Professional Documents
Culture Documents
Organic Chemisty - Reaction Mechanisms
Organic Chemisty - Reaction Mechanisms
(a)
(b)
Give the equation for the reaction between 2-bromobutane and aqueous hydroxide
ions, using structural formulae.
(ii)
(iii)
(c)
(i)
Initial concentration of
RX/mol dm3
Initial concentration of
OH /mol dm3
0.01
0.04
8 10 6
0.01
0.02
4 10 6
0.005
0.04
4 10 6
Initial rate
/mol dm 3 s1
Deduce the order with respect to RX and OH and hence write the rate equation for
the reaction.
www.edexcel-cie.com
(ii)
(4)
(d)
How does the rate of nucleophilic substitution of halogenoalkanes, RX, change with the
halogen in the compound? Give reasons for your answer.
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
(3)
(Total 16 marks)
2.
Give the equation for the reaction between 2bromobutane and aqueous hydroxide ions,
using structural formulae.
(ii)
(iii)
www.edexcel-cie.com
3.
In an experiment designed to find the mechanism of the reaction between a halogenoalkane, RX,
and hydroxide ions, the following data were obtained at constant temperature.
Initial concentration of
RX/mol dm3
Initial concentration of
OH /mol dm3
0.01
0.04
8 10 6
0.01
0.02
4 10 6
0.005
0.04
4 10 6
Initial rate
/mol dm 3 s1
(i)
Deduce the order with respect to RX and OH and hence write the rate equation for the
reaction.
(ii)
(4)
4.
(a)
(b)
(i)
www.edexcel-cie.com
(ii)
Both of the reagents that are used to nitrate benzene are usually regarded as acids.
However, in this instance, one of them behaves as a base. Show how this is so.
..........................................................................................................................
..........................................................................................................................
..........................................................................................................................
(iii)
(iv)
Explain why benzene tends to undergo substitution rather than addition reactions.
..........................................................................................................................
..........................................................................................................................
(8)
(Total 10 marks)
5.
(i)
(ii)
Both of the reagents that are used to nitrate benzene are usually regarded as acids.
However, in this instance, one of them behaves as a base. Show how this is so.
..........................................................................................................................
..........................................................................................................................
..........................................................................................................................
(iii)
(iv)
Explain why benzene tends to undergo substitution rather than addition reactions.
..........................................................................................................................
..........................................................................................................................
(8)
www.edexcel-cie.com
CH 3
6.
CH 2
(b)
If the conditions are altered potassium hydroxide will react to give an elimination reaction
with the same halogenoalkane.
Draw the structural formula and give the name of an organic product of this elimination reaction,
showing all the covalent bonds.
(2)
(c)
Write the formula for this polymer showing the structure of the repeating unit.
(2)
(ii)
Suggest why, in terms of the nature of the bonds in such polymers, they are
persistent in the environment but are not particularly hazardous.
(2)
(d)
(1)
(ii)
If the same halogenoalkane is reacted with cyanide ions instead of hydroxide ions,
and all other conditions remain the same, state with reasons whether the rate of the
reaction would alter.
(3)
(e)
Reaction rates generally increase with an increase in temperature for two reasons.
(i)
(2)
www.edexcel-cie.com
(ii)
Number of
molecules
with a
given
energy
Energy
(4)
(iii)
By using the graph, or otherwise, explain the effect of a catalyst on the rate of
a reaction.
(2)
(Total 22 marks)
7.
Propenal, CH2=CHCHO, is one of the materials that gives crispy bacon its sharp odour. In the
following question assume that the carboncarbon double bond and the aldehyde group in
propenal behave independently.
www.edexcel-cie.com
(a)
Give the structural formulae of the compounds formed when propenal reacts with:
(i)
hydrogen bromide;
(2)
(ii)
hydrogen cyanide;
(1)
(iii)
2,4-dinitrophenylhydrazine.
(2)
(b)
(i)
Give the mechanism for the reaction between hydrogen cyanide and the aldehyde
group. You may represent the aldehyde group as
H
(3)
(ii)
The reaction in (i) occurs best in slightly acidic conditions. It is slower if the pH is
high or low. Suggest reasons why this is so.
High pH .
Low pH ..
.
(3)
(c)
(d)
Suggest reactions, giving equations and conditions, which would convert propenal into a
compound which would react with iodine in the presence of sodium hydroxide solution.
(4)
(Total 17 marks)
www.edexcel-cie.com
8.
(a)
The free radical reaction between methane and chlorine in ultraviolet light has a
mechanism whose initiation step is
Cl2 2Cl
Followed by one of two possible propagation steps
(i)
CH4 + Cl CH3 Cl + H
II
Use the data given below to predict which is the more likely propagation step.
bond enthalpies/kJmol1: ClCl 243;
CH 435;
HCl 432;
CCl 346.
(4)
(ii)
Identify one product you might expect from a termination step following each
reaction that would not be found in the alternative reaction scheme.
I ..
II .
(2)
(b)
The reaction in part (a) is an important industrial source of hydrochloric acid, HCl(aq).
The hydrogen halides HX(aq), sometimes called the hydrohalic acids, are all
Brnsted-Lowry acids.
(i)
(1)
(ii)
(2)
(c)
(2)
(ii)
(3)
(Total 14 marks)
www.edexcel-cie.com
9.
