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SOLUTIONS TO CHEM PROBLEMS

1. a) Rotational conformation refers to different arrangement of atoms in the molecule
whose positions can be interconverted by rotation about single bond

b) Give three physical methods that you may use to separate organic compounds
and in each case indicate why it is possible to use the given method.
 Simple distillation. Used to separate organic compounds with high difference in
boiling point that is greater than 25oC.
 Fractional distillation. Used to separate miscible organic compounds with close
boiling points i.e. less than 25oC
 Chromatography. Used to separate components of complex organic mixture
based on their differing affinities for distinct phases in relative motion.
 Recrystallization. Used to separate soluble salts from their saturated solutions
because of their differences in solubility at different temperatures.

c) Outline the two types of methods that can be used to determine the structure of
an organic compound
 Classical method which involves using infrared machine to determine the
functional group and conformation of the structure of an organic compound
through carrying out chemical tests.
 Instrumental method which involves use of infrared spectroscopy and
chromatographic means to determine the structural formula of an organic
compound
d) Explain how the current use of the term organic chemistry is different from
the traditional use of the same term in around late 1880s
2. Organic chemistry of 1880s was that chemistry of those compounds which were
produced and obtained from living things through agency of vital forces. Explain the
following statements
a) Both Alkenes and carbonyl compounds contain a double bond. However.
Alkenes undergo electrophilic addition while carbonyl compounds undergo
nucleophilic addition to the double bond.

 Both alkenes and aldehydes contains a double with a pi bonds but in alkenes the
pi bonds are exposed thus can easily react with electron deficient species like
hydrogen ions thus undergo electrophilic addition while carbonyl compounds
contain oxygen atom which is more electronegative than carbon thus withdraws
electrons from the carbonyl carbon atom through the double bonds thus the bonds
become electron deficient and thus will seek to react with electron rich species
like oxygen which has more electrons withdrawn from the carbon and the lone

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pairs of electrons in it thus a nucleophillic site the double bonds will undergo
nucleophillic addition reaction faster than alkenes
b) Both carboxylic acids and carbonyl compounds contain oxygen atom in their
functional group. However, carboxylic acids have higher boiling point
compared to corresponding carbonyl compounds of similar hydrocarbon chain.

 Boiling point depends on the electronegativity difference and hydrogen bonds

 Both carboxylic acids and carbonyl compound have C-O with high
electronegativity difference between carbon and oxygen atom but carboxylic
acids contains both C-O and O-H bonds which are polar and capable of forming
hydrogen bonds between two carboxylic acid molecules that require a lot of
energy to be broken before boiling occurs thus higher boiling point compared to
carbonyl compounds that contain only C-O bond and incapable of forming
hydrogen bonds thus lower boiling point.

c) i. Dehydration of propan-1-ol requires 97% sulphuric acid at 1700 while that

of 2-methylpropan-2-ol require only 20% sulphuric acid and heating up to
850
ii. The ease of dehydration of alcohols is in the order of tertiary,
secondary and primary i.e.
where
R-methyl group
 Tertiary alcohols have three alkyl groups bonded to the alpha carbon thus push
electron towards the alpha carbon atom which increases positive inductive effect
and also tertiary alcohols form a stable carbocation thus easily form products
compared to the secondary with two methyl groups and primary with only one
methyl group and presence of electron withdrawing species (oxygen) in –OH
increasing its electron density increasing the ease to pick a proton thus its reaction
occurs at lower temperature and requires less amount of the acid compared to
secondary and primary which forms a less stable carbo cation which can easily
react with water to form back the alcohol thus the reaction is called at relatively
high temperature to increase the rate of the reaction and more concentrated acid.

d) Ethane can be kept with chlorine/ HCl in dark room for some time and no
appreciable reaction takes place. Explain why no reaction takes place.
 Ethane contains carbon and hydrogen with nearly the same electronegativity value
and also contains sigma bonds that overlaps with s orbital of hydrogen with no
lone pair of electrons thus forming C-C and C-H bonds which are slightly
polarized and strong thus greater energy is required to break the bonds before the
reaction occurs thus unreactive and reaction can only occur unless heated to
higher temperatures or subjected to ultraviolet light.

