1.

SOLUTIONS
Synopsis :
• A solution is a homogeneous mixture of two or more substances at molecular or ionic levels.
• Formation of solution is a physical change single phase exists in solution.
Individual molecules or ions will exist in solution.
Components of true solution can not be separated by filtration, settling, centrifugation.
• Solute may lose it’s physical state, but solvent retains it’s physical state.
• Based on the number of components, solutions may be binary, ternary, quaternary etc,.
• A binary solution contains only two components known as solute and solvent.
Solute + Solvent = Solution
• The substance present in smaller proportion in binary solution is known as the solute.
The solute is called the dissolved component (or) dispersed component in the solution.
• The substance present in larger proportion is called as the solvent.
The solvent is called the dissolving component (or) dispersion medium in the solution.
• In case of solid in liquid type solutions, irrespective of their amounts, solid is solute and liquid is solvent.
• Based on the physical state, solutions are of 3 types.
Gaseous solution : Solvent is Gas
The liquid solutions : Solvent is Liquid
Solid solutions : Solvent is solid
• In any type of solution the solute may be gas or liquid or solid.
• Solutions are of 7 types based on the physical states of solute and solvent.
1) Gas in gas : Mixture of any two gases
2) Gas in liquid : Soda water
3) Liquid in liquid : Alcohol in water
4) Solid in liquid : Sugar in water
5) Gas in solid : H2 occluded in Pd
6) Liquid in solid : Amalgams
7) Solid in solid : Alloys
• Liquid in gas and solid in gas are not considered as true solutions as they are not homogenous.
• A solution in which water is used as a solvent is known as aqueous solution.
• A solution in which alcohol is used as a solvent is known as alcoholic solution.
• A solution in which an organic liquid is used as a solvent is known as non – aqueous solution.
• The commonly used solvents in non – aqueous solutions are CCl4, CS2, CHCl3, C6H6 liquid SO2, acetic
acid , liquid NH3 etc.
• Based on the amount of dissolved solute, solutions are of 3 types.
I) Saturated solutions : which can not dissolve any more solute. Usually some amount of undissolved

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solute is present in it. A dynamic equilibrium exists between dissolved solute and undissolved
solute.
II unsaturated solutions : which can dissolve some more amount of solute.
No excess of undissolved solute exists.
No dynamic equilibrium exists.
III) Super saturated solutions : which contain excess of dissolved solute.
No equilibrium [Link] are unstable.
Concentration :
• The quantity of the solute present in a definite quantity of the solution relative to the solvent is known as
the concentration of the solution (or) strength of the solution .
Note: A solution whose concentration is known is called as standard solution. The container used to
prepare a standard solution is known as standard flask.
• A solution which contains less quantity of the solute compared to the solvent is known as ‘dilute
solution’ i.e., the strength of a dilute solution is ‘very low’.
• A solution which contains excess solute, in a definite quantity of the solution is known as a
‘concentrated solution’ i.e., the strength of a concentrated solution is ‘very high’.
• Weight of the solution
= Volume of the solution  density of the solution

W=Vd
• The weight of one milli litre of a solution in grams is known as the density of the solution.
The density of the solution depends on temperature of the solution.
The units for the density of solution are gram/ml. The ratio between the density of solution and the
density of water, both measured at the same temperature is known as relative density of the solution
(or) specific gravity of the solution.
• The specific gravity of solution has no units.
Various terms used in concentration:
Weight percent:
weight of solute
Weight fraction =
weight of solution

Weight percent = weight of solute  100

weight of solution

Volume percent :
volume of solute
Volume fraction =
volume of solution
volume of solute
Volume fraction =  100
volume of solution

• It is applicable for solution containing both solute and solvent as liquids.

Solubility : It is the weight of solute dissolved in 100 grams of solvent to form saturated solution.
weight of solute
Solubility =  100
weight of solvent
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Molarity : The number of gram moles of the dissolved solute per litre of solution is known as the molarity
of the solution. It is represented by ‘M’.
number of moles of the solute
=
volume of the solution in litres

• Units for molarity are moles/litre.

