1. What is lanthanoid contraction?

What is its effect on the chemistry of the elements which follow the
lanthanoids?

2. Why is Cr2+ reducing and Mn3+ oxidising when both have d4 configuration?
3. Write the formula of the following complexes:
i. Hexaammine platinum (IV) chloride.
ii. Dichloro tetrammine cobalt (III) ion.
iii. Potassium tetrahydroxo sincate (II)
iv. Potassium trioxalatoaluminate (III)
v. Dichloridobis cobalt III (ethane - 1, 2 diamine)

4. Answer the following: [2]

(a) a. Write the mathematical relation between rate constant and half-life of a first order reaction.
b. What is collision frequency?
(b) If the rate equation is given below:
Rate = k[A]2[B], then what will be the unit of its rate and rate constant?

5. i. Determine the units of rate constant for first and zero order reaction.
ii. Show that time required for the completion of 99% of the first order reaction is twice the 90% of completion of
the reaction.

6. The vapour pressure of pure benzene at a certain temperature is 0.850 bar. A non-volatile, non-electrolyte solid
weighing 0.5 g when added to 39.0 g of benzene (molar mass 78 g mol-1). Vapour pressure of the solution, then, is
0.845 bar. What is the molar mass of the solid substance?

OR
Calculate the osmotic pressure in pascals exerted by a solution prepared by dissolving 1.0 g of polymer of molar
mass 185,000 in 450 mL of water at 37°C.

7. Predict the products formed when cyclohexanecarbaldehyde reacts with following reagents.
i. PhMgBr and then H3O+
ii. Tollens' reagent
iii. Semicarbazide and weak acid
iv. Excess ethanol and acid
v. Zinc amalgam and dilute hydrochloric acid

8. Calculate the emf of the following cell:

Mg(s)|Mg2+(0.2M) || Ag+(1 x 10-3M) | Ag(s)
E0(Ag+/Ag) = 0.80V
E0(Mg2+/Mg) = - 2.37V

9. Arrange the following compounds in the increasing order of their property indicated:
i. Acetaldehyde, Benzaldehyde, Acetophenone, Acetone (Reactivity towards HCN)
ii. (CH3)2CHCOOH, CH3CH2CH (Br)COOH, CH3CH(Br)CH2COOH (Acidic strength)
iii. CH3CH2OH, CH3CHO, CH3COOH (Boiling point)

10. The first order rate constant for the decomposition of ethyl iodide by the reaction
C2H5I(g) → C2H4(g) + HI(g)
At 600 K is 1.60 x 10-2 s-1. Its energy of activation is 209 kJ/mol. Calculate the rate constant of the reaction at 700
K.

11. Give equations of the following reactions:

i. Oxidation of propan-1-ol with alkaline KMnO4 solution.
ii. Bromine in CS2 with phenol.
iii. Dilute HNO3 with phenol.
iv. Treating phenol with chloroform in presence of aqueous NaOH.

OR
Write the structures of the major products expected from the following reactions:
a. Mononitration of 3-methylphenoI
b. Dinitration of 3-methylphenol
c. Mononitration of phenyl methanoate

12. Consider a certain reaction A Products with k = 2.0 10-2 s-1. Calculate the concentration of a remaining after
100 s if the initial concentration of A is 1.0 mol L-1.

13. One half-cell in a voltaic cell is constructed from a silver wire dipped in silver nitrate solution of unknown
concentration. The other half-cell consists of a zinc electrode in 1.0 M solution of Zn (NO3)2. A voltage of 1.48 V
is measured for this cell. Use this information to calculate the concentration of silver nitrate solution.

[Given, E∘ Zn2+/Zn = −0.763V and E∘ Ag+/Ag = +0.80V].

14. Tert-Butylbromide reacts with aq. NaOH by SN1 mechanism while n-butylbromide reacts by SN2 mechanism.
Why?

15. State Kohlrausch's law of independent migration of ions. How can the degree of dissociation of acetic acid in a
solution be calculated from its molar conductivity data?
16. If the density of some lake water is 1.25 g mL-1 and contains 92 g of Na+ ions per kg of water, calculate the molarity
of Na+ ions in the lake.

OR
a. Differentiate between Ideal solution and Non-ideal solution.

b. 30 g of urea is dissolved in 846 g of water. Calculate the vapour pressure of water for this solution if vapour
Pressure of pure water at 298 K is 23.8 mm Hg.

17. How much charge is required for the following reductions?

i. 1 mol of Al3+ to Al?
ii. 1 mol of Cu2+ to Cu?
iii. 1 mol of MnO4− to Mn2+?

