VJC H2 Chem P3
VJC H2 Chem P3
VJC H2 Chem P3
(ii) Write a balanced equation with state symbols, for each decomposition reaction.
[2]
(b) Magnesium, is an extremely important light weight structural metal which can be
produced by the electrolysis of magnesium chloride. Magnesium chloride can be
prepared from magnesium oxide which is obtained from sea-water containing a
significant amount of Mg2+ and Ca2+. The steps involved are shown below:
Step 1
Controlled Step 2
addition of addition of
Sea water CO32- OH-(aq)
(containing Mg(OH)2
Mg2+ and Ca2+) filtrate
filter
Step 3
heat
Mg MgCl2 MgO
Step 5 Step 4
The numerical values of the relevant solubility products are given below.
(i) Calculate and compare the solubility between magnesium carbonate and
magnesium hydroxide.
[3]
(iii) Explain why the addition of carbonate ions in step 1 has to be controlled.
[1]
(iv) Give a reason why the electrolysis of magnesium chloride is preferred to that of
magnesium oxide.
[1]
(c) Some organic and inorganic compounds are classified under a category called ‘non-
existent compounds’. They are called non-existent because so far chemists had been
unable to synthesise them. Some of the reasons why these compounds are unstable
are:
For the following cases, suggest an explanation for each observation. You may use data
from the Data Booklet to assist you in your answers. Give relevant equations to support
your answers.
O H
C N
H2NCH2CH2CH2CH2CH2CO2H
[3]
[Total: 20]
2 (a) The Contact Process is an industrial process for manufacturing sulfuric acid. The
key stage in this process is the reaction between sulfur dioxide and oxygen.
The flask was then rapidly cooled to liquefy the SO3 so that it can be separated from
the gaseous SO2 and O2. Excess water was carefully added to the liquid SO3,
causing the following reaction to occur:
The resulting solution was made up to 250 cm3 in a standard volumetric flask.
25.0 cm3 of this solution was titrated with 1.00 mol dm−3 NaOH and required
36.0 cm3 for complete neutralisation.
(ii) Hence, calculate a value for Kp, including its correct units.
[1]
(iii) In liquefying the SO3, it was mentioned that the cooling was performed rapidly.
Explain how the titration volume would be affected if the cooling had been
performed slowly.
[2]
(c) One important use of vanadium compounds is the vanadium redox battery, a
rechargeable battery which utilizes graphite electrodes. The electrolytes are pumped
from separate storage tanks A and B into compartments X and Y of the cell
respectively, where they are separated by a semi–permeable proton exchange
membrane which allows only passage of protons.
electrical load
e–
Tank A Tank B
acidified acidified
VO2+(aq) and V3+(aq) and
VO2+(aq) X Y V2+(aq)
membrane
The direction of the electron flow during the discharging process is indicated in the
diagram of the battery above.
(i) By means of the letters X and Y, state and briefly justify the direction of proton
flow across the membrane during the discharging process.
[1]
(ii) With the aid of the Data Booklet, write half–equations for the reactions that
occur at the electrodes in X and Y during the charging process.
[1]
(iii) If the current used for the charging process is 14 A, calculate the time taken, in
hours, needed to restore the concentration of the vanadium-containing ions in
compartment X to their original value.
[2]
(d) Chromium is another transition metal adjacent to vanadium in the Periodic Table.
Some of its reactions are described below:
When chromium metal is dissolved in dilute sulfuric acid, it produces a blue solution
containing Cr2+(aq). The blue solution slowly turns green even in the absence of air.
This mixture is then filtered to remove the unreacted metal. To the green filtrate V,
sodium hydroxide solution was added, forming a grey−green precipitate, W. In
excess sodium hydroxide, the precipitate dissolves to form a dark green solution
containing an anion, X. The dark green solution turns into a yellow solution, Y, upon
warming with hydrogen peroxide solution.
(i) By quoting and using relevant Eo values from the Data Booklet, explain why
the blue solution turns green.
[2]
(ii) Identify the precipitate W and the anion X and suggest ionic equations, with
state symbols, for the formation of W, and for the formation of X.