• The molarity is the most convenient and commonly used method of expressing the concentration of
solution.
• The molarity of a solution slightly decreases with increase in temperature of the solution, due to
increase in volume.
n
M = ; M = [Link] milli moles of solute
v volume of solution in mℓ
[Link] moles of solute = M  V (lit)
[Link] milli moles of solute = M  V (m ℓ )
weight of solute in grams 1
M= 
G.M.W of solute V(lit)
w 1000
M= 
M.W V(ml)

w = M  M.W.  V(lit)
M = %  10 % 
W
 
G.M.W  V 
density  10 %  W 
M= % 
G.M.W  W
• If a solution is diluted
M1V1 = M2V2
M1 = Molarity before dilution
M2 = Molarity after dilution
V1 = Initial volume; V2 = Final volume
V2 = V1 + volume of water added
• When two solutions having same solute are mixed.
The molarity of resultant mixture
M V + M2 V2 + ......
= 1 1
V
• In case of complete neutralizations or complete reaction between two solutions, the molarity in the
resultant mixture is
M1V1 M2 V2
=
n1 n2
• In case of incomplete reaction or incomplete neutralisation , then the molarity in the resultant mixture,
M V − Mb Vb
M= a a ( MaVa> MbVb)
V
M V − M a Va
M= b b (MbVb > MaVa)
V

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Equivalent weight (E):

• The weight of the substance which combines with 1 gram of hydrogen or 8 grams of oxygen is called
equivalent weight.
• Equivalent weight is the weight of the substance which loses or gains 1 mole of electrons
weight of the subs tan ce(g)
[Link] equivalents =
equivalent weight
[Link] milli equivalents =
weight of the subs tan ce(mg)
equivalent weight
Atomic weight
Eelement =
valency
Eacid= molecular weight
number of replaceble hydrogens
molecular weight
Ex: EHCl =
1
molecular weight
• EHNO3 =
1
molecular weight
EH2SO4 =
2
molecular weight
EH3PO4 =
3
molecular weight
EH3PO3 =
2
molecular weight
EH3PO2 =
1
E molecular
= weight
H2C2O4
2
molecular weight
Equivalent weight of base =
number of replaceble OH− ions
molecular weight
Ex : E NaOH =
1
E molecular weight
=
Ca(OH)2
2
molecular weight
E NH3 =
1
• Equivalent weight of salt: = molecular weight
total ch arg e(postive or negative)
molecular weight
Ex: E NaCl =
1
molecular weight
EMgCl2 =
2
molecular weight
EAlCl3 =
3
molecular weight
EAl2 (SO4 )3 =
6

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• Equivalent weight of oxidising or reducing agent
molecular weight
=
change in oxidation state
molecular weight
Ex: E KMnO4 =
5
( MnO 4 → Mn in acid medium)
− 2+

molecular weight
EKMnO4 =
1
( MnO− → MnO2− in basic medium )
4 4
molecular weight
EKMnO =
4 3
( MnO−4 → MnO2 in neutral medium)
molecular weight
EK2Cr2O7 =
6
7 → Cr
( Cr2O2− 3+ in acid and basic medium)

Normality (N):
• The number of gram equivalents of the solute dissolved in one litre of solution is known as its normality.
• Units for normality are gram equivalents/ litre.
• The normality of a solution decreases with increase in temperature of the solution.
[Link] gram equivalent of the solute
N=
volume of the solution in litres
number of milli equivalents of solute
N=
volume of solution (mℓ)
• Number of equivalent weight of solute = N  V(lit)
• Number of milli equivalents of solute = N  V(ml)
weight of solute in grams 1
N= 
gram equivalent weight of solute V(litres)
W 1000
N= 
G.E.W V(ml)

W = N  G.E.W  V(lit)
10  %  w
N= % = 
G.E.W  v
density of solution  10  %  W 
N= % 
G.E.W  W
• If a solution is diluted
N1V1= N2V2
• If two solutions having same solute are mixed, normality of the resultant mixture
N V + N2 V2 + .......
N= 1 1
V
• When two solutions react completely :
N1V1 = N2V2
• When a solid reacts with a solution :

