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UACE chemistry 2022
PAPER 2
DURATION: 2 HOUR 30 MINUTES
Instruction to candidates
Answer five questions including three questions from section A and any two from section B.
Use equations where necessary to illustrate your answer.
Mathematical tables and squared papers are provided
Silent non-programmable scientific calculators may be used
Where necessary use the following:
(H =1, C = 12, O = 16)
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SECTION A (60MARKS)
Answer any three questions from this section
Any additional question answered will not be marked.
1. (a) State what is meant by the term order of reaction. (01mark)
(b) The decomposition of hydrogen peroxide proceeds according to the following equation
2H2O2 (aq) → 2H2O(l)+ O2(g)
(i) Write the expression for the rate law of the reaction. ( 1 ½ marks)
(ii) Describe how the order of the reaction can be determined. (05marks)
(iii) Explain the effect of temperature on the rate of decomposition of hydrogen peroxide.
(3 ½ Marks)
(c) The following kinetic data in table 1 were obtained for the decomposition of hydrogen peroxide.
Table 1
Concentration 1.6 x 10-3 1.3 x 10-3 7.6 x 10- 3.6 x 10-4 1.4 x 10-4 1.0 x 10-4
of H2O2 (moldm-3) 4
Time (minutes) 0 5 12 20 33 40
Pot a graph of concentration of hydrogen peroxide against time (04marks)
(d) Using your graph determine the time required for;
(i) 1.0 x 10-3 moles of hydrogen peroxide to reduce to 5.0 x 10-4 moles (01mark)
(ii) 6.0 x 10-4 moles of hydrogen peroxide to reduce to 3.0 x 10-4moles (01mark)
(e) (i) What conclusion can be drawn from your answers in (d)(i) and (ii)? (1 ½ marks)
(ii) Determine the rate constant for the reaction. (1 ½ marks)
2. Complete the following equations and in each case, write mechanisms for the reactions:
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3. (a) Although the elements: fluorine, chlorine, bromine and iodine belong to group (VII) of the
Periodic Table, fluorine behaves differently from the rest of the group members. State;
(i) two reasons why fluorine differs from the other elements of group (VII). (01mark)
(ii) any two reactions in which fluorine differs from the other elements of group (VII) and write
equations to illustrate your answers. (06marks)
(b) The atomic numbers of group (VII) elements and the boiling points of their hydrides are shown in
table 2
Table 2
Element F Cl Br I
Atomic number 9 17 35 53
Formula of the hydride HF HCl HBr HI
Boiling point of hydride (0C) +19.9 -85.0 -66.7 -35.4
(i) Plot a graph of boiling points of the hydrides against atomic numbers of the elements.
(04marks)
(ii) Explain the shape of your graph. (4 1/2marks)
(c) State what would be observed and write an equation for the reaction that would take place if;
(i) sodium thiosulphate solution was added to iodine solution. (2 ½ marks)
(ii) chlorine gas was bubbled through a solution of potassium bromide. (2marks)
4. (a)(i) State the difference between molar conductivity and electrolytic conductivity of solution.
(01mark)
(ii) A conductivity cell filled with 0.1M aqueous potassium chloride gave a resistance of 484Ω at
250C. Calculate its cell constant.
(The molar conductivity of the solution at 250C = 129Ω-1cm2mol-1)(3 ½ marks)
(b) The electrolytic conductivity of a saturated solution of silver chloride at 250C is
3.41 x 10-6Ω-1cm-1.
Calculate the;
(i) Molar conductivity of silver chloride at infinite dilution (1½ marks)
(The molar conductivities at infinite dilution of silver nitrate, potassium nitrate and
potassium chloride are 133.4, 145.0 and 149.9 Ω-1cm2mol-1 respectively)
(ii) Solubility of silver chloride and hence its solubility product. (7 ½ mark)
(The electric conductivity of water at 250C = 1.60 x 10-6Ω-1cm-1)
(c) Explain the effect of each of the following factors on the molar conductivity of an electrolyte:
(i) ionic radius (2 ½ marks)
(ii) concentration (04 marks)
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SECTION B (40MARKS)
Answer any two questions from this section
Any additional question(s) answered will not be marked
5. (a) The melting points and atomic numbers of some elements of group (IV) of the Periodic Table are
shown in table 3.
