REDOX 3.

Oxidation & Reduction Organic Preparations compound formation reactions

in organic chemistry oxidation states in organic molecules

Doc Brown's Chemistry REDOX CHEMISTRY Part 3

Sections 8 to 10 Organic Oxidation & Reduction - Preparative Reactions in
Organic Chemistry
GCE Advanced Level Theoretical Organic Chemistry Revision Notes on REDOX
reactions involving organic oxidation and reduction
synthesis-preparations. Reactions involving the oxidation or reduction of
the starting reactant molecules and the chemistry of the appropriate
oxidising agents and reducing reagents is described and discussed.
Revising Advanced Organic Chemistry PART 12 ORGANIC REDOX REACTIONS
REDOX section-index: 1. Basic redox definitions * 2. Introducing oxidation
state (with sub-index) * 3. Oxidation state rules-guidelines & inorganic
examples * 4. Naming inorganic compounds * 5. Using oxidation states to
describe redox changes in a given inorganic reaction equation (with
sub-index) * 6. Constructing full inorganic redox equations from
half-equations (with sub-index) * 7. Redox titrations * 8. Organic
synthesis reductions (with summary table) * 9. Organic synthesis
oxidations (with summary table) * 10. Other Organic Redox Reactions (with
sub-index) * 11. Carbon's ox. state in selected organic compounds,
functional group level * See also Equilibria Part 7 Redox Reactions for
half cell equilibria, electrode potential, standard hydrogen electrode,
Simple cells and notation, Electrochemical Series, EØcell for reaction
feasibility, 'batteries' and fuel cell systems etc.

Redox reactions in Organic Chemistry

A summary of some redox reactions used in organic synthesis is given
below. Further details for selected reactions are given below the summary
tables. Most of the reactions described are found in one or other of UK
based GCE-AS-A2 or IB courses. The application of oxidation states to
organic molecules can be tricky, but, (i) use of half-cell equations
usually gets round the problem, and (ii) hopefully the oxidation state
exemplars in the last section will help illuminate the situation if you
are interested, but this knowledge is not required at this level?
Important examination note: Unless hydrogen gas or oxygen gas is used
directly in the redox synthesis reaction [O] and [H] should be used in
simplified equations and examples will be quoted in each section and some
syllabuses specifically state so.
The concept of functional group level is dealt with in appendix 1.
8. Summary of some ORGANIC SYNTHESIS REDUCTION REACTIONS
Guide notes:
YES/NO denotes whether reaction possible.
Lithium tetrahydridoaluminate(III), LiAlH4 (lithium aluminium hydride), is
a more powerful reducing agent than sodium tetrahydridoborate(III), NaBH4
(sodium borohydride) and accounts for the NO/YES differences in columns
(a) and (b).
R = H, alkyl or aryl for aldehydes, carboxylic acids and nitriles, R =
alkyl or aryl for ketones.
Click on 8.1, 8.2, 8.3, 8.4 and 8.5 in the table for more details on
(a), (b), (c) or (d) reaction reagents/conditions and the chemical
outcome.
Important examination note: Unless hydrogen gas or oxygen gas is used
 directly in the redox synthesis reaction [O] and [H] should be used in
simplified equations and examples will be quoted in each section and some
syllabuses specifically state so.
homologous series change on reductionmolecular structure change(a) NaBH4
in water (lab method)(b) LiAlH4 in e.g. ether (lab method)(c) reflux with
Sn/conc. HCl(aq) (lab method)(d) Ni/H2 at 150oC (industry) Pd and Pt are
also used as catalysts
8.1 alkene ==> alkane>C=C< ==> -CH-CH-NONONOYES, used
8.2 aldehyde/ketone ==> primary/secondary alcoholRCHO ==> RCH2OH and R2C=O
==> R2CHOHYESYEScan be reduced with Na/C2H5OH or Zn/CH3COOH mixturesYES,
used?
8.3 carboxylic acid ==> primary aliphatic alcoholRCOOH ==>
RCH2OHNOYESNOYES, used?
8.4 nitrile ==> primary aliphatic amineRCN ==> RCH2NH2NOYESNOYES, used?
8.5 nitro-aromatic ==> primary aromatic aminee.g. C6H5NO2 ==>
C6H5NH2NOYESYESYES
Some further details of the organic reductions tabulated above
8.1 Reduction of alkenes to alkanes
How can you reduce unsaturated compounds like alkenes?
e.g. unsaturated alkenes to saturated alkanes
8.1(a)/(b) Alkenes cannot be reduced by metal hydride complexes (see
8.2/8.3a-b) because the 'attacking' species is nucleophilic e.g. the
negative (e- pair donating) BH4- or AlH4- ions are repelled too strongly
to allow 'disruption' of the electron rich C=C double bond in alkenes.
Alkenes tend to react with electron pair seeking electrophilic reagents
like H&#948;+-Br&#948;-.
8.1(c) Reduction reactions by metal occur on the surface of the metal
and involves reactants weakly bonding with the metal.
8.1(d) e.g. propene ==> propane: CH3CH=CH2 + H2 == Ni catalyst ==>
CH3CH2CH3
This reaction is initiated on the nickel catalyst surface which lowers
the activation energy to help break the H-H bonds and 'half' of the
C=C bond. (see diagram and explanation of the hydrogenation
mechanism).
The catalysed hydrogenation of alkenes is a very important industrial
reaction used to convert natural polyunsaturated oils into low melting
solid more saturated fats like margarine.

