Br + OH- → CH3CH2OH + Br-
- These reactions are a one step mechanism.
- The nucleophile attacks the substrate at the same time as the
leaving group leaves the substrate.
- The nucleophile attacks the carbon atom from the back side,
causing an inversion of the groups in the product.
- The nucleophile attacks from the backside because the large
halogen atom prevents the attack from the other direction.
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What does a SN2 mechanism look like?

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What does a SN2 mechanism look like?

E.g. CH3Cl + OH- → CH3OH + Cl-

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What are the inductive effects of alkyl
groups?

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What are the inductive effects of alkyl groups?

Alkyl groups are electron-donating groups.

They push electrons away, making the alkyl
group have a slight positive charge and the
carbon it is bonded with to have a slight negative
charge. This is called the positive inductive
effect.
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What mechanism (SN1 or SN2) do
primary, secondary and tertiary
haloalkanes react via?

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What mechanism (SN1 or SN2) do primary,
secondary and tertiary haloalkanes react via?
Primary halogenoalkanes tend to react via the SN2
mechanism.

Tertiary halogenoalkanes tend to react via the SN1

mechanism.

Secondary halogenoalkanes react via a mixture of the two,

depending on the structure.
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What are the relative strengths of
carbon-halogen bonds?

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What are the relative strengths of carbon-halogen
bonds?
As you go down Group 7, the carbon-halogen
bond strength decreases.
C-F > C-Cl > C-Br > C-I

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Hence what is the trend in the rate of
hydrolysis of carbon-halogen bonds?

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Hence what is the trend in the rate of hydrolysis of
carbon-halogen bonds?
As you go down the group, the rate of
hydrolysis of carbon-halogen bonds increases
as less energy is required to break the bond
since bond strength weakens down the group.

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What are the uses of fluoroalkanes and
fluorohalogenoalkanes?

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What are the uses of fluoroalkanes and
fluorohalogenoalkanes?
- Refrigerants
- Used in aerosols
- Used in making foamed plastics
They are very chemically inert and will not react
with anything.
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What is the environmental problem with
the use of CFCs (chlorofluorocarbons)?

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What is the environmental problem with the use of
CFCs (chlorofluorocarbons)?
CFCs damage the ozone layer. The ozone is in the upper
atmosphere and it absorbs a lot of UV radiation.

CFCs are broken down by UV light, releasing a chlorine

radical. This chlorine radical react with ozone and breaks it
down to oxygen. This means there is less protection from
UV radiation.
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Give the equations for the reactions that
take place between a chlorine free
radical and ozone

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Give the equations for the reactions that take place
between a chlorine free radical and ozone

Cl. + O3 → O2 + ClO.
. .
ClO + O3 → 2O2 + Cl
Overall: 2O3 → 3O2

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CIE Chemistry A-Level
Topic 17 - Hydroxy Compounds
Flashcards

PMT Education is licensed under https://bit.ly/pmt-cc

This work by https://bit.ly/pmt-edu-cc CC BY-NC-ND 4.0

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What is the chemical equation for the
complete combustion of ethanol?

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What is the chemical equation for the complete
combustion of ethanol?

CH3CH2OH + 3O2 ⟶ 2CO2 + 3H2O

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What condition is required to ensure
complete combustion takes place?

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What condition is required to ensure complete
combustion takes place?

Excess oxygen

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What is the chemical equation for the
incomplete combustion of ethanol to
produce carbon monoxide?

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What is the chemical equation for the incomplete
combustion of ethanol to produce carbon monoxide?

C2H5OH + 2O2→ 3H2O + 2CO

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How do alcohols react to form
halogenoalkanes?

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How do alcohols react to form halogenoalkanes?

There are multiple ways alcohols can react to

form halogenoalkanes:
- React with sodium halides and sulfuric acid.
- React with sodium or potassium iodide and
concentrated phosphoric (V) acid.

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How do alcohols react with sodium?

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How do alcohols react with sodium?

2CH3CH2OH + 2Na → 2CH3CH2ONa + H2

Ethanol reacts with sodium to form hydrogen gas
and sodium ethoxide (an alkoxide).
If the solution is evaporated, sodium ethoxide
remains as a white solid.
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How are primary alcohols oxidised to
aldehydes?

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How are primary alcohols oxidised to aldehydes?
If you heat a primary alcohol with acidified potassium
dichromate(VI), the alcohol will be oxidised to form an
aldehyde:
CH3CH2OH + [O] → CH3CHO + H2O
The acidified potassium dichromate(VI) will change
colour from orange to green.
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How are primary alcohols oxidised to
carboxylic acids?