Table 3
Element Carbon Silicon Germanium Tin Lead
Atomic number 6 14 32 50 82
0
Melting point ( C) 3750 1420 950 232 327
(a)(i) Explain the trend in the melting points of the elements (05marks)
(ii) Describe the reaction of the elements with sulphuric acid. (07marks)
(b) Group (IV) elements form tetrachlorides.
(i) Write equations for the reactions leading to formation of the tetrachlorides of carbon, silicon
and lead. (4½ marks)
(ii) State what is observed when the tetrachlorides of carbon, silicon and lead are reacted with
water. Explain your observations. (3½ marks)
6. (a) State what meant by the following terms:
(i) Electron affinity (01 marks)
(ii) First ionization energy (01 marks)
(iii) Enthalpy of solution (01 marks)
(b) The first ionization energy of an element is always less than the second ionization energy.
Explain. (02 marks)
(c) Describe an experiment to determine the enthalpy of neutralization of hydrochloric acid by
sodium hydroxide (05marks)
(d) Some thermo-chemical data about calcium and oxygen are shown below
Process Energy (kJmol-1)
Enthalpy of formation of calcium oxide = -636.0
Enthalpy of sublimation of calcium = +177.0
First ionization energy of calcium = +590.0
Second ionization energy of calcium = +1100.0
Bond dissociation energy of oxygen = +498.0
First electron affinity of oxygen = -141.4
Second electron affinity of oxygen = +790.8
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(i) Draw an energy level diagram for the formation of calcium oxide (04marks)
(ii) Calculate the lattice energy of calcium oxide (02marks)
(iii) Comment on the stability of calcium oxide. (01 mark)
(e) The hydration and lattice energies for the chlorides of lithium and sodium are shown in the table
4
Table 4
Compound Lattice energy (kJmol-1) Hydration energy (kJmol-1)
LiCl 843 883
NaCl 778 775
(i) Calculate the enthalpies of solution for lithium chloride and sodium chloride. (1 ½
marks)
(ii) Which one of the chlorides in (e)(i) is likely to dissolve more on heating? Explain your
answer (1 ½ marks)
7. Write equations to show how the following conversions can be effected; indicate reagents and
conditions for the reaction in each case.
8. Explain each of the following observations and illustrate your answer with equations where
necessary
(a) The reactivity of alcohols with hydrogen halides is in order;
tertiary > secondary > primary alcohols. (2 ½ marks)
(b) Alcohols are neutral organic compounds whereas phenol is weakly acidic, and yet both have
hydroxyl groups. (04marks)
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(c) Magnesium ions form precipitate with dilute ammonia solution, but no precipitates is formed if
ammonium chloride is added to magnesium ions prior to ammonia solution (06 marks)
(d) Water boils at 1000C whereas hydrogen fluoride boils at 19.50C although both compounds
exhibit hydrogen bonding. (04marks)
(e) The nitronium ion, NO2+ has a linear shape whereas the nitrite ion, NO2- is V-shaped. (3½ marks)
END
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Proposed answers
1. (a) State what is meant by the term order of reaction. (01mark)
Order of reaction is the sum of exponents to the concentration terms in a rate law.
(b) The decomposition of hydrogen peroxide proceeds according to the following equation
2H2O2 (aq) → 2H2O(l)+ O2(g)
(i) Write the expression for the rate law of the reaction. ( 1 ½ marks)
Rate = k[H2O2]x
(ii) Describe how the order of the reaction can be determined. (05marks)
Measure the volume of oxygen gas released over time as the hydrogen peroxide
solution decomposes at room temperature.
