ST ANDREWS JUNIOR COLLEGE

2013 JC2 H2 Chemistry

BT2 Revision Package
(Integrated Questions)
ANSWERS

Name: __________________________
Class: __________________________

1. RJC 2007 P3/Q4 (Mod)

(a) Resultant mixture formed when 1 mol of ClCH2COOH is added to 1 dm3 of
water is the least acidic as ClCH2COOH ionises only partially in water:
ClCH2COOH + H2O
ClCH2COO + H3O+
Resultant mixture formed when 1 mol of CH3COCl is added to 1 dm3 of water is
more acidic as CH3COCl hydrolyses, forming HCl which is a strong acid:
CH3COCl (l) + H2O (l) CH3COOH (aq) + H+ (aq) + Cl (aq)
Resultant mixture formed when 1 mol of SiCl4 is added to 1 dm3 of water is the
most acidic as 1 mol of SiCl4 hydrolyses to form 4 mol of HCl:
SiCl4 (aq) + 2H2O (l) SiO2 (s) + 4H+ (aq) + 4Cl (aq)
Hence, in order of increasing acidity of the resultant mixture formed on reaction
with water: ClCH2COOH, CH3COCl, SiCl4

H H H

(b) (i)

H C C C H
H O Cl
H
(ii)

Propene undergoes electrophilic addition and the first step involves the
addition of the electrophile to carbon1 as the more stable carbocation is
formed:

CH3

H H
C C H + E+

H H
CH3 C C H or
+
E
major intermediate
because more stable

CH3

H H
C C H
+
E

In HOCl, Cl is partially positive so that Cl+ is the electrophile and Cl+ adds
to the carbon1 to form the more stable carbocation.
Subsequent addition of OH results in the formation of the major product
with Cl added to carbon1.
In HCl, Cl is partially negative so that the electrophile is H+ rather than
Cl+. Hence H+ adds to carbon1 to form the more stable carbocation.
Subsequent addition of Cl to carbon2 results in the formation of the
major product with Cl added to carbon2.
(c)

OH

CH3 Cl2 in
CCl4
1 ] dark
In [the
[1]

OH

Cl

CH3 NaOH
[1 ]

ONa+
CH3 ClCH2CO2H

OCH2CO2H
CH3

Heat/

Cl

[1 ]

Cl

(d) (i)

(ii)

O Na

H
CH2 C
OH OH

O C

OH

C
O

(iii)

H
CH2Cl C
OH

C
N
H N

H
NO2

O
CH3

H
H
CH2Cl C
C
O CH O
C 3
O

NO2
(e)

Melting points of sodium chloride and magnesium chloride are higher than that
of aluminium chloride, silicon tetrachloride and phospohorus pentachloride.
This is because NaCl and MgCl2 are ionic and a large amount of heat is
required to overcome strong ionic bonds between the ions in the giant ionic
lattice so that their melting points are high.
Al2Cl6, SiCl4 and PCl5 have simple molecular structure with weak van der
Waals forces between the molecules so their melting points are lower than the
ionic NaCl and MgCl2.
The order of increasing melting point is SiCl4, PCl5 and Al2Cl6 since van der
Waals forces increases also in that order due to greater ease of distortion of
electron cloud as the number of electrons increases from SiCl4 to PCl5 to Al2Cl6.

(f)

(i)
(ii)

AlCl3 (s) + 6H2O (l)
[Al(H2O)6]3+ (aq) + 3Cl- (aq)

[Al(H2O)6]3+ (aq) [Al(H2O)5(OH)]2+ (aq) + H+ (aq)
PCl5 + 4 H2O
H3PO4 + 5HCl

2. TJC 2007 P3/Q3

(a) (i)
Increasing b.p : HFC-152, HCFC-22, HCFC-123
All have simple molecular structures. Boiling involves breaking
intermolecular (or van der Waals) forces.
Mr increases in the order, HFC-152, HCFC-22, HCFC-123. The larger the
Mr, the bigger the electron cloud, the greater the polarization resulting in
stronger induced dipole-induced dipole attractions (or van der Waals)
between molecules. More energy is needed to overcome the
intermolecular forces as Mr increases resulting in an increase in the
boiling point.
(ii)

Refrigerants, aerosols, propellants blowing agents in foam plastic

manufacturing

(iii) CFCs are chemically inert, do not react with air, water and are nonbiodegradable.
causes ozone depletion in stratosphere
(iv) HCFC-123 is the best choice as it is not flammable and it is
biodegradable with a short life span.
(b) (i)

The primary structure of a protein refers to the sequence of -amino acids

linked by strong peptide bonds in the protein chain. The primary structure
determines the folding, shape and function of the protein.

(ii)

Regular coiled (spiral)

polypeptide chain held in
place by intra-chain hydrogen
bonds between the C=O
group of a peptide and the NH group of a peptide which is
four linkages further down
the chain. Hydrophobic R
groups on the -carbon point
outside of the helix.

The hydrogen bonds bind

and stabilize the structure.

(iii) R group interactions: van der Waals, disulphide linkages, hydrogen

bonding and ionic interactions
H2
C

van der Waals

Disulphide linkages: -CH2-S-S-CH2Hydrogen bonding:

CH2
O
H

CH2

HO

CH2

Ionic interactions: CH2CO2 +H3NCH2

(c)

1
2
3
4
5
6
7
8
val phe asp lys gly phe lys val arg
Using chymotrypsin, the polypeptide P will cleave at positions 2 and 6 to give
the fragments val-phe-, asp-lys-gly-phe and lys-val-arg.
Using trypsin, the polypeptide will cleave at positions 4 and 7 to give val-pheasp-lys, gly-phe-lys and val-arg.

(d) Addition of acid causes denaturation and coagulationof the protein present in
cows milk.
Major changes occur in the secondary and tertiary structure of protein. The acid
disrupts the ionic bonds and hydrogen bonding interactions in the secondary
and tertiary structure of protein. New interactions can take place between
adjacent chains bringing about coagulation and hence precipitation occurs.

3.

ACJC 2008 P3/Q4

(a) (i)
Enthalpy change of formation is the energy change when one mole of
compound is formed from its constituent elements in the standard
states at 25oC and 1 atm.
(ii)
4C(g) + 9H (g) + Cl (g)

Energy
BDE(Cl-Cl) =

x 244 kJ mol

4C(g) + 9H (g) +

Cl2(g)

BDE(H-H) =
4C(g) +

H2(g) +

-1

x 436 kJ mol

Cl2(g)

Hatom (CH3CH2CH2CH2Cl)
-1

4 x Hatom (C) = 4 x 716 kJ mol

4C(s) +

H2(g) +

Cl2(g)

Hformation = -188 kJ mol-1

CH3CH2CH2CH2Cl(l)

Hatom (CH3CH2CH2CH2Cl) = -(-188) + 4(716) + 9 (436) + 1 (244)

2
2
= +5140 kJ mol-1
(iii) Hatom (CH3CH2CH2CH2Cl) = BDE (C-Cl) + 3BDE(C-C) + 9BDE(C-H)
= 340 + 3(350) + 9(410)
= +5080 kJ mol-1
(iv) Values in Data Booklet are only averages.
For (ii), vapourisation of CH3CH2CH2CH2Cl(l) into gaseous state is not
taken into account.
H

(b) (i)
H

(ii)

Cl

H
HH

Cl

HH

H
H

Cl

2-chlorobutane, CH3CH2CHClCH3
straight-chain isomer with elongated electron cloud,
largest surface area for interaction between molecules
Largest amount of energy required to break the strongest Van der Waals

forces between molecules, hence highest boiling point.

(c)

(i)

NaOH (aq). Reflux.

(ii)
Nucleophilic substitution.
H
H

HO

d+

H
d-

d-

HO

Cl

H
d-

d+

Cl

d-

HO

R = CH 2CH2CH3

d+

H
R

transition state

Cl xx

(iii) Exothermic.
H = Bonds Broken Bonds Formed
= BDE (C-Cl) BDE (C-O) = 340 360 = -20 kJ mol-1
(iv) CH3CH2CH2CH2OH
Dil. H+ (aq) / K2Cr2O7 (aq). Distil.
*reflux [0]; No distil [0]*

CH3CH2CH2CHO

CH3CH2CH2CH(OH)CN
CH3CH2CH2CHO
HCN with traces of NaOH/ NaCN. 10-20oC
Identify intermediate as CH3CH2CH2CHO

4.

VJC 2008 P3/Q5

(a)
A:

CO2H
H C Cl
Cl

B:

H CH2OH
C C NH3+ ClOHH

Cl- +

H3N

C:

D:

Cl- +

H3N

(b)

H CH2OH
C C NH3+ ClOHH

Step 1:
Reagents: NaBH4 in ethanol / Na in ethanol / H2 over Pt or Ni catalyst
Conditions: Room temperature (140oC if Ni catalyst is used)
Step 2:
Reagents: Excess conc H2SO4
Conditions: 170oC

(c)

Yes, chloramphenicol-X is expected to exist as a solid at room temperature.

This is because there is extensive intermolecular hydrogen bonding due to

the presence of the highly polar N-H and O-H groups.

In addition, there are strong dispersion forces between the molecules due to
the large number of electrons present in the molecule.
Thus, a lot of heat is needed to overcome the intermolecular forces between
the molecules.
(d)

Add NaOH(aq) to each compound separately, followed by heating.

With compound F, NH3(g) is evolved which turns moist red litmus blue.
No NH3(g) is evolved with compound E.

(e)

(f)
(g)

5..

(i)

Quartenary structure is the precise arrangement of 2 or more

polypeptide chains in oligomeric/highly complex proteins, held
together by R group interactions.
Haemoglobin consists of 2 sub-units and 2 sub-units.

(ii)

Haemoglobin is soluble in water as it is a globular protein where the

folding of polypeptide chains caused the hydrophobic R groups to be
internally located away from the aqueous surroundings while the
hydrophilic R groups are located on the surface of the protein.

(iii)

Poison: Carbon monoxide

Carbon monoxide forms strong dative bond with iron atom in
haemoglobin more readily than O2 molecule (since iron-CO bond is
stronger than iron-O2 bond). The reaction is irreversible.
This consequently cuts down the supply of oxygen to the body.

DHS 2008 P3/Q1

(a) (i)
Hess Law states that the enthalpy change accompanying a chemical
reaction is the same regardless of the pathway taken, provided the initial
and final states of reactants and products are the same.

