THE OPEN UNIVERSITY OF SRILANKA

B. Sc Degree Programme – Level 3

Model Paper – 2017/2018

CYU3201 – Basic Principles of Chemistry II

(02 hours)

07th February 2019 9.30 am – 11.30 am

INSTRUCTIONS:

 This question paper consists of two sections.

 Section I – Short answer Questions (Recommended time 30 min).
 Section II – Three (3) Structured/Essay Type Questions (Recommended time 1 hour 30 min).
 Answer all questions in Section I and Section II.
 Submit the answer scripts for each section separately.
 The use of a non-programmable electronic calculator is permitted.
 You are NOT allowed to keep Mobile phones with you during the examination. Please switch
off and leave them in a safe place.

Gas constant = 8.314 J K1mol1 Avogadro constant = 6.023  1023 mol1

Faraday constant (F) = 96,500 C mol1 Planck’s constant (h) = 6.63  1034 J s

Velocity of light (c) = 3.0  108 m s1 Standard Atmospheric pressure = 105 Pa (N m2)

Mass of an electron = 9.1 x 10-31kg Rydberg constant, R = 1.097 x 10 7 m - 1

 Section I – 3 Short answer Questions
(Recommended time 30 minutes)
 This section consists of 3 Short answer Questions.
 Answer all the parts.

Part A
1. a) What is the physical concept of the term “Thermodynamic Process”? (08 marks)
b) Define a thermodynamic process and express its mathematical expression if any.
(08 marks)
c) What do you mean by the term microscopic properties? Briefly explain with suitable example.
(2  = 16 marks)
d) How would you explain that Mass is an extensive property and Mole Fraction is an intensive
property? (08 marks)
e) (i) Write down the Van der Waals equation and identify all the terms in it.
(ii) 0.5 moles of carbon dioxide was filled in a 0.6 litre vessel at 47 0C. Calculate the
pressure expected on the basis of van der Waals equation.
( a = 3.59 atm L2 mol-2, b = 4.27 x 10-2 l mol-1, R = 0.0821 al L mol-1 K-1) (20 marks)

Part B
(i) Write down the rate equation for the reaction A + 2B products
(ii) Transform the following rate equation into its logarithmic form
d [ A]
  k [A]p [B]q
dt
(iii) Name three factors that affect the rate of a reaction
(iv) Write down the Arrhenius equation (20 marks)

Part C

A student prepared two electrodes by inserting a rod of metal A(S) in a solution of its ions, A 2 (aq) ,
and inserting a rod of metal B(S) in a solution of its ions, B3 (aq) . Then she prepared a Galvanic cell
by electrically connecting the solution phases of the two electrodes using a salt bridge.
(a) Write down two non-equivalent cell diagrams for the cell prepared by the student.
(b) Write down the anode, cathode and cell reactions for each of the cell diagrams you have written
above. (20 marks)
 Section II – 3 Structured / Essay Type Questions
(Recommended time 1 hour 30 min)
1. Answer all parts (a) and (b)
a) (i) Calculate the density (in g/l) of a gas with a molar mass of 60 g/mol at 0.75 atm and
27 °C?
(ii) Draw a graph to show the variation of volume (V) of a fixed mass of ideal gas at
constant pressure with absolute temperature (T)? Explain your answer.
(iii) A balloon contains 0.4 mol of an ideal gas with volume 0.5 L. If an additional 0.8 mol of
the gas is added at constant pressure and temperature. What will be the final volume of
the balloon?
(iv) Using sketches of Probability density versus Molecular speed at different temperatures,
briefly explain how the average speed of gas molecules changes with temperature.
(35 marks)
b) i) Write down the mathematical expression for the first law of thermodynamics and define
all the terms involved.
ii) A sample of 1.0 mole of ideal gas initially at 3.50 atm and 300 K undergoes reversible
and adiabatic expansion until its pressure reaches 2.25 atm. During this process the
volume of the gas reaches to 9.20 dm3.
Given that it’s molar constant pressure heat capacity is 20.5 J mol-1K-1. Calculate q, w,
U, H, initial volume, initial temperature and the final temperature. (65 marks)