Set up
- Carry out two experiment using equal volumes but varying concentration of
hydrogen peroxide to which add equal mass of manganese dioxide and start the
clock.
- Measure the volume of oxygen liberated at specified intervals of time.
- Plot graphs of volume oxygen liberated against time.
- Find initial rates from the gradients of the tangent of graphs at zero
concentration.
- Using the initial rates obtained calculate the order of the reaction x from the
equation Rate = k[H2O2]x.
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(iii) Explain the effect of temperature on the rate of decomposition of hydrogen peroxide.
(3 ½ Marks)
Increasing temperature increases the rate of decomposition by providing energy to
break the bonds in hydrogenperoxide
(c) The following kinetic data in table 1 were obtained for the decomposition of hydrogen peroxide.
Table 1
Concentration of 1.6 x 10-3 1.3 x 10-3 7.6 x 10-4 3.6 x 10-4 1.4 x 10-4 1.0 x 10-4
-3
H2O2 (moldm )
Time (minutes) 0 5 12 20 33 40
Pot a graph of concentration of hydrogen peroxide against time (04marks)
(d) Using your graph determine the time required for;
(i) 1.0 x 10-3 moles of hydrogen peroxide to reduce to 5.0 x 10-4 moles (01mark)
8 minutes
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(ii) 6.0 x 10-4 moles of hydrogen peroxide to reduce to 3.0 x 10-4moles (01mark)
8 minutes
(e) (i) What conclusion can be drawn from your answers in (d)(i) and (ii)? (1 ½ marks)
The reaction is a first order
(ii) Determine the rate constant for the reaction. (1 ½ marks)
Rate at the concentration of 1 x 10-3 = 7.43 x 10-5moldm-3min-1
From Rate = k[H2O2]
7.43 x 10-5 =k(1 x 10-3)
k = 0.0743min-1
therefore rate constant = 0.0743min-1
2. Complete the following equations and in each case, write mechanisms for the reactions:
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3. (a) Although the elements: fluorine, chlorine, bromine and iodine belong to group (VII) of the
Periodic Table, fluorine behaves differently from the rest of the group members. State;
(i) two reasons why fluorine differs from the other elements of group (VII). (01mark)
- Fluorine has low bond strength
- Fluorine has high electronegativity
- Fluorine has small atomic radius
(ii) any two reactions in which fluorine differs from the other elements of group (VII) and write
equations to illustrate your answers. (06marks)
- Fluorine displaces chlorine from its salts
2Cl- + F2 (g) → 2F- + Cl2
- Fluorine substitutes oxygen from silicon dioxide and water.
SiO2 (s) + 2F2 (g) → SiF4 (g) + O2 (g)
- Fluorine reacts with cold dilute solutions of alkalis to give oxygen difluoride; F2O, and
with warm concentrated alkalis to give oxygen.
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(Cold dilute) 2OH- (aq) + 2F2 (g) → F2O (g) + 2F- (aq) + H2O (l)
- Fluorine reacts with warm concentrated alkalis to give oxygen.
(Warm conc.) 4OH- (aq) + 2F2 (g) → O2 (g) + 4F- (aq) + 2H2O (l)
(any two reactions)
(b) The atomic numbers of group (VII) elements and the boiling points of their hydrides are shown in
table 2
Table 2
Element F Cl Br I
Atomic number 9 17 35 53
Formula of the hydride HF HCl HBr HI
0
Boiling point of hydride ( C) +19.9 -85.0 -66.7 -35.4
(i) Plot a graph of boiling points of the hydrides against atomic numbers of the elements.
(04marks)
(ii) Explain the shape of your graph. (4 ½ marks)
The boiling point of HF is considerably higher than that of hydrogen chloride because the
individual HF units associate into larger aggregates (HF)n by means of strong hydrogen bonding.