(ii)

Hrxn = +177 + (95) + (286) = 204 kJ mol1

(iii)
energy

Ea, activation energy

C6H4(OH)2
+ H2O2

Hrxn = 204 kJ mol1

C6H4O2 + H2O
reaction pathway

(b) (i)

X is Ag (or silver) metal.

Hydroquinone is a reducing agent in I.

(ii)

Y:

CH3O

OCH3

Type of reactions: neutralisation and nucleophilic substitution

(iii)

O + 4[H]

HO

OH

Br

Br
O

O + 2HBr

or

O
Br

Br

(iv) Orange ppt is formed.

NO2
O2N

N N
H

(v)

O2N
N N

NO2

Student will be unsuccessful because 1,4dichlorobenzene cannot

undergo nucleophilic substitution under the given conditions.

Reasons:
The porbital of the chlorine atom overlaps with the electron
cloud of the benzene ring
The carbonchlorine (CCl) bond is strengthened, thus rendering
nucleophilic substitution by OH difficult.
(c)

(i)

Srxn = [Sf(H2O) + Sf(O2)] Sf(H2O2) = 69.9 + (205) 109.6 =

+62.8 J mol1K1

(ii)

6.

Grxn = Hrxn TSrxn = ( 98.1) (298)(62.8 x 103) = 117 kJ

mol1
Store c.H2O2 at low temperature
Allow gas to escape to prevent build up of pressure
Ensure containers used to store H2O2 are free from impurities as they
can act as catalysts for decomposition

AJC 2008 P3/Q3

(a) NaCl and MgCl2 are both ionic. Hence, they merely dissolve to give ions.
(OR Mg2+(aq) undergoes hydrolysis to a very small extent )
AlCl3 and SiCl4 are simple covalent and hydrolyze in water to give white fumes
of HCl and an acidic solution.
AlCl3 + 6H2O
[Al(H2O)6]3+ + 3Cl[Al(H2O)6]3+ + H2O(l) [Al(H2O)5(OH)]2+ + H3O+
or
AlCl3 + 6H2O
[Al(H2O)5(OH)]2+ + H+ + 3ClSiCl4 + 2H2O
SiO2 + 4HCl
SiCl4 + 4H2O
SiO22H2O + 4HCl

(b) (i)

(ii)

(c)

(i)

Al-H bond is weaker than the B-H bond.

(ii)

H- acts as nucleophile. Alkenes are not attacked by nuclephiles as they

are electron-rich.

(iii)

(iv)

(d) (i)

(ii)

Test: Add I2(aq) in NaOH(aq) to each compound and warm.

Ethanol gives a yellow ppt of CHI3.
For phenyl methanol, no yellow ppt is observed.

7. ACJC 2010 P3/Q1

(a) (i)
Green house effect Due to CO2 emission which traps UV rays
resulting in global warming.
(and any other logic answers)
(ii)

Hydrogen fuel cells.

Indirect combustion of hydrogen gas which produces electric

power to run vehicles without emission of CO2. Product is H2O
which is non-toxic.
[3]

(b)
H

CH3

CH3

CH3

[1]

(c)

CH3

(i)
CH 2
CH 2

CH 2

CH3
CH3
CH 2

Hr0

CH3

(l)

(l)

CH 2

+ 10.5 O2 (g) + 2 O2 (g)

12.5 O2 (g)

Hco (1,2 xylene)

8CO2 (g)

(ii)

4H2 (g)

CH 2

Hco (n-octane)

4Hc o(H2)

9H2O (l)

Hro = -5470 [(-4540) + 4(-286)] = +214 kJ mol-1.

Bond broken
7C-C
18 C H

Bonds formed
2CC

6C

10 C H
4HH
Picking the correct benzene double bond from Data Booklet
Hr = 7(+350) + 18(+410) [2(+350) + 6(+520) + 10(+410) + 4(+436)]
= (+9830) (+9664) = +166 kJ mol-1
The sum of enthalpy change of vaporization of the products is more
endothermic than the enthalpy change of vaporization of the reactant.
(iii)

(iv)

(c)(ii) is more accurate.

Reforming take place at 500oC and pressure of 20 atm which are
non-standard conditions. (Must make reference to the passage.)

G value will be more negative. Since, G = H - TS,

S > 0 because there is a production of 4 moles of H2, which results
in n(gas) to increase after the reaction.
[10]

(d) (i)

(ii)

Electrophilic substitution
NO2+ + 2HSO4- + H3O+

HNO3 + 2H2SO4
NO 2

NO 2

NO 2

slow

fast

+H

H3C

H3C
CH3

CH3

H3C
CH3

Intermediate

[5]
8 AJC 2010 P3/Q4
(a) Observations: Purple colour of KMnO4(aq) turns to a colourless solution.
MnO4 + 8H+ + 5e Mn2+ + 4H2O (x2)
SO2 + 2H2O SO42 + 4H+ + 2e (x5)
Overall eqn:

2MnO4 + 5SO2 + 2H2O 2Mn2+ + 5SO42 + 4H+

(b)(i) Redox reaction or oxidation of butanone.

SeO2 is acting as the oxidising agent.
(b)(ii) CH3COCH2CH3 + SeO2 CH3COCOCH3 + Se + H2O
(b)(iii)

Bonds broken:
CH : 2(410)
Se=O : 2(418)
Total: 1656 kJ mol1

Bonds formed:
C=O : 740
OH : 2(460)
Total: 1660 kJ mol1

H
= bonds broken bonds formed

= 5906 5910 (or 1656 1660)
= 4 kJ mol1

(b)(iv) It is an approximation as the bond energies from the Data Booklet are only
average values.
or
Bond energies are for breaking of bonds in the gaseous phase. However, all
the substances in the reaction are not in the gaseous phase under standard
conditions.
(c)

Reagents and conditions:

Step I : SeO2 , (heat under reflux)
Step II: HCN, NaCN catalyst (or trace of NaOH) , 10 - 20oC
Step III: dilute H2SO4 (or HCl), heat under reflux
(d)(i) Using G
= H
TS
,
G
= (111) (298)(183/1000)
= +56.5 kJ mol1
Since G
is positive, the sublimation process is not spontaneous at room
temperature.
(d)(ii) During sublimation, G
= 0 kJ mol1
H
= TS

T = H
/S

= (111) / (0.183)
= 607 K
= 334 C
(d)(iii) The assumption made is that both H
and S
remain constant at a higher

temperature.
(e) E and F undergo nucleophilic substitution to give G and H.
G undergoes oxidation to give J.
G contains 1 primary OH group and 1 tertiary OH group.
H contains 2 tertiary OH groups.

9. DHS 2010 P3/Q1

(a) Aluminium is the worlds most abundant metal and is the third most common element,
comprising 8% of the earths crust. The versatility of aluminium makes it the most widely
used metal after steel. Although aluminium compounds have been used for thousands of
years, aluminium metal was first produced around 170 years ago.
(i)

It is possible to ionised aluminium to form aluminium negative ion Al in the gaseous

state. Give a balanced equation for this reaction.
Al (g) + e
Al (g)

(ii)

What is the name of the reaction in (i)?

First electron affinity of aluminium

(iii)

Give the full electronic configuration of Al.

1s2 2s2 2p6 3s2

(iv)

How would you expect the magnitude of the enthalpy change of the reaction in (i)
compared to that of sodium? Explain as fully as you can.
The magnitude of the first electron affinity for aluminium will be smaller/lower than
that of sodium.
The nuclear charge of aluminium is higher than sodium
The filled inner s subshell of aluminium provides effective shielding for the
additional electron as compared to sodium.
The additional electron of aluminium resides in a porbital which is further than

the electron in a sorbital of sodium.

[6]
(b)

Solid aluminium chloride sublimes at 6000C. When 1.00 g of the solid is placed in an
evacuated vessel of volume 1.00 dm3 at 6000C, the pressure produced is 207.7 kPa.
(i)

Calculate the apparent relative molecular mass of the aluminium chloride under these
conditions.
207.7 103 1 103 =

1
8.31 (6000 + 273)
Mr

Mr = 250.9 (1 dp)
(ii)

Assuming that, in the vapour phase, aluminium chloride partially exists as dimer,
calculate the percentage of the dimer under these conditions.
x(133.5) + (1x)(267) = 251
x = 0.12
percentage of dimer = 88.0% (3 s.f.)

(iii) Draw the dot and cross diagram for the dimer of aluminium chloride.

(c)

[4]
The GattermannKoch reaction, named after the German chemists Ludwig Gattermann and
Julius Arnold Koch in organic chemistry refers to a FriedelCrafts acylation reaction in which
carbon monoxide and hydrochloric acid are used insitu with FriedelCrafts catalyst, namely
AlCl3. The reaction involves an acylium ion as an electrophile and tetrachloroaluminate ion,
AlCl4. An example is provided below.

(i)

Define the term electrophile.

An electrophile is any species that accepts an electron pair with a vacant orbital/ is
an electron pair acceptor

(ii)

Give the forumla of the acylium ion in this reaction.

CHO+
(iii) State the type of reaction and describe the mechanism of GattermannKoch reaction
(You may omit the step that generates the acylium ion).
Electrophilic substitution.
H

CHO+

slow
+

AlCl4H

CHO

CHO

fast

(d)

CHO

HCl

AlCl3

[6]
The synthesis of compound C involves the GattermannKoch reaction in Step II. Complete
the reaction scheme below by providing the appropriate reagents and conditions for
Step I and IV and give the structural formula for A B.