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How are primary alcohols oxidised to carboxylic
acids?
If a primary alcohol is heated under reflux with acidified
potassium dichromate(VI), the alcohol will be oxidised form a
carboxylic acid.

CH3CH2OH + 2[O] → CH3COOH + H2O

The acidified potassium dichromate(VI) will change colour

from orange to green.
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How are secondary alcohols oxidised to
ketones?

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How are secondary alcohols oxidised to ketones?
If a secondary alcohol is heated under reflux with
acidified potassium dichromate (VI), the alcohol will be
oxidised to form a ketone:
CH3CH(OH)CH3 + [O] → CH3COCH3 + H2O
The acidified potassium dichromate(VI) will change
colour from orange to green.
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How do alcohols undergo dehydration
reactions?

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How do alcohols undergo dehydration reactions?
Alcohols undergo dehydration reactions to form
an alkene and a water molecule.
Two options to carry out dehydration:
- Heat with strong acid catalyst.
- Pass alcohol vapour over Al2O3 powder.
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What is the chemical equation for the
dehydration of propan-2-ol to form
prop-2-ene?

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What is the chemical equation for the dehydration of
propan-2-ol to form prop-2-ene?
CH3CH(OH)CH3 → CH2CHCH3 + H2O

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How do alcohols react with carboxylic
acids?

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How do alcohols react with carboxylic acids?

Alcohols react with carboxylic acids to

form esters. This process is called
esterification and requires heating with a
sulfuric acid catalyst.

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 What is the chemical equation for the
reaction between methanol and ethanoic
acid? Give the name of the ester formed

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What is the chemical equation for the reaction
between methanol and ethanoic acid? Give the
name of the ester formed
CH3OH + CH3COOH → CH3COOCH3 + H2O
Product CH3COOCH3 is methyl ethanoate.

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How do acyl chlorides react to form an
ester? (A-Level only)

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How do acyl chlorides react to form an ester?
(A-Level only)
Acyl chlorides react with primary alcohols to
form esters. Hydrogen chloride is also
produced during the reaction.
CH3COCl + CH3OH → CH3COOCH3 + HCl

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 What is the chemical equation for the
reaction between ethanol and propanoyl
chloride? Give the name of the ester
formed
(A-Level only)

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What is the chemical equation for the reaction
between ethanol and propanoyl chloride? Give the
name of the ester formed (A-Level only)
CH3CH2COCl + CH3CH2OH → CH3CH2COOCH2CH3 +
HCl
The product CH3CH2COOCH2CH3 is ethyl propanoate.

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How are alcohols classified?

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How are alcohols classified?

- Primary, 1° - The carbon bonded to the alcohol group is

bonded to one R (alkyl) group only.
- Secondary, 2° - The carbon bonded to the alcohol group is
bonded to two R groups.
- Tertiary, 3° - The carbon bonded to the alcohol group is
bonded to three other R groups.
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 How can you distinguish between
primary, secondary and tertiary alcohols?

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How can you distinguish between primary, secondary and
tertiary alcohols?
- Tertiary cannot be oxidised and therefore there’s no colour
change (remains orange) when heated with acidified potassium
dichromate (VI).
- Primary and secondary alcohols are able to be oxidised and so
there would be a colour change from orange to green.
- You could run further tests on the resulting solutions from
primary and secondary alcohols by using Fehling’s or Tollens’
reagent.
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How can you deduce the presence of a
CH3CH(OH)– group in an alcohol?

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How can you deduce the presence of a
CH3CH(OH)– group in an alcohol?
- Iodine is added to a small volume of alcohol.
- Some sodium hydroxide is then added to decolourise
the iodine.
- The presence of a CH3CH(OH)- group is indicated by
a very pale yellow precipitate known as
tri-iodomethane, CH3I.
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How does phenol react with bases, e.g.
NaOH? (A-Level only)

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How does phenol react with bases, e.g. NaOH?
(A-Level only)
Phenol reacts with sodium hydroxide to
form sodium phenoxide and water.

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What is the chemical equation for the
reaction of phenol with sodium
hydroxide?
(A-Level only)

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What is the chemical equation for the reaction of
phenol with sodium hydroxide? (A-Level only)

- +
C6H5OH + NaOH → C6H5O Na + H2O

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How does phenol react with sodium?
(A-Level only)

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How does phenol react with sodium? (A-Level only)

Phenol reacts with sodium to form

sodium phenoxide and hydrogen gas.