18. The rate constant for a first order reaction is 60s-1. How much time will it take to reduce the concentration of the
reactant to 1/10 th its initial value?

19. The decomposition of NH3 on platinum surface is zero order reaction. What are the rates of production of
N2 and H2 if k = 2.5× 10−4 mol−1 Ls−1

20. What are fuel cells? Explain the electrode reactions involved in the working of H2 - O2 fuel cell.

21. Read the following text carefully and answer the questions that follow:

a. A raw mango placed in concentrated salt solution loses water via osmosis and shrivel into pickle. Wilted flowers
revive when placed in fresh water. A carrot that has become limp because of water loss into the atmosphere can be
placed into the water making it firm once again. Water will move into its cells through osmosis. When placed in
water containing less than 0.9% (mass/volume) salt, blood cells swell due to flow of water in them by osmosis.

i. People taking a lot of salt or salty food suffer from puffiness or edema. What is the reason behind this?

ii. The preservation of meat by salting and of fruits by adding sugar protects against bacterial action. How?
iii. Why the direction of osmosis gets reversed if a pressure larger than the osmotic pressure is applied to the
solution side? Write its one application.

OR

What care is generally taken during intravenous injections and why?

b. Aariv Sharma is very fond of a special drink made by his grandmother using different fruits available in their
hometown. It has an outstanding taste and also provide great health benefits of natural fruits. He thought of
utilizing his grandmother recipe to create a new product in the beverage market that provide health benefits and
also contain fizziness of various soft drinks available in the market.

i. How he can add fizz to the special drink made by his grandmother?

ii. What is the law stated in the chapter that can help Aariv to make his drink fizzy?

iii. What precautions he should take while bottling so that his product does not lose fizz during storage and
handling across long distances?

OR

The mole fraction of helium in a saturated solution at 20oC is 1.2 10-6. Find the pressure of helium above the
solution. Given Henry’s constant at 20oC is 144.97 kbar.

c. i. Due to the removal of an electron from the stable d10 configuration of Zn2+.

ii. Transition metals despite having high E° oxidation, are poor reducing agents because of their high heat of
vaporization, high ionisation energies and low heats of hydration.

iii. Cr2+ is reducing as its configuration changes from d4 to d3, the having a half-filled t2g level. On the other
hand, the change from Mn3+ to Mn2+ results in the half-filled (d5) configuration which has extra stability.

OR

The Stability of Cu2+ is more than Cu+ as stability depends on the hydration energy of the ions when they bond to
the water molecules. The Cu2+ ion has a greater charge density than Cu+ ion and thus forms much stronger bonds
releasing more energy.

d. The solutions which boil at a constant temperature like a pure liquid and possess the same composition in liquid,
as well as vapour state are called azeotropes. The components of azeotropes cannot be separated by fractional
distillation. Only non-ideal solutions form azeotropes. Solutions with negative deviation form maximum boiling
azeotrope and the solutions with positive deviation form minimum boiling azeotrope. The boiling point of
azeotrope is never equal to the boiling points of any of the components of the azeotrope.

i. The azeotropic solutions of two miscible liquids show what type of deviation from Raoult's law? (1)

ii. The azeotropic mixture of water & HCI boils at 108.5 C. What type of deviation is shown by the solution? Does
this solution behave as ideal or non-ideal? (1)

iii. Do ideal solutions form azeotropes? (2)

OR

Out of pure liquid and azeotrope showing positive deviation, which one has a higher boiling point?

e. Many chemical and biological processes depend on osmosis, the selective passage of solvent molecules through
the porous membrane from a dilute solution to a more concentrated one. The osmotic pressure depends on molar
concentration of the solution ( 𝜋= CRT). If two solutions are of equal solute concentration and, hence, have the
same osmotic pressure, they are said to be isotonic. If two solutions are of unequal osmotic pressures, the more
concentrated solution is said to be hypertonic and the more diluted solution is described as hypotonic. Osmosis is
the major mechanism, for transporting water upward in the plants. Transpiration is the leaves supports the transport
mechanism of water. The osmotic pressure of seawater is about 30 atm; this is the pressure that must be applied to
the seawater (separated from pure water using a semi-permeable membrane) to get drinking water.

i. What will happen if a plant cell kept in a hypertonic solution? (1)

ii. Blood cells are isotonic with 0.9% sodium chloride solution. What happens if we place blood cells in a solution
containing in 1.2% sodium chloride solution? (1)

iii. What happens when the external pressure applied becomes more than the osmotic pressure of solution? (2)