[4]
[Total: 20]

Topics: All topics until Kinetics

10. JJC 2008 P3/Q5
(a) (i)
(Compare Expts 1 and 2)
When VHCl/[HCl] increases by 1.5 times
rate increases by

0.00188
= 1.5 times
0.00125

first order wrt HCl

(Compare Expts 2 and 3)
When Vsucrose/[sucrose] decreases by half/ 0.5 times
rate decreases by (

0.000938
= 0.499 0.5) by half/ 0.5 times
0.00188

OR
When Vsucrose/[sucrose] increases by 2 times

 rate increases by (

0.00188
= 2.00 ) by 2 times
0.000938

first order with respect to sucrose

rate = k[sucrose][HCl]
From Expt 1,
[sucrose] = 0.79 20/50 = 0.316 mol dm3
[HCl] = 1.25 20/50 = 0.500 mol dm3
k=

0.00125
= 7.91 x 103 mol1 dm3 min1
0.316 0.500

or
From Expt 2,
[sucrose] = 0.79 20/50 = 0.316 mol dm3
[HCl] = 1.25 30/50 = 0.750 mol dm3
k=

0.00188
= 7.93 x 103 mol1 dm3 min1
0.316 0.750

or
From Expt 3,
[sucrose] = 0.79 10/50 = 0.158 mol dm3
[HCl] = 1.25 30/50 = 0.750 mol dm3
k=
(ii)

0.000938
= 7.92 x 103 mol1 dm3 min1
0.158 0.750

From Expt 4,
[sucrose] = 0.79 40/70 = 0.451 mol dm3
[HCl] = 1.25 20/70 = 0.357 mol dm3
Initial rate = 7.91 x 103 0.451 0.357
= 1.27 x 103 mol dm3 min1

(b) (i)

Initial rate

zero order
Graph 1
Graph 2

first order
[sucrose]

(ii)

At low [sucrose], reaction is first order wrt sucrose

As [sucrose] increases,
more active sites of enzyme molecules occupied by sucrose
molecules
reaction is no longer first order wrt sucrose
At high [sucrose],
all active sites of enzyme molecules occupied by sucrose
molecules
reaction is zero order wrt to sucrose

(iv)

(c)

(i)

Ag+ forms ionic interactions with COO and disrupts ionic

interactions
Ag+ binds tightly to SH group and disrupts disulphide bridges
small proportion of the enzyme is denatured

exists as zwitterions
giant ionic structure in solid form
can form ion-dipole interactions with water
soluble

(ii)
O
*
H2NCHCOK+
CH2COOK+

(iii)
Type of
Diagram illustrating interaction
interaction

hydrogen
bond

van der

Waals
interaction

ionic
interaction

[7]
[Total: 20]
11. HCI 2008 P3/Q4
(a)

Boltzmann diagram, correct labels for axes, appropriate shading of areas.

When temperature increases, there is an increase in the fraction of reactant
particles with kinetic energy larger than or equal activation energy E (refer to
A

shaded areas).
Thus, frequency of effective collision increases, reaction rate increases.
(b)

(i)

Order of reaction with respect to a reactant is the power to which its

concentration is raised in the rate equation.
The orders of reaction must be found experimentally.
Rate constant (k) is the proportionality constant in the rate equation.
It is a constant at a given temperature.
OR
Rate = k[A]2
Rate order is 2 and rate constant is k.

(ii)

Rate = k [CH COCH ] [H ]

(iii)
(iv)
(v)

(c)

(i)

Rate
1.25 x 10
=
= 5.00 x 10 4 mol 1dm3s 1
+
[CH3COCH3 ][H ] 0.05 x 0.05
catalyst

Constant gradient => rate is independent of change in [I2].

Rate order wrt [I2]= zero
I in NaOH(aq), warm
2

(ii)

(iii)

condensation
phenol in NaOH(aq)

(iv)

Topics: All topics until Chemical Equilibrium

12. AJC 2010 P3/Q5
(a)(i)
CH4 + H2O
3 H2
Initial
P/atm
Eqm
P/atm

+ CO

1.0

1.0

0.0

0.0

0.60

0.60

3(0.40)

0.40

(1.2)3 (0.40)
Kp =
= 1.92 atm2
(0.6) 2
(a)(ii) When temperature increases (from 550oC to 850oC),
Percentage of H2 increases (from 1.68% to 11.9%), thus forward reaction is
I favoured.
By L.C.P, endothermic reaction is favoured.
Hence, production of H2 is endothermic.
When volume changes from Z to X,

II
Percentage of H2 increases (from 0.009% to 1.68%) thus forward reaction is
favoured.
When equilibrium shifts to the right, the number of moles of gas increases.
By L.C.P. pressure has decreased / volume has increased.
Hence, increasing order: Z < Y < X

(b)(i)
Mr of R =
(b)(ii)

0.10 8.31 (127 + 273 )

= 56.0
101 10 3 58.8 10 6

Q: CH2=CHCH3
R: CH3CH

CHCH3
CH3

S: CH3CH2CH2CH3

or

CH3

C
H

CH3

(c)(i)
+

4H2

(c)(ii) Oxidation / aromatization / cyclisation

(c)(iii)

CH3

CH3

CH3

or

CH3CHCH2CH2CHCH3

CH3CH2CHCH2CH2CH2CH3

(d)(i) Oxidation number of C in glucose = 0

Oxidation number of C in methane = 4
Oxidation number of C in ethanol = 2
(d)(ii) Bubble gaseous products through sodium hydroxide to remove the acidic CO2.
(d)(iii) More heat is produced during production of methane / reaction is more
exothermic.
Advantage:
The heat could be recycled and used in other industrial processes.
Disadvantage:
The combustion of methane produces less heat than the combustion of
ethanol.
or
The production of methane has a higher maintenance cost.
(d)(iv) CH4 + 2O2 CO2 + 2H2O
C2H5OH + 3O2 2CO2 + 3H2O
One mole of glucose will burn to give 6 moles of CO2, regardless of whether it
is used to form methane or ethanol.

13. DHS 2010 P3/Q2

(a)

Methane is used to produce synthesis gas (syngas), a mixture that includes carbon
monoxide and hydrogen, by reacting with steam on a nickel catalyst. Syngas is then
used to produce liquid hydrocarbons and methanol.
CH4 (g) + H2O (g)

CO (g) + 3H2 (g)

When a 1:1 ratio of methane and steam at a total initial pressure of 10 atm is mixed,
50% conversion is achieved.

(i)

Write an expression for the equilibrium constant, Kp, and determine its value,
including units.

Kp =

( )

PCO PH2

PCH4 PH2O

Initial P
Eqm P

Kp =
(ii)

CH4 (g) +
5
5 50%(5) = 2.5

( )

PCO PH2

PCH4 PH2O

H2O (g)
5
2.5

CO (g) +
0
2.5

3H2 (g)
0
3(2.5) = 7.5

(2.5)(7.5 )
=
= 168.75 169 atm2
2.5(2.5)
3

It is known that this reaction is an endothermic process.

the term in italics?

What is meant by

Endothermic means that heat/energy is absorbed from the surrounding.

(iii) Predict and explain the effect of separately increasing pressure and
decreasing temperature on the above equilibrium as well as on the yield.
On increasing the pressure,
by Le Chateliers Principle, the position of equilibrium will shift to the left to
reduce the total number of moles of gas .
On decreasing the temperature,
by Le Chateliers Principle, the position of equilibrium will shift to the left
towards the exothermic reaction to release heat.
In both cases, yield decreases.
(iv) In practice, a moderately high pressure is used in the production of syngas.
Suggest a reason for this.
Using too high a pressure is expensive / costly due to thick pipes needed , or
it increases rate of reaction , or
too high a pressure will result in low yield,

hence a moderately high pressure is used instead.

(v)

Sketch a graph showing how the rates of the forward and reverse reactions
change with time, from the point of mixing to the point after equilibrium is
established. Label your graphs clearly.

[11]

(b)

To manufacture methanol, the carbon monoxide and hydrogen mixture is passed

over a mixutre of copper, zinc oxide and alumina catalyst. Besides being a common
laboratory solvent, the largest use of methanol (CH3OH) is to produce methanal
(HCHO).

(i)

Industrially, oxygen is used to react with methanol to produce methanal. Write

an equation for this reaction.
CH3OH + O2 HCHO + H2O

(ii)

Alternatively, what reagent and condition can be used in the laboratory to

convert methanol to methanal?
K2Cr2O7 in dilute H2SO4, heat with distillation

(iii) Sketch the shapes of the hybrid orbitals around each carbon in the methanol
and methanal molecule.
CH3OH:

HCHO:

sp3

sp2

(c)

Methane reacts with a chlorinating agent, sulfur dichloro dioxide (SO2Cl2) by a free
radical mechanism to yield choromethane in the following equation.
CH4 + SO2Cl2 CH3Cl + CH3SO2Cl + SO2 + HCl

(i)

The initiation stage of this reaction occurs in two steps, both of which form the
chlorine radical. Write an equation for each step at this stage.

Initiation:
SO2Cl2 Cl + SO2Cl
SO2Cl Cl + SO2
(ii)

Propose two equations to represent the propagation stage of this reaction.

Propagation:
CH4 + Cl CH3 + HCl
CH3 + SO2Cl2 CH3Cl + SO2Cl
(iii) Given that CH3SO2Cl is produced at the termination stage, write the formulae
of the radicals that produce it.

SO2Cl and CH3

[5]
[Total: 20]

Topics: All topics until Ionic Equilibrium

14 NJC 2007 P3/Q3
.
(a) (i)

benzoate ion is a strong conjugate base (), therefore it will readily

extract a proton, H+ from H2O to give OH. () Therefore pH of this salt
is alkaline.
(ii)

(I)
(II
)

buffer
Amount of HCl added = amount of benzoic acid formed
= 1.50 x 10-3
1.5 x 10 3
[benzoic acid] =
= 0.0429 mol dm 3
35
100
20
Amount of benzoate left =
x0.1 - 1.5 x 10 -3 = 0.5 x 10-3 mol
1000
0.5 x 10 3
[benzoate salt] =
= 0.0143mol dm 3
35
100

(b
)

(i)
[Cr2O72-] =

1
x 1 x 10 3 = 4.97 x 10 6 mol dm 3
201

(ii)
(c)

(i)

The Cr2O72- ion is orange in colour and is reduced to Cr3+ which is green
in colour. The litmus turns blue due to the presence of the basic amine
group.

(ii)

2,4-Dinitrophenylhydrazine can be used as G will form an orange ppt

with it but no orange ppt for H.

(iii
)

CH3CH2CH2NH2 is the most basic as the alkyl group is electron

releasing and will make the lone pair on N most available for donation.
The lone pair on N of CH2=CHNH2 is less available for donation as they
are delocalized within the 2 p-orbitals of the C=C bond. Hence it has the
lowest tendency to accept a proton, making it the least basic.