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W
= NV
(lit)
G.E. W
• Normality  Equivalent weight
= molarity  molecular weight
For any given solute , [Link]  equivalent weight.
For any given solution . M  N
Formality (F) :
• Fomality is the number of formula weights of solute per litre of solution.
• Ionic compounds and polymers do not contain molecules and molecular weights.
Instead of molecular weight, the formula weight to be taken and instead of molarity the formality to be
considered.
• For any given solution, molarity and formality are same.
weight of solute 1000
Formality= 
formula weight volume of solution(mℓ)

• Molality : The number of gram moles of the solute dissolved in one kilogram of the solvent is known as
the molality of the solution. It is represented by ‘m’.
• The units for molality are mole / kg.
• Molality is independent of temperature.
• Molality is the most inconvenient method of expressing concentration of a solution because it involves
determining the weights of liquids.
number of gram moles of the solute
m=
weight of solvent in ki log rams
weight of solute in grams 1000
m= 
G.M.W of solute weight of solvent in grams

• The molality of a saturated solution is given by

10  so lub ility
m=
[Link] solute
If molarity is given :
m= 1000  M
(
1000  d) − (M [Link] )
Mole fraction :
• The ratio between the number of moles of solute and the total number of moles of solute and solvent in
the solution is known as the mole fraction of the solute. It is represented by X 1.
n
X1 = n = [Link] moles of solute
n+N
N = [Link] moles of solvent
• The ratio between the number of moles of solvent and the total number of solute and the solvent in the
solution is known as the mole fraction of the solvent. It is represented by X 2.
N
X2= N = [Link] moles of solvent
n+N
n = [Link] moles of solute
• Mole fraction can be expressed with reference to any component of the solution.

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• If molality of aqueous solutions is known, then
m
X1=
m + 55.55
• Mole fraction of solute has no units. The sum of mole fractions of all components in a solution = 1.
• Mole fraction is independent of temperature.
Mole percent :
• The number of moles of solute present in 100 moles of a homogenous mixture of solute and solvent is
known as the mole percent of the solute.
Mole percent of solute=Mole fraction of solute100
Mole percent of solvent=Mole fraction of solvent100
Vapour pressure :
• Liquids having low boiling points are called volatile liquids.
Ex: Ether, acetone, benzene, carbondisulphide, carbon tetrachloride are volatile liquids.
• Liquids having high boiling points are called non volatile liquids.
Ex: Aniline, Nitrobenzene, Con.H2SO4, water are non volatile liquids.
• Volatile liquids have
i) Weak intermolecular forces
ii) High vapour pressure
iii) Low boiling point
• Non – volatile liquids have

i) Strong intermolecular forces

ii) Low vapour pressure

iii) High boiling point

• When a liquid is in equilibrium with its own vapour the pressure exerted by the vapour on the surface of
the liquid is known as the vapour pressure of the liquid.

• The vapour pressure of the liquid must be called as saturated vapour pressure, because actually the
atmosphere over the liquid, which is saturated with the vapour of the liquid, exerts the pressure on the
liquid.
• The vapour pressure of the liquid is represented by P.

• The vapour pressure of water is known as aqueous tension.

• The vapour pressure of the liquid is directly proportional to the temperature of the liquid.
• The vapour pressure of a liquid is independent of shape of the vessel.

• Vapour pressure of liquid increases exponentially with increase in temperature.

1
• Log P Vs gives a straight line with – ve slope. This is called Clausius – clapeyoron curve.
T
• The temperature at which the vapour pressure of the liquid is equal to the atmospheric pressure is
known as the boiling point of the liquid.

• Boiling point of a liquid can be changed by changing the external pressure. If external pressure is

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increased, the boiling point of a liquid is increased and vice- versa.

Lowering of vapour pressure :

• When a non – volatile solute is added to a solvent, the vapour pressure of pure solvent decreases. This
is called lowering of vapour pressure.