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What is the chemical equation for the
reaction of phenol with sodium?
(A-Level only)

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What is the chemical equation for the reaction of
phenol with sodium? (A-Level only)

C6H5OH + Na → C6H5O-Na+ + ½H2

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How does phenol react with diazonium
salts?
(A-Level only)

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How does phenol react with diazonium salts?
(A-Level only)
In a coupling reaction:

C6H5OH + NaOH → C6H5O-Na+ + H2O

The sodium phenoxide solution reacts with a

benzenediazonium salt solution:

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How does phenol react with dilute nitric
acid?
(A-Level only)

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How does phenol react with dilute nitric acid?
(A-Level only)
Phenol reacts readily with dilute nitric acid at room temperature
to form a mixture of 2-nitrophenol and 4-nitrophenol.

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How does phenol react with
concentrated nitric acid?
(A-Level only)

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How does phenol react with concentrated nitric acid?
(A-Level only)
Phenol reacts with concentrated nitric acid to form
2,4,6-trinitrophenol.

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How does the bromination of phenol
occur?
(A-Level only)

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How does the bromination of phenol occur?
(A-Level only)
Phenol reacts with bromine to form a white
precipitate of 2,4,6-tribromophenol.

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What are the relative acidities of water,
phenol and ethanol?
(A-Level only)

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What are the relative acidities of water, phenol and
ethanol? (A-Level only)

Phenol > water > ethanol

Phenol is the most acidic.
Ethanol is the least acidic.

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Explain the relative acidities of water,
phenol and ethanol
(A-Level only)

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Explain the relative acidities of water, phenol and
ethanol (A-Level only)
- Phenol is the most acidic because the phenoxide ion is relatively stable. The
lone pair on the oxygen atom is delocalised into the pi system meaning the
negative charge is dispersed among the carbon atoms so phenol is most likely
to donate a hydrogen ion.
- Ethanol and water have similar acidities but ethanol is the least acidic. This is
because of the positive inductive effect. The alkyl group in the ethoxide ion
“pushes” electrons away from itself. This increases the electron density of the
oxygen, making it more likely to bond to a hydrogen ion and reform ethanol.

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CIE Chemistry A-Level
Topic 18 - Carbonyl Compounds
Flashcards

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How are primary alcohols oxidised to
aldehydes?

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How are primary alcohols oxidised to aldehydes?
If a primary alcohol is heated with acidified potassium
dichromate(VI), the alcohol will be oxidised to form an
aldehyde.
CH3CH2OH + [O] → CH3CHO + H2O
The acidified potassium dichromate(VI) will change
colour from orange to green.
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How are secondary alcohols oxidised to
ketones?

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How are secondary alcohols oxidised to ketones?

If a secondary alcohol is heated under reflux with

acidified potassium dichromate(VI), the alcohol will be
oxidised to form a ketone:
CH3CH(OH)CH3 + [O] → CH3COCH3 + H2O
The acidified potassium dichromate(VI) will change
colour from orange to green.
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How are aldehydes and ketones reduced
using cyanide ions?

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How are aldehydes and ketones reduced using
cyanide ions?

By using HCN in ethanol or NaCN solution:

CH3CHO + HCN → CH3CH(OH)CN
CH3COCH3 + HCN → CH3C(OH)CNCH3

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How are aldehydes and ketones reduced
using NaBH4 or LiAlH4 ions?

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How are aldehydes and ketones reduced using
NaBH4 or LiAlH4 ions?

NaBH4 and LiAlH4 are reducing agents

and can both be represented as [H] in
chemical equations:
CH3CHO + 2[H] → CH3CH2OH
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What is the mechanism for the reaction
between HCN and aldehydes and
ketones?

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What is the mechanism for the reaction between
HCN and aldehydes and ketones?

Nucleophilic addition

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What is the test for a carbonyl
compound?

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What is the test for a carbonyl compound?
Brady’s reagent / 2,4-dinitrophenylhydrazine
(2,4-DNPH):
- Add a few drops of the unknown sample to 5 cm3 of
Brady’s reagent.
- The presence of a carbonyl compound is indicated by
a yellow/orange precipitate.
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How can you test for an aldehyde using
Fehling’s solution?

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How can you test for an aldehyde using Fehling’s
solution?

Warm the sample with Fehling’s solution.

If an aldehyde is present, the blue
solution will form a brick red precipitate.

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How can you test for an aldehyde using
Tollens’ reagent?

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How can you test for an aldehyde using Tollens’
reagent?
Add Tollens’ reagent to the sample and warm in a
water bath.
The presence of a silver mirror on the test tube
indicates that the sample contains an aldehyde
functional group.
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How do CH3CO- compounds react with
alkaline aqueous iodine?