Two types of reaction in organic chemistry are electrophilic addition and nucleophilic
substitution.
(a)
Nucleophile:
(1)
(ii)
Electrophile:
(1)
(iii)
Substitution:
(1)
(iv)
Addition.
(1)
(b)
Give the mechanism of a reaction of your choice which proceeds by electrophilic addition.
(3)
(c)
(i)
Describe, briefly, a reaction you could carry out in the laboratory which occurs by
nucleophilic substitution.
(1)
(ii)
(iii)
(1)
www.edexcel-cie.com
(d)
(ii)
(2)
(Total 15 marks)
10.
(a)
Outline the reaction of propanone with the following reagents. Give the equation for the
reaction, the conditions, and the name of the organic product.
(i)
Hydrogen cyanide
Equation:
Conditions:
Name of product:
(3)
(ii)
Conditions:
Name of product: ..
(3)
(b)
(i)
(ii)
(1)
(iii)
What feature of the carbonyl group makes this type of mechanism possible?
www.edexcel-cie.com
(2)
(iv)
Explain briefly, by reference to its structure, why ethene would not react with HCN
in a similar way.
(1)
(Total 13 marks)
11.
Benzene reacts with concentrated nitric acid in the presence of concentrated sulphuric acid at
about 50 C in an electrophilic substitution reaction to give nitrobenzene.
(a)
(i)
(ii)
(1)
(iii)
Give the mechanism for the reaction of the electrophile with benzene.
(3)
(b)
In an experiment to determine the kinetics of this reaction, it is found that the attack of the
electrophile on the benzene ring is the rate determining step. The following data shows the
effect of changing the concentrations on the rate:
(i)
[benzene]
(relative)
[electrophile]
(relative)
Rate
(relative)
(ii)
(1)
(iii)
www.edexcel-cie.com
(1)
(c)
H2C
(i)
CH2+H2 H3CCH3
H = 120 kJ mol1
Assuming that benzene consists of a ring with three double bonds, predict the
enthalpy change for the reaction
+ 3H 2
(1)
(ii)
The enthalpy of hydrogenation of benzene is actually 205 kJ mol1. What can you
deduce from this and your answer to part (i) about the stability of the benzene ring?
Use an enthalpy level diagram to illustrate your answer.
(2)
(iii)
(2)
(Total 14 marks)
12.
Sodium hydroxide is a very important substance. Potassium hydroxide is also important but it is
produced in smaller quantities and is costlier. For some purposes, potassium hydroxide is
necessary; it will take part in substitution, elimination, hydrolysis, acidbase and redox
processes.
(a)
www.edexcel-cie.com
(b)
(i)
(ii)
(c)
(d)
Tristearin is an ester found in animal fats, especially beef tallow, which can be hydrolysed
by potassium hydroxide solution. Write an equation to represent the reaction, and state the
importance of the potassiumcontaining product.
C 17 H 35 COOCH 2
C 17 H 35 COOCH
C 17 H 35 COOCH 2
Tristearin
(4)
(e)
13.
The reactions of chlorine are important in both inorganic and organic chemistry, the chemistries
of the resulting compounds also being linked.
(a)
Chlorine reacts with aluminium in a similar fashion to its reaction with iron.
(i)
Sketch an apparatus which you could use to make aluminium chloride from
aluminium and dry chlorine, indicating one safety precaution specific to this
reaction.
(3)
(ii)
Explain in terms of bonding and structure why aluminium chloride sublimes and
has a relative molecular mass of 267.
(3)
www.edexcel-cie.com
(iii)
(iv)
Aluminium was first produced by the reaction of sodium with aluminium chloride.
Write an equation representing the reaction and explain why, although it is
apparently simpler than the electrolysis of purified bauxite it is not more
economical.
(2)
(b)
+ CH 3 Cl
AlCl 3
Cl 2
AlCl 3
C 7 H 7 Cl (three isomers)
S
(i)
(ii)
Suggest a structural formula for any one of the three isomers of compound S
produced by the reaction shown.
(1)
(c)
Compound Q has both chlorine atoms attached to the same carbon atom.
(i)
www.edexcel-cie.com
(ii)
H
C
OH
OH
In practice, this reacts further to give an aldehyde and water. Use the bond
enthalpies given to suggest why this is so.
Bond enthalpy/kJ
mol1
C O
358
C H
413
C O
736
H O
464
(4)
(iii)
Suggest the structure of the product when R is reacted with sodium hydroxide
solution.
(1)
(Total 25 marks)
14.
CH 3 CHCH
CHCH 3
OH
(a)
Give the structural formula of a compound isomeric with Q which does not contain a
carbon-carbon double bond.
(1)
(b)
Draw the geometric isomers of Q, and state why Q shows this type of isomerism.
...........................................................
...........................................................
(2)
www.edexcel-cie.com
(ii)
Draw the optical isomers of Q and state what effect such isomers have on the plane
of plane polarised monochromatic light.
...........................................................
...........................................................
(3)
(c)
Give the mechanism for the reaction of bromine with Q; you may represent the compound
in this margin as >C=C< for the purposes of this question.
(3)
(d)
(i)
Give the structural formula of the product obtained when Q is reacted with
potassium dichromate(VI) solution in the presence of dilute sulphuric acid.