From HCl to HI boiling points increase due to increase in molecular mass and thus the strength
of molecular forces
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(c) State what would be observed and write an equation for the reaction that would take place if;
(i) sodium thiosulphate solution was added to iodine solution. (2 ½ marks)
The brown Iodine color is discharged
I2(a) + 2S2O32-(aq) → 2I-(aq)+ S4O62-(aq)
(ii) chlorine gas was bubbled through a solution of potassium bromide. (2marks)
A yellow solution forms due to liberation of bromine
2Br-(aq) + Cl2 (aq) → Br2(aq) + 2Cl-(aq)
4. (a)(i) State the difference between molar conductivity and electrolytic conductivity of solution.
(01mark)
Electrolytic conductivity is the reciprocal of resistance of a solution between electrodes each
1cm2 in area and 1cm a part while molar conductivity is the contactivity of a solution that
contain 1 mole of an electrolyte.
(ii) A conductivity cell filled with 0.1M aqueous potassium chloride gave a resistance of 484Ω at
250C. Calculate its cell constant.
(The molar conductivity of the solution at 250C = 129Ω-1cm2mol-1)(3 ½ marks)
K = Λc x C = 129 x 0.1 x 10-3 = 0.0128 Ω-1cm-1.
From K = x cell constant
Cell constant = 0.0129 x 484 = 6.24cm-1
(b) The electrolytic conductivity of a saturated solution of silver chloride at 250C is
3.41 x 10-6Ω-1cm-1.
Calculate the;
(i) Molar conductivity of silver chloride at infinite dilution (1½ marks)
(The molar conductivities at infinite dilution of silver nitrate, potassium nitrate and
potassium chloride are 133.4, 145.0 and 149.9 Ω-1cm2mol-1 respectively.)
Λ(AgCl) = Λ(AgNO3)+ Λ(KCl) – Λ(KNO3)
= 133.4 + 149.9 – 145.0
= 138.3 cm2mol-1
(ii) Solubility of silver chloride and hence its solubility product. (7 ½ mark)
(The electric conductivity of water at 250C = 1.60 x 10-6Ω-1cm-1)
Electric conductivity of AgCl solution = 3.41 x 10-6 - 1.60 x 10-6 = 1.81 x 10-6 Ω-1cm-1
Let the solubility of silver chloride be C
From Λc =
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C= = 1.3 x 10-8molcm-3 = 1.3 x 10-5 moldm-3
Ksp = [Ag+][Cl-]= [1.3 x 10-5] [1.3 x 10-5]= 1.69 x 10-10mol2dm-6
(c) Explain the effect of each of the following factors on the molar conductivity of an electrolyte:
(i) ionic radius (2 ½ marks)
The size of an ion: small ions have high speed of movement leading to high conductivity.
However, small ions with high charge have high density that may attract a big cloud of water of
hydration that its effective mass may bigger than that of a big ion. That is why the small cations
may have lower conductivity that big cation.
(ii) concentration (04 marks)
For strong electrolyte at high concentration lowers conductivity high density of ions lead ion
interaction which reduce mobility of ions
For weak electrolytes, high concentration lowers conductivity because it suppresses
ionization.
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SECTION B (40MARKS)
Answer any two questions from this section
Any additional question(s) answered will not be marked
5. (a) The melting points and atomic numbers of some elements of group (IV) of the Periodic Table are
shown in table 3.
Table 3
Element Carbon Silicon Germanium Tin Lead
Atomic number 6 14 32 50 82
0
Melting point ( C) 3750 1420 950 232 327
(a)(i) Explain the trend in the melting points of the elements (05marks)
- Generally melting points decrease down the group due to reduction of electronegativity.
- Carbon, has a very high melting point because each carbon atom is bonded to four others
with strong covalent bonds in a 3D network.
- Silicon (Si) and Germanium (Ge) also form giant covalent structures similar to diamond,
but the bonds are slightly weaker due to the larger atomic size, leading to lower melting
points compared to carbon.