15. VJC 2007 P3/Q1

(a) (i)

(ii)

2 dative bonds are formed since there are two lone pairs of e- on two N
atoms in N2H4 to donate into the two empty orbitals of B in 2 moles of
BF3.
(iii) Hydrazine is soluble as the energy evolved to form hydrogen bonding
with water molecules is more exothermic than the energy required to
break the hydrogen bonding between water molecules and hydrazine
molecules.
(iv) Both NH3 and N2H4 molecules are held together to each other by

hydrogen bond.
However, there is only one hydrogen bond formed on average for each
NH3 molecule while two H bonds formed on average for each N2H4
molecule. (OR more extensive hydrogen bond formed between N2H4
molecules due to greater number of lone pairs present.)
Hence, N2H4 has a higher boiling point than NH3.
On the other hand, PH3 molecules are held together by permanent
dipole- permanent dipole attraction, which is weaker than H bond, hence
the lower boiling point of PH3.

(b) (i)

The production of NH3 is an exothermic process since at higher

temperature, there is a lower % of NH3 at equilibrium, implying that the
equilibrium shifted to the left at higher temperature.
OR equilibrium shifted to the right at lower temperature.

(ii)

(c)

(i)

To form NO43-, N must be able to accommodate 10 electrons in its

valence shell.
Since N is in period 2, it has no d-orbitals to expand its octet.

(ii)

(iii)

(iv) Solubility of calcium phosphate in solution A is lower.

Presence of common ion, Ca2+, shifts position of equilibrium (1) above to

the left by Le Chateliers Principle.

(v)

H+ reacts with PO43- to form the weakly dissociated acid, H3PO4.

PO43- is removed from solution, position of equilibrium (1) shifts to the
right, thus increasing solubility.

16 HCI 2008 P3/Q5

(a) (i)
A Bronsted-Lowry base is a proton acceptor
(ii)

(iii)

[OH-] =

(iv)

Indicator: methyl orange

Reason: A weak base-strong acid titration. pH at equivalence point (< 7)
is within working pH range of methyl orange OR equivalent

K b (0.100) = 6.86 x 10-3 mol dm-3

(b)

The strength of the base depends on the availability of the lone pair on the
nitrogen atom (the more available the lone pair, the more the above
equilibrium lies to the right, the stronger the base)
In phenylamine, the lone pair is delocalised into the benzene ring, making it
much less available to accept a proton.
Hence phenylamine is a weaker base than propylamine
In N-methylpropylamine, there are extra electron-donating alkyl groups on the
N-atom, this enhances the availability of the lone pair.
Hence N-methylpropylamine is a stronger base than propylamine

(c)

(i)

heat with excess NH in a sealed tube

3

(ii)

(d)

17. RJC 2008 P3/Q1

(a) (i)
A buffer solution can resist small change in pH when a small
quantity of acid or base is added.
(ii)

When a small amount of H+ is added:

CO32(aq) + H+(aq) HCO3(aq)

When a small amount of OH is added:

HCO3(aq) + OH(aq) CO32(aq) + H2O(l)

The high concentration of the CO32(aq) and HCO3(aq) ions can resist
a change in pH.

(iii)
(iv)

The buffer action would be most effective in the range of 9.3 to 11.3
(or 10.3 1).
Use pH = pKa + log[CO32]/[HCO3]
When [CO32]/[HCO3] = 0.30, pH = 9.728
When [CO32]/[HCO3] = 0.96, pH = 10.233
Therefore, change in pH = 10.233 9.728 = 0.505

(b)

(i)

[Al(H2O)6]3+(aq)
[Al(H2O)5(OH)]2+(aq) + H+(aq)

The hydrolysis of the [Al(H2O)6]3+(aq) would release H+ ions which
would turn blue litmus red.

(ii)

Al2O3(s) +2OH(aq) + 3H2O(l) 2Al(OH)4(aq)

Al2O3 is predominantly ionic with some covalent character. Hence
it is amphoteric and is able to react with alkali.

(c)

(d)

(i)

W can be AlCl3/ FeCl3

AlCl3 (FeCl3 ) is able to act as a catalyst for the reaction because the Al
(Fe) atom is electron-deficient and has a low-lying vacant orbital to
accept an electron pair from Cl of the DCl molecule.
AlCl3 (FeCl3) has to be anhydrous because it hydrolyses in / reacts
with water to yield [Al(H2O)6]3+ ([Fe(H2O)6]3+) and Cl ions. Al atom in
[Al(H2O)6]3+ is coordinatively saturated (has no lowlying vacant
orbitals) and cannot function as a catalyst.

(ii)

Name : electrophilic substitution

(iii)

Z would not be formed.

The D+ electrophile would not be attracted to the carbon atom in the
CH3 group since this carbon atom is not electron-rich. (or it would
require a D radical to react with the nonpolar CH3 sidechain)

18. RJC 2008 P3/Q3

(a) (i)
HCO3 is a weak base.
concentration/mol
dm-3
initial
equili rium

Kb of HCO3-

HCO3-(aq) + H2O(l)

H2CO3(aq) + OH-(aq)

0.100

(0.100 y)
y
y
0.100
(since HCO3- has a relatively small Kb such that y <<
0.1.00)

[H 2 CO 3 ][OH ]

[HCO 3 ]

y2
= 2.34 x 10-8 mol dm-3
(0.100 )

= (2.34 x 10-9)1/2 = 4.84 x 10-5

[OH-]

= 4.84 x 10-5 mol dm-3

pOH

= lg(4.84 x 10-5) = 4.32

pH = 14 4.32 = 9.68
Hence pH of the HCO3- solution = 9.68
(ii)

Reaction upon addition of HCl(aq) : HCO3-(aq) + HCl(aq)

H2CO3(aq) + Cl-(aq)
Volume of 0.100 mol dm-3 HCl(aq) needed to reach equivalence point
= 25.0 cm3
Total volume of resultant solution = 25.0 + 25.0 = 50.0 cm3

At the equivalence point, the resultant solution contained H2CO3(aq).

Assumption: H2CO3(aq) did not decompose to yield CO2(g) and H2O(l).
Amount of H2CO3 = Amount of HCO3- reacted = (25.0/1000)(0.100) =
2.50 x 10-3 mol
[H2CO3] in solution = 2.50 x 10-3/0.050 = 0.0500 mol dm-3
Kw

Ka of H2CO3 =

K b of HCO 3

concentration/mol
dm-3
initial
equilibrium

14
= 1.0 x 10

2.34 x 10

H2CO3(aq) + H2O(l)
0.0500
(0.0500 w)
0.0500

= 4.27 x 10-7 mol dm-3

HCO3-(aq) + H3O+(aq)

Assumptions:
(1) H2CO3 has a relatively small Ka such that w << 0.0500.
(2) H+ (or H3O+) from the second dissociation of H2CO3 (i.e. from
the hydrolysis of HCO3-) is negligible and is ignored.
Ka of H2CO3

w2
[HCO 3 ][H3 O + ]
=
=
= 4.27 x 10-7 mol dm-3
0.0500
[H 2 CO 3 ]

w = 1.46 x 10-4
[H3O+] = 1.46 x 10-4 mol dm-3
pH = lg(1.46 x 10-4) = 3.84
Hence pH of the solution at the equivalence point = 3.84
(iii)

Volume of HCl needed to reach equivalence point = 25.0 cm3

Excess volume of HCl added = 37.5 25.0 = 12.5 cm3
Reaction: HCO3-(aq) + HCl(aq) H2CO3(aq) + Cl-(aq)
The resultant solution contained both H2CO3(aq) and unreacted
HCl(aq).
Note:
HCl(aq) is a strong acid. The presence of H+ from the complete
dissociation of HCl(aq) suppressed the dissociation of H2CO3 (a weak
acid) by common ion effect such that any contribution of H+ from
H2CO3 can be ignored. All the H+ in the solution can be assumed to
come from HCl(aq).
Amount of H+ from HCl(aq) = Amount of HCl = (12.5/1000)(0.100) =
1.25 x 10-3 mol
Total volume of resultant solution = 25.0 + 37.5 = 62.5 cm3
[H+] = 1.25 x 10-3/0.0625 = 0.0200 mol dm-3
pH = lg [H+] = lg(0.0200) = 1.70

(iv)

(b)

(c)

(i)
(ii)

Add Tollens reagent to both compounds separately with warming.

For the 1st compound (aldehyde), there would be a silver mirror formed.
For the 2nd compound, there would be no silver mirror formed.
First, add dil H2SO4 (aq) to both compounds separately, and heat.
Then, cool and add aqueous bromine to both samples.
For the 1st compound, the reddish-brown bromine remains, with the
absence of the formation of any ppt.
For the 2nd compound, there would be a decolourisation of reddishbrown bromine, with the formation of a white ppt.

Or
Add K2Cr2O7 (aq), dil H2SO4, heat
For the 1st compound, orange solution turns green.
For the 2nd compound, orange solution does not turn green
(d) (i)

rate = k[(CH3)3CBr]
kt = ln 2
k = (ln 2) / 5 = 0.139 min-1 or 2.31 x 103 s1

(ii)

19. TJC 2008 P3/Q4

(a) (i)

H2NCH2CH
L
(ii)

OH

CH2

Cl

Step 1
Cl

Cr2O72-/ H+

CH2CH2OH

Cl

CH2C

Heat to distill

J
Step 2
Step 3

H
Cl

CH2

CH2NH2

(iv)

anhydrous LiAlH4

H
Cl

CH2

ether solvent
at room temp

OH

(iii)

KCN(s)/ dil H2SO4

10 - 20oC

CN

OH

optical isomerism
2
Cl
O

O CH CH2

Cl

CH2
NH2
Esterification takes place in the reaction between COCl and OH
functional groups
(v)
(b) (i)

(ii)

I: redox reaction
II: electrophilic addition
The solubility product of copper phosphate is the product of the
concentrations of the copper ions and phosphate ions in moldm-3,
raised to appropriate powers depending on the stoichiometry of the
equation, in a saturated solution at a given temperature.
Ksp increases with increasing temperature or
Ksp of Cu3(PO4)2 = [Cu2+]3[PO43-]2
Let x mol dm-3 be the solubility of copper(II) phosphate in water at
25oC.
Cu3(PO4)2 (s)
x

3Cu2+ (aq) + 2PO43- (aq) .(1)

3x
2x

Ksp = [Cu2+]3[PO43-]2 = 1.40 x 10-37 mol5dm-15

(3x)3 (2x)2 = 1.40 x 10-37 mol5dm-15

x = 1.67 x 10-8 moldm-3

(iii)

pH = 7.5
[OH-] = 10-7.5 = 3.16 x 10-7 mol dm-3

Ksp of Cu(OH)2 = [Cu2+]total [OH-]2 = 4.80 x 10-20 mol3 dm-9

[Cu2+]total (3.16 x 10-7)2 = 4.8 x 10-20
[Cu2+]total = 4.81 x 10-7 mol dm-3
[Cu2+]3total [PO43-]2 = 1.40 x 10-37
(4.81 x 10-7)3 [PO43-]2 = 1.40 x 10-37
[PO43-] = 1.12 x 10-9 mol dm-3

Cu3(PO4)2 2PO43

Hence solubility of copper(II) phosphate in solution P

= 1 (1.12 x 10-9) = 5.60 x 10-10 mol dm-3

20. HCI 2008 P3/Q1

(a) (i)
Dynamic equilibrium refers to a state of balance in a reversible
reaction or process in which the rates of the forward and reverse
processes are equal.
(ii)

(iii)

NaOH neutralises the ethanoic acid. [CH CO H] decreases.

