SOLUTION

1. Write the differences between ideal and non-ideal solution

Ideal solution Non ideal solution showing -ve deviation
∆Hmix = 0 ∆Hmix ≠ 0
∆Vmix = 0 ∆Vmix ≠ 0
The solutions which obey Raoult’s law Solution does not obey Raoult’s law
Solutions do not form azeotropes. Solutions form azeotropes.
Ex: Benzene and Toluene Ex: phenol and aniline
2. Write the differences between non-ideal solution showing positive and negative deviation.

Non ideal solution showing Non ideal solution showing

+ve deviation -ve deviation
∆Hmix = +ve ∆Hmix = -ve
∆Vmix = +ve ∆Vmix = -ve
Solute-solvent intermolecular forces are Solute-solvent intermolecular forces are
weaker than those between solute-solute stronger than those between solute-solute
and solvent-solvent. and solvent-solvent.
It forms minimum boiling azeotropes It forms maximum boiling azeotropes
Ex: n-heptane and ethanol Ex: phenol and aniline
3. State Henry’s law and write its mathematical form.
“The partial pressure of the gas above the solution is directly proportional to the mole traction of the gas
in the solution”

4. Write any two applications of Henry’s law:

a. Aquatic species are more comfortable in cold water than warm streams because there is more
dissolved oxygen in such cold water.
b. It is used to increase the solubility of CO2 in soft drinks and soda water, as the bottle is sealed under
high pressure.
5. State Raoult’s law and write its mathematical form.
“In a solution of volatile liquids, the partial vapour pressure of each component is directly proportional to
its mole fraction in the solution at a given constant temperature.”

6. Factor affecting the solubility of a solid in a liquid

a. Effect of temperature: If the ∆H of solution is positive i.e. endothermic process, increase in
temperature increases the solubility.
If the ∆H of solution is negative i.e. exothermic process, increase in temperature
decreases the solubility.
b. Effect of pressure: Pressure has no effect on the solubility of solid solutes in a liquid.
7. Factor affecting the solubility of a gas in a liquid
a. Temperature: Solubility of a gas in a liquid generally decreases with increase in temperature. This is
because, in general, gases dissolve in a liquid with evolution of heat i.e. exothermic process.
b. Pressure: The solubility of a gas in a liquid is very much affected by pressure, if the pressure of the
gas above the liquid surface increases then, the solubility of the gas also increases.
8. Define Molarity.
Molarity of a solution is defined as the number of moles of the solute dissolved per litre
(1000cc) of the solution. SI unit of molarity is moles per litre (mol L-1)

9. Define Molality.
Molality of a solution is defined as the number of moles of a solute dissolved in 1kg of the
solvent. SI unit of molality is molkg-1.

10. What is Osmosis?

Movement of solvent molecules from solution of lower concentration to the solution of higher
concentration through the semipermeable membrane.
11. What is Reverse osmosis? Give one application.
If a pressure larger than the osmotic pressure is applied to the solution side, the pure solvent flows out
of the solution (higher concentration) through the semi permeable membrane. This phenomenon is
called reverse osmosis. Reverse osmosis is used in desalination of sea water.
12. What is Semi permeable membrane? Give one example each for natural and synthetic SPM.
The membrane which allows only solvent molecules to pass through it but not the solute molecules.
Example: Natural - pig bladder,
Synthetic - cellulose acetate.
13. What is Osmotic pressure?
The minimum pressure applied to the solution in order to prevent the process of osmosis.
14. What are Isotonic solutions? Give example
Two solutions having same osmotic pressure at a given temperature are called isotonic solutions.
Example: blood cell is isotonic with 0.9% sodium chloride solution.
15. What is Hypertonic solution?
The solution having more osmotic pressure than other is called hypertonic solution.
Example: More than 0.9% saline is hypertonic with blood cell (blood cell shrinks)
16. What is Hypotonic solution?
The solution having less osmotic pressure than other is called hypotonic solution
Example: Less than 0.9% saline is Hypotonic with blood cell (blood cell swells)
17. Define Azeotropes and explain the types.
Binary mixtures having the same composition in liquid and vapour phase and boil at a constant
temperature are called azeotropes.
➢ The solutions which show a large positive deviation from Raoult’s law form
minimum boiling azeotrope at a specific composition.
Ex: 95% by volume of ethanol-5%water, with a boiling point of 78.5℃
➢ The solutions that show large negative deviation from Raoult’s law form
maximum boiling azeotrope at a specific composition.
Ex: 68% nitric acid and 32% water by mass, with a boiling point of 393.5 K.
18. Define Colligative Properties and write the names of all Colligative Properties.
Properties depend on the number of solute particles irrespective of their nature
➢ Relative lowering of vapour pressure of the solvent
➢ Depression of freezing point of the solvent
➢ Elevation of boiling point of the solvent
➢ Osmotic pressure of the solution.
19. What is van’t Hoff factor (i)

i = 1 No Dissociation or Association. Examples: urea, glucose.

i > 1 Dissociation. Example: sodium chloride
i < 1 Association. Example: acetic acid in benzene
20. Write the SI unit of Cryoscopic Constant Kf and Ebullioscopic Constant Kb.
K kg mol−𝟏