2. Answer all parts (a), (b), (c) and (d)

(a) A certain reaction [A P] is reported to be first order with respect to A
(i) With the aid of the rate equation, derive the integrated form of this equation
(assume the initial concentration of A as Ao).
(ii) If 40% of A undergoes reaction in 45 minutes at 25 oC, determine the rate
constant of this reaction at the same temperature. Hence, determine its half-life at
the same temperature. (24 marks)

(b) What do you understand by the following terms used in the study of Kinetics?
(i) molecularity
(ii) an elementary reaction (12 marks)

(c) A certain reaction has a rate constant of 5.70 x 10-5 mol-1dm3 s-1 at 27 oC. [Assume that the
activation energy (Ea) and the pre-exponential factor (A) are constants in the above temperature
range involved]. Calculate the expected rate constant at 47 oC. (14 marks)

(d) A cell diagram for the cell constructed by a student is shown below.

X(s) X  (aq) c  X
 0.01mol dm 3  
Y3 (aq) c
Y2 
 0.02 mol dm 3 Y(s)

X and Y are metals. At 25o C , the student found out that the emf assigned to the above cell
diagram to be 1.53 V .

(i) Write down the anode, cathode and cell reactions corresponding to the above cell
diagram.
(ii) Giving reasons state whether the cell reaction you have written is spontaneous or not.
(iii) What is the charge number of the cell reaction you have written above?
(iv) Calculate the Gibbs free energy change for the above mentioned cell reaction.
(50 marks)
3. Answer any TWO (02) parts out of (a), (b) and (c)
 A Z Z I RT 
 G   nFE I  0.5   c j Z2j log       E  E0  ln  Q  
 j 1  aB I nF 
 
 
 Data : F  96500 C mol 1 , R  8.314 J K 1 mol 1, A  0.509 dm 3 2 mol 1 2 
 
 aB  1.25 dm3 2 mol 1 2 

(a) (i) Explain the importance of the Debye-Huckel laws for activity coefficient in studying
Galvanic cells.
(ii) Consider an aqueous solution of CaCl2 at 298 K with  CaCl 2   0.1 mol dm 3 .

   Calculate the ionic strength of this solution.

   Calculate the mean activity coefficient of CaCl2 in this solution using the Debye-
Huckel limiting law.
(50 marks)
(b) (i) Define the electrode potential of an electrode.
(ii) Using the definition of electrode potential show that the electrode potential of the
standard hydrogen electrode is zero.
(iii) Consider a metal-metal ion electrode whose half reaction is
P3 (aq)  3e  P(s) at 298 K when a P3  x . Explain why the electric potential of this
electrode can be different from its electrode potential.
(50 marks)
(c) At 298 K, a student conducted a potentiometric titration using an aqueous solution of
X n  (aq) as titrant and an aqueous solution of Y m  (aq) as titrand. He measured the electrode
potential of a platinum rod immersed in the titration vessel (titrand) during the titration. The
titration reaction was Xn  (aq)  Ym (aq)  X(n 1) (aq)  Y(m1) (aq) .
From a book of constants he found the following information.
Xn  (aq)  e  X(n 1) (aq) E0298  1.1 V

Y(m1) (aq)  e  Ym (aq) E0298  0.8 V

(i) Sketch the variation of the electrode potential of the platinum rod as a function of the
volume of titrant during the titration. Denote the volume of titrant at end point by Vend .
Indicate the following on your sketch.
 The end point of the titration.

  The values of the electrode potential of the redox electrode formed at the platinum
1
electrode when the volume of titrant added is 2
Vend and 2 Vend .

(ii) Denoting the activity of an ionic species  by a  , write down the thermodynamic
equilibrium constant of the titration reaction in terms of the activities of the ionic species.
(iii) Calculate the thermodynamic equilibrium constant of the titration reaction at 298 K.
(50 marks)