8.2 Reduction of aldehydes to primary alcohols and ketones to secondary

alcohols
How can you reduce carbonyl compounds like aldehydes and ketones?
These reactions are essentially the reduction of the carbony1 group >C=O
to >CHOH.
8.2(a) Using sodium tetrahydrioborate(III), NaBH4 (sodium borohydride)
The reaction can be carried out in water. The reduction mechanism is
very complicated, but can be considered in a simplistic way as
involving the donation of a hydride ion to the aldehyde/ketone.
An outline of the nucleophilic addition mechanism is given on the
Organic Mechanisms Part III page, but the simple equation will suffice
here.
aldehyde: RCHO + 2[H] ==> RCH2OH (R = H, alkyl or aryl)
e.g. ethanal to ethanol: CH3CHO + 2[H] ==> CH3CH2OH
 ketone: R2C=O + 2[H] ==> R2CHOH (R = alkyl or aryl)
e.g. propanone to propan-2-ol: CH3COCH3 + 2[H] ==> CH3CH(OH)CH3
8.2(b) Using lithium tetrahydridoaluminate(III), LiAlH4 (lithium
tetrahydride)
LiAlH4 is a more powerful reducing agent than NaBH4 and reacts
violently with water (and reacts with ethanol too?, so the reaction
must be carried out in an inert solvent like ethoxyethane ('ether').
The initial product is hydrolysed by dil. sulphuric acid. The
simplified equations above in 8.2(a) apply.
8.2(c) Aldehydes and ketones can be reduced to alcohols by reacting them
with a sodium/ethanol ('alcohol') mixture or a zinc/ethanoic acid
mixture, but these reactions are not usually dealt with in UK AS-A2 or
IB chemistry. Reduction reactions by metal/acid occur on the surface of
the metal and involve electron transfer from the metal to the organic
compound.
The reduction involves the half-cell reaction: >C=O + 2H+ + 2e- ==>
>CHOH.
The reaction at the zinc metal surface via the half-cell reaction:
Zn(s) ==> Zn2+(aq) + 2e-.
8.2(d) I don't know if reduction of aldehydes/ketones with hydrogen/Ni
catalyst is used in industry? but it is a feasible and cheap reaction
method.
aldehyde: RCHO + H2 ==> RCH2OH (R = H, alkyl or aryl)
ketone: R2C=O + H2 ==> R2CHOH (R = alkyl or aryl)
8.3 Reduction of a carboxylic acid to a primary aliphatic alcohol
8.3(a) NaBH4, is not a powerful enough reducing agent to reduce
carboxylic acids.
8.3(b) LiAlH4 is a more powerful reducing agent than NaBH4, and in ether
solvent, readily reduces carboxylic acids to primary alcohols. The
reaction can be summarised as:
RCOOH + 4[H] ==> RCH2OH + H2O (R = H, alkyl or aryl)
e.g. propanoic acid to propan-1-ol: CH3CH2COOH + 4[H] ==> CH3CH2CH2OH
+ H2O
or benzoic acid to phenylmethanol: C6H5COOH + 4[H] ==> C6H5CH2OH +
H2O
8.3(c) As far as I know, metal/acid reducing agents are not powerful
enough to reduce carboxylic acids.
8.3(d) I don't know if hydrogen/Ni is used to reduce carboxylic acids
and I can't see any synthetic use, but it is a feasible reaction.
RCOOH + 2H2 ==> RCH2OH + H2O (R = H, alkyl or aryl)