NUMERICALS
21. On dissolving 2.34 g of solute in 40 g of benzene the boiling point of solution was higher than that of
benzene by 0.81 K. Kb value of benzene is 2.53 K kg mol-1. Calculate molar mass of solute.
Ans:
𝑊 1000
∆Tb = 𝑀2 x x Kb
2 𝑊1
1000 2.34
0.81 = x x 2.53
40 𝑀2
1000 2.34
M2 = x 0.81 x 2.53
40
= 182.72 g mol-1
22. 31 g of unknown mol.mass material is dissolved in 500 g of water the resulting solution freezer at 271.14
K calculate molar mass of the material given Kf of water 1.86 K Kg mol-1. Freezing point of water = 273
K.
Ans:
∆Tf = 𝑇𝑓𝑜 - 𝑇𝑓
= 273 – 271.14
= 1.86
1000 𝑊
∆Tf = x 𝑀2 x Kf
𝑊1 2
1000 31
= x x 1.86
500 𝑀2
1000 𝑋 31 𝑋 1.86
M2 = 500 𝑋 1.86
= 62 g mol-1
23. Calculate the Osmotic pressure at 273 K of a 5% (W/V) solution of urea. (molar mass 60), R = 0.0821
L atm K-1 mol-1.
Ans:
𝑊 1
T1 = 𝑀2 x 𝑉 x R X 7
2
5 1
= 60 x 0.1 x 0.0821 X 273
= 18.677 atm
24. 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 of benzene (molar mass 78g mol-1). Vapour pressure of solution
then is 0.845 bar. What is the molar mass of solid substance.
Ans:
0
𝑃1− 𝑃1 𝑊2 𝑀1
= x
𝑃10 𝑀2 𝑊1
0.850−0.845 0.5 78
= 𝑀 x 39
0.850 2
0.005 0.5 78
= 𝑀 x 39
0.850 2
0.5 78
M2 = 0.005 x 39 x 0.850
= 170 g mol-1.
 Unit  3  

Electrochemistry  
One  mark  questions  

1. What  is  an  electrolyte?  

An  electrolyte  is  a  compound  which  conducts  electricity  either  in  its  aqueous  solution  or  in  its  molten  
state.  
e.g    Acids    HCl,  CH3COOH,  HNO3  
                   Bases    NaOH,  NH4OH  
                   Salts        CuSO4,  NaCl    etc    
 
2. Define  conductivity  of  an  electrolytic  solution.  
Conductivity  of  a  solution  of  an  electrolyte  is  the  conductance  of  a  solution  placed  between  two  
electrodes  each  of  one  square  meter  area  kept  at  a  distance  of  1  meter  apart.  
 
3. Write  the  S.I  unit  for  conductivity.  
SI  unit  for  conductivity  is  Sm-­‐1.  
 
4. Give  the  S.I  unit  for  molar  conductivity.  
Sm2  mol-­‐1  
 
5. State  Kohlrausch    Law.  
The  limiting  molar  conductivity  of  an  electrolyte  can  be  represented  as  the  sum  of  the  individual  
contributions  of  the  anion  and  cation  of  the  electrolyte.  
 
6. Define  electrode  potential.  
The  potential  difference  developed  between  the  electrode  (metal)  and  the  electrolyte  (solution  
containing  its  own  ions)  when  both  the  metal  and  the  solution  are  in  equilibrium  is  called  electrode  
potential.  
 
7. Define  standard  electrode  potential.  
Standard  electrode  potential  is  the  electrode  potential  when  the  concentrations  of  all  the  species  
involved  is  unity  (1M)  and  if  a  gas  is  involved  its  pressure  should  be  1  bar.      
 
8. Write  Nernst  Equation.  
0.059 1
E( = E o( - log10  
M n+ / M) M n+ / M)
n ⎡⎣M n+ ⎤⎦
 
9. State  Faradays  second  law  of  electrolysis.  
The  amounts  of  different  substances  liberated  by  the  same  quantity  of  electricity  passing  through  the  
electrolytic  solution  are  proportional  to  their  chemical  equivalent  weights.  
10. Define  cell  potential.  
Cell  potential  is  the  potential  difference  between  the  two  electrodes  of  the  galvanic  cell.  
 
11. Define  EMF  of  the  cell.  
It  is  the  difference  between  the  electrode  potential  of  the  cathode  and  anode  when  no  current  is  
drawn  through  the  cell.  
 
12. What  is  Fuel  cell?  
Galvanic  cells  that  are  designed  to  convert  the  energy  of  combustion  of  fuels  like  hydrogen,  methane  
etc  directly  into  electrical  energy  are  called  fuel  cells.  
 
13. Give  a  method  to  prevent  rusting.  
Rusting  may  be  prevented  by  barrier  protection  like  painting,  metal  plating  etc.  
 
14. Write  the  relationship  between  cell  potential  and  Gibb’s  energy  

                                                                    Δ r G o = − nFE o cell  
15. Write  the  relationship  between  equilibrium  constant  and  Eocell  
0.059V
E o cell = log K c    
n

2  mark  questions  

1. What  are  redox  reactions?  Give  an  example.  

Reactions  in  which  both  oxidation  and  reduction  taken  place  simultaneously  are  called  redox  reactions.  
e.g         Zn + Cu2+ ⎯⎯ → Zn2+ + Cu  
 In  this  Zn  is  oxidised  to  Zn2+                            Cu2+  is  reduced  to  Cu  
 
2. Mention  any  two  factors  on  which  the  conductivity  of  an  electronic  conductor  depends.  
The  electronic  conductance  depends  on    
(i) The  nature  and  structure  of  the  metal  
(ii) The  number  of  valence  electrons  per  atom.  
(iii)  Temperature  (it  decreases  with  increase  in  the  temperature)  (any  two)  
 
3. Mention  any  two  factors  on  which  the  conductivity  of  an  electrolytic  conductor  depends.  
The  conductivity  of  electrolytic  solution  depends  upon    
(i)    The  nature  of  the  electrolyte  
(ii)    Size  of  the  ions  produced  and  their  solvation.  
(iv) The  nature  of  the  solvent  and  its  viscosity.  
(iv)    Concentration  of  the  electrolyte  and  
 (v)  Temperature  (increases  with  increase  in  temperature  (any  two)  
 
4. Give  two  difference  between  the  conductivity  of  an  electronic  conductor  and  electrolytic  conductor.  
 
1.  On  passing  direct  current  composition  of  electronic  conductor  does  not  change  but  that  of    
         electrolytic  conductor  changes.  
2.  On  increasing  the  temperature  in  case  of  electronic  conductor  conductivity  decreases  in  case  of    
         electrolytic  conductor  conductivity  increases.  
 