• With increase in the concentration of solution, the lowering of vapour pressure further decrease.
Ps < P° Ps = vapour pressure of solution

P°= vapour pressure of pure solvent

P° –Ps = lowering of vapour pressure

• The ratio of lowering of vapour pressure to the vapour pressure of pure solvent is called relative
lowering of vapour pressure.
P0 − Ps
= Relative lowering of vapour pressure.
P0
Raoult’s law :
• I) For a solution containing non volatile solute, the relative lowering of vapour pressure is equal to mole
fraction of solute.
P0 − Ps
= XB
P0
P0 − Ps nB
=
P0 nA + nB

Simplified (or) reduced form of Raoult’s law :

P0 − Ps n
= B (for dilute solutions, nB is very small and it can be neglected)
P0 nA
P0 − Ps w M
= 
P0 m W
P°= Vapour pressure of pure solvent
Ps= Vapour pressure of solution
XB = mole fraction of solute
m = molecular weight of solute
M = molecular weight of solvent
w = weight of solute W = weight of solvent
Relation between Raoult’s law and molality :
P0 − Ps molality  M
= (M=[Link] solvent)
P0 1000

• II) Raoult’s law for solution containing two or more miscible liquids is “the partial vapour pressure of a liquid
component in the solution is directly proportional to it’s mole fraction”.
• If solution contains two miscible liquids A and B , then
PA  xA PB  xB

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PA = P .xA PB = P . xB
A B

Ptotal = PA + PB
Ptotal = P . xA + P . xB
A B

• Ideal solutions: The solutions which obey Raoult’s law at all concentrations of temperatures are called
ideal solutions.
• In case of ideal solutions,
I) Vmixing = 0
ii) Hmixing = 0
iii) No change in interactions
• Solutions behave ideally at infinite dilution.
• Raoult’s law is applicable to
i) Ideal solutions
ii) dilute solutions
iii) solutions containing non volatile solute
iv) no change in the interactions before and after mixing of liquid components in case of solution
containing miscible liquids.
v) Solute which neither dissociate nor associate.
COLLIGATIVE PROPERTIES:
• The properties of dilute solutions which depend on the number of particles (ions or molecules)
of the solute dissolved in the solution are called colligative properties.
They are
i) Relative lowering of vapour pressure (RLVP) of solution
ii) Elevation in the boiling point of the solution (Tb )
iii) Depression in the freezing point of the solution (T )
f

iv) Osmotic pressure of the solution ( ) .

1. RELATIVE LOWERING OF VAPOUR PRESSURE

• Ostwald’s dynamic method is based on the measurement of RLVP of a solution due to addition
of a non volatile solute
• RLVP as per Raoult’s law, is equal to the mole fraction of solute
Po − P
= xs
Po
• Where xs = mole fraction of solute
Po − P ns
=
Po no + ns
a b
ns = :no =
M W
For dilute solutions ns  no
Po − P a W a W Po
=  or M = 
Po M b b

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2. ELEVATION IN BOILING POINT
• The temperature at which the vapour pressure of a liquid becomes equal to the atmospheric pressure
(i.e., one atmosphere) is known as the boiling point of the liquid.
• The vapour pressure (P) of a dilute solution of the non-volatile solute is less than the vapour pressure
of the pure ( Po ) solvent in which the non-volatile solute is dissolved.
• Boiling point of solution (T) is grater than the boiling point of solvent (To ) .

• (T − To ) = Tb = elevation of Boiling point.

• According to the principle of elevation in boiling point

BE BF
=
BK BL
Or
Po − P1 To − T1
= (a) P T
Po − P11 To − T11

• As per Raoults law P X s , is Tb Xs

Or

Tb = Kb Xs
• Kb = proportionality constant
• X s = Mole Fraction of solute.
• From thermodynamic laws
RT 2
• Kb = o
, Hvap = molar heat of vapourisation of liquid
Hvap
• To = boiling point
• R = gas constant.

