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KHESSUS

ADVANCED EXAMINATION SERIES


CHEMISTRY 1
Time: 2: 30HRS NOV, 2019

Instructions:
i. This paper consists of fourteen (14) questions in section A, B and C.
ii. Answer four questions from section A and only three questions from each of section B
and C.
iii. For calculations you may use the following constants;
-Rydberg constant, RH = 1.09678 × 107 m-1
-Gas constant, R= 8.314 Jmol-1 k-1 or 0.0821 atm mol-1 k-1 dm3
-GMV= 22.4 dm3mol-1 or 22400 cm3mol-1
-Standard temperature = 273 k
-Standard pressure = 760 mmHg
-Plank’s constant, h = 6.63 × 10-34Js
-Velocity of light, c = 3.0 × 108m/s
-Mass of an electron, m = 9.11 × 10-31kg
(Cl=35.5, Ba= 137, Fe= 56, Cr= 52, I= 127, Cu= 63.5, Ag= 108, K= 39, Na= 23, N= 14, Br = 80,
Kr = 84)

SECTION A (40 marks)

Answer four questions


1. (a) State:
i) Aufbau principle
ii) Hund’s rule of maximum multiplicity
iii) The uncertainty principle (1.5 marks)
b)(i) The H atom and the Be3_ ion each have one electron. Does the Bohr model predict their spectra
accurately? Would you expect their line spectra to be identical? Explain (2marks)
ii) How does an atomic spectrum differ from a continuous spectrum? (0.5 marks)
(iii) What is the wavelength (in nm) of the least energetic spectral line in the visible series of the H atom (
2marks)
c) The wavelength of the lines in the Balmer series of the hydrogen spectrum is
given by the expression: 1/λ = RH (1/22– 1/ n2)
where RH is a constant and n is an integer greater than 2.
i) Draw an energy level diagram to show the origin of the first and the third lines in the Balmer
series.
ii) Calculate the wavelength of the first line in i.(c) above. (4 marks)
2. (a) Write the short notes on the following
(i) Nascent hydrogen
(ii) Van der Waals forces
(iii) VSEPR theory. (1.5 marks)
(b) Use the VSEPR theory to predict the molecular geometry of the following species:
(i) PCl2 (ii) SO3 (iii) CS2 (iv) SO4-2 (2 marks)
(c) Explain why carbon-dioxide is non polar molecule while sulphur-dioxide is polar despite the
fact that both have the same empirical formula. (1 marks)
(c) Give reason; state which of the following substances are polar and which are non-polar.
(i) CO2 (ii)CHCl3 (iii) NH3 (iv) SO2 (02marks)
(d(i)) Give short notes on hybridization of atomic orbitals as illustrated in methane and ethene.
(02 marks)
(ii) NH3 and CH4 are isoelectronic but the bond angle in NH3 is less than that of CH4.
(1.5marks)

3. (a)Supply the missing quantum numbers and sublevel names.


n l ml Name
(i) ? ? 0 4p
(ii) 2 1 0 ?
(iii) 3 2 -2 ?
(iv) ? ? ? 2s (03marks)

(b) Are the following quantum number combinations allowed? If not, show two ways to correct
them:
(i) n = 2; l = 0; ml = -1 (ii) n = 4; l = 3; ml = -1
(ii) n = 3; l = 1; ml = 0 (iv) n = 5; l = 2; ml = +3 (02 marks)
(c) What feature of an orbital is related to each of the following quantum numbers?
(i) Principal quantum number (n)
(ii) Angular momentum quantum number (l)
(iii) Magnetic quantum number (ml) (1.5 marks)

(d)Write the electronic configuration of the following species:

i. Cr+2 (ii) Ar (iii) B (iv) Be ( v) Mn (vi) Sc +


( 03marks)
(e) State paul’s exclusive principle ( 0.5 marks)

4. (a) State each of the following


(i) Boyle’s law
(ii) Avogadro’s law
(iii) Graham’s law of diffusion and effusion
(iv) Dalton’s law of partial pressure (02 marks)
(b) (i) A mixture of helium and oxygen is used in diving tanks instead of nitrogen which at elevated
pressure a
large quantity is dissolved in blood producing an agonizing condition called the “band”. For a
particular
dive 40L of oxygen at 25℃ and 1atm was pumped along with 12L of helium at 25℃ and 1
atmosphere into a tank with volume of 5L. Calculate the partial pressure of each gas and the
total pressure in the tank at 25℃. (03 marks)
(c) A container contains 7g of oxygen.