5. What  is  a  strong  electrolyte?  Give  an  example.  
A  strong  electrolyte  is  an  electrolyte  that  dissociates  completely  into  ions  at  moderate  concentrations  
of  its  aqueous  solution  
Ex:  acids  HCl,  H2SO4,  HNO3  
Base  NaOH,  KOH  
Salts  NaCl,  CuSO4  (any  salt)  
 
6. What  is  a  weak  electrolyte?  Give  an  example.  
A  weak  electrolyte  is  an  electrolyte  that  dissociates  partially  into  ions  in  its  aqueous  solution.  
Ex:  CH3COOH,  NH4OH  
 
7. Define  molar  conductivity.  How  is  it  related  to  conductivity?  
Molar  conductivity  of  a  solution  at  a  given  concentration  is  the  conductance  of  the  volume  V  of  a  
solution  containing  one  mole  of  electrolyte  kept  between  two  electrodes  with  area  of  cross  section  A  
and  distance  of  unit  length.      
It  is  represented  by  λm  
λm  =  kv    where  k  is  conductivity  and  v  is  volume  of  the  solution  containing  1  mole  of  the  electrolyte  
                                                                                                 or  
If  λm    is  in  Sm2mol-­‐1  and  k  in  Sm-­‐1    
k
                                                              λm =          where  C  is  conc.  in  mol  L-­‐1  
1000C
                                                                                         or  
                               When  λm        is  in  S  cm2mol-­‐1  and  k  is  in  Scm-­‐1  
1000k
                                                                                      λm =  
C
 
8. How  does  conductivity  of  a  solution  change  with  change  in  concentration  of  the  solution?  Give  
reason.  
 
Conductivity  of  a  solution  decreases  with  decrease  in  concentration  of  the  solution  due  to  decrease  in  
the  number  of  ions  per  unit  volume  of  the  solution.    
 
 
9. Define  limiting  molar  conductivity.  Write  the  relationship  between  molar  conductivity  and  limiting  
molar  conductivity.  
Limiting  molar  conductivity  is  the  molar  conductivity  of  a  solution  when  concentration  approaches  zero  
or  molar  conductivity  at  infinite  dilution.  
1
λm = λo m - AC 2  where  λ m  is  molar  conductivity  and  λ om  is  limiting  molar  conductivity,  C  is  
concentration  in  mole/L  and  A  is  constant  which  depends  on  nature  of  the  electrolyte,  solvent  and  
temperature.  
 
10. Draw  a  graph  of  molar  conductivity  verses  square  root    of  the  molar  concentration  for  KCl  and  
CH3COOH  mentioning  clearly  each.    

                                                                                     
 
11. How  is  limiting  molar  conductivity  for  a  strong  electrolyte  found  out  by  extrapolation  method?  
Prepare  four  solutions  of  given  strong  electrolyte  of  different  concentrations.  Measure  the  
conductivities  of  each  solutions  using  conductivity  cell  and  calculate  the  molar  conductivities  of  each  
solution.  Plot  a  graph  of  molar  conductivity  verses  square  root  of  the  molar  concentration  for  these  
solutions.  A  straight  line  is  obtained  which  is  to  be  extrapolated  back  so    as  to  touch  the  vertical  axes  
.This  point  of  intersection  on  the  vertical  axes  gives  the  limiting  molar  conductivity.  
 
12. State  and  illustrate  Faradays  first  law  of  electrolysis.  
The  amount  of  chemical  reaction  which  occurs  at  any  electrode  during  electrolysis  by  a  current  is  
proportional  to  the  quantity  of  electricity  passed  through  the  electrolyte  either  through  its  aqueous  
solution  or  molten  state.    
If  w  is  the  mass  of  the  substance  deposited  and  Q  is  the  current  passed  in  coulombs  
                                   w  ∝    Q  
But  Q  =  I  t    where  I  is  the  current  strength  in  ampere  and  t  is  time  in  seconds.  
 
13. Conductivity  of  0.01  M  NaCl  solution  is  0.12  Sm-­‐1.  Calculate  its  molar  conductivity.  
k 0.12
λm = = = 1.2 ×10 -2 Sm 2 / mol  
1000C 1000 × 0.01
 
 
14.  The  molar  conductivity  of  0.1M  nitric  acid  is  630  S  cm2  /mol.  Calculate  its  conductivity.  
 
1000k
λm =
                      C  
1000k
630 =
0.1
630 × 0.1
∴k = = 0.063 Scm-1
1000
 
15. A  solution  of  Ni(NO3)2  is  electrolysed    between  platinum  electrodes  using  a    current  of  5  amperes  for  
20  minutes.    What  mass  of  nickel  is  deposited  at  the  cathode?  (Mol  mass  of  Ni  =  58.7)  
                                                                                                       Q  =  I    t      
                                                                                                             =  5×20×60  =  6000C  
Ni 2 + + 2e - ⎯⎯⎯⎯⎯→ Ni
                                                2 × 96500C  
193000C 58.7g
For  193000C  of  electricity  mass  of  nickel  obtained                                                      =  58.7g  
6000 × 58.7
For  6000C  of  electricity           = 1.812g  
193000
 
