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Unit 2: Solution
Normality 0.05N
Basicity of oxalic acid 2
By the formula,
Normality Basicity molarity
0.05 2 molarity
0.05
molarity
2
0.025M
Q2. Why is the molality considered as better for expressing concentration than molarity?
Ans: Molality involves mass of the solvent which does not change with temperature. But the
molarity involves volume of the solution which changes with temperature
So, molality is considered as better for expressing concentration than molarity.
Q3. Calculate the mole fraction of solute of 1m aqueous solution.
Ans: 1m aqueous solution means 1mole of the solute dissolves in 1000g of H2O
1000
Now, number of moles of H 2O, n1 M H 2O 18 g / mol
18
55.55 moles
n2
Mole fraction of solute
n1 n2
1
1 55.55
1
56.55
0.0176
= (Mole fraction of solvent in the solution) × (Vapour pressure of the pure solvent) 1
Subtracting each side from 1 , we get
p n1
1 1
p 0
n1 n2
p 0 p n1 n2 n1
p0 n1 n2
p0 p n2
p 0
n1 n2
p0 p
i.e. ∝ x2 Where x2 mole fraction of solute
p0
Hence, shown.
Thus, the relative lowering in vapour pressure of solution is directly proportional to the mole
fraction of the solute
Q6. The vapour pressure of pure water at 30 0 C is 31.80mm of mercury. How many grams of
urea should be dissolved in 1000 g of H2O to lower the vapour pressure by 0.25mm of Hg ?
Ans: Here,
p0 31.80mmHg
MB 60g / mol
p0 p 0.25mm
M A 18g / mol
WA 1000g
WB ?
By Raoult’s law,
p 0 p M AWB
p0 M BWA
0.25 W 18
B
31.80 60 1000
3
25 60 1000 500
WB
3180 18 9
159 3
12500
WB
477
26.25g
26.25g of urea should be dissolved in 1000 g of H2O to lower vapour pressure by 0.25mm of
Hg
Q7. An aqueous solution freezes at 0.186 0 C k f 1.86, k b 0.512 . What is the elevation in
boiling point?
Ans: Here,
Tf 0.1860 C
T f 0 00 C
k f 1.86
kb 0.512
By the formula,
Tf k f m
T f 0 T f 1.86 m
00 0.186 1.86 m
0.186
m
1.86
0.1m
Again,
Tb kb m
0.512 0.10 C
0.05120 C
Q8. Two aqueous solutions containing 7.5g of urea mol.wt 60 and 42.75g of substance X
in 100g of water freeze at the same temperature. Calculate the molar mass of X .
Sol:
Here,
Tf k f m As in same for the two solutions, their molarity will be equal
42.75 60
MX
7.5
171855 2
4275 60
25 750
5
M X 342g / mol
Q9. What is Van’t Hoff factor? How does it help in determining the degree of dissociation and
association of solute in a solution?
Ans: Van’t Hoff factor is defined as the ratio of the experimental value of the colligative property to
the calculated value of the colligative property.
i.e.
experimental value of the colligative property
i=
calculated value of the colligative property
Q10. What is Van’t Hoff equation for dilute solution? In what ways is it helpful in calculating
the osmotic pressure of a solution?
According to Boyle – Van’t Hoff law
i.e. ∝ C
n
∝ 1
V
Where n no of moles of the solute
dissolved in 'V ' volume of the solution
According to Charle’s Van’t Hoff law,
i .e . ∝ T ii
The osmotic pressure of a solution is proportional to its absolute temperature for a solution of
some definite concentration
Combining i and ii
n
∝ T
V
RnT
Where R is solution constant
V
V nRT Which is Van’t Hoff Equation.
Mass
Moles of water in 1000 g
Molar mass
1000 g
18 gmol 1
55.55mol
moles of water
Molarity M
volume of water in litres
55.55mol
1L
55.55M
Q13. A 5% solution of sucrose is isotonic with 0.877% solution of substance X . Calculate the
molar mass of X .
Ans:
5% solution of sucrose means 5 g of sucrose in 100 ml of the solution
WB
V RT where WB 5g , M B 342g / mol
MB
5
V RT
342 V
5 1000 100
RT i V 100 ml L
342 100 1000
WB 100
V RT where W 0.877 g , V 100ml L
1000
B
MB
0.877 1000
RT ii
M B 100
≈ 60 g / mol
Q14. 2g of benzoic acid dissolved in 25 g of benzene shows a depression in freezing point equal
1
to 62k .Molar depression constant for benzene is 4.9k kg mol .What is the percentage
association of the acid?