- Tin (Sn) and lead (Pb) are metal with low melting points because metallic bonds are
generally weaker than covalent bonds.
(ii) Describe the reaction of the elements with sulphuric acid. (07marks)
With dilute sulphuric acid
- C, Si and Ge do not react.
- Sn and Pb reacts hot concentrated sulphuric acid liberating sulphur dioxide.
Pb (s) + 2H2SO4(aq) → PbSO4(s) + SO2(aq)+ 2H2O(l)
With hot concentrated sulphuric acid
- C, Si and Ge react to form dioxides
C(s) + 2H2SO4(aq) → CO2(g) + 2SO2(g) +2H2O(l)
Sn(s) + 4H2SO4(aq) → Sn(SO4)2(aq) + 2SO2(g) +2H2O(l)
Ge (s) + 4H2SO4(aq) → Ge(SO4)2(aq) + 2SO2(g) +2H2O(l)
- Pb is oxidized to lead II sulphate but the reaction is short lived due to insoluble
lead II sulphate
Pb(s) + 2H2SO4(aq) → PbSO4(s) + SO2(g) +2H2O(l)
(b) Group (IV) elements form tetrachlorides.
(i) Write equations for the reactions leading to formation of the tetrachlorides of carbon, silicon
and lead. (4½ marks)
CS2 (l) + 3Cl2 (g) → CCl4 (l) + S2Cl2 (l)
Si(s) + 2Cl2(g) → SiCl4 (l)
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PbO2(s) + 4HCl (Conc.and cold) → PbCl4 (aq) + 2H2O(l)
(ii) State what is observed when the tetrachlorides of carbon, silicon and lead are reacted with
water. Explain your observations. (3½ marks)
- CCl4 – no observation
- SiCl4 and PbCl4 white fumes of HCl due to hydrolysis
SiCl4 (aq) + 2H2O(l) → SiO2 (s) + 2H2O(l)
PbCl4 (aq) + 2H2O(l) → PbO2 (s) + 2H2O(l)
6. (a) State what meant by the following terms:
(i) Electron affinity (01 marks)
It enthalpy change when 1 mole of electrons is added to gaseous 1 mole of gaseous atoms
or anions.
(ii) First ionization energy (01 marks)
It enthalpy change when 1 mole of electrons is removed to gaseous 1 mole of gaseous
atoms to form 1 mole of gaseous cations with single positive charge
(iii) Enthalpy of solution (01 marks)
It is enthalpy change when 1 mole of ionic solid ionic compound is dissolved in excess water.
(b) The first ionization energy of an element is always less than the second ionization energy.
Explain. (02 marks)
When the first electron is removed from an atom, the remaining electrons are strongly attracted
to the nucleus, thus removal of the second electron requires extra energy.
(c) Describe an experiment to determine the enthalpy of neutralization of hydrochloric acid by
sodium hydroxide (05marks)
Set up
stirrer thermometer
Vacuum flask
Mixture
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A neutralization reaction is carried out in the calorimeter of known heat capacity, C .
50cm3 of 1M HCl (v cm3) and 50cm3 of 1M NaOH (v cm3) of are added to calorimeter, and temperature
change θ0C is noted.
Calculations
The number of moles of water formed = = 0.05moles
Assumptions:
(i) The density of water = density of solution = 1gcm-3.
(ii) Specific heat of solution = specific heat capacity of water = 4.2 Jg-1K-1
(iii) Heat given out on neutralization = Heat received by water + calorimeter of capacity, C.