16. How  long  it  will  take  for  the  deposition  of    0.2g  of  silver  when  silver  nitrate  solution  is  electrolysed  
using  0.5  ampere  of  current  (Mol  mass  of  Ag  =  108)    
 
Ag + + e - ⎯⎯
→ Ag
 
96500C 108g
For  108g  of  silver  to  be  deposited  current  required  is  96500C.  
For  0.2g  of  Ag    
 
0.2 × 96500
= 178.7C = Q  
But  Q  =  I  t        
108
Q 178.7
t= = = 357.4 se  
I 0.5
17.    The  cell  in  which  the  following  reaction  occurs   2Fe3+ ( aq ) + 2I −( aq ) ⎯⎯
→ 2Fe2+ ( aq ) + I 2( s )  
Has  Eocell  =  0.236V  at  298K.  Calculate  the  standard  Gibb’s  energy  and  the  equilibrium  constant  for  the  
cell  reaction.  
               n  =  2  
                Δ.Go  =  -­‐nFEo    
                                               =  -­‐  2×96500×0.236  
                                                                                                       =  -­‐  45548  J  
0.059
                                                                                  Ecell = log K  
n
 0.059
                                                                              0.236 = log K  
2
2 × 0.236
                                                                                log K = = 8  
0.059
Taking  the  antilog    K  =  108    
 
18. Write  the  reaction  taking  place  at  cathode  and  anode  when  aqueous  solution  of  copper  sulphate  is  
electrolysed  using  copper  electrodes.  
oxdn
A t anode Cu( s ) ⎯⎯⎯ → Cu 2+ ( aq ) + 2e −
                                                     
redn
A t cathode Cu 2+ ( aq ) + 2e − ⎯⎯⎯ → Cu( s )
Thus  copper  from  anode  dissolves  and  an  equivalent  amount  of  pure  copper  is  deposited  on  cathode.  
This  technique  is  used  in  electrolytic  refining  of  crude  copper.    
 
19. Write  the  reaction  taking  place  at  anode  and  cathode  when  molten  NaCl  is  electrolysed.  
When  molten  sodium  chloride  is    electrolysed  using  inert  electrodes  
oxdn
At anode 2Cl − ⎯⎯⎯ → Cl2 + 2e−
                                                     
redn
At cathode Na + + e− ⎯⎯⎯ → Na
Thus  chlorine  gas  is    liberated  at  anode  and  Sodium  metal  is  formed  at  cathode.  
 
20. Write  the  reaction  taking  place  when  aqueous  solution  of  NaCl  is  electrolysed.  
When  aqueous  solution  of  NaCl  is  electrolysed,  
NaCl ⎯⎯
→ Na + + Cl −
                                                                                                                               
H 2O áà àÜ
àà H + OH
+ −

The  reaction  taking  place  at  cathode  is    

1
                                                              H + aq + e− ⎯⎯
→ H 2( g )  
2
The  reaction  taking  place  at  anode  is    
1
                                                  Cl - aq ⎯⎯
→ Cl 2 aq + e -  
2
 
21. What  is  a  primary  battery/cell  ?Give  an  example.  
Primary  battery  is  one  in  which  reaction  occurs  only  once  and  cannot  be  recharged.  Eg  Dry  cell  or  
Leclanche  cell  and  Mercury  cell  
 
22. What  is  a  secondary  battery/cell  ?  Give  an  example.  
Secondary  battery  is  one    which  can  be  recharged  by  passing  current  through  it  in  opposite  direction,so  
that  it  can  be  Reused.  
Eg:    Lead  storage  battery  and  Nickel  cadmium  cell.  
 
 23. EoCu  =  +0.34V  and  EoZn  =-­‐0.76V.  Daniel  cell  is  obtained  by  coupling  these  two  electrodes.  
(i)  represent  the  cell  symbolically  
(ii)  calculate  the  EMF  of  the  cell  
 
(i)  Daniel  cell  can  be  represented  as  
                                                                                                     Zn/  Zn2+  (aq)  ||  Cu2+  (aq)  /Cu  
 
(ii)  EMF  of  Daniel  cell  Eo  cell  =  EoR  -­‐  EoL    
                                                                                                     =  EoCu  -­‐  EoZn  =  0.34-­‐(-­‐0.76)  
                                                                                                     =  1.10V  
 
24. Calculate  the  molar  conductivity  of  a  solution  of  MgCl2  at  infinite  dilution  given  that  the  molar  ionic  
conductivities  of     λo = 106.1 Scm 2 mol -1 and λo( = 76.3 Scm 2 mol -1  
( Mg 2+ ) Cl - )

λ o MgCl 2 = λ o Mg 2+ + 2λ o Cl -
                                                                                                          = 106.1 + 2( 76.3)  
= 258.7 Scm 2 mol -1
 
25. The  resistance  of  a  conductivity  cell  containing  0.001  M  KCl  solution  at  298K  is  1500Ω .  What  is  the  
cell  constant  if  the  conductivity  of  0.001M  KCl  solution  at  298K  is  0.146×10-­‐3  Scm-­‐1?  
 