3

By Le Chateliers Principle, position of equilibrium shifts to the left.

(iv)
(b)

(i)

CH COCl
3

(ii)

Solution A contains unreacted CH CO H and its salt, CH CO K . It

3

is a buffer.
When a small amount of acid is added,

CH COO + H CH CO H.
3

When a small amount of base is added,

CH CO H + OH CH CO + H O.
3

3
+

The small amount of H or OH added is removed.

Hence, the solution resists changes in pH.
(iii)

pH= - lg 1.84x10 5 + lg

0.006
= 4.43
0.012

(c)

(d)

Warm each compound with a solution containing AgNO in excess

3

NH (aq) (Tollens reagent). Only P gives silver mirror.

3

OR Warm each compound with complex copper(II) ions in alkaline

solution (Fehlings solution). Only P gives reddish-brown precipitate.
OR Heat each compound with dilute H SO and K Cr O (aq). Only P turns
2

the orange solution green.

Topics: All topics until Electrochemistry

21. HCI 2007 P3/Q5
(a) (i)

(ii)
(iii) MnO4- will oxidize Cl- to Cl2 in addition to oxidizing Fe2+ to Fe3+, results
will therefore not be reliable.

(b) (i)

(c)

(ii)

cis-isomer has lower boiling point than the trans-isomer because of

intramolecular hydrogen bonds due to proximity of the 2 CO2H groups.
Intermolecular hydrogen bonding will be less extensive for the cis-isomer.
Hence, less energy is required to break the intermolecular hydrogen bonds
in the cis isomer, resulting in lower boiling point.

(i)

Calcium hydroxide will be less soluble at higher temperature.

Reaction is exothermic, an increase in temp will shift equilibrium to the
left (backward reaction is endothermic), lowering the solubility.

(ii)

[5]
(d) Laboratory synthesis of P results in a pair of optical isomers.
==> P has 1 chiral carbon.
P reacts with hydrogen and a nickel catalyst to give Q, C10H22O.
==> electrophilic addition of hydrogen, since 4H added, P has 2 C=C bonds.
P is oxidized by warming with acidified potassium dichromate(VI) to give a
ketone R, C10H16O.

==> P is a 2o alcohol.
Q reacts with concentrated sulphuric acid to give two isomeric products,
(CH3)2CHCH(CH3)CH=CHCH2CH2CH3 and
(CH3)2CHCH(CH3)CH2CH=CHCH2CH3.
==> elimination of water in Q gives 2 possible alkenes as H and OH are removed
from adjacent C.

On strong oxidation with hot acidified potassium manganate(VII), P gives S,

C8H12O4. S reacts with 2, 4-dinitrophenylhydrazine to give an orange precipitate,
C20H20N8O10. One mole of S reacts with one mole of NaOH for complete
neutralization.
==> Oxidative cleavage of P cleaves off 2 carbon, showing that P has 2 terminal
alkene groups, =CH2.
==> 1 mole of S reacts with 2 moles of 2,4-DNPH in the condensation reaction, S
has 2 ketone groups,
==> S is monocarboxylic acid.

22. VJC 2008 P3/Q3 and Q4 (mod)

(a) (i)

(ii)

As E

(NiO ( OH) Ni ( OH) ) > E (Fe ( OH)

2

Fe , during discharge,

NiO ( OH) will be reduced to Ni ( OH)2 , while Fe is oxidised to

Fe ( OH)2 :
Ecell = Ereduced Eoxidised = E

(NiO (OH) Ni (OH) ) E (Fe (OH)

2

Fe

= +0.48 ( 0.90 ) = +1.38 V

The cell equation is
2NiO ( OH )( s ) + 2H2O ( l ) + Fe ( s ) 2Ni ( OH)2 ( s ) + Fe ( OH )2 ( s )

(b)

(i)
(ii)

No. of moles of O2 =

VO2
Vm

48.0
= 2.00 10 3 mol
24000

No. of moles of H = 2 No. of moles of OH

= 2

Number of moles of e =

19.90
0.20 = 7.96 103 mol
1000
Q I t 0.40 16 60
=
= 3.979 10 3 mol
=
F
F
96500

Number of moles of Ni2+ = 2 ne = 3.98 10 3 mol

2

(iii)

nO2 : nH+ : nNi2 + = 1.99 : 7.96 : 3.98 = 1: 4 : 2

2K x NiF6 + 2H2O 2xKF + 2NiF2 + O2 + 4HF

Considering the number of F, 12 = 2 x + 4 + 4 x =
Hence, compound D is K2NiF6.

12 8
=2
2

(c)

OCOCOCH3

W:

CH3COCO2H

X:

CH2Br

Y:

CH3CH(OH)CO 2H

CH3

H 3C

Z:

W is an ester that has undergone hydrolysis, which upon acidification gives

an acid and an alcohol/phenol.
W is a halogenoalkane that has undergone nucleophilic substitution with
NaOH(aq) to give an alcohol.
X is a carboxylic acid which is acidic enough to liberate CO2 from HCO3- via a
neutralisation reaction.
X contains a CH3CH(OH)- or CH3CO- structural unit since it has undergone
oxidative cleavage with alkaline aqueous iodine to give a pale yellow ppt of
CHI3.
X is a carbonyl compound and undergoes reduction with NaBH4 in ethanol.
Carboxylic acid cannot be reduced by NaBH4 in ethanol.
Y is an -hydroxyacid which undergoes nucleophilic substitution to form Z, a
cyclic diester.

23. YJC 2008 P3/Q1

(a) (i) H1 = ethalpy change of solution
H3 = lattice energy
(ii)

 H = -772 +(-2) (-390) = - 384 kJmol-1

(b)

(i)

q = mcT =

30 4.2 5.2
= 0.655 kJ
1000

H = 0.665/0.02 = + 32.8kJmol-1
(ii)

From reaction, the change in physical state for the solid to aqueous
results in more ways of arranging particles leading to increase in
disorderliness, therefore
S is positive.
G = 0, H = TS

T(154.3)
1000
T = 212.6K = 213K
+ 32.8 =

(c)

(i)
CO(g) + 2 H2(g)
Initial/ mol
Change/
mol
Equilibrium/
mol

CH3OH(g)

40.8
-30.2

146
-60.4

0
+30.2

10.6

85.6

30.2

30.2
7.5 = 1.792MPa
126.4
85.6
PH 2 =
7.5 = 5.044MPa
126.4
10.6
PCO =
7.5 = 0.629MPa
126.4
1.792
= 0.112MPa 2
Kp =
2
(5.044) (0.6290)
PCH3OH =

(ii)

In order to increase the yield of methanol, H2 is added to the equilibrium

system. Predict, with reasons, whether this attempt is valid.
With increase in [H2], position of equilibrium shifts right to
decrease the amount of H2, hence percentage yield of methanol
should increase. Therefore attempt is valid.

(i)

(CH3OH + H2O CO2 + 6H+ + 6e) 2

(4e + O2 + 4H+ 2H2O) 3

(d)

(e)

2CH3OH + 3O2 4H2O + 2CO2

(ii)

CH3OH burns more cleanly, therefore less pollutants given off.

(iii)

No problem of leakages when electrolyte changes to a solid film.

(iv)

Greater energy efficiency; clean water forms.

24. SAJC 2008 P3/Q1 & 4 (mod)

(a) (i)
CrO43- + 8H+ + 2e  Cr3+ + 4H2O
(ii) 2CrO43- + 2H+  Cr2O72- + H2O + 2e
(iii) 3CrO43- + 10H+  Cr3+ + Cr2O72- + 5H2O
(b) No. of mole of S2O32- = 0.30 x 32.00/1000 = 0.0096 mol
No. of mole of I2 = x 0.0096 = 0.0048 mol
Since Cr2O72- 3I2
From equation (iii), 3CrO43- Cr2O72Thus, Cr2O72- 3 I2 3CrO43No. of mole of CrO43- = No. of mole of K3CrO4 = No. of mol of I2 = 0.0048 mol
Mass of K3CrO4 used = 0.0048 x 233.3 = 1.12 g
(c)

Mass = density x volume = 7.3 x 0.5 x 1.0 x 10-5 x 106 = 36.5 g

No. of mole of Cr =

36.5
= 0.702 mol
52

Cr2O72- (or Cr+6) + 6e  Cr(s)

6 F 1 mole Cr
6 x 0.702 mol x 96500 C 40 x time
Time = 10161.45 sec = 2.82 hr

(d) H2O is preferentially reduced rather than Al3+ ions.

(e)

(i)

(ii)

Geometric isomerism

(iii)

CH3
CH3CH2

N CH3

Cl-

CH3
CH3

CH3
CH3CH2

CH3CH2

N CH3 + CH3Cl

N CH3

Cl-

CH3

(f)

(i)

CH3 O H
H2N

CH C N CHCOOH
CH2
H N

[1]
N

(ii)

H
H N CHCOOH
CH2
H2N

CH C N
CH3 O

[1]
N
[2]

(g) Ala-His-His-Pro-Ser
25 NJC 2010 P3/Q3
(a) (i) The pH value of 2.2 represents the maximum buffer capacity.
(a) (ii) pH = 1.65
(a) (iii) NaH2PO4.
(b) (i) H2PO4- + OH- HPO42- + H2O
(b) (ii) Mass of NaOH = 0.366 grams
(c)

The NH3 gas that is formed dissolves in the water present in soil to give OH- ions,
thus increasing the soil pH temporarily.

Over time, the NH3 gas escapes and NH4H2PO4 dissociates to give NH4+ and
H2PO4-, which will hydrolyse in water to give H3O+, therefore the soil becomes
more acidic than before.