Thus, heat given out = Cθ + 100 x 4.2θ
Thus 0.05 mole of water formed produce = (Cθ + 420θ)J
1mole of water will produce = Jmol-1
(d) Some thermo-chemical data about calcium and oxygen are shown below
Process Energy (kJmol-1)
Enthalpy of formation of calcium oxide = -636.0
Enthalpy of sublimation of calcium = +177.0
First ionization energy of calcium = +590.0
Second ionization energy of calcium = +1100.0
Bond dissociation energy of oxygen = +498.0
First electron affinity of oxygen = -141.4
Second electron affinity of oxygen = +790.8
(i) Draw an energy level diagram for the formation of calcium oxide (04marks)
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(ii) Calculate the lattice energy of calcium oxide (02marks)
∆(lattice) + 177.0 + 590.0 + 1100.0 + 498/2 – 141.4 + 790.8 = - 636.0
∆(lattice) = -3,401.8
(iii) Comment on the stability of calcium oxide. (01 mark)
Very stable because high negative lattice energy
(e) The hydration and lattice energies for the chlorides of lithium and sodium are shown in the table
4
Table 4
Compound Lattice energy (kJmol-1) Hydration energy (kJmol-1)
LiCl 843 883
NaCl 778 775
(i) Calculate the enthalpies of solution for lithium chloride and sodium chloride. (1 ½
marks)
Enthalpy of solution of LiCl = 843 – 883 = -40kJmol-1
Enthalpy of solution of NaCl = 778 – 775 = +3kJmol-1
(ii) Which one of the chlorides in (e)(i) is likely to dissolve more on heating? Explain your
answer (1 ½ marks)
NaCl because it has positive enthalpy of solution
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7. Write equations to show how the following conversions can be effected; indicate reagents and
conditions for the reaction in each case.
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19
8. Explain each of the following observations and illustrate your answer with equations where
necessary
(a) The reactivity of alcohols with hydrogen halides is in order;
tertiary > secondary > primary alcohols. (2 ½ marks)
Hydrogen halides react alcohols via formation of carbonium ions
Tertiary alcohols react fast because tertiary carbonium ions are stable readily formed from
tertiary alcohols; and secondary alcohols are less reactive the tertiary alcohol because
secondary carbonium ions are less readily formed; similarly primary alcohols are less reactive
than secondary alcohols because primary carbonium ions are unstable and less likely to form.
(b) Alcohols are neutral organic compounds whereas phenol is weakly acidic, and yet both have
hydroxyl groups. (04marks)
The alkyl group in alcohol has a positive inductive effect; it pushes electrons towards OH group
and stabilizes O – H bond
The aromatic group in phenol has a negativr inductive effect; it withdraws electrons from OH
group and destabilizes O – H bond
(c) Magnesium ions form precipitate with dilute ammonia solution, but no precipitates is formed if
ammonium chloride is added to magnesium ions prior to ammonia solution (06 marks)
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Ammonia hydrolyses in water to hydroxyl ions
NH3 (aq) + H2O (l) → NH4+(aq) + OH-(aq)
Hydroxyl ions react with magnesium ions to form white ppt. of magnesium hydroxide
Mg2+(aq) + 2OH-(aq) → Mg(OH)2(s)
In presence of ammonium chloride magnesium ions do not form ppt. the hydroxyl ions are
neutralized by ammonium ions
NH4+ (aq) + OH- (aq) → NH3 (aq) + H2O(l)
(d) Water boils at 1000C whereas hydrogen fluoride boils at 19.50C although both compounds
exhibit hydrogen bonding. (04marks)
Water has higher boiling point than hydrogen fluoride because water molecule has two
hydrogen atoms and two lone pairs on the oxygen atom; this makes able to form four hydrogen
bonds with surrounding water molecules. While HF forms fewer hydrogen bonds per mole with
surrounding HF molecules since it has fewer Hydrogen atoms per molecule. The hydrogen bonds
in water thus, require higher temperature to beak leading to higher boiling point.
(e) The nitronium ion, NO2+ has a linear shape whereas the nitrite ion, NO2- is V-shaped. (3½ marks)
Nitronium ion lack a lone pair of electron while nitrite ion has alone pair of electron.
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Thanks
Dr. Bbosa Science
END
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