Cell  constant  G*=  Rk    
                                                       =resistance  ×  conductivity  
                                                       =0.146×10-­‐3  Scm-­‐1×1500S-­‐1  
                                                       =  0.219  cm-­‐1  
 
Question  carrying  3  or  4  marks  
 
1. Explain  the  construction  of  Daniel  cell.  Write  the  reaction  taking  place  at  anode  and  cathode  and  the  net  
cell  reaction.  (3  mark)  
To  prepare  Daniel  cell  get  a  zinc  electrode  by  dipping  zinc  rod  in  1M  ZnSO4  solution.  Get  a  copper  
electrode  by  dipping  a  copper  plate  in  1  M  CuSO4  solution.  Couple  these  two  electrodes  using  a  salt  bridge  
to  get  Daniel  cell.  Reactions  taking  place    
+
oxdn
A t anode Zn ⎯⎯⎯ → Zn 2 + 2e −
redn
At cathode Cu 2+ + 2e− ⎯⎯⎯ → Cu
                                 
2+ 2+
Net cell reaction Zn( s ) + Cu ( aq ) → Zn
⎯⎯ ( aq ) + Cu( s )

 
2. With  a  labeled  digram  explain  standar  hydrogen  electrode.  Represent  it  symbolically.  Write  the  reduction  
reaction  at  the  anode.  What  is  its  electrode  potential?    (4  marks)  
                                                                                     

 
It  consists  of  a    platinum  electrode  coated  with  platinum  black.  The  electrode  is  dipped  in  1M  HCl.  Pure  
hydrogen  gas  is  bubbled  through  it  under  a  pressure  of  1  bar.  S.H.E  is  represented  as    
                                                                                                   Pt(s)  |H2  (g)(1bar)  |H+(aq)(1M)          
The  reduction  reaction  taking  place  is    
1
                                                                                        H + (aq) + e − ⎯⎯
→ H 2 ( g )  
2
S.H.E  is  assigned  an  electrode  potential  of  0.0  V  at  all  temperatures.    
 
3. Explain  the  use  of  standard  hydrogen  electrode  in  measuring  the  standard    electrode  potentials  of  copper  
and  zinc  electrode  (4  mark)  
Construct  a  standard  electrode  of  the  given  metal  by  dipping  the  pure  metal  in  1M  solution  of  its  own  ion  
at  25o  C  Couple  this  standard  electrode  with  SHE  using  a  salt  bridge  to  get  galvanic  cell.  Measure  the  emf  
of  the  cell  using  suitable  instrument  like  potentiometer.  
                             Eo  =  EoR  –  EoL    
One  of  the  electrodes  of  the  cell  is  SHE  and  its  electrode  potential  is  0.0V.  So  the  electrode  potential  of  the  
given  electrode  will  be  the  emf  of  the  cell  in  magnitude.  If  reduction  takes  place  at  the  given  electrode  its  
Eo  will  be  +ve  but  if  oxidation  takes  place  at  the  given  electrode  is  Eo  will  be  –ve.    
e.g  if  SHE  is  coupled  with  standard  copper  electrode  reduction  takes  place  at  copper  electrode  cell  can  be  
represented  as  
   Pt  (s)  |H2(g.  1bar)|H+(aq1M)||Cu2+(aq.1M)|Cu  
E o cell = E o Cu 2+ / Cu - E o H + / H  
2

0.34 = E o
Cu 2+ / Cu
-0 ∴ E oCu 2+ / Cu = 0.34V          
 If  SHE  coupled  with  standard  zinc  electrode  oxidation  takes  place  at  zinc  electrode.  Cell  can  be  
represented  as    
 Zn2+ ( aq.1M ) / Zn( s ) ⏐⏐Pt( s )⏐H 2( g .1bar )⏐H + ( aq.1M )  
E ocell = E o H + / H − E o Zn2+ / Zn  
2

o
0.76 = 0 − E Zn2+ / Zn
∴ EZn2+ / Zn = −0.76V  
 
4. How  is  Kohlrausch  law  helpful  in  finding  out  the  limiting  molar  conductivity  of  a  weak  electrolyte?  (3  m)  
Let  us  try  to  calculate  λom  for  a  weak  electrolyte  CH3COOH.  Select    three  strong  electrolytes  whose  λom  can  
be  found  by  extrapolation  method  in  such  a  way  that  if  we  subtract  λom  for  one  electrolyte  from  the  sum  
of  λoms  of  the  remaining  two  electrolyte  λom  for  CH3COOH  can  be    obtained.  The  three  electrolytes  to  be  
selected  are  CH3COONa,  HCl  &  NaCl  
                                    λo CH = λo CH3COONa + λo HCl - λo NaCl  
3 COOH

 
5. The  values  of  limiting  molar  conductivities  (λ om)  for  NH4Cl,  NaOH  and  NaCl  are  respectively  149.74;  248.1  
and  126.4  Scm2mol-­‐1.  Calculate  the  limiting  molar  conductivity  of  NH4OH      (3M)  
                                                                        λo NH = λo NH 4Cl + λo NaOH - λo NaCl  
4 OH

                                                                                                         =  149.74+248.1-­‐126.4  
                                                                                                         =  271.44  Scm2  mol-­‐1    
→ Cu 2+( aq ) + 2 Ag( s )  
6. Calculate  the  equilibrium  constant  for  the  reaction  at  298K   Cu( s ) + 2 Ag + (aq) ⎯⎯
Given  that  Eo  Ag+/Ag  =  0.80V  and    Eo(Cu2+/Cu)  =  0.34V  
0.059
                                                      E o cell = log K c  
n
nE o cell
                                               ∴ log K c =  
0.059
                                                            E o cell = E o + − E o(Cu2+ /Cu )  
( Ag / Ag )

                                                                                 =0.80-­‐0.34=0.46V  
2 × 0.46
                                                      log K c = = 15.59  
0.059
                         Taking  the  antilog  Kc  =3.92×1015        
 
7. In  Leclanche  cell  (dry  cell)  what  are  anode  and  cathode?  What  is  the  electrolyte  used?  Write  the  reactions  
at  each  electrode.  What  is  the  role  of  zinc  chloride?  
 