(1)
(ii)
Describe a test to show that the product formed in (i) is not an aldehyde. Suggest a
positive test which would give the identity of the new functional group which is
present in the molecule, and state what you would see.
...........................................................
...........................................................
...........................................................
...........................................................
(4)
www.edexcel-cie.com
(e)
(3)
(Total 17 marks)
15.
(a)
(ii)
(iii)
State the name of one other product formed in this reaction which does not contain
chlorine and account for its formation.
...........................................................
...........................................................
...........................................................
...........................................................
(3)
(b)
Methylbenzene reacts with chlorine in the presence of u.v. light in a similar way
to methane:
CH 3
+ Cl 2
CH 2 Cl
+ HCl
In order for the reaction to take place, chlorine must be passed into boiling methylbenzene
in the presence of u.v. light over a period of time.
www.edexcel-cie.com
(i)
(3)
(ii)
(iii)
Assuming that the organic product from this reaction consists only of
methylbenzene and (chloromethyl)benzene, and that Raoult's Law applies to the
mixture of the two liquids, sketch a boiling-point/composition diagram for the
mixture and use it to show how fractional distillation enables the components of the
mixture to be separated. Methylbenzene boils at 111oC, (chloromethyl)benzene at
179C.
179 C
111 C
...........................................................
...........................................................
...........................................................
(4)
(Total 14 marks)
16.
Time/min:
Conc. mol dm 3
15
27
44
60
0.080
0.065
0.054
0.041
0.028
0.020
www.edexcel-cie.com
(a)
(i)
(ii)
(iii)
The reaction is in fact first order with respect to the halogenoalkane. Write the
mechanism for the substitution reaction, identifying the rate-determining step.
(4)
(iv)
(b)
Representing the alcohol as ROH, use dot-and-cross diagrams to show the structure
of the protonated alcohol, and suggest why this species is substituted by a chloride
ion whereas in the absence of acid the reaction does not work.
(4)
(ii)
Explain why the organic product is treated with sodium hydrogen carbonate
solution, then with water, and then with anhydrous calcium sulphate. Show, on the
basis of the quantity of alcohol used, that the yield of the product is 90% as
claimed, and give reasons why the yield is less than 100%.
(7)
(Total 25 marks)
www.edexcel-cie.com
17.
(a)
Ammonia is manufactured by passing hot nitrogen and hydrogen at high pressure over a
catalyst containing iron.
In an experiment, 9.0 moles of nitrogen and 27 moles of hydrogen were put into an iron
vessel of volume l0 dm3. This was then heated to 250 C and allowed to reach
equilibrium. It was found that two thirds of the nitrogen and hydrogen were converted into
ammonia.
N2(g) + 3H2(g) 2NH3(g)
(i)
H = 92.4 kJ moll
(1)
(ii)
moles at start
N2
H2
NH3
9.0
27
moles at equilibrium
concentration at equilibrium
/mol dm3
(2)
(iii)
(2)
www.edexcel-cie.com
(iv)
(v)
State the effect, if any, of an increase in pressure on the value of the equilibrium
constant, giving a reason.
....
....
....
(2)
(b)
Some of the ammonia manufactured in this way is converted into nitric acid, HNO3. The
first step in this process is the oxidation of ammonia.
4NH3(g)+ 5O2(g) 4NO(g) + 6H2O(g)
(i)
Calculate the standard enthalpy change for this reaction given the following
standard enthalpies of formation in kJ mol1:
NH3(g) 46.2
NO(g) + 90.4
H2O(g) 242
(3)
(ii)
Enthalpy
(2)
www.edexcel-cie.com
(c)
A mixture of concentrated nitric and sulphuric acids is used in the nitration of benzene to
form nitrobenzene.
(i)
(ii)
The formation of the NO 2 ion occurs in two steps, the first of which is:
base .
(iii)
(iv)
Give the mechanism for the reaction of the NO 2 ion with benzene.
(3)
(v)
(1)
(Total 22 marks)
www.edexcel-cie.com
18.
(i)
Experiment
[BrCH2CH2Br]
/mol dm3
[I]
/mol dm3
Initial rate of
reaction
(relative)
0.01
0.01
0.01
0.02
0.02
0.01
0.02
0.02
(ii)
What is the order of reaction with respect to sodium iodide? Give your reasoning.
(2)
(iii)
(iv)
Suggest what the first step in the reaction mechanism might be, giving your
reasons. The detailed mechanism for the reaction is not expected.
(2)
(v)
Explain why the mechanism for the reaction must contain at least two steps.
(2)
(b)
Propanone is chosen as the solvent because iodine, 1,2-dibromoethane and sodium iodide
are soluble in it; sodium bromide is not.
(i)
By considering this information and the equation for the reaction say what you
would expect to see as the reaction proceeds.
(2)
(ii)
www.edexcel-cie.com
(iii)
The progress of the reaction could be followed by titrating the liberated iodine with
sodium thiosulphate solution. Describe how you would perform such titrations on
portions of the reaction mixture.
(6)
(iv)
Calculate the volume of 1.00 mol dm3 sodium thiosulphate solution required to
titrate one-tenth of the reaction mixture in (ii) after the reaction was completed.