RTo2
Tb =  Xs
Hvap
ns a W
• For dilute solutions, X = = 
s
no M b
 = RT 2
  
a W
o
Tb  
Hvap M b 

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• But (Hvap = W  lv = latent heat of boiling point)
RTo2 a 1
Tb =  
lv M b
• for 1 molal solution,
RTo2 1
Tb = 1
lv 1000
 a 
= 1, b = 1000gr
M 
 
RTo2
Kb =
lv 1000
• Tb and Kb are related by the equation
• Tb = Kb  m (m=molality)
Or
a 1000
Tb = K b  
M b
• The elevation in boiling point observed in one molal solution of a non-volatile solute is called
molal elevation constant ( Kb ) (or) Ebullioscopic constant.
• The molal elevation constant of a solvent does not change with the change in the nature of
solute dissolved in it.
• Cottrell’s method is used for determination of molar mass of solute using elevation of boiling point.
3. DEPRESSION OF FREEZING POINT
• Freezing point is the temperature at which the solid form of liquid begins to separate out from
the liquid. At this temperature solid and liquid will be in equilibrium.
• When non volatile solute in dissolved in a solvent the freezing point decreases.
• For dilute solutions the curves are considered almost linear.

• From OBC, OEF,

OC BC
=
OF EF
Or

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Po − P1 To − T1
= (or ) P T
Po − P11 To − T11

• As per Raoults law, P X s is Tf  Xs

Or
Tf = K f Xs
• K f = proportionality constant or molal depression constant or cryoscopic constant
• X s = Mole Fraction of solute.
• From thermodynamic laws
RT 2
Kf = H f =
o
• molar heat of freezing
H f
• To = freezing point
• R = gas constant.

RTo2
Tf =  Xs
H f
ns a W
• For dilute solutions, X = = 
s
no M b
RT  2
 = a w
o 
Tf  
H+  M b 
• But H f = W  l f ( l f = latent heat of freezing point)
RTo2 a 1
Tf =  
lf M b
• for 1 molal solution,
RT 2 1
Tf = 1
o

lf 1000
 a 
= 1, b = 1000gr
M 
 
RTo2
Kf =
l f 1000
• Tf and K f are related by the equation
• Tf = K f  m (m=molality)
Or
a 1000
T f = K f  
M b

• The depression of freezing point observed in 1 molal solution of a non volatile solute is known as Kf

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• K f depends on chemical nature of solvent but not solute in the solution.
• Rast method is used for determination of molar mass of solute. Using depressing in freezing point.
• Rast method is used for solid solutions.
4. OSMOSIS:
• The spontaneous flow of the solvent through semipermeable membrane from pure solvent to
solution (or) from a dilute solution to concentrated solution is known as osmosis.
• The membranes which allow to pass only solvent molecules through it but not solute molecules
is called semipermeable membrane.
• Ex. Animal membranes like pig’s bladder, membrane round the red blood corpuscle, cell
membrane, parchment paper, cellophane paper, inorganic precipitate membranes like cupric
ferro cyanide
• Cu2 Fe (CN )6 
• Calcium phosphate Ca3 ( PO4 ) 2
OSMOTIC PRESSURE
• The hydrostatic pressure developed on the aqueous dilute solution at equilibrium state due to inflow of
water when the solution is separated from the water by a semipermeable membrane.
(or)
• The pressure required to be applied on the solution to just stop the inflow of solvent into the solution,
when the solution is separated from the solvent by a semipermeable membrane.
• VANT HOFF’S THEORY OF DILUTE SOLUTIONS
• According to vant Hoff’s, dilute solutions behave as gases. Hence the laws that applicable to gases
are also applicable to dilute solutions.