Ans:
Observed
Tf 1.62k
k f 4.9k kg mol 1
72 5 12 32 1
122 g mol 1
122
0.504
242
C6 H 5COOH
2C6 H 5COOH 2
Initial moles 1 0
After association 1
2
Total number of moles after association 1 1
2 2
1
i 2 0.504
1
or 1 0.504
2
1 0.504 2
0.496 2 0.992
% association 99.2%
Q15. Out of 1M of NaCl aqueous solution and 1m NaCl aqueous solution, which one has higher
concentration?
Q17. Define Van’t Hoff factor. What does it indicate when Van’t Hoff factor of a solution is
less than 1?
Ans: Van’t Hoff factor is defined as the ratio of experimental value of colligative property to
calculate value of colligative property.
When the Van’t Hoff factor i of a solution is less than 1,the solute will undergo association.
We have,
WB 1000
m
M B WA
Now, T f k f m
k f WB 1000
T f
M B WA
k f WB 1000
MB
T f WA
Q19. What type of deviation is shown by a mixture of ethanol and aceton? Give example
Ans: Positive deviation is shown by a mixture of ethanol and aceton.
This is because the interaction between the components i.e. ethanol and aceton are less than in the
pure component.
Q20. What are azeotropes? Name the two types of azeotropes with suitable examples?
Ans: Mixture of liquids which boil at constant temperature like a pure liquid such that the distillate
has the same the composition as that of the liquid mixture are called constant boiling mixture or
azeotropes
Q21. What are colligative properties? Derive an equation to express the relative lowering of
vapour pressure of solution is equal to the mole fraction of the solute in it when solvent alone is
volatile?
Ans: Those properties of ideal solutions which depend only on the number of particles of the solute
dissolved in the definite amount of the solvent and do not depend on the nature of the solute are
called colligative properties.
We have,
If the solute is non - volatile, it will not contribute to the vapour pressure of the solution.
vapour pressure of solution
vapour pressure of solvent in solution
mole fraction of the × vapour pressure
from i
solvent in solution of the pure solvent
Symbolically,
p x1 p
p
x1
p0
p n1
p0 n1 n2
p n1
1 1
p0 n1 n2
p0 p n1 n2 n1
p0 n1 n2
p0 p n2
p0 n1 n2
Hence, shown.
Q22. A solution containing 15g of urea molar mass 60 g / mol per litre of solution in water
has the same osmotic pressure as a solution of glucose molar mass 180 g / mol in water.
Calculate the mass of glucose present in 1litre of its solution.
Ans: For urea solution,
15 g R T
1
60 g mol 1 1L
1 2
15 g WB
1
60 g mol 180 g mol 1
180 15
3
WB 45 g
60
mass of glucose 45g
p x p0
A A
p p0 x
A A A
i.e. Vapour pressure of the volatile component (solvent or solute) is directly proportional to the mole
fraction of that component in the solution.
Now, if the gas is a solute and liquid is the solvent, than according to Henry’s law pA kH xA
i.e. Partial pressure of the volatile component (gas) is directly proportional to the mole fraction of
that component (gas) is the solution.
Thus, Raoult’s law and Henry’s law becomes identical except that their proportionality constant are
different, being equal to p 0 for Raoult’s law and kH (Henry’s constant) for Henry’s law.
A
Q26. Draw vapour pressure curve showing the depression of freezing point of solution and
pure solvent.
Ans:
Q28. Explain the positive and negative deviation with suitable example.
Ans: Non - ideal solution shows positive deviation if the interactions between the component are less
than in the pure components
Q28. Show how the vapour of a solvent is affected when a non volatile solute is dissolved in it.
Ans: The vapour pressure of the pure solvent decrease when a non volatile solute is dissolved in it
this is due to the presence of less no of solvent molecules on the surface of the solution than that of
the pure solvent.
Q29. What mass of a solute molar mass 62 g / mol must be added to 5.50kg of water to lower
freezing point of H2O from 00 C to 10.00 ? k f forwater 1.86 kkgmol 1
Ans: Here,
WB ?
WA 5.50 kg
k f 1.86
62
M B 62 g / mol kg / mol
1000
T f 0 10 100 C
Now,
Tf k f m
WB
1.86
M B WA
WB
10 1.86
62
5.50
1000
31
10 62 5.50 62 55
WB 1.833kg
1.83 1000 1860
930
1.833 kg
Unit 3: electrochemistry
If we keep diluting an electrolytic solution, the value of m keep on increasing until they
attain maximum value .The maximum m are called molar conductance at infinite dilution(
m ).