(i) How many molecules of oxygen are there ?

(ii) How many grams of Hydrogen will be needed to synthesize water using 7g of oxygen?
(02marks)

(d) The time taken for effusion of equal volume of CO 2 and a mixture of CO2 and CO are
32.second and 27 secondds respectively. Calculate the composition of each gas in the mixture
( 03 marks)

5. (a) (i)State four postulates of the kinetic theory of gases (2 marks)

(ii) Define root mean square speed of gas molecules. (1 mark)

(iii) The root mean square speed of hydrogen molecules at a fixed temperature is

1600m/s. What is the root mean square speed of oxygen molecules at the same temperature ( 02marks)

(iv) How the postulates of the kinetic-molecular theory are applied to explain the origin of
pressure and the gas (02marks) laws

(v) Why intermolecular attractions and molecular volume cause gases to deviate from ideal
behavior at low temperatures and high pressures ( 02 marks)

(b) A 6.0-L flask contains a mixture of methane (CH4), argon,and helium at 45 0C and 1.75 atm. If
the molefractions of helium and argon are 0.25 and 0.35, respectively, how many molecules of
methane are present? (3 marks)
6. (a) Forthereaction; CO2(g)+H2(g) CO(g)+ H2O(g)
0
The value of Kc at552 C is 0.137.If 5moles o fCO2,5mole so fH2,1mole of CO and 1mole of H2O are
initially present,what is the actual concentration of CO2,H2,CO and H2O at equilibrium ( 04marks)
(b)At 1atm and 850C ,N2O4 is 50% dissociated,Calculate the equilibrium constant in terms
Of pressure and calculate the degree of dissociation of the gas at10 0Cand550C.
(c)For the reaction; N2O4 2NO2 ⠈†H=61.5KJmol-1
KP=0.113at298K
i)What is the value of KP at 00C?
ii)At what temperature will KP=1? (04marks)
(c) Explain the factors which affect the position of chemical equilibrium ( 02marks)
SECTION B ( 30 marks)
Answer three questions
7. (a) Define the following terms
(i) Lattice energy
(ii) Atomization energy
(ii) Enthalpy of neutralization (1.5marks)
(b) Given:
-Atomization energy of chlorine Cl2 = 121kJ/mol
- Atomization energy of Ba = 175kJ/mol
- Standard Enthalpy of formation of BaCl 2 = -860k/Jmol
- 1st Ionization energy of Ba = 550kJ/mol
- 2nd Ionization energy of Ba = 1000kJ/mol
- Electron affinity of Cl = -364k/Jmol
(i) From the data above draw the Born Haber Cycle for BaCl 2 (02marks)
(ii) Use the data to calculate the Lattice energy. (01marks)
(C) Given the enthalpies of combustion of Hydrogen, Benzene, Cyclohexene and Cyclohexane
are -242, -3302, -3746 and -3940kJ/mol respectively. Calculate the enthalpies of hydrogenation of
cyclohexene and Benzene. (04marks)
(d) Give three applications of Hess’s law of heat summation (1.5marks )
8. (i) State distribution law (0.5 marks)

(ii) State two conditions for efficient solvent extraction. (01marks)

(iii) Give four limitations of distribution law. (02marks)

(b) A weak monobasic organic acid HA is soluble in both water and CHCl 3. 500.0 cm3 of a solution of HA
in CHCl3, with a concentration of 0.057 moldm−3, is shaken well with 500.0 cm3 of water and allowed to
attain equilibrium at 27 C. An aqueous layer and CHCl 3 layer then separate out; the pH of the aqueous
layer is found to be 3.21 under these conditions. The dissociation constant of HA in water at 27 0C is
1×10−5 moldm−3.