(d) (i)

Anode: C2H5OH + 3H2O 2CO2 + 12H+ + 12eCathode: 4H+ + O2 + 4e- 2H2O

Overall: C2H5OH + 3O2 2CO2 + 3H2O

(d) (ii) Phosphoric acid can act as a charge carrier.

(d) (iii)

Carbon paper is porous. Platinum acts as catalyst for oxidation of ethanol.

(d) (iv)

High costs involved in maintaining the high temperature.

High costs involved as platinum catalyst is expensive.

(e)

Q at 75% efficiency = 759 kJ

Topics: All combined

26 RIJC 2010 P3/Q4
(a) (i) By Le Chateliers Principle, when pressure increases, the position of equilibrium
shifts to lower pressure by favouring the side with fewer gaseous species. Since
there are fewer moles of gaseous species on the right, position of equilibrium shifts
right and more NH3 is produced.
(ii)

T2, since by Le Chateliers Principle, the endothermic reaction is favoured at the

highest temperature as equilibrium will shift to the left to absorb heat. Since yield is
lowest for T2, T2 has the highest value.

(iii)
total no. of particles with
energy Ea (without catalyst)

number of particles
with a given energy

total no. of particles with

energy Ea (with catalyst)

>

Ea

Ea

kinetic energy

The mixture acts as a catalyst, which lowers the activaton energy and increases the
proportion of molecules with sufficient energy to overcome the energy barrier upon
collision/increases the proportion of molecules with energy greater and equal to
activation energy. The frequency of effective collisions increases, and hence, the
rate of reaction increases.

(iv)
Initial/ mol
Change / mol
Equilibrium /mol

N2
1
-x
1-x

H2
3
-3x
3-3x

NH3
0
+2x
2x

Total mole = 4-2x

[NH3] = 0.44 =

2x
4 2x

PN2= 0.14 atm

PH2 = 0.42 atm
PNH3 = 0.44 atm
Kp = 18.7 atm-2
(b) (i)

(c)

(ii)

M(OH)2(s)
MO(s) + H2O(g)

Down the group, the decomposition temperature of the metal hydroxide increases.
As the cationic radius of M2+ increases down the group, polarizing power decreases
since charge density decreases.
The OH electron cloud is polarized to a smaller extent and the OH bond is
distorted less, making it harder for the hydroxide to decompose.

(i)

Aqueous NaOH, heat

Product: CH3CH2COONa+

(ii)

27 NJC 2010 P3/Q5

(a) (i) Electrophilic Substitution

(ii)

(b) (i)
(ii)

Add aqueous NaOH to a separating funnel containing the mixture of phenol and
propanone. Shake thoroughly and drain off the aqueous layer. Acidify the aqueous
layer with dilute HCl to recover the phenol.

Step
1

Reagents & Conditions

NaCN + dil HCl(to generate
HCN)
trace amt of base

Product

OH
CH3

C CH3
CN

dil H2SO4
heat with reflux

OH
CH3

C CH3
COOH

(c)

CH3OH, conc H2SO4

Reflux

(i)

Iodine oxidizing agent

H2SO4 catalyst

(ii)

NaHCO3 quench reaction by reacting with the catalyst, H2SO4:

conc of iodine present at diff time intervals can then be found.

NaOH cannot be used as it can react with iodine producing sodium iodide and
sodium iodate.
(iii)

Zero order wrt iodine

First order wrt sulphuric acid
(support answers with relevant explanation or working)

(iv) Extrapolate curve to y-axis to find volume of thiosulfate required to react with the
iodine present initially or at t = 0 min in a 10.0 cm3 reaction mixture.
Vol of thiosulfate reqd = 20.0 cm3
Use the equation I2 + 2S2O32 2I + S4O62 to find amount of thiosulfate
required to react with iodine present in 10.0 cm3 reaction mixture and hence conc
of thiosulfate used. Conc. of thiosulfate used = 1.00 x 104 mol dm3
(v)

Overall order of reaction is 2.

Since reaction is 1st order wrt sulphuric acid, zero order wrt iodine, hence it is 1st
order wrt propanone
Features of graph:
1) Gradient of curve between expt 1 and expt 2

28 TJC 2010 P3/Q1

(a) (i) Standard enthalpy change of combustion is the heat evolved when one mole of the
substance is completely burnt in oxygen at 298 K and 1 atm.
(ii)

(1 mark working, 1 mark answer)

Hc
C8H18(l) +

25
O2(g) 8CO2(g) + 9H2O(l)
2

8C(s) + 9H2(g) +

25
O2(g)
2

By Hess Law,
Hc = 269 + 8(-394) + 9(-286) = - 5460 kJ mol-1
Heat evolved per gram of octane =

(iii)

5460
= 47.9 kJ g-1
114

(1 mark working, 1 mark answer)

CH3OH(g) +

3
O2(g) CO2(g) + 2H2O(g)
2

Bonds broken: 3C-H, C-O, O-H,

3
O=O
2

Bonds formed: 2C=O, 4O-H

Hc = 3(410) + 360 + 460 +

3
(496) 2(740) 4(460) = -526 kJ mol-1
2

Heat evolved per gram of methanol =

526
= 16.4 kJ g-1
32

(iv) As weight considerations are usually important is racing car, one advantage of
using petrol (octane) is that it produces more heat energy per gram of fuel.
(b)

As B is achiral, it does not contain a chiral centre or it has a plane of symmetry.

B undergoes elimination with alcoholic potassium hydroxide to form alkenes C,
D and E.
Alkenes C and D undergo oxidation with hot concentrated acidic potassium
manganate(VII).
(1 mark for each correct structure)
C and D are geometrical isomers:
CH3

CH3

CH2CH3
C

CH3CH2CH2

CH3CH2CH2

C
CH2CH3

CH2

E: CH3CH2CH2

CH2CH2CH3

CH3
CH3CH2CH2

B:

CH2CH2CH3

Cl
CH3
CH3CH2CH2

A:
marks]

(c)

C
H

(i)

CH3CH2OCH2CH3

(ii)

CH2=CH2

CH2CH2CH3

[8 marking points, maximum 7

(iii)

(1 mark for each step)

Br2

CH3CH2OH

UV light

Na

BrCH2CH2OH

Room Temp

BrCH2CH2O-Na+
Heat

CH2

CH2

O
epoxyethane

(iv)

Possible answers:

As the first step involves free radical substitution, a mixture of bromosubstituted products will be obtained and BrCH2CH2OH may not be the major
product.

can
react
with
another
BrCH2CH2OBrCH2CH2OBrCH2CH2OCH2CH2O and other straight chain products.

Epoxyethane has a highly strained three-membered ring which makes it

reactive/unstable.

to

give

29 TJC 2010 P3/Q5

(a) (i)
Na2O has a giant ionic structure and consists of strong ionic bonds. When
dissolved in water, it gives a strongly alkaline solution of pH = 13.

(ii)

Na2O + H2O 2NaOH

SiO2 is a covalent oxide with a giant molecular structure. Strong covalent bonds
are present between its atoms. It is insoluble in water. Hence pH remains as 7.

P4O10 (or P4O6) is a covalent oxide with a simple molecular structure. Weak van
der Waals forces are present between the molecules. There are energetically
accessible vacant d orbitals for dative bonding with water molecules. P4O10 (or
P4O6) dissolves readily in water to give an acidic solution of pH 2.

P4O10 + 6H2O 4H3PO4

OR

All pH correct

Silicon dioxide has a giant molecular structure while P4O10 (or P4O6) has a
simple molecular structure.

Melting of silicon dioxide involves breaking of strong covalent bonds, while

melting of P4O10 (or P4O6) involves breaking of weak van der Waals forces.

pH= 2

P4O6 + 6H2O 4H3PO3 pH=3

Since van der Waals forces are weaker than covalent bonds and require less
energy to overcome. Hence the melting point of P4O10 (or P4O6) is lower.
(iii)

BeO + 2H+ Be2+ + H2O

BeO + 2OH- +H2O Be(OH)42-

OR

(b) (i)

BeO + 2HCl
BeCl2 + H2O

BeO + 2NaOH + H2O
Na2[ Be(OH)4]

M(NO3)2 (s) MO (s) + 2NO2 (g) + O2 (g)

(ii)
O

O
N
O

(iii)

Trigonal planar

Ionic radii of Mg2+ 0.065nm, Ca2+ 0.099nm, Sr2+ 0.113nm

Ionic radius increases down the group. Since charge density

charge
,
ionic radius
the charge density and hence polarising power of M2+ decreases and nitrate is
polarised to smaller extent and N-O bond is less easily broken.

Thermal stability increases from magnesium nitrate to strontium nitrate.

(iv)

pV = nRT

(v)

number of moles of O2 =

PV 101 103 95 10 6
= 3.81 x 10-3 mol
=
RT
8.31 (30 + 273)

number of moles of M(NO3)2.xH2O = 0.00762 mol

number of moles of H2O =

0.55
= 0.0306 mol
18.0

0.0306
=4
0.00762

x=

Mr of M(NO3)2 =

1.80 0.55
= 164.0
0.00762

Ar of M = 164.0 2[14.0 + 3(16.0)] = 40.0

M is calcium

[the hydrate is Ca(NO3)2.4H2O]

30 DHS 2010 P3/Q4
(a) (i) Nucleophilic substitution/condensation

(ii)

A dimer might be obtained with the reactive COCl group hydrolysed by the water
present to form a COOH group.
(iii)

H2SO4(aq), heat followed by careful addition of NaOH(aq) or NaOH(aq), heat

followed by careful addition of H2SO4(aq),

OR

H2SO4(aq)

OR
O
C
-

NH2

NaOH(aq), heat

Step I
Sn, concentrated HCl, reflux (followed by NaOH)
Step II
PCl5, PCl3, or SOCl2, r.t.
Step III
C6H5OH (with NaOH (aq)), r.t.
(ii)

Add aqueous bromine at r.t. to the reaction mixture. If phenyl4aminobenozate

is present, it will decolourise orange red aqueous bromine with a white
precipitate formed together with white fumes.

(iii)

Due to the close proximity of the OH and COOH groups in

4nitrosalicylic acid, intramolecular hydrogen bonding can be formed and this
decreases the extent of intermolecular hydrogen bond between 4nitrosalicylic
acid and water molecules.
OR
As there is no OH group in close proximity to the COOH group in
4nitrobenzoic acid, intramolecular hydrogen bonding is not formed. Hence
the extent of intermolecular hydrogen bond between 4nitrobenzoic acid and
water molecules is higher than 4nitrosalicylic acid.