OR

Which mechanisms helps in the transportation of water in a plant? (2)

22. Attempt any five of the following: [5]

(a) Define native state in reference to proteins. [1]
(b) Define the following terms:
a. Polysaccharides
b. Nucleotides
(c) Deficiency of which vitamin causes scurvy? [1]
(d) What happens when D-glucose is treated with the following? Give equations to support your answer.
a. HI
b. HNO3
(e) Name the disaccharide which on hydrolysis gives glucose and galactose. [1]
(f) Write the products obtained after hydrolysis of lactose. [1]
(g) Give the reaction of glucose with hydrogen cyanide. Presence of which group is confirmed by this reaction?

23. Attempt any five of the following: [5]

(a) What is the structural feature characterising reducing sugars? [1]
(b) What type of linkage is present in polysaccharides? [1]
(c) Give examples of fat soluble vitamins. [1]
(d) The two strands in DNA are not identical but are complementary. Explain. [1]
(e) Write uses of B-Complex. [1]
(f) Name the disaccharide which on hydrolysis gives two molecules of glucose. [1]
(g) Name purines present in DNA?

24. Give the oxidation state, d-orbital occupation and coordination number of the central metal ion in the following
complexes:
i. K3 [Co(C2O4)3]
ii. cis−[Cr(en)2Cl2]Cl
iii. (NH4)2 [CoF4]
iv. [Mn(H2O)6]SO4

OR
Write the formulas for the following coordination compounds:
a. Tetraammineaquachloridocobalt(III) chloride
b. Potassium tetrahydroxidozincate(II)
c. Potassium trioxalatoaluminate(III)
d. Dichloridobis(ethane-1, 2-diamine)cobalt(III)
e. Tetracarbonylnickel(0)

25. Write the IUPAC names of the following coordination compounds:

a. [Pt (NH3)2Cl NO2]
b. K3 [Cr (C2O4)3]
c. [Co Cl2 (en)2]Cl
d. [Co (NH3)5 (CO3)]Cl
e. Hg [Co (SCN)4]

OR

Using Valence bond theory, explain the following in relation to the paramagnetic complex Mn(CN)6]3-

a. type of hybridisation
b. magnetic moment value
c. type of complex - inner, outer orbital complex

26. Draw all the isomers of: (geometrical and optical)

i. [CoCl2(en)2]+
ii. [Co(NH3)Cl(en)2]2+
iii. [Co(NH3)2Cl2(en)]+

OR
Using crystal field theory, draw energy level diagram, write the electronic configuration of the central metal atom/ion
and determine the magnetic moment value in the following:
i. [CoF6]3-, [Co(H2O)6]2+, [Co(CN)6]3-
ii. [FeF6]3-, [Fe(H2O)6]2+, [Fe(CN)6]4-

27. i. Write structures of different isomeric amines corresponding to the molecular formula, C4H11N.
ii. Write IUPAC names of all the isomers.
iii. What type of isomerism is exhibited by different pairs of amines?

OR
Arrange the following compounds in a decreasing order of basic strength in their aqueous solutions.
NH3, CH3NH2, (CH3)2NH, (CH3)3N

28. i. Illustrate the following reactions giving suitable example in each case:
a. Ammonolysis
b. Coupling reaction
c. Acetylation of amines

ii. Describe Hinsberg method for the identification of primary, secondary and tertiary amines. Also, write the
chemical equations of the reactions involved.

29. An organic compound A with molecular formula C7H7NO reacts with Br2/aq. KOH to give compound B, which
upon reaction with NaNO2 and HCl at 0oC gives C. Compound C on heating with CH3CH2OH gives a hydrocarbon D.
Compound B on further reaction with Br2 water gives white precipitate of compound E. Identify the compound A, B, C,
D and E; also justify your answer by giving relevant chemical equations.

OR
i. Write one chemical reaction for each
a. Carbylamine reaction
b. Acetylation reaction
ii. Write structure of N,N-ethylmethylethanamide

30. Using IUPAC norms write the formulas for the following:
a. Tetrahydroxozincate(II)
b. Potassium tetrachloridopalladate(II)
c. Diamminedichloridoplatinum(II)
d. Potassium tetracyanonickelate(II)
e. Pentaamminenitrito-O-cobalt(III)
f. Hexaamminecobalt(III) sulphate
g. Potassium tri(oxalato)chromate(III)
h. Hexaammineplatinum(IV)
i. Tetrabromidocuprate(II)
j. Pentaamminenitrito-N-cobalt(III)