[2]
(iii) State the role of hydrogen peroxide in converting the dark green solution into
Y.
[1]
(e) A particular chromium compound has the formula Cr(H2O)6Cl3. It contains a complex
Z in which the coordination number of chromium is 6.
When a solution containing 0.02 mol of the compound, Cr(H2O)6Cl3, is treated with
excess aqueous Pb(NO3)2, a white precipitate is formed. After filtration and drying,
the mass of the precipitate is found to be 2.78 g.
(i) Use the given information to determine the formula of the complex, Z.
[1]
(ii) Z is known to exist as two stereoisomers. Draw the structures of these two
stereoisomers, showing clearly the spatial arrangement of the ligands around
the central metal ion.
[2]
[Total: 20]
3 Phosphorus belongs to Period 3, an element that is essential for life. The elemental form
of phosphorus consists of tetrahedral P4 molecules, in which each phosphorus atom forms
three single bonds with three other phosphorus atoms. Phosphates, compounds
containing the PO43 ion, are a component of DNA, RNA, ATP and also the phospholipids,
which form all cell membranes.
(a) Each of the Period 3 elements, Na to S, reacts at a different rate with oxygen to form
oxides of different oxidation states.
(i) Describe what you see when magnesium and sulfur are separately burned in
air or oxygen. Write equations for the reactions that occur.
[3]
(ii) Explain briefly why the bonding of the oxides of Period 3 elements vary from
ionic to covalent.
[1]
Element X forms a white oxide that is slightly soluble in cold water. Its chloride
dissolves in water to form a weakly acidic solution.
Element Y forms two oxides. 0.03 mol of one of the two oxides produces
6.99 g of white precipitate when shaken with excess barium chloride solution.
Another solution containing 0.05 mol of this oxide of element Y forms a neutral
solution when the same amount of the oxide of the element X is added to it.
Identify the elements X, Y, the oxide of Y and the white precipitate that is
formed in the above reaction. Explain why the chloride of element X is acidic.
[3]
(b) Sulfur, another Period 3 element, forms a wide range of sulfides with phosphorus.
One of the most well-known examples is the three-fold symmetric P4S3 used in
strike-anywhere matches.
(i) State the two oxidation states of phosphorus that exist in P4S3.
[1]
(ii) P4O3 has a structure that is similar to P4S3. Explain why the OPO bond angle
is smaller than the SPS bond angle.
[2]
(iii) The bond energy for the PP single bond is 197 kJ mol1.
(iv) In the presence of excess sulfur, P4S3 can be converted to P4S10, which is
structurally and chemically similar to P4O10. Give a balanced equation for the
reaction between P4S10 and H2S which does not involve any change in
oxidation state. Hence, state the role that P4S10 plays in the reaction.
[2]
(c) Aluminium is an important element in the reducing agent, LiAlH4, for organic
synthesis. When benzoic acid is reduced by LiAlH4 in dry ether followed by addition
of heavy water (D2O), the product, benzyl alcohol-OD, is formed:
C6H5CH2OD
(ii) LiAlH4 reacts with H2O to give two insoluble hydroxides and a gas. Give a
balanced equation for the reaction.
[1]
[Total: 20]
4(a) Nitrous oxide is a chemical compound with formula N2O. It is commonly known as
laughing gas due to the euphoric effects of inhaling it, a property that had led to its
recreational use as a hallucinogenic anaesthetic.
The rate of decomposition of pure N2O may be followed by measuring the total pressure
of the system. In such an experiment, the total pressure, p, increased as follows:
(i) Explain mathematically, or otherwise, that the partial pressure of N2O at 1030 s is
20 kPa.
[1]
(ii) By using a graphical method, determine the order of the reaction with respect to
N2O.
[1]
(iv) Suggest a reaction mechanism consisting of two elementary steps for the
decomposition of nitrous oxide that is consistent with the rate equation.
(b) Alkene metathesis is a reaction that breaks the double bond in an alkene and then
rejoins the fragments. When the fragments are joined, each new double bond is formed
between two sp2 carbons that were not previously bonded. Metathesis is a Greek word
that means “transposition.”