(3)
(v)
The solubility of sodium iodide in propanone suggests that it has somewhat more
covalent character than sodium bromide, which is not soluble. Suggest why the
bonding in the two salts is different.
(2)
(Total 25 marks)
19.
Chlorine forms oxyacids such as HOCl. Until 1973 HOF was believed not to exist.
(a)
(i)
Give the equation for the reaction of chlorine with water at room temperature.
By considering oxidation states explain why this is a disproportionation reaction.
(3)
(ii)
If sodium hydroxide solution is added to the solution of chlorine in water from (i)
and the mixture is heated, a further disproportionation reaction occurs. Write an
ionic equation to represent this further reaction, and hence show that chlorine reacts
with hot sodium hydroxide solution to give the two chlorine-containing products in
a mole ratio of 5 to 1.
(3)
(b)
(ii)
(iii)
Suggest why the oxidation state of F in HOF cannot be the same as that
of Cl in HOCl.
(2)
(c)
(ii)
Approximately how long would it take for the concentration of HOF to fall to 1.5%
of its initial value?
(2)
www.edexcel-cie.com
(d)
40C
HOF(g) + HF(g)
HOF must be rapidly removed from the reaction site since it reacts with HF, F2 and water.
The apparatus is made from poly(l-chloro-1,2,2-trifluoroethene).
(i)
(ii)
Draw enough of the polymer chain formed by this material, to make the repeating
structure clear.
(2)
(iii)
(e)
Organic fluorine compounds are often different from their analogues with other halogens.
(i)
Chloromethane reacts with a solution of hydroxide ions in an SN2 reaction. Give the
mechanism for this reaction.
(3)
(ii)
CF 0.139 nm
suggest why fluoromethane does not react with a solution of hydroxide ions.
(2)
(Total 25 marks)
20.
(a)
H /kJ mol1
C (graphite)
393.5
H2(g)
285.8
ethane C2H6(g)
(i)
1560.0
(ii)
Complete the following thermochemical equation for the standard enthalpy change
of combustion of ethane.
..C2H6(..)+..O2(..) ..CO2(..)+..H2O(..)
=............................................
(3)
www.edexcel-cie.com
(iii)
Use the data to calculate the standard enthalpy change of formation of ethane.
Draw a Hesss Law cycle as part of your answer.
(3)
(b)
= 112.6 kJ mol1
This reaction does not proceed at room temperature in the absence of light, but reacts
rapidly when exposed to a bright light. Use these facts to illustrate the concept of
thermodynamic and kinetic stability.
Thermodynamic stability ...........................................................................................
....................................................................................................................................
Kinetic stability .........................................................................................................
....................................................................................................................................
(2)
(c)
Ethane and chlorine react in a homolytic free radical substitution reaction when
exposed to light. The two propagation steps are
H
C H
CH 3
step 2
(i)
Cl
CH 3
step 1:
CH 3
C
H
+ Cl
Cl
CH 3
Cl
Cl
+ Cl
(ii)
(iii)
(iv)
www.edexcel-cie.com
.........................................................................................................................
(1)
(d)
The reaction of ethane with bromine proceeds in a similar way. Given the following
average bond enthalpies in kJ mol1
CH + 412
HBr + 366
calculate the enthalpy change for step 1 of the reaction involving bromine.
(2)
(e)
[CN]/mol dm3
[C2H5Br]/mol dm3
0.060
0.020
1.0 105
0.060
0.040
2.0 105
0.120
0.020
2.0 105
(3)
(f)
CN
+ CH 3 CH 2 Br
H
CH 3
NC .... C .......... Br
CH 3 CH 2 CN + Br
H
Route II
CH 3 CH 2 Br
slow
CH 3 CH 2+ + Br then
CH 3 CH 2+ + CN
fast
CH 3 CH 2 CN
www.edexcel-cie.com
(i)
(ii)
This exothermic reaction is catalysed by iodide ions. Draw the enthalpy level
diagram for both the uncatalysed reaction, labelling each clearly.
enthalpy
(3)
(Total 24 marks)
21.
Ethyl benzene is prepared by the reaction between bromoethane and benzene, using anhydrous
aluminium bromide as a catalyst in a solution of ethoxyethane (ether). After the reaction is
complete the ether and any unreacted bromoethane are distilled off. Finally the ethyl benzene
and unreacted benzene are separated by fractional distillation.
(a)
Suggest the mechanism for the reaction between benzene and bromoethane.
(4)
www.edexcel-cie.com
(b)
Benzene (boiling temperature 80C) and ethyl benzene (boiling temperature 136C)
dissolve in each other and form solutions which obey Raoults Law.
Draw a boiling temperature/composition diagram, labelling the liquid and vapour lines.
Use your diagram to explain what happens when a mixture containing 40% benzene and
60% ethylbenzene is fractionally distilled.
Boiling temperature /C
% composition
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
(6)
(c)
Give the reagents and conditions necessary for the conversion of ethyl benzene,
C6H5CH2CH3, into potassium benzoate C6H5COOK.
Reagents ....................................................................................................................
....................................................................................................................................
Conditions .................................................................................................................
....................................................................................................................................
(3)
(Total 13 marks)
22.
(a)
Give the principles which enable you to predict the shape of a particular molecule, given
its formula. Draw dot-and-cross diagrams for SiCl4 and XeF4, and hence draw the shapes
of each of these molecules.