e) Carboxylic acids are more acidic than alcohols

RCOOH and RCH2OH

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 Acidic strength depends on; The higher the negative inductive effect, the
higher the acidity, and the more the presence of electron withdrawing groups
the higher the acidity.
 Carboxylic acids contains C-O & O-H bond, oxygen has higher electronegativity
compared to carbon thus withdraws electrons more towards its self which
increases the negative inductive effect which decreases the O-H bonding thus can
easily accept an electron & the ease with which the hydrogen atom in the –OH
group is lost increase and increase in resonance increases acidity which enables
negative charge to be distributed over several atoms thus higher acidity of
carboxylic acids and alcohols due to higher negative inductive effect and
resonance in alcohols

3. Explain why the staggered conformation are more stable than the eclipsed one
 The staggered form is more stable than the eclipsed form due to minimum
electrostatic repulsive force between the two atoms as they are far apart thus
higher stability compared to eclipsed form where they are close to each other
which increased the electrostatic repulsive force.
 The new man conformation for ethane is more stable than that of butane due to
the presence of bulky group (methyl) on butane which increases steric hindrance
thus higher repulsion compared to ethane with hydrogen atoms which are far apart
thus minimum electrostatic repulsion and as result more stable than butane.

4. Explain why alcohols are amphoteric

 Alcohols have amphoteric character because alcohols react as both acids as it
reacts with metals like sodium metal to give off hydrogen and bases due to the
presence of lone pair of electrons on the oxygen atom that pick up a proton or
donate electrons in solution thereby making the alcohol act like a base.
̅
̈

5. Arrange the following compounds in the order of decreasing acidic strength and
support your answer.
A. Cl3CCOOH B. HCOOH C. CH3COOH D. Br3CCOOH
 A > D > B > C. The acidic strength of acids depends on the ease with which they accept
an electron or they donate a proton; the number of electron withdrawing species and the
negative inductive effect.
Acidic strength in carboxylic acids depends on the ease with which the hydrogen atom in
the –OH group is lost and this effect is increased by the number of electron withdrawing
species on the alpha carbon atom which increases negative inductive effect. A is more
acidic than D because chlorine atoms being more electronegative than bromine atoms
thus with draws more electrons compared to others; C is least acidic because it has an

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alpha methyl group with a positive inductive effect than the hydrogen thus electron are
more towards the alpha carbon atom thus cannot easily accept an electron and as a result
least acidic compared to B with only a hydrogen atom and increase in resonance
increases acidity.

6. Amines are basic organic compounds considered to be derivatives of ammonia.

a) Explain why amines are basic compounds
 Amines are organic compounds that a derived from ammonia which is a weak base and
they are basic in nature due to the presence of lone pair of electrons on nitrogen thus
easily donate electrons thus basic.

b) What determines the strength of amines as bases?

 Basic strength of amines depends on the availability of the lone pairs of electrons on the
nitrogen atom and the ease with which they are accessible to a proton in solution or they
donate an electron.
c) Arrange the following compound in order of decreasing basic strength
A. (CH3)3N B. CH3NH2 C. (CH3)2NH
 C > B > A. A is more basic than B because its nitrogen has two methyl groups attached
to it with a positive inductive effect thus pushing electrons more towards the nitrogen
atom increasing the availability of the lone pairs compared to B which has one thus more
electrons are released into the solution in C than in B. A is least basic because of the
bulkiness of the methyl groups around the nitrogen atom which increases steric hindrance
thus decreasing accessibility of the lone pair electrons on nitrogen atom because the
inductive effect increases with increase in molecular weight and as a result cannot easily
release electrons into the solution (hydrogen<methyl<ethyl<propyl..).