One mole of compound C gave two moles of carbon dioxide gas and one mole of
compound D (C4H6O3) when treated with hot acidified concentrated KMnO4.
Compound D
(c) Geraniol (C10H18O) appears as a clear to pale-yellow oil that is insoluble in water but
soluble in most common organic solvents. It has a rose-like scent and is commonly used
in perfumes.
Geraniol
Intermediate X
Step 2 In a concerted manner, the C–O bond breaks resulting in the expulsion of a water
molecule and the carbon atom is attacked by an electron-rich double bond leading to the
formation of a carbocation with a six-membered ring.
Step 3 The octet electronic configuration is restored to the positively charged carbon in the
carbocation by a transfer of electrons from a C–H bond. The transfer of electron is
facilitated by H2PO4− acting as a base.
Dipentene, with the following structure, is formed as the product:
Dipentene
Copy the structure of the organic intermediate X formed in step 1 onto your answer
script and complete the remaining steps 2 and 3 of the mechanism.
In the description of the mechanism, you should clearly show curly arrows, charges,
dipoles and any relevant lone pair.
[2]
(d) (i) Name the mechanism of the reaction between dipentene and bromine.
[1]
(ii) Draw the structure of the tetrabromide that is produced from the reaction between
dipentene and bromine.
[1]
(iii) State the type of stereoisomerism exhibited by the tetrabromide compound and the
number of isomers present.
[2]
(e) Nerol, which is present in the essential oil, bergamot, has the same formula as geraniol
and undergoes the same dehydration reaction to give the same dipentene. The main
difference between geraniol and nerol is the melting point. Geraniol has a melting point
of 15°C while nerol has a melting point of around −10°C.
(i) Draw the structure of nerol and state the type of isomerism that exists between
geraniol and nerol.
[2]
(ii) Hence, explain why there is a difference in melting point between the two isomers.
[2]
[Total: 20]
5 This question is about the chemistry of some nitrogen and oxygen containing compounds.
Nitrogen and oxygen are two very electronegative elements which make up about 78%
and 20% of the atmosphere by volume respectively. Nitrogen containing compounds are
vital components of foods, fertilizers, and explosives while oxygen is the third most
abundant element found in the sun.
(a) Procaine is a nitrogen containing compound which is used primarily to reduce the
pain of intramuscular injection of penicillin.
CO2CH2CH2N(C2H5)2
NH2
Procaine
Draw the structure of the compound(s) formed when procaine reacts with:
(b) Compare and explain the relative basicity between the two nitrogen-containing
compounds below in terms of their structures.
CO2CH2CH2N(C2H5)2 CO2CH2CH2N(C2H5)2
Cl Cl
NH2 NH2
Procaine Compound L
[2]
(c) Suggest a chemical test that allows you to distinguish procaine from compound L.
[2]
(i) Given the following reactions and their standard enthalpy changes, construct
an energy cycle to calculate the enthalpy change for the reaction below
involving the formation of gaseous N2O4.
(ii) The standard molar entropy, S is the entropy content of one mole of
substance under standard conditions of 298 K and 1 atm. The S values of
some nitrogen oxides are given in the table below:
(iii) Hence, calculate the minimum temperature at which the reaction will take
place.
[1]
(e) The graph below is an Ellingham diagram, which shows the variation in the Gibbs
free energy change of formation, ∆Gf, with temperature, T, for some oxides. This
graph is used to evaluate the ease of reduction of metal oxides.
∆Gf
/ kJ mol−1
0
4Ag + O2 2Ag2O
−200 2Zn + O2 2ZnO
−400
2C + O2 2CO
−600
(ii) What does the gradient of the graph in the Ellingham diagram represent?
Hence, explain why the sign of the gradient for 2Zn + O2 2ZnO is as
reflected on the graph.
[2]
(iii) Calculate the ∆G value for the reduction of zinc oxide by carbon at 2000K.
Hence, comment on the feasibility of the reaction at 2000 K.
[3]
[Total: 20]