KATHMANDU UNIVERSITY

Marks scored:
End Semester Examination
2008

Level : B.E./B.Sc./B.Pharm./B.Tech. Course : CHEM 101

Year : I Semester: I
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Roll No.: Time : 30 mins

Date : F. M. : 20
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SECTION “A”
[20 Q. × 1 = 20]
Select the most appropriate answer.

1. At certain temperature, 0.1mole of H2 and 0.1 mole of I2 were placed in one liter flask.
After a time, the equilibrium was established and concentration of I2 decreased to 0.02
mole per liter then Kc for the reaction at given temperature is -
[a] 65 [b] 64 [c] 68 [d] 60

2. Which one of the following is the Michaelis Menten equation?

K 2 [E] [S] K 2 [E o ] [S] K 2 [E o ] [S]
[a] V = [b] V = [c] V = [d] V =
Km + [S] Km + [S] [E] Km + [S]
K 1 [E ] [S]
Km + [S]

3. Which one of the following is the conjugate acid of the base CO3 – – ?
[a] H2CO3 [b] HCO3 - [c] OH- [d] CO2
4 50ml of 6.0x10 M CaCl2 is mixed with 30 ml of 0.04 M NaF (Ksp for CaF2= 1.7x10-10)
-3

What will happen upon the mixing?

[a] Saturated solution will form [b] Unsaturated solution will form
[c] Remains unchanged [d] Precipitation will occur

5. The equilibrium constant for the following reactions have been measured at 1000 K.
CaCO3(s) = CaO(s) + CO2(g) K1 = 3.9 × 10-2,
C(s) + CO2(g) = 2CO(g) K2 = 1.9
and the equilibrium constant for the overall reaction CaCO3(s) + C(s) = CaO(s) + 2CO(g) is
given by K3 then the pressure of [CO] at equilibrium is,
[a] 0.57atm [b]0.37 atm [c] 0.72 atm [d] 0.27 atm

6. 75% of a reaction of the first order was completed in 60 minutes and its half life was given
by
[a] 30 mins. [b] 15 mins. [c] 60 mins. [d] 40mins.

7. A solution contains 0.1M Cl- and 0.01M CrO4- -. Upon the addition of Ag + to this solution,
what its concentration would almost complete the precipitation of AgCl leaving CrO4- - in
the solution?
(Ksp for AgCl = 2.8 × 10-10 and Ksp for Ag2CrO4 = 1.9 × 10-12)
 [a] 1.4 × 10-5 M [b] 2.8 × 10-9M [c] 1.3 × 10-5M [d] 1.4 × 10-9M

8. When a half reaction is multiplied by positive number 2, its electrode potential would;
[a] Increase by four times [b] Increase by two times
[c] Become one half [d] Remain un changed

9. If the He gas is introduced into the reaction mixture; 2NO(g) + O2(g) = 2NO2(g) in a
container at constant pressure then equilibrium will,
[a] Shift towards more amount of NO2 [b] Shift towards more amount of NO and O2
[c] Remains unchanged [d] non of above

10. If the enthalpy change ( Hsoln) for the dissolution of the solute is negative then the
solubility of the solute;
[a] Increases as temperature increases. [b] Remains un changed
[c] Decreases as temperature increases. [d] Non of the above
.
Fill in the blanks:
11. The volume of 0.1M KMnO4 required to react completely with 0.01 mole of the oxalate ion
for the reaction 2MnO4- + 5C2O4-- + 16H+ 2Mn2+ + 10CO2 + 8H2O is given by
40 ml
………………………
Azeotrope
12. A mixture which boils off like a single pure compound is called ………………….
13. If Eo for the reaction Fe + Zn +2 = Zn + Fe+2 is -0.32V then the equilibrium constant will be
1.4 X 10-11
……………………………..
14. constant and in an irreversible
In a reversible process, the entropy of the universe is …..…….
increases
process, the entropy of the universe………………..
15. If 10mL of 0.1M HCl is mixed to 20mL of 0.2M HCl. The new concentration of the
0.166 M
solution will be ……………..
d [C ]
16. For a reaction, A + B C, the rate law is = K [ A] 2 × [ B ] . On doubling the
dt
8 times
concentration of A and B, the rate of reaction increased by ………….….times.