8.4 Reduction of nitriles to primary aliphatic amines

8.4(a) NaBH4, is not a powerful enough reducing agent to effect the
change.
8.4(b) LiAlH4 is a more powerful reducing agent than NaBH4 and in ether
solvent will reduce nitriles to primary aliphatic amines. The reaction
can be summarised as:
RCN + 4[H] ==> RCH2NH2 (R = H, alkyl or aryl)
e.g. propanenitrile to propylamine: CH3CH2CN + 4[H] ==> CH3CH2CH2NH2
8.4(c) Sn/HCl(aq), is not a powerful enough reducing agent to reduce
nitriles to amines.
8.4(d) Hydrogen/150oC?/Ni catalyst conditions will reduce nitriles to
primary aliphatic amines.
RCN + 2H2 ==> RCH2NH2 (R = H, alkyl or aryl)
8.5 Reduction of nitro-aromatics to primary aromatic amines
8.5(a) NaBH4, is not a powerful enough reducing agent to reduce
nitro-aromatic compounds.
8.5(b) LiAlH4 is a more powerful reducing agent than NaBH4 and in ether
solvent readily reduces nitro-aromatics to primary aromatic amines, the
simplified equation for nitrobenzene to phenylamine is ...
C6H5NO2 + 6[H] ==> C6H5NH2 + 2H2O
and methylnitrobenzenes would be reduced to methylphenylamine primary
amines, i.e.
CH3C6H4NO2 + 6[H] ==> CH3C6H4NH2 + 2H2O
as will any aromatic compound with a nitro group (-NO2) attached
directly to the benzene ring.
8.5(c) The reduction of nitro-aromatics with tin and concentrated
hydrochloric acid.
In the laboratory, reacting a nitro-aromatic with a mixture of tin and
conc. hydrochloric acid by heating under reflux will reduce it to a
primary aromatic amine (-NH2 directly attached to benzene ring). In
industry a cheap metal like iron powder and acid are used or a direct
reduction in the gas phase with hydrogen/transition metal catalyst
(8.5(d).
In the 'laboratory' preparation, the mixture may need heating to
complete the reaction (can be refluxed?) and formation of phenylamine
(aniline) from nitrobenzene can be summarised as
C6H5NO2 + 6[H] ==> C6H5NH2 + 2H2O
but the 'real' equations are rather more complicated, the simplest redox
equation I can come up with is
2C6H5NO2(aq) + 14H+(aq) + 3Sn(s) ==> 2C6H5NH3+(aq) + 3Sn4+(aq) + 4H2O(l)
which shows the formation of the phenylammonium cation because the amine
is a base and formed in an acid medium. The tin(IV) ion is actually a
chlorocomplex ion of tin, SnCl62-, the hexachlorostannate(IV) ion, so
the full ionic-redox equation is more correctly written as ... if you
really must!
2C6H5NO2(aq) + 14H+(aq) + 18Cl-(aq) + 3Sn(s) ==> 2C6H5NH3+(aq) +
3[SnCl6]2-(aq) + 4H2O(l)
Oxidation state changes: 3Sn (0) inc. to (+4) balanced by 2N decreasing
from (+3) to (-3).
and then solid or conc. aqueous sodium hydroxide is added to free the
amine (immiscible) from its arylammonium cation
C6H5NH3+(aq) + OH-(aq) ==> C6H5NH2(l) + H2O(l)
The primary aromatic amine is then be extracted by steam distillation.
For more on the theory of steam distillation see Equilibria Part 8.5
On addition of the strong alkali the amine separates out as an oily
layer and the mixture is heated with the steam input. A mixture of the
amine and water 'steam distils' into the condenser and separates into
two layers in the collection flask which can then be further processed
using a separating funnel. The phenylamine may have to be extracted with
'ether' solvent? Phenylamine or mixture with ether, can be dried with
solid sodium hydroxide and fractionally distilled to obtain pure
phenylamine liquid.
8.5(d) Aromatic nitro-compounds are reduced with hydrogen/Ni or Cu
catalyst at elevated temperatures and the resulting primary aromatic
amines are very important intermediate compounds in dye and drug
manufacture e.g.
C6H5NO2 + 3H2 ==> C6H5NH2 + 2H2O
CH3C6H3(NO2)2 + 6H2 ==> CH3C6H3(NH2)2 + 4H2O
9. Summary of some ORGANIC SYNTHESIS OXIDATION REACTIONS
Guide notes
Some direct catalytic oxidations at higher temperatures used in industry
are included, but most are 'school laboratory' reactions.
YES/NO - for a laboratory synthesis.
R = alkyl or aryl for primary/secondary alcohols.
Click on 9.1, 9.2, 9.3, 9.4 and 9.5 in the table for more details on (a),
(b) etc.
Important examination note: Unless hydrogen gas or oxygen gas is used
directly in the redox synthesis reaction [O] and [H] should be used in
simplified equations and examples will be quoted in each section and some
syllabuses specifically state so.
homologous series change on oxidationmolecular structure change(a) heat
with mod conc. H2SO4 and K2Cr2O7(aq) (lab method)(b) reflux with
KMnO4/NaOH(aq) (lab method)(c) oxygen + catalyst or thermal decomposition
(industrial methods)
9.1 primary alcohol ==> aldehyde ==> carboxylic acidRCH2OH ==> RCHO ==>
RCOOHYESYES but only get RCOOH and of little synthetic usee.g. CH3CH2OH
==> CH3CHO (Cu/500oC)
9.2 secondary alcohol ==> ketoneR2CHOH ==> R2C=OYESYES but of little
synthetic use(CH3)2CHOH ==> CH3COCH3 (Cu/500oC)