If we keep on diluting an electrolytic solution the value of eq keep on increasing until they
attained maximum value .The maximum value of eq are called equivalent conductivity at
infinite dilution.
c) Electro chemical series:-
The arrangement of various electrons in decreasing or increasing order of their standard
reduction potential is called electrochemical series
d) Electro chemical equivalent:-
It is the amount of substance deposited when current of 1 A is passed for 1 sec i.e. for 1C of
charge.
e) Cell constant:-
l
It is the ratio of distant between the electrodes and area of cross section .It is denoted by .it
A
unit is cm1 .And Its SI unit is m1
f) Specific conductivity Specific conductance
It is defined as conductance of electrolyte when distance between electrolytes is 1cm and area
of cross section is 1cm 3.
Q3. What is the relation between molar conductivity m and equivalent conductivity e ?
Ans: On dilution, number of ions present per unit volume of solution decrease and hence the value of
conductivity decease in case of both weak and strong electrolyte.
Ans: ZnCl2 Combines with NH 3 released in electrodes reaction, Otherwise the cell may damage due
to extra pressure of ammonia gas ZnCl2 4 NH 3 Zn NH 3 4 Cl2
Q6. How many coulombs of electricity are required for the reduction of 1mole of Cu 2 ions to
Cu ( s)
Ans: Cu 2 2e Cu ( s )
1 mole 2F
2 96500C
1,93,000C
Ag e Ag ( s )
4OH H 2O O2 2e
b) In Aqueous state,
NaCl Na Cl
H 2O H OH
At cathode : H 1e H [H
Has high reduction
H H H2 potential than Na
]
1
At anode : Cl 1e Cl2 ( g )
2
Cl Cl Cl2
EH0 / H EMg
0
2
/ Mg
2
0 E 0
Mg 2 / Mg
E 0
M g 2
/ M g
E 0
c e ll
Q11. What is the different between emf of a cell and potential difference?
Ans:
EMF of cell Potential difference
i) It is the potential difference between the i) It is the difference of electrode potential of
electrodes current is flowing in the circuit the two electrodes when the cell is under
operation
ii) It is the maximum voltage offered by the
cell ii) It is always less than the maximum voltage
Q12. What volume of Oxygen (measured at NTP) is produced by Oxidation of water in the
electrolysis of CuSO4 during the passage of 2.50 ampere of current for 45 mins?
Ans: 2 H 2O O2 4 H 4e
1mole 4 95600C
386000C
Q I t 2.5 45 60 6750C
22.4L at NTP
(22.4 6750)
386000
0.3917L
wQ
w ZQ
Then, Q I t
w ZQ
w Z I t
Thus, if Q 1 coulomb, I 1 ampere, t 1 second; then
wZ
It state that when the same quantity of electricity is passed through solution of different
electrolyte connected in series ,the wt of the substance produced at the electrode are directly
proportional to their equivalent wts.
Eg:For AgNO3 solution and CuSO4 solution connected in series, if the same quantity of
electricity is passed.
Wt. of deposited Equivalent wt.of Ag
Wt.of Cu deposited Eq.wt of Cu
Q14. The conductivity of 0.001M acetic acid is 4 105 Scm1 calculate the dissociation constant
of acetic acid if molar conductivity at infinite dilution for acetic acid is 390Scm2 / mol .
Ans: Calculation of
k 1000
cm
M
4 105 1000
0.001
4 10Scm 2 mol 1
Calculation of degree of dissociation,
cm 40
0.1024
m 390.5
Calculation of dissociation constant ( ka )
C 2
(ka ) 1.85 105
(1 )
Q15. What type of battery is lead storage battery? Write the anode and cathode reaction and
overall reaction acquiring in a lead storage battery when it discharging.
Ans:
At cathode
PbO2 ( s ) SO4 2 (aq ) 4 H (aq ) 2e PbSO4 2 H 2O (l )
Overall reaction
Pb( s) PbO2 ( s) 2 H 2 SO4 (aq) 2 PbSO4 ( s) 2 H 2O(l )
Q16. An iron wire is immersed in a solution containing ZnSO4 and NiSO4 with reason predicts
which of the following reaction is lightly to proceed.
a) Iron reduced Zn 2 ions
b) Iron reduced Ni 2 ions
Ans:
0
Given: EZn 2
/ Zn
0.76V ; EFe
0
2
/ Fe
0.44V ; E Ni0 2 / Ni 0.25V
a)
Fe Zn 2 (aq ) Zn Fe 2 (aq )
0
Ecell EZn
0
2
/ Zn
EFe
0
2
/ Fe
ENi0 2 / Ni EFe
0
2
/ Fe
0.25 (0.44)
0.19V
0
Since, Ecell has positive value, iron reduce Ni 2 to Ni( s)
Q17. Calculate the cell emf and G for the cell reaction at 298k for the cell.