• VANT HOFF’S BOYLES LAW

• At constant temperature the osmotic pressure ( ) of a dilute solution is directly proportional to its
concentration (C)
• C = mole / litre
1
  1
V ∵C  V 
 
• V = K ............(1)
• VANT HOFF’S CHARLE’S LAW
• The osmotic pressure ( ) of a solution of constant concentration (C) is directly proportional to the
temperature in Kelvin Scale (T)
T

•  = KT ............ (2)
T
• from (1) and (2) 
V
T
 =S
V
 = CST ∵ 1 = C 
 V 
 
• here S = solution constant

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• The value of ‘S’ is similar to the value of ‘R’
• (gas constant)
• Hence  V = RT for 1 mole

• for ‘n’ mole  V = nRT

• If ‘a’ is weight of the solute and ‘m’ is its molecular weight then
a
n=
M
a
• for ‘n’ moles V = RT
M
aRT aRTC
(a) M= (b) M=
V 
• osmotic pressure is determined by Berkely - Hartely method

REVERSE OSMOSIS
• When a pressure greater than that of osmotic pressure ( ) is applied on solution side, then
the solvent from the solution flows into pure solvent this process is called reverse osmosis.
• It used in desalination of sea water
ISOTONIC SOLUTIONS:
• At a given temperature solutions of same osmotic pressure are called isotonic solutions:
• eg: Blood is isotonic with saline (0.9% w/v NaCl solution)
HYPOTONIC SOLUTIONS
• Solutions having lower osmotic pressure

HYPER TONIC SOLUTIONS

• Solutions having higher osmotic pressure
PLASMOLYSIS
• The flow of the liquid from the plant cell when placed in a hypertonic solution is called
plasmolysis. The plant cell undergoes shrinkage. It is an example to exo-osmosis
HAEMOLYSIS:
• When a plant cell is placed in hypotonic solution then the solvent flows into plant cell. This is
known as Haemolysis. The plant cell finally bursts. It is an example to endo-osmosis.
• Plants taken up water from soil through the phenomenon of osmosis through root hairs
• A raw mango placed in salt solution loses water via osmosis. This is a pickle.
• Osmotic pressure of solutions have high values and are of the order of about 20-200 atm.
• Ordinary membranes can’t with stand pressure. Hence Berkely - Hartley measured osmotic
pressure using cupric ferrocyanide as semipermeable membrane.
The osmotic pressure of a solution containing 1 mole of solute particles per litre (1M) at is
22.4 atm.

FORMULAE:
1. V = nST
w Hence 
 =wOsmotic
 pressure
V = ST  n = S = Solution constant
m  m
 
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wST
m= T = absolute temperature
V
2. V = nST W=Weight of solute
n
 = ST = MST m = molecular wt of solute
v
V = volume of the solution
N = no. moles of solute
M=Molarity of the solution
3. Consider two solutions I and II having n1 and n2 moles of the solute in V1 and V2 litres of the solution
respectively let P1 and P2 be their osmotic pressures at the same temperature (T)
IfP1 = P2 i.e., isotonic solutions
n n
then 1 = 2
V1 V2
W1 W2
(a) =
M1V1 M 2V2
OSMOTIC PRESSURE OF MIXTURE OF TWO SOLUTIONS
Case(I) Let two solutions of same substance having different osmotic pressures 1 and 2 are mixed then
osmotic pressure of the resultant solution can be calculated as 1V1 +  2V2 = r (V1 + V2)

Here  r =osmotic pressure of resulting solution

Case (II)Let n1 and n2 are the number of moles of two different solutes present in V1 and V2 volumes
respectively. Osmotic pressure of the mixture can be calculated as
 = 1 +  2 n i ST n i2 ST
= (V1 +1 V ) + (V2 + V)
1 2 1 2