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How do CH3CO- compounds react with alkaline
aqueous iodine?
Iodine is added to the aldehyde or ketone
solution. Just enough NaOH is added until the
iodine is decolourised.
A pale yellow precipitate of tri-iodomethane,
CH3I, is formed.
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CIE Chemistry A-Level
Topic 19 - Carboxylic Acids and
Derivatives
Flashcards

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How are primary alcohols oxidised to
carboxylic acids?

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How are primary alcohols oxidised to carboxylic
acids?
If a primary alcohol is heated under reflux with acidified
potassium dichromate(VI), the alcohol will be oxidised to form
a carboxylic acid.

CH3CH2OH + 2[O] → CH3COOH + H2O

The acidified potassium dichromate(VI) will change colour

from orange to green.
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How are aldehydes oxidised to
carboxylic acids?

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How are aldehydes oxidised to carboxylic acids?

If an aldehyde is heated under reflux with acidified potassium

dichromate(VI), the aldehyde will be oxidised to form a
carboxylic acid.

CH3CHO + [O] → CH3COOH

The acidified potassium dichromate(VI) will change colour
from orange to green.
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How do nitriles react to form carboxylic
acids?

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How do nitriles react to form carboxylic acids?

Nitriles react via acid hydrolysis to form carboxylic

acids.
Heat the nitrile under reflux with a strong acid
catalyst:
CH3CN + 2H2O + HCl → CH3COOH + NH4Cl
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How do carboxylic acids react with
metals?

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How do carboxylic acids react with metals?

Carboxylic acids react with metals to

form a salt and hydrogen gas.

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 What is the chemical equation for the
reaction of ethanoic acid with sodium?

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What is the chemical equation for the reaction of
ethanoic acid with sodium?

2CH3COOH + 2Na → 2CH3COO-Na+ + H2

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How do carboxylic acids react with
carbonates?

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How do carboxylic acids react with carbonates?

Carboxylic acids react with carbonates to

form a salt, carbon dioxide and water.

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What is the chemical equation for the
reaction of ethanoic acid with sodium
carbonate?

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What is the chemical equation for the reaction of
ethanoic acid with sodium carbonate?

2CH3COOH + Na2CO3 → 2CH3COO-Na+ + CO2 + H2O

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How do carboxylic acids react with
alkalis?

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How do carboxylic acids react with alkalis?

Carboxylic acids react with alkalis to

form a salt and water:
- +
CH3COOH + NaOH → CH3COO Na + H2O

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How do alcohols react with carboxylic
acids?

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How do alcohols react with carboxylic acids?

Alcohols react with carboxylic acids to

form esters. This process is called
esterification and requires heating with a
sulfuric acid catalyst.

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 What is the chemical equation for the
reaction between methanol and ethanoic
acid? Give the name of the ester formed

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What is the chemical equation for the reaction
between methanol and ethanoic acid? Give the
name of the ester formed
CH3OH + CH3COOH → CH3COOCH3 + H2O
Product CH3COOCH3 is methyl ethanoate.

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How do carboxylic acids form alcohols?

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How do carboxylic acids form alcohols?

Reduction with LiAlH4

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What is the chemical equation for the
reduction of ethanoic acid?

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What is the chemical equation for the reduction of
ethanoic acid?

CH3COOH + 4[H] → CH3CH2OH + H2O

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How do carboxylic acids react to form
acyl chlorides?
(A-Level only)

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How do carboxylic acids react to form acyl
chlorides? (A-Level only)
Carboxylic acids react with sulfur dichloride
oxide to form an acyl chloride, sulfur dioxide
and hydrogen chloride.
CH3COOH + SOCl2 → CH3COCl + SO2 + HCl

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What is the chemical equation for the
reaction between ethanoic acid and
sulfur dichloride oxide?
(A-Level only)

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What is the chemical equation for the reaction
between ethanoic acid and sulfur dichloride oxide?
(A-Level only)

CH3COOH + SOCl2 → CH3COCl + SO2 + HCl

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How is methanoic acid further oxidised?
(A-Level only)

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How is methanoic acid further oxidised?
(A-Level only) Although methanoic acid is a carboxylic
acid, it also has an aldehyde functional
group. This means the aldehyde group
can be oxidised further by using Tollens’
reagent or Fehling’s solution.
The methanoic acid is oxidised to carbon
dioxide and water.
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What is the chemical equation for the
oxidation of methanoic acid?
(A-Level only)

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What is the chemical equation for the oxidation of
methanoic acid? (A-Level only)

HCOOH + [O] → CO2 + H2O

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How is ethanedioic acid oxidised further?
(A-Level only)

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How is ethanedioic acid oxidised further?
(A-Level only)

Ethanedioic acid is oxidised to carbon

dioxide and water using warm acidified
potassium manganate(VII) solution.