(6)
www.edexcel-cie.com
(b)
Write an equation for the reaction between 2-bromopropanoic acid and hydroxide
ions.
(1)
(ii)
Explain why 2-bromopropanoioc acid can show optical isomerism. State how this
could be detected.
(2)
(iii)
(c)
Optical activity is not confined to organic compounds; chirality is also seen in some
chromium compounds. 1,2-diaminoethane, H2NCH2CH2NH2, forms an octahedral
complex with chromium (III) ion. This complex ion [Cr(H2NCH2CH2NH2)3]3+ is chiral,
and the structure of one isomer is shown below.
N
N
N
Cr +
N
N
N.
Sketch the structure of the other isomer and say why the complex ion is chiral.
(2)
(d)
www.edexcel-cie.com
23.
One of the isomers of C4H10O is the alcohol 2-methylpropan-2-ol which has the structural
formula
CH 3
CH 3
CH 3
OH
(a)
There are three other structural isomers of C4H10O which are also alcohols.
(i)
(3)
(ii)
(3)
www.edexcel-cie.com
(iii)
Describe a test to show that each of the isomers in (i) contains an OH group.
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)
(b)
Draw the structural formula of the final organic product of the reaction when each of the
three alcohols in (a)(i) is heated under reflux with a solution of potassium dichromate(VI)
in dilute sulphuric acid.
ALCOHOL
(3)
www.edexcel-cie.com
(c)
(3)
(ii)
(1)
(Total 15 marks)
24.
(a)
Define:
(i)
(ii)
www.edexcel-cie.com
(b)
Calculate the standard enthalpy of formation of benzene, C6H6(l), using the following
enthalpy of combustion data:
Substance
H c /kJ mol1
C6H6(l)
3273
H2(g)
286
C(s)
394
(3)
(c)
If the standard enthalpy of formation is calculated from average bond enthalpy data
assuming that benzene has three C==C and three CC bonds, its value is found to be
+215 kJ mol1.
Explain, with reference to the structure and stability of benzene, why this value differs
from that calculated in (b). Use an enthalpy level diagram to illustrate your answer.
................................................................................................................................
................................................................................................................................
................................................................................................................................
(4)
www.edexcel-cie.com
(d)
Benzene reacts with bromine when gently warmed in the presence of a catalyst of
anhydrous iron(III) bromide.
(i)
The reaction is first order with respect to benzene and first order with respect to
bromine. Write the rate equation for the reaction.
......................................................................................................................
(1)
(ii)
The mechanism of this reaction involves an attack by Br+ followed by loss of H+.
Step 1.
Br +
Br
Step 2.
+
Br
Br
+H +
25.
(a)
step 1
CH 3 CH 2 OH
step 2
CH 3 CH 2 Br
step 3
CH 3 CH 2 CN
CH 3 CHO
ethanal
step 4
CH 3 CH(OH)CN
www.edexcel-cie.com
(i)
(ii)
Give the mechanism in step 4 which is the reaction between ethanal and hydrogen
cyanide.
(3)
(iii)
(iv)
www.edexcel-cie.com
(b)
The nitrile group, CN, can also be introduced into a molecule by dehydration of an
amide.
Outline a reaction scheme, giving names or formulae for the reagents, for the preparation
of ethanonitrile, CH3CN, from ethanal, CH3CHO.
(7)
(Total 20 marks)
26.
(a)
The kinetics of the hydrolysis of the halogenoalkane RCH2Cl with aqueous sodium
hydroxide (where R is an alkyl group) was studied at 50 C. The following results were
obtained:
Experiment
[RCH2Cl]
[OH]
0.050
0.10
4.0 104
0.15
0.10
1.2 103
0.10
0.20
1.6 103
(i)
Deduce the order of reaction with respect to the halogenoalkane, RCH2Cl, and with
respect to the hydroxide ion, OH, giving reasons for your answers.
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
(4)
(ii)
www.edexcel-cie.com
(iii)
Calculate the value of the rate constant with its units for this reaction at 50 C.
(2)
(iv)
Using your answer to part (ii), write the mechanism for this reaction.
(3)
(b)
(i)
Write the equation for the reaction of concentrated sulphuric acid with solid sodium
chloride.
......................................................................................................................
(1)
(ii)
When concentrated sulphuric acid is added to solid sodium bromide a different type
of reaction occurs. Explain why the reactions are different. Identify the gases
produced with sodium bromide and write an equation to show the formation of
these gases.
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
(4)
(Total 15 marks)
27.
(a)
www.edexcel-cie.com
(ii)
(iii)
Using the bond enthalpy data below, calculate the enthalpy change for the reaction.
Bond
Bond
enthalpy/
kJmol1
CC
+348
C==C
+612
CH
+412
CBr
+276
BrBr
+193
(3)
(iv)
The enthalpy change for this reaction found using the enthalpies of formation of
ethene and the product is 90 kJ mol1 - Suggest which value is more likely to be
accurate and explain your answer.
......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)
(b)
(3)
www.edexcel-cie.com
(c)
The product, C2H4Br2, is a typical bromoalkane. Suggest the structural formulae of each
of the products of the reaction of C2H4Br2 with the reagents given below and identify the
type of reaction involved.
(i)
Type of reaction................................................................................................