It  consists  of  a  zinc  container  as  an  anode.  A  graphite  rod  surrounded  by  a  mixture  of  manganese  dioxide  
and  carbon  powder  is  cathode.      
The  space  between  the  electrodes  is  filled  with  electrolyte  a  moist  paste  of  ammonium  chloride  and  zinc  
chloride  
 
 
 
 Reaction  taking  place  
At anode Zn( s) ⎯⎯
→ Zn 2+ + 2e -  
At cathode MnO 2 + NH 4 + + e - ⎯⎯
→ MnO( OH) + NH 3  
NH3  produced  in  the  reaction  forms  a  complex  with  Zn2+  to  form  [Zn(NH3)4]2+.  
 
8. What  are  the  anode  and  cathode  of  lead  acid  battery?  What  is  the  electrolyte?  Write  the  reactions  taking  
place  at  anode  and  cathode  and  the  overall  reaction  during  discharging  of  the  battery.  (3  M)  
It  consists  of  lead  anode  and  a  grid  of  lead  packed  with  lead  dioxide  (PbO2)  as  cathode.    
Electrolyte  is  38%  solution  of  sulphuric  acid.  The  reactions  taking  place  when  the  battery  is  in  use  are    
Anode Pb( s ) + SO4 2− ( aq ) ⎯⎯
→ PbSO4( s ) + 2e−
                                                     
Cathode PbO2 ( s) + SO4 2− ( aq ) + 4 H + ( aq ) + 2e− ⎯⎯
→ PbSO4 ( s ) + 2 H 2O (l )

The  overall  reaction  is   Pb( s ) + PbO2 ( s) + 2H 2 SO4 ( aq ) → 2PbSO4

⎯⎯ ( s) + 2 H 2O (l )
 
 
9. In  Hydrogen  oxygen  fuel  cell  (i)  Draw  the  schematic  diagram  mentioning  the  anode  and  cathode.  What  is  
the  electrolyte?  Write  the  reaction  taking  place  at  each  electrodes  and  the  net  cell  reaction.  (4M)  

                                                                                                                   
In  this  hydrogen  and  oxygen  gases  are  bubbled  through  porous  carbon  electrodes  into  concentrated  
aqueous  sodium  hydroxide  solution.  Catalyst  like  finely  divided  platinum  or  palladium  is  incorporated  into  
the  electrodes  for  increasing  the  rate  of  electrode  reaction    
Reaction  taking  place  are  
Cathode O 2 ( g)+ 2H 2 O ( l)+ 4e - ⎯⎯
→ 4OH -( aq)
 
Anode 2H 2( g) + 4OH (
-
aq) → 4H 2 O( l) + 4e -
⎯⎯
Overall  reaction  is    
2H 2 ( g)+ O2 ( g) ⎯⎯
→ 2H 2O ( l)  
 
10. What  is  corrosion?  During  rusting  of  iron  write  the  anodic  and  cathodic  reactions.  Give  the  composition  
of  rust.  (3M)  
When  a  metal  is  exposed  to  the  atmosphere  it  is  slowly  attacked  by  the  constituents  of  the  environment  
as  a  result  of  which  the  metal  is  slowly  lost  in  the  form  of  its  compound  .  This  is  called  corrosion.    
 
Reaction  taking  place  are  
At Anode 2Fe( s) → 2Fe 2+ + 4e -
⎯⎯
 
At Cathode O 2 ( g)+ 4H +( aq)+ 4e - ⎯⎯
→ 2H 2O( l)

H  are  produced  from  H2CO3  formed  due  to  dissolution  of  carbon  dioxide  from  air  into  water  The  Fe2+  ions  
+

are  further  oxidised  by  atmospheric  oxygen  to  ferric  ion  which  are  ultimately  converted  to  hydrated  ferric  
oxide  called  rust.  Composition  of  rust  is  (Fe2O3.xH2O).    
 
11. A  conductivity  cell  when  filled  with    0.01M  KCl  has  a  resistance  of  747.5  ohm  at  25oC.  When  the  same    
cell  was    filled  with  an  aqueous  solution  of    0.05M  CaCl2  solution  the  resistance    was  876  ohm.  Calculate    
(i)    Conductivity  of  the  solution  
(ii  )Molar  conductivity  of  the  solution            (given  conductivity  of  0.01M  KCl  =  0.14114  sm-­‐1)                                (3M)  
 
Cell  constant  G*  =  Rk    
                                                         =  747.5×0.14114  
                                                         =0.105.5m-­‐1    
cell constant 105.5m -1
Conductivity k = = = 0.1204Sm -1  
R 876 ohm
k 0.1204
Molar conductivity λm = = = 0.00241sm 2 mol -1  
1000C 1000 × 0.05
12. The  electrical  resistance  of  a  column    of  0.05M  NaOH  solution  of  diameter  1cm  and  length  50cm  is  
5.55×103  ohm.  Calculate  its  
 (i)  resistivity  
 (ii)  conductivity  
 (iii)  molar  conductivity                                    (3M)  
l
Cell  constant   G o =  
a
l  =  50  cm  
Diameter  =  1  cm  ∴  radius  =  0.5  cm  
Area  of  cross  section  A  =  πr2  =  3.14×(0.5)2      =  0.785  cm3  
 