9.3 tertiary alcohol ==> ?R3C-OH fairly stable (if oxidised C-C bonds
broken ==> lower RCOOH, CO2, H2O)not readily oxidised - no synthetic
usenot readily oxidised - no synthetic usenot readily oxidised - no
synthetic use
9.4 alkyl groups on benzene ringe.g. C6H5CH3 ==> C6H5COOHYESYESYES
air/150oC/Co salt
9.5 alkene ==> ?details in appropriate boxNOethene ==> ethane-1,2-diol (at
room temp.)e.g. ethene ==> epoxyethane (Ag/250oC)
Some further details of the organic oxidations tabulated above
9.1 Oxidation of primary alcohols to aldehydes and carboxylic acids
(includes oxidation of aldehydes to carboxylic acids)
9.1(a) It is possible using the same reagent of aqueous sodium/potassium
dichromate(VI)-sulphuric acid to oxidise a primary alcohol to either the
aldehyde, or the carboxylic acid, depending on the reaction conditions.
In order to selectively isolate the aldehyde this initial oxidation
products must be removed from the reaction mixture as quickly as
possible, otherwise oxidation proceeds to the carboxylic acid.
The method involves heating under reflux if an aldehyde/ketone is to be
prepared in the way illustrated in the detailed diagram PD1 below.
The 25% sulphuric acid is placed in the flask and gently simmered. The
alcohol and aqueous sodium/potassium dichromate(VI) solution is dripped
onto the hot acid. Immediately, the orange dichromate(VI) is reduced by
the alcohol to the green chromium(III) ion and the alcohol is oxides to
the aldehyde or ketone.
The technique illustrated above is called heating under reflux, a method
which enables a reaction to be carried out at a higher temperature than
room temperature to speed up the reaction AND retain the solvent
(reaction medium e.g. water) and any volatile reactant or product (e.g.
an alcohol/aldehyde/ketone). As the mixture boils, the vapours of the
solvent or volatile reactant/product are condensed back into the flask
in the vertical condenser, so any volatile reactant is used up and no
volatile product lost (at least at this stage in a preparation!).
The diagram shows a bunsen burner being used to supply the heat ('my
days'), these days its more likely, and safer, to use an electrical
 heater that the round bottomed flask fits in snugly.
A spot of theory to explain the separation of the aldehyde/ketone from
the reaction mixture.
For the same carbon number, the boiling point of the polar
aldehyde/ketone (&#948;+C=O&#948;-, but no H bonding) is lower than th
e original
more polar alcohol (&#948;-O-H&#948;+, hydrogen bonding) whose bpt. is
higher.
Therefore, as long as the bpt. of the aldehyde/ketone is not too high,
in the set-up shown above, the aldehyde rapidly distils over and
condenses in the collection tube/flask with some water.
This rapid in situ extraction ensures that most of the aldehyde (or
ketone), 9.1(a) is not oxidised further.
If the carboxylic acid of the same carbon number is required from a
primary alcohol, the mixture is refluxed using the set-up illustrated
in diagram PD2.
(i) primary alcohol ==> aldehyde
Cr2O72-(aq) + 3RCH2OH(aq) + 8H+(aq) ==> 3RCHO(aq) + 2Cr3+(aq) +
7H2O(l)
reduction half reaction: Cr2O72-(aq) + 14H+(aq) + 6e- ==> 2Cr3+(aq)
+ 7H2O(l)
oxidation half reaction: RCH2OH(aq) ==> RCHO(aq) + 2H+(aq) + 2e-(aq)
(R = alkyl or aryl)
Examples using simplified symbol equations e.g.
ethanol ==> ethanal: CH3CH2OH + [O] ==> CH3CHO + H2O
propan-1-ol (1-propanol, n-propyl alcohol, n-propanol) ==> propanal
CH3CH2CH2OH + [O] ==> CH3CH2CHO + H2O
then under reflux conditions the further oxidation ...
(ii) aldehyde ==> carboxylic acid
Cr2O72-(aq) + 3RCHO(aq) + 8H+(aq) ==> 3RCOOH(aq) + 2Cr3+(aq) + 4H2O(l)
(R = alkyl or aryl)
oxidation half-reaction: RCHO(aq) + H2O(l) ==> RCOOH(aq) + 2H+(aq) +
2e-(aq)
Examples using simplified symbol equations:
ethanal ==> ethanoic acid, CH3CHO + [O] ==> CH3COOH
propanal (propionaldehyde) ==> propanoic acid (propionic acid)
CH3CH2CHO + [O] ==> CH3CH2COOH
butanal (butyraldehyde) ==> butanoic acid (butyric acid)
CH3CH2CH2CHO + [O] ==> CH3CH2CH2COOH
so overall for reflux conditions (i) + (ii) gives
(iii) primary alcohol ==> carboxylic acid
2Cr2O72-(aq) + 3RCH2OH(aq) + 16H+(aq) ==> 3RCOOH(aq) + 4Cr3+(aq) +
11H2O(l)
oxi'n half-reaction: RCH2OH(aq) + H2O(l) ==> RCOOH(aq) + 4H+(aq) +
4e-(aq) (R = alkyl or aryl)
Examples using simplified symbol equations:
ethanol ==> ethanoic acid
CH3CH2OH + 2[O] ==> CH3COOH + H2O
propan-1-ol (1-propanol, n-propyl alcohol, n-propanol) ==> propanoic
acid
CH3CH2CH2OH + 2[O] ==> CH3CH2COOH + H2O
9.1(b) Heating a primary alcohol with a aqueous sodium
hydroxide/potassium manganate(VII) mixture under reflux (diagram PD2)
will give the sodium salt of the carboxylic acid and it is not possible
to isolate the intermediate aldehyde.
However, the acid/dichromate(VI) method 9.1(a) under reflux is better,