7. a)Write the International Union of Pure and Applied Chemistry (IUPAC) names of
the following organic compounds
a)
1-hydroxybut-2-ene
b)
2-aminopropane

c)

1,3-dichloro-3-methylbutane

b) Describe briefly two types of bond breakage in organic chemistry and the nature
of the products formed in each case.
i. Homolytic bond breakage, is where electrons are shared equally between two atoms
leading to formation of free radicles

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̇ ̇
ii. Heterolytic bond cleavage; is where the bond electrons are taken by a more
electronegative atom leading to formation of carbonium ions that is carbo cation and
carbo anion

c) Arrange the following compounds in order of increasing rate of reaction towards

nucleophilic reagents

Rate of reaction towards nucleophiles, R>P>S>Q

 The lower the positive inductive effect, the higher the reaction towards nucleophiles
R is an intermediate compound formed after the protonation of oxygen atom thus electron
deficient and as a result it easily withdraws electrons from the alpha carbon atom when
reacted with nucleophiles. P contains a methyl group, contains bromine on the ethyl
group which is more electronegative than carbon thus withdraws some electrons from the
alpha carbon atom than Q with the ethyl group thus Q has a higher positive inductive
effect compared to P and S thus P reacts nucleophiles more than S and Q due to its lower
positive inductive effect.

d) Explain why 2,2-dimethyl propan-1-ol when treated with hydrogen bromide

forms 2-bromo-2-methylpropane
 ( ) ( )


( )

8. Explain the following statements:

i. The boiling points of carbonyl compounds are lower than those of alcohols of similar
hydrocarbon chain
ii. The boiling point of carboxylic acids is higher than those of alkenes of similar
hydrocarbon chain?
Boiling point stability;
HYDROGEN BONDING
 carboxylic acids contains C-O and O-H bonds which are capable of forming hydrogen
bonds which are polar between two carboxylic acid molecules that require an a lot of
energy to be broken before boiling occurs and also the big electronegativity difference
between carbon and oxygen thus higher boiling point.
 Alcohols contain O-H bonds which are polar and capable of forming hydrogen bonds
which requires extra energy to be broken before boiling point.
 carbonyl compounds contains C-O bond which is polar because of the big
electronegativity difference between carbon and oxygen thus high boiling point but their

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boiling point is lower than that of alcohols and carboxylic acids due to the absence of O-
H bonds thus incapable of forming hydrogen bonds.
 Amines are contains N-H bond thus capable of forming the hydrogen bonds which
requires energy to be broken but the hydrogen bonds in amines are less than those of
alcohols and carboxylic acids.
 Alkyl halides contains C-X bond with high electronegativity difference between carbon
and halogens thus high melting point but they are incapable of forming hydrogen bonds.
 Alkenes, alkynes and alkane are non-polar thus incapable of forming hydrogen bonds
and also the electronegativity of carbon and hydrogen is nearly the same thus low boiling
point.

iii. Protonated carboxylic acids are more reactive towards esterification with
alcohols as compared to the one which is not protonated.

 In protonated carboxylic acids, the carbonyl oxygen atom attains a positive charge
after picking a proton making it more electrophile than before thus strongly pulls
electrons from the carbonyl carbon more towards its self. This effect increases the
electrophillicity of the carbonyl carbon making it more susceptible to alcohol attack
as a nucleophile.

iv. Ketones are less reactive than aldehydes towards nucleophilic addition reactions

 Reactivity of carbonyl compounds depend on steric hindrance and presence of electron

withdrawing species. Both ketones and aldehydes contain oxygen atom with high
electronegativity than carbon thus withdraws electrons more towards its self-making it
acquire a partial negative charge (electrophilic site) and the carbonyl carbon a partial
positive charge (nucleophilic site). Ketones have two alkyl groups attached to carbonyl
carbon that push electrons more towards it which increases positive inductive effect thus
increase in steric hindrance in ketones than in aldehydes with only one alkyl group
attached to a carbonyl carbon making the lone pair in ketones unavailable for reaction
with nucleophiles than in aldehydes.
 Also the intermediate formed by ketones after the nucleophilic attack is less stable than
the one formed by aldehydes hence aldehydes easily form products compared to ketones.
Stability of intermediate formed decreases with an increase in the bulkiness of atom
groups involved.