(2)
(ii)
Type of reaction................................................................................................
(2)
(d)
Suggest, giving the reagents and conditions, how compound A could be converted in two
steps into compound B.
CH 3
CH 3 CH 3
CH 3
H
H
CN
Step 1.......................................................................................................................
................................................................................................................................
Step 2......................................................................................................................
................................................................................................................................
(4)
www.edexcel-cie.com
(e)
(ii)
(2)
(Total 21 marks)
28.
This question concerns reaction sequences for the conversion of propan-1-ol into
2-bromopropane and butanoic acid.
(a)
Give the reagents and conditions necessary for the conversion of CH3CH2CH2OH
into CH3CH==CH2
......................................................................................................................
......................................................................................................................
(2)
www.edexcel-cie.com
(ii)
Give the reagent and write the mechanism for the conversion of CH3CH==CH2 into
CH3CHBrCH3
......................................................................................................................
(4)
(iii)
Briefly explain why 2-bromopropane is the main product of this second reaction
rather than 1-bromopropane.
......................................................................................................................
......................................................................................................................
......................................................................................................................
(1)
(b)
CH 3 CH 2 CH 2 OH 2
(i)
Step 2
Step 3
(ii)
(iii)
29.
www.edexcel-cie.com
Identify the electrophile involved in this reaction and write an equation to show its
formation.
................................................................................................................................
................................................................................................................................
(2)
(b)
Draw the mechanism for the electrophilic substitution of benzene by ethanoyl chloride.
(3)
(c)
Suggest a reaction scheme, stating reagents and conditions, to convert the product of the
above reaction into
OH
C 6H5
COOH
CH 3
(5)
(Total 10 marks)
www.edexcel-cie.com
30.
There is considerable concern about the depletion of the ozone layer. Ozone, O3, is constantly
being formed in the upper atmosphere by oxygen molecules reacting with oxygen atoms. These
atoms are formed when other oxygen molecules absorb high energy ultra-violet radiation and
undergo homolytic bond fission.
O2 O + O
[Reaction 1]
O + O2 O3
[Reaction 2]
The ozone formed absorbs ultra-violet radiation and breaks down to oxygen molecules and
atoms
O3 O2 + O
[Reaction 3]
[Reaction 4]
Over time the ozone and oxygen concentrations reach a steady state.
(a)
(i)
(ii)
(iii)
Use the reactions above to explain what is meant by the term steady state.
(3)
(b)
Reaction 2 has an enthalpy change of 100kJ mol1 and Reaction 4 an enthalpy change of
390kJ mol1. Assuming that Reactions 1 and 2 are followed by Reaction 4 show how
this results in the upper atmosphere warming up by effectively converting light energy
into heat energy. Calculate the amount of heat produced per mole of oxygen molecules.
(4)
(c)
In the upper atmosphere chlorofluorocarbons, CFCs, such as CCl2F2 break down to give
chlorine atoms and these chlorine atoms react with ozone molecules
Cl + O3 ClO + O2 [Reaction 5]
(i)
Write an equation to show how the ClO radicals can react with oxygen atoms to
form oxygen molecules.
(1)
(ii)
Use the equations given in (i) and that given for Reaction 5 to explain how the
formation of only a few chlorine atoms can cause the removal of a large number of
ozone molecules.
(2)
www.edexcel-cie.com
(iii)
Reaction 5 is first order with respect to both chlorine atoms and ozone molecules.
Write the rate equation and use it to explain why continual release of CFCs into the
atmosphere seems to have an increasing effect on the depletion of the ozone
concentration.
(5)
(iv)
Suggest TWO reasons why the rates of all the reactions in the upper atmosphere are
likely to be slow.
(2)
(d)
HO
C
OCH 3
O
(i)
(ii)
Suggest why the release of CFCs into the environment may lead to an increase in
sales of lotions containing 2-hydroxy-4-methoxybenzophenone.
(2)
(Total 25 marks)
31.
(a)
(i)
(ii)
(b)
Draw the full structural formulae, showing all the bonds, for each of the following:
(i)
The organic product of the reaction of ethene, C2H4, with aqueous potassium
manganate(VII) and sulphuric acid.
(2)
www.edexcel-cie.com
(ii)
3,4-dimethy1hex-2-ene.
(2)
(iii)
(2)
(c)
(ii)
32.
(a)
(2)
(ii)
(2)
www.edexcel-cie.com
(b)
Draw the structural formula of the product(s) of reacting the alkane you have chosen with
chlorine gas.
(2)
(c)
Draw the structural formula of the product(s) of reacting the alkene you have chosen with
chlorine gas.
(2)
(d)
www.edexcel-cie.com
(e)
Draw the structure of part of the poly(ethene) molecule clearly showing the
repeating unit.
(2)
(ii)
Classify the reaction for the formation of poly(ethene) from ethene as one of:
free radical addition,
electrophilic addition,
hydrolysis or oxidation.
..
(1)
(iii)
33.
In this question you will need to use some or all of the following terms
heterolytic
homolytic
electrophilic/electrophile
nucleophilic/nucleophile
free radical
addition
substitution
oxidation
catalysis
www.edexcel-cie.com
(a)
Electrophile.
..
..
..
..
(2)
(ii)
Nucleophile.
..
..
..