 and the carboxylic acid is less liable to further degradative
oxidation. The complex reaction can be summarised as:
RCH2OH(aq) + NaOH(aq) + 2[O] ==> RCOO-Na+(aq) + 2H2O(l) (R = alkyl or
aryl)
After removing the excess KMnO4/MnO2 the weak acid is freed from its
sodium salt by adding strong dilute hydrochloric acid.
RCOO-(aq) + H+(l) ==> RCOOH
9.1(c) Many chemical feedstocks are oxidised directly with molecular
oxygen/transition metal catalyst to produce useful products in industry.
e.g. 2CH3OH + O2 ==> 2HCHO + 2H2O (Ag/500oC, methanol ==> methanal)
or 2CH3CH2OH + O2 ==> 2CH3CHO + 2H2O (Ag/500oC, ethanol ==> ethanal)
and the latter reaction can also be achieved via a thermal
decomposition using a different catalyst,
e.g. CH3CH2OH ==> CH3CHO + H2 (Cu/500oC),
which is still an oxidation, right carbon (-1) to (+1) and 2 x
hydrogen (+1) to (0).
9.2 Oxidation of secondary alcohols to ketones
9.2(a) In the case of secondary alcohols you only get the ketone, unless
you reflux the alcohol/K2Cr2O7/H2SO4(aq) for a long time, in which case
the ketone can be oxidised to lower carbon number carboxylic acids,
carbon dioxide and water etc. if the carbon chain is broken
Ketones are quite stable to further oxidation due to the strong
carbon-carbon (C-C) bonds that have to be broken.
To be on the safe side it is better to make the ketone under the same
restricted reaction conditions used to produce the aldehyde (details
above with diagram PD1).
Cr2O72-(aq) + 3R2CHOH(aq) + 8H+(aq) ==> 3R2C=O(aq) + 2Cr3+(aq) +
7H2O(l)
oxidation half-reaction: R2CHOH(aq) ==> R2C=O(aq) + 2H+(aq) + 2e-(aq)
(R = alkyl or aryl)
9.2(b) Ketones are produced by refluxing secondary alcohols with
NaOH/KMnO4(aq), but further oxidation is likely to take place because
this reagent is a stronger oxidising agent than acidified potassium
dichromate(VI).
(CH3)2CHOH + [O] ==> (CH3)2C=O + H2O (propan-2-ol ==> propanone)
9.2(c) Many chemical feedstocks are oxidised directly with molecular
oxygen/transition metal catalyst to produce useful products in industry.
2(CH3)2CHOH(g) + O2(g) ==> 2(CH3)2C=O(g) + 2H2O(g) (Ag/500oC)
and this reaction can also be achieved via a thermal decomposition
using a different catalyst.
(CH3)2CHOH(g) ==> (CH3)2C=O(g) + H2(g) (Cu/500oC)
which is still an oxidation, right carbon (-1) to (+1) and 2 x
hydrogen (+1) to (0).
9.3 Oxidation of tertiary alcohols
9.3(a)-(d) Tertiary alcohols, R3COH (R = alkyl or aryl), are not
readily oxidised because strong carbon-carbon bonds have to be broken.
The products would be lower chain carboxylic acids, carbon dioxide and
water and therefore of no synthetic use.
9.4 Oxidation of alkyl-aromatic hydrocarbons to aromatic carboxylic acids
9.4(a) Acidified potassium dichromate(VI) will oxidise alkyl benzene
compounds to benzoic acid, but I think it is slower than with the
alkaline manganate(VII) method described below.
Overall change is represented by the equations ...
C6H5CH3 + 3[O] ==> C6H5COOH + H2O
9.4(b) Aromatic are not easily oxidised and longish reflux times are
 necessary (illustrated, fig. PD2 below).
Hydrocarbons are difficult to oxidise with typical organic oxidising
agents compared to compounds like alcohols. However, aromatic
hydrocarbons with an alkyl side chain can be oxidised with strong
reagents such as aqueous potassium manganate(VII)/sodium hydroxide.
Whatever the length of the alkyl group on a benzene ring it gets
whittled down to carbon of the carboxylic acid group e.g. propyl benzene
ends up as benzoic acid. The more stable aromatic benzene ring is left
intact.
The overall process for producing benzoic acid from methylbenzene can be
summarised ..
C6H5CH3 + NaOH + 3[O] ==> C6H5COO-Na+ + 2H2O
After removing the excess KMnO4/MnO2 the weak benzoic acid is freed
from its sodium salt by adding strong dilute hydrochloric acid.
C6H5COO-(aq) + H+(l) ==> C6H5COOH
or in principle you eventually get benzene-1,2-dicarboxylic acid from
1,2-dimethylbenzene
+ 6[O] ==> + 2H2O
9.4(c) Aromatic hydrocarbons with alkyl groups can be directly oxidised
with air/oxygen at elevated temperatures and pressures.
C6H5CH3(g) + 3/2O2(g) ==> C6H5COOH(g) + H2O(g) (e.g. air/150oC/Co salt
catalyst)
9.5 Oxidation of alkenes
9.5(a) There are no useful oxidations of alkenes with acidified
potassium dichromate(VI) as far as I know.
9.5(b) At room temperature alkenes react with alkaline potassium
manganate(VII), KMnO4/NaOH(aq), to form diols e.g.
ethene ==> ethane-1,2-diol (at room temp.)
CH2=CH2 + H2O + [O] ==>
9.5(c) In industry alkenes can be oxidised directly with molecular
oxygen to useful products e.g. epoxyalkanes at elevated temperatures and
transition metal catalysts.
ethene + oxygen ==> epoxyethane (Ag catalyst/250oC)
2CH2=CH2 + O2 ==> 2
propene + oxygen ==> epoxypropane (Ag catalyst/250oC ?)
2CH3-CH=CH2 + O2 ==> 2