Zn( s ) / Zn 2 (0.0004 M Cd 2 (0.2 M ) / Cd ( s )
Ans: Given
0
EZn 2
/ Zn
0.783V
0
ECd 2
/ Cd
0.403V
R 8.314 Jk 1mol 1
0
Ecell ECd
0
2
/ Cd
EZn
0
2
/ Zn
0.403 (0.783)
0.36V
Zn( s ) Cd 2 (aq ) Zn 2 (aq ) C
Cell reaction is Zn( s ) Cd 2 (aq ) Zn 2 (aq ) Cd ( s )
0.0591 Q
Ecell Ecell
0
log10
n
0.0591 0.004
0.36 log
2 0.2
0.44
G nFEcell
2 96500 0.44
84920 J
Q18. With help of the graph explain why it is not possible to determine 0m for a weak
electrolyte by extrapolation.
Ans: Conductance of a weak electrolyte increase exponentially is dilution due to increase in no of
ions as well
as inter-ionic distances. The curved meets the axis at infinity. Thus 0m of weak electrolyte
cannot be determined by extrapolation electrochemical series.
m
Q19. State Kohlrausch’s law .How will you determined using Kohlrausch’s
c
For a weak electrolyte if mc be the molar conductivity of a solution at any concentration c and m0 be
the molar conductivity at infinite dilution (zero conc.) then, we have
mc
Degree of dissociation ( )
m0
The value of m0 for the weak electrolyte can be calculated in Kohlrausch’s law
Salts such as AgCl , BaSO4 , PbSO4 etc. which dissolve to a very small extent in water are
called sparingly salt
By determining the specific conductivity (k ) and the molar conductivity (m ) such a solution, we
can obtain solubility as follows
1000
m0 k
molarity
1000
k
Solubility
k 1000
Solubility
m0
aA bB cC dD
1 d A 1 d B
*Rate of the reaction
2 dt 2 dt
1 d C 1 d D
2 dt 2 dt
concentration time 1 k
1 n
Ea
*Arrhenius equation, k Ae RT
Ea Activation energy
R Gas constant
Ea
ln K ln A
RT
Ea
log K log A
2.303RT
*Rate constant at two different temperatures:
k2 Ea T2 T1
log
k1 2.303RT T1T2
2.303 R 0
k log
t R
*Half life of zero order reaction:
1 R 0
t1
t1
2 k 2 2
*Half life of first order reaction:
t1
0.693
slope tan
1 R 0
2 k 2k
*Radioactive decay follows first order reaction: t1
Ea EThr ER , Where EThr Threshold energy, 2
ER Energy of reactant
Ans: It is defined as the sum of powers of all the concs. terms present in the experimental rate law equation.
E.g. N 2 O2 2 NO
order 1 1 2 nd order
Q2 Define molecularity of a reaction.
Ans: Molecularity of an elementary reaction is the total no. of reactant molecules that gives the products.
Q9 Explain the difference between the average rate and instantaneous rate of a chemical
reaction
Ans: Average rate of reaction:
The rate of reaction measured over a long time interval is called average rate of reaction.
It depends upon the change in conc.of reactants or products and time taken for the
change to occur.
x
In general rav
t
Instantaneous rate:
It is the rate of reaction when the average rate is taken over a small interval of time
dx
It is equal to .
dt
Instantaneous rate Average rate as t approaches zero.
dy d R d P
rinst
dt dt dt
Q10 Distinguish between the rate of reaction and rate constant of a reaction
Ans:
Rate of reaction Rate constant
i) This stand for the rate of decrease of the i) It is the rate of reaction when the conc. of
conc.of the reactants on the rate increase of the reactant is unity rate
conc. Of product with time
ii) It is independent of the conc. of the reactant
ii) It depends upon the conc.of the reactants at but depend upon the temperature
the particular moment
iii) The unit of the rate constant depend upon
1 1 1 1 the order of the reaction.
iii) Units mol sec or mol min
Q11 The rate of reaction triples when temperature changes from 20 0 c to 50 0 c calculate energy
of activation for the reaction for the reaction assuming that it doesn’t change with temperature.