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What is the chemical equation for the
oxidation of ethanedioic acid?
(A-Level only)

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What is the chemical equation for the oxidation of
ethanedioic acid? (A-Level only)

(COOH)2 + [O] → 2CO2 + H2O

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State the relative acidities of carboxylic
acids, alcohols and phenols
(A-Level only)

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State the relative acidities of carboxylic acids,
alcohols and phenols (A-Level only)

Carboxylic acids → Phenol → Alcohols

→ Decreasing acidity →

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Explain the relative acidities of carboxylic
acids, alcohols and phenols
(A-Level only)

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Explain the relative acidities of carboxylic acids,
alcohols and phenols (A-Level only)
● Carboxylic acids are the most acidic as the carboxylate ion has a delocalised pi system
that develops over the -COO- group. This distributes the negative charge, making the
carboxylate ion more stable.
● Phenols are more acidic than alcohols because the the phenoxide ion is relatively stable.
The lone pair on the oxygen is delocalised into the pi system so the negative charge is
dispersed. This makes phenol more likely to donate a hydrogen ion compared with
alcohols.
● Alcohols are the least acidic because of the positive inductive effect. In the alkoxide ion,
the alkyl groups “push” electrons away from themselves, increasing the electron density
of the oxygen, making it more likely to bond to a hydrogen ion and reform an alcohol.
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What determines the acidity of chlorine
substituted ethanoic acids?
(A-Level only)

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What determines the acidity of chlorine substituted
ethanoic acids? (A-Level only)
- You can strengthen an acid by pulling charge away
from the -COO- end. This can be done by adding a
chlorine atom to the chain.
- Chlorine is very electronegative and so will have a
tendency to attract electrons towards itself.
- The more chlorines bonded, the stronger the acid.
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How do acyl chlorides react with water?
(A-Level only)

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How do acyl chlorides react with water?
(A-Level only)
Hydrolysis reaction:
The acyl chloride reacts with water to form a
carboxylic acid and hydrochloric acid.

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What is the chemical equation for the
hydrolysis of ethanoyl chloride?
(A-Level only)

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What is the chemical equation for the hydrolysis of
ethanoyl chloride? (A-Level only)

CH3COCl + H2O → CH3COOH + HCl

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How do acyl chlorides react with
alcohols? (A-Level only)

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How do acyl chlorides react with alcohols?
(A-Level only)
Acyl chlorides react with alcohols to form
an ester and hydrochloric acid:
CH3COCl + CH3OH → CH3COOCH3 + HCl

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How do acyl chlorides react with phenol?
(A-Level only)

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How do acyl chlorides react with phenol?
(A-Level only)

An acyl chloride reacts with phenol to

form an ester and hydrochloric acid.
CH3COCl + C6H5OH → CH3COOC6H5 + HCl

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How do acyl chlorides react with
ammonia?
(A-Level only)

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How do acyl chlorides react with ammonia?
(A-Level only)
Acyl chlorides react with ammonia to
form a primary amide and hydrochloric
acid:
CH3COCl + NH3 → CH3CONH2 + HCl
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How do acyl chlorides react with a
primary amine?
(A-Level only)

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How do acyl chlorides react with a primary amine?
(A-Level only)
Acyl chlorides react with a primary amine
to form a secondary amide and
hydrochloric acid:
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Compare the relative ease of hydrolysis
of acyl chlorides, alkyl chlorides and aryl
chlorides
(A-Level only)

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Compare the relative ease of hydrolysis of acyl
chlorides, alkyl chlorides and aryl chlorides
(A-Level only)
- Acyl chlorides react vigorously with cold water to
produce a carboxylic acid and hydrogen chloride gas.
E.g. CH3COCl + H2O → CH3COOH + HCl
- Alkyl chlorides have almost no reaction with water.
- Aryl chlorides have no reaction with water.

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How do esters undergo acid hydrolysis?

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How do esters undergo acid hydrolysis?

Heat the ester under reflux with dilute aqueous

acid. The ester will be hydrolysed into a
carboxylic acid and alcohol.
The reaction is slow and reversible.
CH3COOCH3 + H2O ⇌ CH3COOH + CH3OH
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How do esters undergo base hydrolysis?

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How do esters undergo base hydrolysis?
Heat the ester under reflux with a dilute alkali.
The ester will be hydrolysed into the salt of the
carboxylic acid, and the alcohol. The reaction is
one-way and faster than acid hydrolysis.
CH3COOCH3 + NaOH → CH3COO-Na+ + CH3OH

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State the major commercial uses of
esters

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State the major commercial uses of esters

- Perfumes
- Solvents
- Flavourings

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