10. Other miscellaneous Organic Redox Reactions

This is a 'collection' of reactions not dealt with in sections 8. and 9.
They may/may not be useful reactions.
Section 10. reaction sub-index: 10.1 Cannizzaro reaction * 10.2
aldehydes/ketones tests * 10.3 Combustion * 10.4 Fuel cells * 10.5 The use
of 1,4-dihydroxybenzene (quinol, hydroquinol) in photography
10.1 The Cannizzaro reaction
Aldehydes which do not have a hydrogen atom on the carbon next to the
carbon of the carbonyl group (C=O) undergo the Cannizzaro reaction
with concentrated aqueous sodium hydroxide in which one molecule of
the aldehyde is reduced to a primary alcohol and another is oxidised
to the sodium salt of a carboxylic acid.
This is an organic example of disproportionation in which the same
carbon atoms of the reactant molecule simultaneously increase and
decrease their oxidation state e.g.
methanal changes to methanol and sodium methanoate
 2HCHO + Na+OH- ==> CH3OH + HCOO-Na+
benzaldehyde changes to phenylmethanol (benzyl alcohol) and sodium
benzoate
2C6H5CHO + Na+OH- ==> C6H5CH2OH + C6H5COO-Na+
10.2 Simple chemical tests to distinguish aldehydes from ketones
The tests depend on the relative redox stability of ketones compared
to the much more readily oxidised aldehydes. These tests also give
positive results with many reducing sugars and some rather more stable
aromatic aldehydes e.g. benzaldehyde, may not give a positive result
at all.
In these tests, because aldehydes are stronger reducing agents than
ketones, they reduce the metal ion and are oxidised in the process
i.e. RCHO + [O] ==> RCOOH, a change which is equivalent to a 2
electron loss by the RCHO.
Tollens reagent is a colourless solution of silver nitrate in aqueous
ammonia.
When an aldehyde is warmed with Tollens reagent it is oxidised to a
carboxylic acid and the silver ion (in ammine complex form) is
reduced to silver, forming a silver mirror on the side of the test
tube.
2[Ag(NH3)2]+(aq) + R-CHO(aq) + H2O(l) ==> 2Ag(s) + 4NH3(aq) +
R-COOH(aq) + 2H+(aq)
simplified: 2Ag+(aq) + R-CHO(aq) + H2O(l) ==> 2Ag(s) + R-COOH(aq) +
2H+(aq)
or 2[Ag(NH3)2]+(aq) + R-CHO(aq) + 2OH-(aq) ==> 2Ag(s) + 4NH3(aq) +
R-COOH(aq) + H2O(l)
simplified: 2Ag+(aq) + R-CHO(aq) + 2OH-(aq) ==> 2Ag(s) + R-COOH(aq)
+ H2O(l)
Ketones show no reaction because of their greater stability to
oxidation.
Fehlings or Benedict's solution consists of a copper(II) ion complexed
with an organic carboxylic acid.
The deep blue copper(II) ion in the complex is reduced to a
red-brown precipitate of copper(I) oxide.
Ketones show no reaction due to their greater oxidation stability.
2Cu2+(complex/aq) + R-CHO(aq) + 2H2O(l) ==> Cu2O(s) + R-COOH(aq) +
4H+(aq)
or: 2Cu2+(complex/aq) + R-CHO(aq) + 4OH-(aq) ==> Cu2O(s) +
R-COOH(aq) + 2H2O(l)
Ketones show no reaction because of their greater reluctance to
oxidation.
There are lots more organic chemical tests described - Chemical
Identification Tests (with alphabetical index).
10.3 All organic compound air/oxygen combustion reactions are oxidations
in terms of the carbon atoms of the organic molecule e.g. carbon's
oxidation state is increased from (-4) in methane to (+4) in CO2 for
complete combustion and (+2) if carbon monoxide formed or (0) in carbon
(soot) if the combustion is inefficient/incomplete. In each case
oxygen's oxidation state changes from (0) to (-2) to offset the increase
in carbon's oxidation state. e.g.
CH4(g) + 2O2(g) ==> CO2(g) + 2H2O(l)
2CH4(g) + 3O2(g) ==> 2CO(g) + 4H2O(l)
CH4(g) + O2(g) ==> C(s) + 2H2O(l)
10.4 Organic Fuel Cells
Many hydrocarbon molecules are burned as fuels, but since it is a
 redox reaction, theoretically it can be done as a combined half-cell
oxidation/reduction electron transfer reaction.
In practice organic compounds can be oxidised by oxygen in a way that
can be used to generate electricity directly in a fuel cell (right
diagram) rather than release the energy as heat e.g.
In reaction 9.1(a) ethanol was oxidised to ethanoic acid by acidified
potassium dichromate(VI). The same result can be obtained by reaction
of ethanol with oxygen in a fuel cell.
The reaction is very exothermic, so ethanol is a good source of
chemical potential energy.
Ethanol is used directly as a fuel in a direct ethanol fuel cell (a
DEFC fuel cell).
(i) CH3CH2OH(aq) + O2(g) ==> CH3COOH(aq) + H2O(l) (&#916;HØ = -494 kJ
mol-1)
The half-cell reactions are:
(ii) Reduction, +ve electrode: O2(g) + 4H+(aq) + 4e- ==> 2H2O(l) (EØ
= +1.23V)
(iii) Ox'n, -ve electrode: CH3CH2OH(l) + H2O(l) ==> CH3COOH(aq) +
4H+(aq) + 4e- (EØ = +0.06V)
Adding (ii) + (iii) = equation (i) and EØcell = EØ+/red'n - EØ-/ox'n
= 1.23 - 0.06 = +1.17V
The reactions must take place on catalytic electrodes made of
platinum and other transition metals and here the inner
'electrolyte' is as a polymer proton exchange membrane of the fuel
cell (a PEFC fuel cell), though it can be a concentrated phosphoric
acid solution (in a PAFC fuel cell).
The electrons will flow through the external circuit from the -ve
electrode to the +ve electrode.
Free energy change: &#916;GØ = -nEØF = - 4 x 1.17 x 96500 = -451620 J
mol-1 = -451.6 kJ mol-1
n = number of electrons transferred, EØ = cell voltage, F = Faraday