                                                                                                                                                                   G * 50
= = 63.694 cm -1  
0.785
 1 1
Resistivity ρ = = = 87.135 Ω  
k 1.148 ×10 -2
1000k
Molarconductivityλm =
C
1000 ×1.148 ×10 -2
=  
0.05
= 229.6 S cm 2 mol -1
13. Calculate  the  emf  of  the  cell  in  which  the  following  reaction  takes  place.  
→ Ni 2+ (0.160M ) + 2 Ag( s )  
Ni( s ) + 2 Ag + (0.002M ) ⎯⎯
 
Given  that  Eocell  =  1.05V    
0.059 [ Ni 2+ ][ Ag( s ) ]2
Ecell = E o cell − log10  
2 [ Ni( s ) ][ Ag + ]2
But  [M]  for  any  element  is  taken  as  unity  
 
0.059 ⎡Ni ⎤⎦ 2+

E cell = E o
cell - log10 ⎣  
2 + 2
⎡⎣ Ag ⎤⎦
0.059 0.160
= 1.05 - log  
2 (0.002 )
2

=  0.914V  
 
 
 
 
 
 
 
 
 d AND f- BLOCK ELEMENTS

1. Explain the method of preparation of POTASSIUM DICHROMATE: (K2Cr2O7) by Chromite ore.

4FeCr2O4 + 8Na2CO3 + 7O2 → 8Na2CrO4 + 2Fe2O3 + 8CO2

2Na2CrO4 + 2H+ → Na2Cr2O7 + 2Na+ + H2O

Na2Cr2O7 + 2KCl → K2Cr2O7 + 2NaCl

2. Explain the method of preparation of POTASSIUM PERMANGANATE: (KMnO4) by pyrolusite ore.

3. What is Lanthanide contraction and write Consequences of lanthanoid contraction.

The steady decrease in atomic and ionic radii of lanthanoids across the period from lanthanum to
lutetium due to the poor (or ineffective) shielding of the 4f-electrons
Consequences:
• Difficult to separate Lanthanoids because of same size.
• Lanthanides exist together in nature due to lanthanide contraction.
• Zr and Hf have similar atomic radii due to lanthanide contraction.
4. Why transition elements forms coloured compounds?
• Due to the presence of unpaired d- electrons.
• Due to internal d-d transition.
5. Why transition elements shows paramagnetic nature?
• Due to the presence of unpaired d- electrons in transition metals and their ions.
6. Why transition elements forms complex compounds?
• Small size of the metal ions and their high ionic charges.
• The availability of d-orbitals for bond formation.
7. Why transition elements shows catalytic nature?
• They show variable oxidation state,
• They provide larger surface area for catalytic activity.
• They form intermediate compounds.

8. Write spin only formula to calculate magnetic moment.

BM = Bohr magneton
 9. What are interstitial compounds? Write the properties of interstitial compounds.
Compounds formed when small atoms like H, C or N are trapped inside the crystal lattice of metals.
Ex: VH056, TiH1.7, Fe3H, Mn4N
The properties of interstitial compounds are
They are non-stoichiometric and are neither ionic nor covalent
They have high melting point than pure metals.
They are very hard.
They retain metallic conductivity.
They are chemically inert.

10. Calculate the magnetic momement for the following ions.

11. Give the composition of Mischmetal ?

Mischmetal is an alloy consists of a lanthanoid metal (~95%) and Iron (5%) and traces of S, C, Ca and Al.
12. Name the 3d transition metal which exhibit highest oxidation state.
Mn (+7).
13. Name the 3d transition metal which exhibit +1oxidation state.
Cu
14. Name the highest oxidation state shown by any transition elements.
+8 by Os or Ru
15. Name the transition element which does not exhibit variable oxidation state.
Sc
16. Actinoid contraction is greater from element to element than lanthanoid contraction.
This is due to poor shielding effect of 5f electrons than 4f electrons.
17. Study of actinoid elements is difficult. Give 2 reasons.
They are radio active elements and prepared in nanograms. Hence their study more difficult.
18. What happens when a lanthanoid reacts with i) H2 ii) C iii) dilute acids iv) X2 ( halogen)
v) O2 vi) water viii) N2 viii) S2
(i) with hydrogen to form hydrides of the type LnH3.
(ii) They react with carbon to form carbides of the type Ln3C, Ln2C3 and LnC2.
(iii) They liberate H2 from dilute acids.
(iv) They burn in halogen to form halides.
(v) They burn in O2 to from oxides of the type Ln2O3.
(vi) They react with water to from hydroxides of the type Ln(OH)3.
(vii) They react with N2 to form nitrides of the type LnN.
(viii) They react with sulphur to form sulphides of the type Ln2S3.
19. Write the differences between lanthanides and actinides

Lanthanides Actinides
1. Except promethium, all the lanthanides 1. All the actinides are radioactive
are non-radioactive
2. In addition to +3 oxidation state, they 2. In addition to +3 oxidation state,they
show +2 and +4 states also show +4, +5, +6 and +7 states also
3. Their magnetic properties can 3. Their magnetic properties are difficult
explained easily to explain
4. They have less tendency to form 4. They have more tendency to form
complex compounds complex compounds
5. Their compounds are less basic 5. Their compounds are more basic
6. They do not form oxocations 6. They form oxocations like UO22
PuO22+ UO+ etc.

20. Write the Similarities between lanthanides and actinides

1) Both are f-block elements.
2) Both can be represented by the same general electronic configuration.
3) Both show oxidation state of +3.
4) Both are silvery in appearance, electropositive and are reactive.
5) Both form coloured ions and show paramagnetism.
6) Actinides show actinide contraction similar to lanthanide contraction.
7) Both exhibit ion exchange behaviour.