17. The standard potential for Fe +2 and Zn +2

Fe Zn are -0.44V and -0.76V. then the
Fe+2
strongest oxidizing agent among the species is ……………….
18. For the reaction, NO(g) + 1/2O2(g) = NO2(g) , K1 = 1.28 × 106 at 298K and K2 = 14.4 at
-13.5
598K. Then Ho for this reaction is given by …………..…….Kcal.
19. is less
Work done by a system in a reversible process is ……..….…. than in irreversible process.
20. The positive deviation from the Raoults law for a solution is accompanied by
absorption of heat
………………………
 KATHMANDU UNIVERSITY
End Semester Examination
2008
Level : B.E./B.Sc./B.Pharm./B.Tech. Course : CHEM 101
Year : I Semester: I
Time : 2 hrs. 30 mins. F.M. : 55
SECTION “B”
Attempt ANY FIVE questions.

1.a. A galvanic cell consists of a strip of cobalt metal dipping into 1.0M Co ++ solution and
another half cell in which a piece of platinum dips into 1.0M solution of Cl-. Chlorine gas
at 1 atm. is bubbled into this. The observed cell voltage is 1.63V and as cell operates the
cobalt electrode is negative. The standard potential for, ½ Cl2 /Cl- half cell is +1.36V.
Answer the following questions.
i. What is the spontaneous cell reaction? [1]
ii. What is the standard potential of cobalt electrode? [0.5]
iii. Would the cell voltage increase or decrease if the pressure of Cl2 gas increased? [0.5]
iv. What would the cell voltage be if the concentration of Co++ were reduced to 0.01M?

[1]
v. What is the equilibrium constant of this reaction? [1]

b. Calculate the concentration of the sodium formate that must be present in a 0.10M solution
of formic acid to produce a pH of 3.80. [Ka for formic acid= 1.8x10-4] [2]

2.a. Distinguish between followings. [1+1+1=3]

i. Order of reaction and molecularity of reaction.
ii. Extensive properties and Intensive properties.
iii. Primary cell and Secondary cell.

b. Nitramide, O2NNH2 decomposes slowly in aqueous solution according to the reaction;

O2NNH2 N2O + H2O
The mechanism of the reaction is:
K 1 - +
step 1. O 2NNH2 O 2NNH + H (fast equilibrium)
K -1

K -
- 2 N2O + OH (slow)
step 2. O 2NNH

+ - K 3
step 3. H + OH H2O
Answer the following questions.
i. Write down the rate law in terms of O2NNH2 and H+ [1]
ii. What is the order of reaction with respect to O2NNH2. [1]
iii.Which step is the rate determining step and why? [1]

3.a. Balance the following reactions by ion-electron method. [1.5+1.5=3]

i. ClO- + CrO2- CrO4- - + Cl- (Basic medium)
-
ii. ClO3 + As2S3 Cl- + H2AsO4- + SO4- - (Acidic medium)
b. The solubility product of Mg(OH)2 is 1.8x10 -11.
Calculate (i) the solubility of Mg(OH)2 in pure water.
(ii) the solubility of Mg(OH)2 in 0.1M MgCl2 solution.
 (iii) pH of pure the solution . [1+1+1=3]
+
4.a. A mixture of KBr and NaBr weighing 0.560gm was treated with aqueous Ag ions and all
bromide ions were recovered as 0.970 gm of pure AgBr. What are the weight of KBr and
NaBr in the original sample? [3]
b. Give the reasonable explanations. [1+1+1=3]
i. Work done is not the state function.
ii. For elementary process, molecularity and order are the same.
iii. Weaker the acid, the stronger is its conjugate base and vice-versa.