constant in coulombs mol-1
This sort of chemistry is being developed to make reasonably
efficient portable fuel cells
Commercially developed fuel cells will hopefully convert the ethanol
completely into water and carbon dioxide to give a greater and more
efficient energy output, but its still generates a voltage of 1.0-1.2V
per cell, in this case ...
(i) Oxidation, -ve electrode: C2H5OH(l) + 3H2O(l) ==> 12H+(aq) +
2CO2(aq/g) + 12e-
(iii) Reduction, +ve electrode: 3O2(aq/g) + 12H+(aq) + 12e- ==>
6H2O(l)
adding (i) + (iii) gives: C2H5OH(l) + 3O2(aq/g) ==> 3H2O(l) +
2CO2(aq/g)
+ other organic products as the reaction is not completely
efficient.
The cells can obviously be connected in series to give larger
voltages.
The ethanol ('alcohol', C2H5OH) can be bio-sourced from sugar beet,
potatoes and cereal crops and other plant material that can
fermented with enzymes. The ethanol is fractionally distilled from
the fermented mixture and constitutes a renewable fuel.
However there seems to have been more work done? on the Direct
Methanol Fuel Cell (a DMFC fuel cell), though there are concerns over
methanol's toxicity and the very costly platinum catalytic electrodes
required, but the DMFC is essentially like the DEFC described above
and the principles illustrated in the diagram.
The methanol can be synthesised in the reforming reaction CO(g) +
 2H2(g) ==> CH3OH(l)
half-cell reactions for the DMFC cell:
(i) Red'n, +ve electrode: 3/2O2(g) + 6H+(aq) + 6e- ==> 3H2O(l) (EØ
= +1.23V)
(ii) Ox'n, -ve electrode: CH3OH(aq) + H2O(l) ==> CO2(aq/g) +
6H+(aq) + 6e- (EØ = ?V)
so overall the cell reaction is ... with a maximum output voltage
of about 1.0V.
CH3OH(aq) + 3/2O2(g) ==> CO2(aq/g) + 3H2O(l)
Hopefully, efficient cells using ethanol can be developed because
ethanol compared to methanol has a higher energy density (e.g. kJ/kg),
is less toxic and can be bio-resourced as a renewable fuel.
There is a huge amount of research going on in fuel cell development
to try to use cheaper, but equally effective tiny particle metal
catalysts of Fe, Co and Ni instead of costly platinum, but the most
efficient metals are still the most costly?
10.5 The use of 1,4-dihydroxybenzene (p-quinol, hydroquinol) in
photography
1,4-dihydroxybenzene (Quinol) is an ingredient in photographic
developing solutions. In the transparent plastic emulsion film of the
exposed film it will reduce the silver ions in silver halide salts,
(which have not already been decomposed by light to silver and
bromine), to silver as well. It would appear that these extra silver
atoms produced by the developer, cluster around the already formed
silver atoms (acting as 'nuclei') from the action of light, to enhance
the image in 'shades' and 'contrast' to give a more clearly defined
negative.
The relevant half-cell reactions and their standard redox electrode
potentials are ...
AgBr(s) + e- ==> Ag(s) + Br-(aq) (E&#952;Ag/AgBr = +0.073V at 298K)
(aq) + 2H+(aq) + 2e- ==> (aq) (E&#952;Q/QH2 = +0.059V at 298K, pH 8
.5)
These two organic molecules are referred to by a variety of
systematic and trivial names, confusing when searching the web! e.g.
left (ref Q): 2,5-cyclohexadiene-1,4-dione, p-quinone, ('one'
higher ranking than 'ene')
right (ref QH2): 1,4-dihydroxybenzene, 1,4-benzenediol,
benzene-1,4-diol, p-quinol, p-hydroquinone, p-dihydroxybenzene
It is convention to show the half-cell reactions as reductions when
quoting them with the half-cell potential.
In the reactions the silver ions in the silver bromide salt are
reduced to silver atoms and 1,4-dihydroxybenzene (quinol) is oxidised
to 2,5-cyclohexadiene-1,4-dione (quinone). The bromide ions 'dissolve'
and two hydrogen ions are released from the quinol. Therefore the
basic reaction via the alkaline developer is ....
(aq) + 2AgBr(s) ==> (aq) + 2Ag(s) + 2Br-(aq) + 2H+(aq)
Sometimes more simply written as ...
C6H4(OH)2(aq) + 2AgBr(s) ==> C6H4O2(aq) + 2Ag(s) + 2HBr(aq)
E&#952;reaction = E&#952;red - E&#952;ox = E&#952;AgBr/Ag - E&#952;Q
/QH2
E&#952;reaction = (+0.073) - (+0.059) = +0.014V
The positive value for E&#952;reaction shows the reaction is feasibl
e. In
fact the E&#952;Q/QH2 becomes less positive as the pH is increased m
aking
the reaction more feasible, but the EAgBr/Ag is theoretically
independent of pH. The hydrogen ions would be neutralised by the
 alkaline media.
Oxidation number analysis for the molecules in question is shown below
...
using graphic structural formulae and
Oxidation states in organic compounds is explained in section 11.
below.
Note: Not all the silver bromide reacts in this way, so in the fixing
process the remaining silver bromide is removed by sodium thiosulphate
to produce the 'light stable' negative.
The transition metal complex ion [Ag(S2O3)2]3-(aq) is formed when
sodium thiosulphate (Na2S2O3) is used to remove unreacted silver
bromide (AgBr) crystals in developing photographic films.
AgBr(s) + 2S2O32-(aq) ==> [Ag(S2O3)2]3-(aq) + Br-(aq)
This is NOT a redox reaction, Ag is +1 and Br is -1 throughout the
reaction. The thiosulfate ion is here acting as a ligand and not a
reducing agent e.g. like its reaction with iodine.
-