(2)
(b)
(c)
Classify the following reactions using the terms listed at the start of the question.
(i)
(ii)
(d)
A catalyst is used in the industrial manufacture of sulphuric acid. Justify the economic
benefits of using a catalyst in terms of:
(i)
(ii)
www.edexcel-cie.com
..
..
..
..
(2)
(Total 13 marks)
34.
(a)
(ii)
(b)
(c)
Tristearin is an ester found in animal fats, especially beef tallow, which can be hydrolysed
by potassium hydroxide. Write an equation to represent the reaction, and state the
importance of the potassium-containing product.
(4)
C 17 H 35COOCH 2
C 17 H 35COOCH
C 17 H 35COOCH 2
Tristearin
(Total 18 marks)
35.
Alkenes undergo electrophilic addition whereas arenes, such as benzene, undergo electrophilic
substitution.
(a)
What is an electrophile?
....................................................................................................................................
(1)
www.edexcel-cie.com
(b)
Propene, CH3CH==CH2, reacts with HBr to give CH3CHBrCH3 as the major product.
(i)
(ii)
(3)
(iii)
(c)
(ii)
Give the mechanism for the reaction. You should include the step that forms the
electrophile.
(4)
www.edexcel-cie.com
(d)
Explain in terms of structure and bonding why benzene and propene react differently with
electrophiles.
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
(4)
(Total 16 marks)
36.
(a)
(i)
(ii)
Explain why the order of reaction cannot be deduced from the stoichiometric
equation for a reaction.
.......
.......
.......
(1)
www.edexcel-cie.com
(b)
Give the mechanism for the SN1 reaction between 2-bromobutane and
hydroxide ions.
(3)
(ii)
(iii)
Initial concentration of
OH / mol dm3
0.10
0.10
1.2 102
0.20
0.10
2.4 102
0.30
0.20
3.6 102
Use the data to deduce the rate equation for the reaction of 2-bromo-2methylpropane with sodium hydroxide solution.
.......
.......
.......
(3)
www.edexcel-cie.com
(c)
Suggest, in outline, a method you could use to follow the progress of the reaction between
a bromoalkane and aqueous sodium hydroxide.
.......
.......
.......
.......
.......
.......
(3)
(Total 14 marks)
37.
(a)
Identify another substance that must be present for this reaction to occur and state
the function of this substance in this reaction.
.......
.......
(2)
(ii)
(4)
www.edexcel-cie.com
(b)
Phenol, C6H5OH, reacts differently from benzene with ethanoyl chloride. State the type of
reaction that would occur between phenol and ethanoyl chloride and give the structure of
the organic product.
Type of reaction ..
Structure of the organic product
(2)
(c)
A benzene ring containing two hydroxy groups, C6H4(OH)2, can exist as a range
of isomers.
(i)
(2)
(ii)
A polymer can be formed by reacting one of these isomers with the di-acyl
chloride, ClCOCH2COCl.
Draw a diagram indicating clearly the structure of such a polymer.
(2)
www.edexcel-cie.com
(d)
OH
can be obtained from phenylamine and phenol in two steps. Identify the intermediate
formed and give the reagents and conditions for each step.
.........
.........
.........
.........
.........
.........
(4)
(Total 16 marks)
38.
(a)
Alkenes such as ethene will take part in homolytic, free radical addition reactions to form
polymers such as poly(ethene).
(i)
(ii)
Draw a repeating unit of the polymer that would be made by the same mechanism
from phenylethene, C6H5CH=CH2.
(2)
(iii)
(iv)
(b)
Ethene, C2H4, reacts with concentrated sulphuric acid by electrophilic addition of H+ and
HSO4 across the double bond to give CH3CH2OSO3H.
(i)
(ii)
Describe a simple chemical test to confirm that the carbon-carbon double bond is
not present in the product.
(2)
(c)
(i)
Use the concepts of the different types of covalent bonds and bond enthalpy to
explain the structure of the benzene ring.
(5)
www.edexcel-cie.com
(ii)
(d)
Outline how a sample of pure benzene, C6H6 (boiling temperature 80 C), could be
converted to a pure sample of nitrobenzene, C6H5NO2, (boiling temperature 211 C).
Include in your answer the reagents and conditions involved and the technique for
obtaining a sample of pure nitrobenzene from the reaction mixture.
(5)
(Total 25 marks)
39.
(a)
(ii)
Write the mechanism for the reaction, including the formation of the species that
attacks the benzene molecule.
(4)
(iii)
www.edexcel-cie.com
(b)
Further reaction produces trinitrobenzene. Draw the structural formulae of the three
isomeric trinitrobenzenes.
(3)
(c)
Give the reagents and conditions required for the conversion of nitrobenzene into
phenylamine, C6H5NH2.
...............................................................................................................................
...............................................................................................................................
(2)
(d)
(i)
Draw the structural formula of the organic product of the reaction between
phenylamine and ethanoyl chloride, CH3COCl.
(1)
www.edexcel-cie.com
(ii)
The organic product of the reaction in (d) (i) is a solid at room temperature.
An impure sample of the solid can be purified by recrystallisation.
Describe how this recrystallisation can be carried out.
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
(6)
(Total 19 marks)
40.
Consider the reaction scheme shown below, which starts with phenylethene.