5.a. Show that reciprocal of the reactant concentration is linear function of time for 2nd order
reaction. Also explain that half life period depends upon the initial concentration of the
reactant. [2+1=3]
o
b. Calculate the G and K for the reaction. [3]
NO(g) + ½ O2(g) = NO2(g)
Which factor, enthalpy or entropy makes K greater than unity and thereby provides the
principle driving force for the reaction? (R= 1.987 cal/mol-deg)
Given that, Gof (NO2) = 12.39 Kcal/mole; Hof (NO2) = 8.09 Kcal/mole
Gof (NO) = 20.72 Kcal/mole Hof (NO) = 21.60 Kcal/mole
And S (NO2) = 57.5 cal/mole-deg, So (O2) = 49.0 cal/mole-deg,
o

So (NO) = 50.3 cal/mole-deg

6.a. Nitrogen and Hydrogen react to form ammonia by the reaction;

1/2 N2 (g) + 3/2 H2(g) = NH3(g) H = -11.0 Kcal
A mixture of these gases was in equilibrium. What would be effect upon the amount of
NH3 if
i. The mixture was compressed. [0.5]
ii. Temperature was raised. [0.5]
iii. Inert gas helium was added at constant pressure. [0.5]
iv. Nitrogen was introduced. [0.5]
b. Define the molar heat capacity. Cp is always greater than Cv, justify it. [1+2=3]
c. What do you mean by azeotropic mixture? Illustrate with example. [1]

7.a. State third law of thermodynamics. How does it help to calculate absolute entropy of pure
water at 25oC? [1+2=3]
b. The vapor pressure of ethanol and methanol are 44.5mm and 88.7mm at 20oC if the
solution is prepared by mixing 60gm of ethanol and 40gm of methanol then
i. Calculate the mole fraction of methanol and ethanol.
[1]
ii. Calculate the partial pressure and total pressure of this solution
[1]
iii. Calculate mole fraction of methanol and ethanol in vapor.
[1]

SECTION “C”
Attempt ANY THREE questions. (Question no 8 is compulsory)

8.a. Define the term "electrochemical cell." Deduce the Nernst equation for electrochemical
cell. [1+3=4]
b. A mixture of N2O4 and NO2 has at equilibrium a total pressure of 1.5 atm. What fraction of
N2O4 has dissociated to NO2 at 25oC. (Kp = 0.14) [2]
 c. A Non-ideal solution formed upon the mixing of two components is accompanied by
evolution of heat. Discuss if briefly. [3]

9.a. Define the acidic buffer solution. Derive an expression relating the POH of the buffer
solution with the concentration of its components. [1+3=4]
b. The solubility product of Ag2CrO4 in the pure water is 0.78 x 10-4 M. Calculate its solubility
in 0.05M AgNO3 solution. [2]
c. Discuss briefly the electrochemical theory of corrosion of iron and its prevention. [2]

10.a. Define the term "entropy change". Derive an expression for the entropy changes for the
ideal gases with temperature and volume changes. [1+3=4]
b. What is the conjugate acid-base pair? Explain with suitable examples. [2]
c. What is the salt bridge? What is its significance? [2]

11.a. Obtain a relation to show that boiling point of a solution elevate with its concentration. [3]
b. Define the hydrolysis. Establish a relation:
Kh = Kw/Kb where Kh, Kw and Kb have their usual meanings. [1+2=3]
+
c. Calculate the concentration of H3O in the equilibrium with a pure solution of NH4Cl whose
chloride ion concentration is 0.1M. (Kh = 5.6x10-10 ) [2]

12. Attempt any TWO [4+4=8]

a. Homogeneous and heterogeneous catalysis.
b. Acid-base titrations.
c. Steady-state approximation.
d. Hess' law of constant heat summation.
e. Phase equilibria and its important features.
Answer KEY

Question no / Answer Question no / Answer

1. [b] 64 11. 40 mL
K 2 [E o ] [S] 12. Azeotrope
2. [c] V =
Km + [S] 13. 1.4 X 10-11
3. [b] HCO3 - 14. Constants increases
4. [d] Precipitation will occur 15. 0.166 M
5. [ d ] 0.27 atm 16. 8 times
6. [ a ] 30 mins. 17. Fe+2
7. [ a ] 1.4 × 10-5 M 18. - 13.5 Kcal
8. [ d ] Remain un changed 19. is less
9. [ b ] Shift towards more amount of NO and O2 20. Absorption of heat
1.0 [ c ] Decreases as temperature increases.