11. Oxidation state and organic compounds

Usually the oxidation state of hydrogen is +1, and oxygen -2 in organic
compounds.
(The quoted Pauling electronegativities are C = 2.5, H = 2.2 and O = 3.5
which gives the lead in assigning oxidation numbers in this section i.e.
the highest oxidation state is assigned to the least electronegative atom
and vice versa for hydrogen and oxygen BUT beware for carbon, logical
deduction can give some surprising, but correct results!)
On this basis you can achieve a useful oxidation number analysis of simple
organic compounds in an oxidation sequence.
e.g. the oxidation sequence below, with the oxidation state of carbon in
() and in hydrogen in ().
CH4 (-4) == ox'n ==> CH3OH (-2) == ox'n ==> HCHO (0) == ox'n ==> HCOOH
(+2) ==> CO2 (+4)
The above sequence can described in terms of the 'level of the functional
group' which is equal the number of bonds the carbon atom forms with more
electronegative atoms like oxygen. Therefore in the above sequence: alkane
hydrocarbons are level zero (carbon and hydrogen have virtually the same
electronegativity), alcohols are level 1 (C-OH, as are
halogenoalkanes/haloalkanes e.g. C-Cl), carbonyl is level 2 (e.g. C=O in
aldehydes/ketones), carboxylic acids are level 3 (C=O and C-OH) and
finally the fully oxidised carbon in carbon dioxide is level 4. Note that
a functional group level applies to a single carbon atom e.g. the carbon
of the functional group, and not the full molecule.
Similarly for the oxidation sequence from ethane to ethanoic acid ...
CH3CH3 (-3,-3) = ox'n => CH3CH2OH (-3,-1) = ox'n => CH3CHO (-3,+1) = ox'n
=> CH3COOH (-3,+3)
Note the rise of carbon's oxidation state in increments of 2, see
oxidation equations for acidified potassium dichromate(VI) reaction with
alcohols and aldehydes in section 9.1(a) where the half-cell oxidation
equations involve a 2 electron loss from the organic molecule.
Other organic molecules and redox sequences can be similarly 'analysed'
ethene H2C=CH2 (-2,-2) + H2 (0) == reduction/Ni ==> ethane CH3-CH3
(-3,-3), (+1)
propene CH3-CH=CH2 (-3,-1,-2) + H2 == reduction/Ni ==> CH3-CH2-CH3
(-3,-2,-3)
ethanol CH3-CH2-OH (-3,-1) == ox'n ==> ethanal CH3CHO (-3,+1) == ox'n ==>
CH3COOH (-3,+3)

Appendix 1. The Concept of Functional Group Level

This concept of functional group level has been introduced into some UK
A level pre-university courses.
It can be related to an increasingly oxidation state of carbon.
In the explanation with examples below assume R = a H, alkyl or aryl
grouping.
The concept of functional group level of a carbon atom is derived from
counting the number of bonds form an individual carbon atom to
electronegative atoms (C-X, where I assume X more electronegative than
carbon i.e. oxygen, nitrogen or halogens such as chlorine).
If no such C-X bonds exist the carbon is described as being at the
hydrocarbon level.
With one C-X bond the carbon atom is at the alcohol level e.g. alcohols
(C-OH), monohaloalkanes (R3C-Cl).
With two C-X bonds the carbon atom is at the carbonyl level e.g.
aldehydes and ketones (R2C=O), ethers (R3C-O-CR3)
With three C-X bonds the carbon atom is at the carboxylic acid level
RCOOH (RO-C=O grouping), esters RCOOR, amides RCONH2, nitrile RCN (RN)
Finally with four C-X bonds we reach the carbon dioxide level e.g.
carbon dioxide itself CO2 or an ether such as C(OR)4
The concept of functional group level often applies to a single carbon
atom, not the whole molecule e.g.
alcohol COH, chloroalkane C-Cl, aldehyde CHO,
carboxylic acid level: carboxylic acid COOH, amide CONH2,
but not exclusively e.g. C=C in alkenes, but would this would be
considered at the hydrocarbon level despite being at a higher
oxidation state than a saturated alkane? (see section 11).
If a reaction takes place within a level you are swapping one heteroatom
(non-carbon atom) for another
e.g. hydrolysis of a halogenoalkane: R3C-Cl + NaOH ==> R3COH + NaCl
which is occurring at the alcohol level
In order to move a carbon atom up a level requires an oxidizing agent
(dealt with on this page in section 9).
e.g. the oxidation of alcohols using acidified potassium
dichromate(VI) solution
R-CH2OH == Cr2O72-/H+ ==> RCHO == Cr2O72-/H+ ==> RCOOH
alcohol level ==> carbonyl level ==> carboxylic acid level
To move a carbon atom down a level requires a reducing agent (dealt with
in section 8) or carbanion equivalent (not dealt with yet)
e.g. the reduction of carboxylic acids to primary alcohols with
lithium tetrahydridoaluminate(III)
RCOOH + 4[H] ==> RCH2OH + H2O
In this case the carbon atom of the functional group is reduced two
levels i.e. from the carboxylic level to the alcohol level.
-

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