(iv)

(c)

(i)

8
x 0.1 = 8.0 x 10 3 mol dm3
100
pH = log10[H+] = log10(8.0 x 103) = 2.10

[H+] =

(ii)

Ka =

[H + ][O 2 N(C 6 H 4 )CO 2 ]

[O 2 N(C 6 H 4 )CO 2 H]

pKa is defined as the negative logarithm to base 10 of the acid dissocation

constant, Ka
OR pKa = log10Ka
(iii)

[ 8.0 x 10 3 ][ 8.0 x 10 3 ]
= 0.0006957
[0.1 - 8.0 x 10 3 ]
pK a = log10Ka = log10 (0.0006957) = 3.16

Ka=

Note: Ka=

[H + ]2
since % dissociation is given.
[HA ]i

31 RIJC 2010 P3/Q2

(a) (i) Phenoxide
NaOH is used to generate the phenoxide which is a better nucleophile than phenol.
(ii)

CH3CH2COOCOCH(CH3)2

(b) (i)
The ethoxide ions act as base / remove H+.
(ii)

Test: Warm both compounds with separate samples of aqueous iodine in aqueous
NaOH.

Observation: A yellow precipitate is formed for butanone but no yellow precipitate

for butan-1-ol.
CH3COCH2CH3 + 3I2 + 4OH-
CHI3 + CH3CH2COO + 3I + 3H2O
Other possible tests: 2,4-DNPH, PCl5, Na(s), KMnO4 with H2SO4(aq) and heat,
K2Cr2O7 with H2SO4(aq) and heat
(c)

(i)

Nucleophilic addition

(ii)

Geometric isomerism

(iii)

Comparing Expt 1 and 2, when [CH3CH=CHCH2Cl] doubles, rate doubles. Hence

order of reaction with respect to CH3CH=CHCH2Cl is 1.
Comparing Expt 1 and 3, when [CH3CH=CHCH2Cl] is tripled, rate should triple.
When [OH] is tripled, there is no further change to the rate. Hence order of
reaction with respect to OH is 0.
Hence, mechanism is nucleophilic substitution (SN1).

(iii)

The p-orbital of chlorine overlaps with the pi-electron cloud of the double bond or
there is partial double character between C and Cl hence C-Cl bond is
strengthened.

32. MJC 2008 P3/Q5

(a) (i)
+H N
3

O
CH

CH 2

H
N

CH
H

NH +

CH

COOH

(CH2) 2
COOH

+H N
2

(ii)

When a small amount of acid (H+) is added,

+
H+ + +NH3CH2COO
NH3CH2COOH
+
+
H added is removed by NH3CH2COO- to form +NH3CH2COOH
[H+] is slightly changed and pH of buffer solution remains fairly constant.
When a small amount of base (OH) is added,
OH + +NH3CH2COO-
NH2CH2COO- + H2O
OH added is removed by NH4+ to form H2O and NH2CH2COO[OH] is slightly changed and and pH of buffer solution remains fairly constant.

(iii)

pH = 6.0
Glycine will have no net charge as the pH is at its isoelectric pH. Hence, it will

remain stationary. Histidine will have a net positive charge and it will move
towards the cathode (negative electrode). Glutamic acid will have a net negative
charge and it will move towards the anode (positive electrode)

(iv)

Glycine exists as zwitterions which is a giant ionic lattice structure whereas 2hydroxyethanamide exists as simple covalent molecules.
A larger amount of energy is required to overcome the stronger electrostatic
forces
of
attraction
between
the
zwitterions
in
2-aminoethanoic
acid
than
the
hydrogen
bonding
between
2-hydroxyethanamide.

(b)

Phenylamine is a weaker base than benzylamine due to the delocalisation of the lone
pair of electron on the nitrogen atom into the benzene ring.
Hence, the lone pair on N atom is less available to accept a proton.
The electron donating alkyl group (C6H5CH2-) increases the electron density on the
lone pair of N atom.
Hence, the lone pair on N atom is more available to accept a proton.
Phenylamine is more reactive than benzylamine towards electrophilic substitution.
For phenylamine, there is delocalisation of the lone pair of electron on the nitrogen
atom into the benzene ring which increases the electron density in the ring which
makes the benzene ring more susceptible to electrophiles for electrophilic substitution.

(c)

P and Q have comparable number of C and H atoms and

no. of C atoms 6
P and Q contains benzene ring
P undergoes neutralization with sodium hydrogencarbonate.
P is a carboxylic acid
P undergoes oxidation with hot acidified KMnO4 to form product with 2 carbon atoms
less.
P is an alkene
Q undergoes oxidation with hot acidified KMnO4 to liberate CO2.
Q is a terminal alkene
P undergoes electrophilic addition with aqueous Br2 in the dark
P is an alkene
Q undergoes electrophilic substitution with aqueous Br2
Q is a phenol
T undergoes elimination with excess concentrated H2SO4 to form Q
T is an alcohol

T undergoes oxidation with alkaline iodine

CH3
C

T contains

OH

Q undergoes nucleophilic addition with a mixture of NaCN and HCN to from U.

Q is carbonyl compound
P

OR

33. HCI 2010 P3/Q1

(a)

(i)

P4(s) + 5O2(g) P4O10(s)

OR

4P(s) + 5O2(g) P4O10(s)

OR

2P(s) +

O2(g) P2O5(s)

P4O10(s) + 6H2O(l) 4H3PO4(aq)

OR

(ii)
(b) (i)

P2O5(s) + 3H2O(l) 2H3PO4(aq)

pH = 2
It is the enthalpy change when 1 mol of POCl3(l) is formed from its
constituent elements in their standard states ( i.e., P4(s), O2(g) and Cl2(g) )
under standard conditions of 25 oC and 1 atm.

(ii)

By Hess law,
H,r = +730 + (1370) = 640 kJ mol1

(c)

(i)

(ii)

Q:

R:

T:

OH

OH

OH

CH2CH2Cl

CH2CH2NH2

CH2CH2 O

K2Cr2O7(aq), H2SO4(aq), heat under reflux

(iii) LiAlH4 in dry ether

(iv) White fumes of corrosive (OR irritating) fumes of HCl formed.
The reaction should be carried out in a fume cupboard (OR fumehood).
(d)

(i)
Ka =

[H + ][HPO 24 ]
[H2PO 4 ]

[H + ][salt]
[weak acid]
500 0.3

[H+] = K a

[weak acid]
[salt]

= 6.30 10 7

600
100 0.2

= 4.725 106 mol dm3

600

pH = lg [H+] = 5.33

(ii)

When a small amount of H+(aq) ions are added, it is absorbed by the excess
HPO42, hence pH is maintained.
HPO42 + H+ H2PO4
When a small amount of OH(aq) ions are added, it is absorbed by the excess
H2PO4 hence pH is maintained.

H2PO4 + OH HPO42 + H2O

(e)

(i)

O
O

O
O

(ii)

Tetrahedral about P
Bent (or V-shaped) about O

34. VJC 2010 P3/Q2

(a)(i)
PCO =

1
6
x
x 500
3 298

= 3.36 atm

(ii)
Kp =

PCH3OH
PCOPH2 2

(iii)
PH2 =

2
6
x
x 500 (ecf)
3 298

= 6.71 atm
CO(g)
Initial / atm

3.36

2H2(g)

CH3OH(g)

6.71

Change / atm

3.2

6.4

3.2

Equ librium / atm

0.16

0.31

3.2

(iv)
Kp

3.2
0.16 x 0.312

(ecf)

= 208 atm2 (ecf)

(b)(i)
a is dependent on the strength of the attractive forces between molecules while
b is dependent on the volume of the molecules.
(ii)
Attractive forces slow down the movement of a molecule approaching the wall of the
container.
This causes the actual pressure to be lower than that of an ideal gas.
Hence, the term is added to P.

The volume of the molecules is not negligible and causes the free space within which
molecules
can move to be less than the entire volume of the container.
Hence, the b term is subtracted from V.
(iii)
Both helium and carbon dioxide are made up of nonpolar molecules held by
dispersion forces.
Dispersion forces in CO2 are stronger due to the higher number of electrons present.
Hence, CO2 has a higher value of a than He.
Ammonia molecules are held by hydrogen bonding
which is stronger than dispersion forces. Hence, ammonia has the highest a value.
(c)(i) A buffer solution is a solution whose pH remains almost unchanged when a small
amount of H+ or OH- is added to it. It maintains the pH by removing the extra H+ or
OH- added.
(ii)
7.90 107

= [H+][HCO3] / [H2CO3]
= 107.4 [HCO3] / [H2CO3]

[HCO3] / [H2CO3] = 19.8

(iii)
HCO3 + RCO2H H2CO3 + RCO2
(iv)
As more H2CO3 is formed,
position of equilibrium I shifts left to reduce [H2CO3].
This increases [CO2(aq)]
and in turn causes the position of equilibrium III to shift right, i.e. breathing rate
increases.
(v)
Let the volume of NaOH added be V cm3.
Initial moles of H2CO3
= 0.20 x 25.0 x 103
= 5.0 x 103 mol
Moles of H2CO3 left after neutralisation

= 5.0 x 103 0.30 V x 103

= 0.005 3 x 104 V mol

Moles of HCO3 formed = moles of NaOH used = 3 x 104 V mol

3 x 104 V / [0.005 3 x 104 V] = 19.8 (ecf from (c)(ii))
V = 15.9 cm3

35 MJC 2010 P3/Q1

(a)
(i)
For the amide, the electron-withdrawing effect of the carbonyl group
reduces the electron density on the N atom, making the lone pair less

available to accept a proton, hence it is a weaker base compared to the

amine.
(ii)

Kb

[BH+ ] [OH- ]
[B]

[OH- ]2
[B]

By approximation method,
-6.1

[OH-] = 10 0.025
= 1.41 x 10-4 mol dm-3
pH
(iii)

= 10.1

Let x be the number of moles of HCl required, and v be the total volume.
pOH

= pKb + lg

14 7

= 6.1 + lg

[BH+ ]
[B]
x

v
(0.025 - x )
v

= 2.23 x 10-2

Volume of HCl required

2.23 x 10-2
0.5

= 4.46 x 10-2 dm3

= 44.6 cm3
(iv)

When a small amount of base (OH) is added,

OH + BH+

H2O + B

In the buffer solution, [OH] is absorbed by the large amount of BH+

hence pH of buffer solution is almost unchanged.