************
 Very important questions
I. One mark questions

1. EDTA is an example of which polydentate ligand?

2. Define the term coordination number of a central metal
atom or ion in a complex compound.
3. Define Coordination entity of coordination compounds.

4. Give the IUPAC name of [Pt(NH3)2Cl(NO2)]

5. What is a heteroleptic complex?

II. Two mark questions

6. What is linkage isomerism? Give an example

7. Explain coordination isomerism in complexes. Give one
example.
8. Explain ionization isomerism in complexes. Give an example
9. What is solvate isomerism? Explain with an example.
10. Give the IUPAC name of [Co Cl2 (NH3)4]Cl. Draw cis and
trans isomers of [Co Cl2(NH3)4] + ion.
11. Draw figure to show splitting of degenerated orbitals in an
octahedral crystal field
12. Draw the structures of [CoCl2(en)2]Cl and [Co(NH3)3(NO2)3]
III. Three marks questions

13. State the postulates of Werner’s theory of coordination

compounds.
March-2016 , July 2017

14. Give the geometry, hybridization and magnetic property of

[Co(NH3)6]3+ based on VBT. July-2016

15. Using VBT, explain the type of hybridization, geometry and

magnetic property of [NiCl4]2-
March-2018

16. Explain the hybridization, geometry and magnetic property

in the complex compound [Ni(CN)4]2 –
Marh-2014, July-2014, March-2015, March-2017

17. Explain the formation of [CoF6]3- based on VBT. Is this

complex paramagnetic?
July-2015, March-2016July-2017

*************
HALOALKANES & HALOARENES

1. Explain SN1 reaction mechanism: NUCLEOPHILIC SUBSTITUTION UNIMOLECULAR

When tertiary-butyl bromide upon boiling with aqueous KOH or NaOH, ter-butyl alcohol is
formed.

Mechanism: The reaction takes place in two steps.

Step-1: Formation of carbocation: The tertiary butyl bromide undergoes dissociation to produce tertiary
butyl carbocation which is stable.

Step-2: Attack of nucleophile: The tertiary butyl carbocation is attacked by the nucleophile
(OH-) to form tertiary butyl alcohol.

2. Explain SN2 reaction mechanism: NUCLEOPHILIC SUBSTITUTION BIMOLECULAR

When methyl bromide is reacted with aqueous NaOH or KOH, it forms methyl alcohol. This
reaction follows SN2 mechanism.

The reaction takes place in one step and it involves the formation of transition state.
3. Explain FINKELSTEIN reaction with an example.
When alkyl chlorides and alkyl bromides are reacted with a solution of sodium iodide in acetone or
methanol to get alkyl iodides. This reaction is known as Finkelstein reaction.
 Ethyl chloride reacts with a solution of sodium iodide in acetone gives ethyl iodide.
4. Explain SWARTS reaction with an example.
When alkyl chlorides or bromide are heated with metallic fluorides such as AgF, Hg2F2, CoF2, or SbF3
gives respective alkyl fluorides. The reaction is known as Swarts reaction.

Methyl bromide heated with silver fluoride give methyl fluoride.

5. Explain Sandmeyer’s Reaction.
When freshly prepared diazonium salt is mixed with cuprous chloride or cuprous bromide it result in replacement
of diazonium group by Cl or Br

6. Write the difference between SN1 and SN2 reaction.

7. What are Enantiomers? Give example:

Pair of optical isomers which form non superimposable mirror images to each other are known as
enantiomers.
 Example:

8. What is racemic mixture? Why racemic mixture is optically inactive?

An equimolar mixture of two enantiomers of the same compound is known as racemic mixture.
As rotation due to one isomer will be cancelled by the rotation due to the other isomer.
9. What is Asymmetric carbon or Chiral carbon? Give example
A carbon atom attached to four different atoms or groups is said to be a chiral carbon.

10. What are Freons?

The chlorofluoro carbon compound of methane and ethane are collectively known as Freons.
11. Define Chirality?
The objects which are non superimposable on their mirror image are said to be chiral and this property is
known as chirality.
12. Name dehydrohalogenating agent.
Alcoholic KOH
13. What is racemisation?
The process of conversion of enantiomer into racemic mixture.
14. Explain Wurtz reaction with an example.
Alkyl halides react with dry sodium metal in presence of dry ether medium to form respective higher
alkanes.

When ethyl chloride reacts with dry sodium metal in presence of dry ether medium to give n-butane.
15. Explain Wurtz – Fittig’s reaction with an example.
When an alkyl halide reacts with aryl halide in the presence of sodium metal and dry ether medium, it
forms alkyl benzene.

When a mixture of chlorobenzene and methyl chloride reacts with dry sodium metal in dry ether
medium it forms toluene.

16. Explain Fittig's reaction with an example.

When chlorobenzene reacts with dry sodium metal in dry ether medium, biphenyl is formed.
17. Why aryl halides are less reactive than alkyl halides towards nucleophilic substitution reaction?
• In aryl halides, halogen is attached to sp2 hybridised carbon atom of benzene ring
• In aryl halides due to resonance, the C-X bond acquires partial double bond character which is
difficult to break.
• The phenyl carbocation formed in aryl halides is unstable.
18. Explain Friedel crafts alkylation of chlorobenzene.
When chlorobenzene is heated with methyl chloride in the presence of anhydrous aluminium chloride
as a catalyst a mixture of ortho and para substituted product is obtained.

19. Explain Friedel crafts acylation of chlorobenzene.

When chlorobenzene is heated with acetyl chloride in the presence of anhydrous AlCl3 catalyst ortho
and para chloro acetophenones are obtained.