C 6 H 5 CH
CH 2
HBr
C 8 H 9 Br
A
C 8 H 9OH
B
(i) KMnO4 / NaOH heat
(ii) HCl(aq)
C 7 H 6 O2
C
(a)
(i)
State the conditions under which hydrogen bromide could react with phenylethene.
Give the structural formula of the major product.
.....................................................................................................................................
.....................................................................................................................................
(3)
www.edexcel-cie.com
(ii)
Give the mechanism for the reaction of hydrogen bromide with phenylethene. You
may represent phenylethene as RCH==CH2.
(3)
(iii)
State why one isomer is the major product in the reaction in (i).
.....................................................................................................................................
.....................................................................................................................................
(1)
(b)
B is a secondary alcohol.
(i)
(ii)
(1)
(iii)
www.edexcel-cie.com
41.
(a)
Give the half-equations for the processes that occur at the anode and at the cathode
of the electrolytic cell. Name the other important product from this process.
(3)
(ii)
Use the equations and the E values below to predict what happens if chlorine and
aqueous sodium hydroxide solution are mixed, and write the overall ionic equation
for the reaction.
E/V
Cl2 + 2e
2Cl
OCl + H2O + 2e
+1.36
Cl + 2OH +0.89
(3)
(iii)
(b)
(ii)
Most PVC is used for durable products, but some is waste. Suggest a use for PVC
and comment on the difficulties that might arise from the disposal of PVC in
landfill sites and by incineration.
(4)
www.edexcel-cie.com
(c)
The chlorination of ethane in ultra-violet light has a free radical chain mechanism. The
first step is:
Cl2 2Cl
The next step could be either:
CH3CH3 + Cl CH3CH2Cl + H
(step I)
(step II)
or
Use the mean bond enthalpy data given below to show which of these two steps, I or II, is
the more likely.
CH
CCl
HCl
Bond enthalpy
/kJ mol1
+413
+346
+432
(4)
(Total 20 marks)
42.
Aluminium chloride can be obtained in two forms: anhydrous, often represented as AlCl3, and a
hydrate, AlCl3.6H2O.
(a)
If anhydrous aluminium chloride is heated it sublimes at 185 C. In a closed vessel the gas
is an equilibrium mixture of substances with molecular formulae AlCl3 and Al2Cl6.
Al2Cl6(g)
(i)
2AlCl3(g)
At a given temperature a vessel of volume 10.0 dm3 contained initially 2.0 moles of
Al2Cl6. When equilibrium was achieved 0.50 mol of Al2Cl6 remained.
Write an expression for Kc for the equilibrium and calculate its value under the
stated conditions.
(4)
(ii)
www.edexcel-cie.com
(b)
(ii)
Give the mechanism for the reaction, including the formation of the electrophile.
(4)
(iii)
By comparing the bonding in ethene and in benzene, explain why ethene usually
undergoes addition reactions whereas benzene usually undergoes substitution
reactions.
(3)
(c)
(i)
Suggest why heating hydrated aluminium chloride gives hydrogen chloride gas, and
identify the residue.
(2)
(ii)
Dissolving the hydrate in water does not cause liberation of HCI gas but gives an
acidic solution. Explain why the solution is acidic.
(3)
(Total 20 marks)
43.
(a)
+ H2
(i)
+ 2H2
.....................................................................................................................................
(1)
(ii)
+ 3H2
.....................................................................................................................................
(1)
www.edexcel-cie.com
(iii)
(b)
Benzene, C6H6, reacts with bromine to form bromobenzene, C6H5Br, and hydrogen
bromide.
(i)
Give the formula of the catalyst that is needed for the reaction.
.....................................................................................................................................
(1)
(ii)
Give the mechanism for the reaction, making clear the role of the catalyst.
(4)
(iii)
State the type of mechanism that is commonly found with reactions of benzene and
its derivatives.
.....................................................................................................................................
(1)
www.edexcel-cie.com
(c)
(i)
H
C6H5
CH 3
OH
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(ii)
44.
CH 2
CH
CH 2
CH 2
CH 3
CH
C
C
CH 3
CH 2
CH 3
CH 2
www.edexcel-cie.com
(a)
(i)
Limonene is a chiral molecule found in oil of orange and oil of lemon. Refer to its
structure to explain why the molecule is chiral.
(2)
(ii)
Some reactions and extraction processes can destroy the optical activity of the
product. Give the mechanism for the following reaction and hence explain why the
reaction, if performed on a single optical isomer, would produce a mixture that was
no longer optically active.
CH 3
CH 3 CH 2
CH 3
Br
OH
CH 3CH 2 C OH
CH 2 CH 2 CH 3
Br
CH 2 CH 2 CH 3
(7)
(b)
CH3
CH3
H3C
CH2
limonene
H3C
CH2
compound A
CH3
CH3
CH
H3C
CH3
menthane
CH3
CH 3
OH
CH
H3C
CH2
menthol
O
CH 3
pulegone
www.edexcel-cie.com
(i)
(ii)
(iii)
What particular features would enable the IR spectra of menthol and compound A
to be distinguished?
(2)
(c)
(i)
(ii)
If compound A were reacted with lithium aluminium hydride in dry ether, explain
whether or not menthol would be the product.
(2)
(Total 20 marks)
www.edexcel-cie.com