v. The lower members of carboxylic acids are soluble in water but the higher
members are not.
 Solubility , The higher the molecular weight, the lower the solubility and the
lower the molecular weight, the higher the solubility.
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 Carboxylic acids contain both the hydrophilic group (COOH) which is water loving and
the hydrophobic part (alkyl part) that is water repelling. Lower chain carboxylic acids are
soluble in water because their capable of forming hydrogen bonds with water molecule
compared to higher members of carboxylic acids since they have little access to water
molecules due to a very big portion of the alkyl part than the hydrophilic part making
them insoluble in water.

9. Write short notes on the following terms and in each case give one example to illustrate
your answer.
i. Inductive effect
 Is the tendency of an atom or a group of atoms to push or pull bonding electrons towards
the carbon atom. Their two types of inductive effect.
 Positive inductive effect is the tendency of an atom or a group of atoms to push bonding
electrons towards the carbon atom of the organic compound e.g. alkyl groups in a tertiary
carbocation
 Negative inductive effect is the tendency of an atom or a group of atoms to pull bonding
electrons from the carbon atom in an organic compound e.g. chlorine atom in
chloroalkanes
ii. Addition reactions
 These are reactions where a molecule is added to unsaturated organic compounds such as
alkenes and alkynes. The relative molecular mass of the product is similar to that of
reactants. E.g. addition of hydrogen molecules to alkenes to form alkanes.
iii. Substitution reaction
 This is a type of reaction where an atom or a group of atoms is replaced with another
atom or a group of atoms. It can occur in all organic compounds especially those with
halogens. E.g.
CH3CH2Cl + OH- CH3CH2OH + Cl-
iv. Nucleophile
 This is an atom or a group of atoms with at least a lone pair of electrons and seeks to
react with an electron deficient species. E.g. NH3, Cl-.
v. Electrophile
 This is an atom or a group of atoms that lacks at least a lone pair of electrons and seeks to
react with electron rich species. E.g. carbanions and H3O+.
10. One of the physical methods for purification of organic compounds is
recrystallization. Briefly explain how you would select the solvent for
recrystallization of a given sample.
 The compound should be very soluble at the boiling point of the solvent and only
sparingly soluble at room temperature
 The un wanted impurities should either be very soluble in the solvent at room
temperature or insoluble in the hot solvent
 The solvent should not react with the compound being purified

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 The solvent should be volatile enough to be easily removed after the compound has
crystallized.
PRACTICAL QUESTIONS
2014/2015
Qn. 5c) SOLUBILITY
Compound H2O NaHCO3 NaOH HCl
Methanoic acid + + + -
Benzene - - - -
Aminoethane + - - +
Butadiene + - - -
propanol + - - -
dii) limiting reagent is salicylic acid, to determine the limiting reagent you consider the
compound with least number of moles

diii)

Qn 2015/2016
a) i) physical appearance description, solubility and ignition test, elements test, group classification
test and lastly derivatisation
b) i) to account for the error made in the experiment and to cater for the heat losses to the
surrounding
ii) to determine the limiting reagent , you first calculate the number of moles and the least is the
limiting reagent
c) i) organic compound when heated to a certain extent become flammable and result into explosion
and also a test tube containing a liquid is more uniformly heated in the water bath.
ii) because free nitrous acid is unstable and readily decomposes thus prepared by situ by reacting
sodium nitrite with and mineral acids and consumed in situ and the reaction is done at ice bath
because at low temperature it doesnot decompose.
iii) Primary diazonium salts are unstable and at temperatures greater than 5 degrees it readily
decomposes explosively and at low temperature it recrystallizes out.
d) I)practical losses during the experiment eg during pouring and filtering
Incomplete reactions and side reactions
Heat losses to the surrounding leading to errors in the results
ii) adding the reagent drop wise if necessary and continue stirring thoroughly
Monitoring the reaction carefully thought the experiment

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