(b)

(i)

Kb value of Procaine > Kb value of Lidocaine. For the 2 samples of equal

concentration, number of free mobile ions for Procaine is greater than that
of Lidocaine.

(ii)

Add aqueous Br2 at r.t.p separately to each of the unknown compounds.

Orange red Br2 decolorizes in Procaine and a white ppt is formed while
orange red Br2 does not decolorize in Lidocaine.

(iii)

(c)

(d)

(i)

Reaction I:
Reduction
Reaction III: Elimination

(ii)

Perform Reaction II first, then Reaction I.

Topics: Entire Chemistry Syllabus

36 ACJC 2010 P3/Q5
(a) (i) Rate = k [S2O82-][ I-]
Since total volume of solution is constant,
concentration of a reactant volume of reactant
rate 1/time
1/time = k (volume of S2O82-)(volume of I-)
(volume of S2O82-)(volume of I-) x time = constant
time for expt 3 = 96 s
(ii)

Heterogeneous catalysis
The catalyst (Fe) provides an alternative pathway with lower
activation energy, Ea2

As shown by the Maxwell-Boltzmann Distribution curve, the fraction

of molecules with energy Ea2 (catalysed) is greater. Hence there are
more effective collisions, leading to an increase in rate of reaction.
(b)

(i)

Fe3+(aq) has high charge density and can undergo hydrolysis with
water
[Fe(H2O)6]3+ + H2O

(ii)

Cu2+ + 2e
2Fe3+ + 2e
2Fe3+ + Cu
reaction is
Feasible

(iii
)

Green ppt of Fe(OH)2

[Fe(OH)(H2O)5]2+ + H3O+

Cu
2Fe2+

E = +0.34V
E = +0.77V
Cu2+ +

2Fe2+

E = +0.43V>
> 0,

(c)

(i)

2I2Fe2+

I2 + 2e
2Fe3+ + 2e
2Fe3+ +
feasible.

2I-

I2 +

2Fe2+

E = +0.0.54V
E = +0.77V
E = +0.23V>
> 0, reaction is

Fe3+ will oxidize I- to I2 while itself is reduced to Fe2+

(ii)

co-ordination number =5
shape trigonal bipyramidal
bonding between iodine and iron-dative covalent bond/co-ordinate
bond /dative bond
2FeC4O4I2 + I2

(d)

(i)

2FeI3 + 8CO

Ba
53.4
53.4/137
= 0.390
simplest ratio
1
Mass/g
No of mol

Fe
21.7
21.7/55.8
=0.390
1

O
24.9
24.9/16
= 1.56
4

Empirical formula = BaFeO4

oxidation number = +6
(ii)

Fe2O3 + 3OCl- + 4OH-

2FeO42- + 3Cl- + 2H2O

37 AJC 2010 P3/Q1

(a)(i) Cl2 + H2 2HCl
(a)(ii) Cl2 and H2 explodes in the presence of light.
Br2 and H2 needs heating and a catalyst.
I2 and H2 needs heating and reaction is reversible.
Reactivity with H2: Cl2 > Br2 > I2
as HX bond becomes weaker down the group.
(b)(i) White solid of AgCl turns yellow.
AgI is precipitated as AgI is less soluble than AgCl
(b)(ii) To precipitate AgCl,

[Ag+][Cl] > Ksp (AgCl)

2.02 x 10 10
[Ag+] >
0 .1

minimum [Ag+] = 2.02 x 109 mol dm3

[Ag+]2 [CrO42] > Ksp (Ag2CrO4)

To precipitate Ag2CrO4,

[Ag+] >

3.01 x 10 12
0.01

minimum [Ag+] = 1.73 x 105 mol dm3

(b)(iii) At the endpoint, a red precipitate of Ag2CrO4 is seen.
(b)(iv) When Ag2CrO4 is first precipitated,
[Ag+] in the solution = 1.73 x 105 mol dm3
[Cl] in the solution
K sp of AgCl 2.02 x 10 10
=
= 1.17 x 105 mol dm3
=
+
5
[Ag ]
1.73 10
(b)(v) % of Cl precipitated out as AgCl
0.1 (1.17 x 10 5 )
=
x 100% = 99.988% 100%
0 .1
Hence, Ag2CrO4 is only precipitated when all the AgCl has been formed.
(c)(i) The halogen is bromine.
Cr
% mass
13.0
Moles
0.25
1
Ratio

H2O
27.0
1.5
6

Br
60.0
0.75
3

Empirical formula is Cr(H2O)6Br3

(c)(ii) n(A) = 0.400 399.7 = 0.001 mol
n(AgBr) = 0.188 187.9 = 0.001 mol
1 mol of A contains 1 mol of free Br ion.
A is [Cr(H2O)4Br2]Br2H2O
(c)(iii) +3
(c)(iv)

H2 O
H 2O

Br
III
Cr
Br

H 2O
H2 O

38 AJC 2010 P3/Q3

(a)(i) A transition element is a dblock element which forms one or more stable ions
with incomplete d orbitals.

(a)(ii) 1s22s22p63s23p63d6
(a)(iii) Pink solution turns purple, then blue.
Pink [Co(H2O)6]2+ undergoes ligand exchange to form blue [CoCl4]2.
(b)(i)

e.m.f. = (+1.82) (+0.77) = +1.05V

(b)(ii) E
(Fe3+/Fe2+) = +0.77V
E
(Fe(OH)3/Fe(OH)2) = 0.56V
Addition of OH forms Fe(OH)2 and Fe(OH)3.
E
value becomes more negative. Fe(II) is more easily oxidized.
(b)(iii) e.m.f. increases/ more positive than +1.05V.
(b)(iv) 4Co3+ + 2H2O 4Co2+ + O2 + 4H+
(b)(v) The reduction of Co(III) by water has a high activation energy .
(c)

n(Co) plated =
Q=

8.00
58.9

8.00
x 2 x 96500 = 26214 C
58.9

Time needed =

26214
= 5240 s (= 87.3 min)
5

(d)(i) Bidentate
(d)(ii) Six
(d)(iii) Excess NH3 in ethanol, heat in sealed tube
(e)(i) Transition metals are able to exist in variable oxidation states.
(e)(ii) Step 1: 2Co3+ + 2I 2Co2+ + I2
Step 2: 2Co2+ + S2O82 2Co3+ + 2SO42

39

HCI 2010 P3/Q4

(a) (i) +3

(b)

(ii)

Orange / red

(iii)

In the presence of an octahedral ligand field, the degenerate d-orbitals will

split into two energy levels.
In the partially filled d-orbitals (d4) , electrons are able to promote from the
lower to the higher level by absorbing energy in the visible spectrum (bluegreen).
The colour shown is the complementary colour that is not absorbed.
(orange-red).

(i)

SO42
[R] MnO4 + 8H+ + 5e
Mn2+ + 4H2O
[O] SO42 + 2H+ + 2e
SO32 + H2O

(ii)

From the titration results,

n MnO
25.0 0.020
4
=
n SO 2
12.5 0.10

0.4 or

E +1.52 V
E < +1.52 V

2
5

Each mol of MnO4 accepts 5 mol of electrons when reduced to Mn2+.

This means 2 mol of MnO4 accepts 10 mol of e- from 5 mol of SO32;
10
or each SO32 ion loses
= 2 electrons.
5
Hence oxidation state of S increases by 2 units from +4 (in SO32) to + 6
(in SO42)

(c)

(i)

When [Fe2+] = [Fe3+] , ln

Hence,

[Fe 3+ ]
= 0.
[Fe 2+ ]

E = E (Fe3+/Fe2+) = +0.77 V.

(ii)

Vol of KMnO4 = 50.0 cm3

(iii)

The equivalence point is reached between 80 and 120 cm3 (precisely at

100 cm3).
Hence the E value increases from a E0 Fe3+/Fe2+ to E0

2+
MnO4 /Mn .

(iv)

The E value of MnO4/Mn2+ (and hence, the oxidizing power of MnO4) is

dependent on [H+];
MnO4 + 8H+ + 5e = Mn2+ + 4H2O.

(d)

Observations
Oxidation of J gives hot acidified
KMnO4 to give K C9H8O3

Deductions
J undergoes vigorous oxidation
K has acidic group and ketone
group

K reacts with aq. I2 to give yellow

precipitate upon acidification gives
benzene-1,2-dicarboxylic acid

J reacts with steam

K contains methyl ketone.

K contains a carboxylic group
side chain.
J has a alkyl side chain
undergoing side chain oxidation
Electrophilic addition reaction of
water.
L does not contain methyl alcohol.
L is chiral

L
CO2H

CH3

40 RI 2010 P3/Q3
(a)(i) The CF bond is stronger than the CCl bond, hence the latter bond is easier
to cleave and chlorine radicals are more readily produced.
(a)(ii) O+: 1s22s22p3
F+: 1s22s22p4
Due to the interelectronic/electron-electron repulsion between the paired p
electrons in F+, it is easier to remove the electron from F+ than O+. Hence the
second IE is higher for O / lower for F.
(b)(i)

Add sodium chloride crystals to concentrated sulfuric acid.

Hydrogen iodide will be further oxidised by sulfuric acid to form iodine.
To produce hydrogen iodide, a non-oxidising acid such as concentrated H3PO4
should be used.

(b)(ii) Electrophilic substitution

AlCl3 + Cl2
AlCl4 + Cl+

(b)(iii) Ultraviolet light or strong heating

(b)(iv)
H
H
Cl

C
H
H

Cl
H
H

6x1=6

1x5=5

H
H

Cl

H
H

H
H

2x4=8

(c)(i) Disproportionation
(c)(ii)

ClO + 2I + 2H+
Cl + H2O + I 2

(c)(iii) Amount of thiosulfate = 50/1000 x 0.100 = 5 x103 mol

I2 + 2S2O32
2I + S4O62
Amount of I2 2S2O32 ClO
Amount of ClO
= x 5 x103 = 2.5 x103

Concentration of ClO = 2.5 x103 / (25/1000) = 0.100 mol dm3

(c)(iv) With hot NaOH, 3 Cl2 + 6 NaOH
5 NaCl + NaClO3 + 3 H2O
For cold NaOH, Cl2 : NaCl = 1:1
For hot NaOH, Cl2 : NaCl = 3: 5
Therefore, volume of Ag+ required = 5y/3

C
H
H

Cl

3x1=3