(i) Calculate the partition coefficient at 27 C for the partitioning of HA between water and CHCl 3. ( 2.5
marks)

(ii) In a second experiment, a further 500.0 cm 3 portion of the same HA solution in CHCl 3 in which the
concentration of HA is 0.057 moldm−3, is shaken well with 500.0 cm3 of a 0.027 moldm−3 aqueous NaOH
solution and allowed to reach equilibrium at 27 0C. Calculate the pH of the aqueous layer under these
conditions. State the assumptions you make, if any, in the above calculations. (4 marks)

9. Give short notes on the following

(i) Colligative properties

(ii) Molality
(iii) Osmotic pressure (1.5 marks)

(b) Highlight the applications of colligative properties. (02marks)

c) 3.42g of sodium chloride were dissolved in 100g of water. If the osmotic pressure of this

solution at 60 0C was 22680 mm Hg, calculate the percentage dissociation of the sodium chloride.
(2.5 marks)
(d) Two flasks of equal volume were connected by a narrow tube of negligible volume, initially each
flask was at 270C and consist a total of 0.7 moles and 0.5 atm of hydrogen gas. Then one of the flasks was
immersed in a hot oil bath at 127°C while the other remained at 27°C.
(i) Find the final pressure of H2
(ii) Calculate the number of moles of hydrogen gas in each flask (04 marks)

10. (a) State a Raoult’s law ( 01marks)


(b) A liquid camphor freezes at 1750C . A solution of 1.54g of Naphthalene(C10H8) in 18g of
camphor freezes at 148.30C .What is the freezing constant per 100g of camphor? ( 04 marks)
(c ) The air in a hot-air balloon at 744 torr is heated from 17 0C to 60.00C. Assuming that the moles
of air and the pressure remain constant, what is the density of the air at each temperature? (The
average molar mass of air is 28.8 g/mol.) ( 03 marks)
(d) A sample of a liquid hydrocarbon known to consist of molecules with five carbon atoms is
vaporized in a 0.204L flask by immersion in a water bath at 101 0C. The barometric pressure is
767 torr, and the remaining gas weighs 0.482 g. What is the molecular formula of the
hydrocarbon? (02 marks)

SECTION C ( 30 marks)

Answer three questions

11. Give the mechanism for the following

(a) Chlorination of Benzene (05marks)

(b) Nitration of benzene (05marks)

12. (a) State markownkovs rule of electrophilic addition and show it by using propene with HBr
(O3marks)

(b) Give the structural formula of the two carbonium ions which could be formed when but-1-

ene react with gaseous HCl. Explain your reason for deciding one of these structural

formula and identify the carbonium ions as 1°, 2°, or 3°. (03 marks)

(c) (i) Which of the following carbonium ion in (b) is likely to be formed? Why? Hence

predict the product of reaction in (b) (02 marks)

(ii) Write a balanced chemical equation when but-1-ene react with HBr in presence of an organic
peroxide. (02 marks)

13. (a) Write the IUPAC names of the following organic compounds.
(C) Complete the following organic reactions:
(i) CH3 CHBr CH2CH3 + Alioholic KOH →
(ii) CH3CH2CH2OH + conc H2SO4 /1700C →
(iii) 2CH3CH2Br + 2Na / dry Ether → (02marks)
(iv) CH2 = CH2 + KMnO4/OH -→
14. ( a) Write down the structural formula for the following compounds.
(i). 3-methyl pentane
(ii). 3,3-dimethly -4 –ethyl hexane
(iii). 3—Methyl -1-pentyne
(iv). 1,4 -hexadiene (02marks)
b) Reaction of concentrated sulphuric acid with C4H9OH in the presence of heat provides a hydrocarbon
X, C4H8. When X is treated with trioxide followed by water hydrolysis only one product is formed which
is A
(i) Write five isomers of X
(ii) Identify X and A.
(iii) Write equation for all chemical reactions involved. (06 marks)
c) Write chemical equations to show how you would prepare the following compounds
(i) Propane from 1-bromopropane
(ii) 1-Iodobutane from 1-bromobutane (0 2 marks

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