Ans: Given:
k2
3, T1 20 273 293k
k1
T2 50 273 323k
R 8.314 Jk 1mol 1
Arrhenius equation is
k Ea T2 T1
log 2
k1 2.303RT T1T2
Ea 323 293
log 3
2.303 8.314 293 323
Ea 28811.8Jmol 1
28.8118kJmol 1
Q12 A reaction of the second order w.r.t. a reactant. How is the rate of reaction affected if the
conc.of the reactant is reduced to half? What is the unit of the rate constant for such a reaction?
Ans: Rate1 k R
2
2
1
Rate1
4
The rate of the reaction is reduced to one-fourth of its initial rate.
1
N 2O5 2 NO2 O2
2
At a certain time interval, the rate of decomposition of N 2O5 is 1.8 10 3 molL1 min 1 ,what will
be the rates of formation of NO2 and O2 during the same time interval?
N 2O5
1 N 2O5 O2
Rate 2
t 2 t t
3 1 1
1.8 10 molL min
NO2 N 2O5
Rate of formation of NO2 , 2
t t
2 1.8 103
3.6 103 molL1 min 1
O2 1 N 2O5
Rate of formation O2 ,
t 2 t
1
1.8 103
2
0.9 103 molL1 min 1
Q14 Half life and three-fourth life of a first order reaction are t1 and t2 respectively. What is the
relation between them?
Ans:
0.693 0.693
t1 or k
2 k t1
2
2.303 a
t log
k ax
3
When x a , t t2
4
2.303 a
t2 log
k 3
a a
4
2.303 2 log 2
k
2.303 0.3010
0.693
t1
2
2 t 1 2t1
2
t2 2t1
Q15 For the reaction 2 NO 2 H 2 N 2 2 H 2O , the kinetics of this reaction is explained by the
following steps
1
Ans: H 2O H 2O O2 or CH 3COOH 3 H 2 O CH 3COOH CH 3OH
2 acid
Polymers:
These are the molecules of high mass formed by the combination of a large number of simple
molecules .The simple molecules are called monomers.
Polymerisation: It is the reaction in which the monomers are converted into polymers.
Classification of polymers:
Polymers are classified into many ways as followed:
i) Classification based on the nature of repeating unit
ii) Classification based on the source
iii) Classification based on the structure
iv) Classification based on mode of reaction
v) Classification based on molecular force
polymerisation
nCH 2 CH 2 ( CH 2 CH 2 ) n
The repeating unit is CH 2 CH 2
ii) Copolymers: These are the polymer which are derive from the two or more different monomers
e.g Nylon – 66
Hexameltyenediamine
CH 2 6 NH 2 nHOOC CH 2 4 COOH
Adipic acid
NH CH
2 2 6 NH CO CH 2 4 CO H 2O
n
Nylon 66
ii) Fibres: These are the polymers in which the molecules have strong intermolecular force of
attraction. The intermolecular force is either hydrogen bond or dipole - dipole interactions. They
have high tensil strength and low elasticity. They have sharp melting point e.g: Nylon-66 Dacron etc
iii) Thermoplastics: These are the polymers which can be easily softened when heated and can be
hardened when cooled with little change in the properties. They have intermolecular force between
those Elastomer and fibres e.g: polythene p.v.c
iv) Thermosetting polymers: These are the polymer which undergoes permanent change on heating
On Heating; they get highly cross- linked thereby holding molecules so rigid that the molecules
cannot move freely.
e.g: Bakelite, melamine formaldehyde etc.
Plasticizers: Certain do not soften much on heating, but they can be softened easily by the addition
of some organic compounds. These organic compounds are called plasticizers.
e.g: P.V.C
Biodegradable polymers: these are the polymers which can be degradable by micro- organism so
that biodegradable polymers and their degraded products do not cause any kind of pollution to the
environment. In true sense, biodegradable polymers are environment friendly.
e.g Polyactic acid .Polgycolic acid PGA etc
Q2 Distinguished between chain growth polymerisation and step growth polymerisation and
give one examples of each process.
Ans:
Q3 How is Bakelite made and what is its major used? Why is baketlite a thermosetting
polymer?
Ans: Bakelite is formed by the condensation reaction of Phenol with formaldehyde i.e. the presence
of acid or base catalyst.
Uses:
It is mainly used in making electrical goods. Bakelite is thermosetting plastics because plastics
because it cannot be reshaped on heating due to high degree of cross –linking between polymers
chain