=
(n1i1 + n2i2 ) ST
(V1 + V2 )
here i1 and i2 are vant Hoff’s factors for the two solutes.
OSTWLAD’S -DYNAMIC METHOD :-
• This method is used to measure the molar mass of a solute based on the measurement of
relative lowering of vapour pressure of a solution.
• solution is taken in first two bulbs( A - bulbs) and solvent is taken in the other two bulbs [B].
CaCl2 is present in ‘U’ tube [C- bulb]
• Above 3- bulbs weights are determined before and after experiment.
• dry air in passed through the bulbs
• x= loss of weight solution bulbs  P.
• y = loss of weight of solvent bulbs  P0 − P
• Total loss = gain (Z) in weight of U- tube [C]
 Z = ( x + y ) = P0
x + y = P + ( P 0 − P) = P0
P0 − P y
=
x+ y
0
P
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y a W
= 
x+ y M b
aW ( x + y )
M= 
b y
COTTRELL’S METHOD :-
• This method is used to measure the molar mass of a solute using elevation of boiling point.
• Beckman thermometer is used to measure the elevation or depression in temperature.
• This thermometer does not measure absolute values of [Link] and [Link].
• This thermometer contains Hg-reservoir at one end mercury bulb at the another end. these two are
connected by capillary.
• It measures the elevation or depression temperature level of - 60 C to 3000 C
T = K  a  1000
b b
M b
Kb = molal elevation constant of solvent
 M = K  a 000
Tb
b
b

RAST’S METHOD :-
• This method is used to measure the molar mass of a solute using depression in freezing point.
• In this method Camphor is used as a solvent.
• This method is generally used for solid solutions i.e. a sold solute in a solid solvent.
• Wt of Camphor = b gm
• Wt of solute = a gm
• [Link] of solute = M.
T = K  a  1000
f f
M b
M = K  a  1000
Tf
f
b

BERKELY- HARTLEY METHOD :-

• This method is used to determine the Osmotic pressure which is used to measure the molar
mass of a solute.
• A porous tube whose both ends are open is taken and its pores are precipitated with copper
ferrocyanide.
• Copper ferro cyanide can act as semi permiable membrane
• Porous tube is fixed in an outer cylendrical tube made from gun metal.
• As Osmosis strarts the level in the capillary decreases due to flow of water from inner tube in to
outer tube.
• Now pressure is applied extermally on the piston and the level of liquid in the capillary is
brought to initial position, called as Osmotic pressure .
V = nRT
a
V = RT
M
aRT
M =
V

16
 Solutions
a = wt of solute M = mol. wt of solute
• ABNORMAL MOLAR MASS
• Colligative properties are shown by dilute solutions.
• solutions which obey Raoult’s law are called ideal solutions.
• Deviations in Raoult’s law are observed due to increase in concentration of solutions.
• Solutions which deviate from Raoult’s law are known as non-ideal solutions.
• In ideal solutions intermolecular forces in the solvent are negligible.
• But in non ideal solutions intermolecular forces are considerable.
• Non ideal solutions show deviations in colligative properties.
• Electrolytes undergo ionisation in aqueous solutions as a result number of particle in the
solution increases hence magnitude of colligative properties increases.
• Colligative property and molar mass of solute are inversely proportional.
• So molar mass of electrolytic solutes determined experimentally is less than true value.
• Some solutes when dissolved in solvents may undergo association i.e, solute molecules combine to
form dimers or trimers etc.
• Due to association number particles in the solution decreases, as a result magnitude of
colligative property decreases. So molar mass of such solute will be higher than true value.
• Van’t Hoff introduced a factor ‘i’ in the equations to equalise the experimental value and
calculated value.
• For example, osmotic pressure ( ) equation is

• V = RT (calculated)
• V = iRT (experimental )

 exp t = i
cal
experimental valueof colligative property
• i=
Calculated valueof colligative property
observed osmotic pressure
example i =
Calculated osmotic pressure
• For solutes which undergo dissociation and ionisation of a solute on ionisation gives ‘n’ ions
(particles) and ' ' is degree of ionisation at the given concentration, we will have
1+ (n −1)  particles (ions)
An → nA
1 0
1−  n

• Total no of particles after dissociation = 1−  + n = 1+ (n −1) 

[Link] particles after dissociation
i=
[Link] particles before dissociation
 1+ (n −1) 
i= 
1
i −1
=
n −1

17
 Solutions

• ' ' is degree of dissociation or ionisation.

• For solutes which undergo association

• If ‘n’ ‘A’ molecules combine to give An , we have
nA UA n
• 1 O (  =degree of association at the given concentrate)

1− 
n
• Total particle after association

= 1−  +
n

1−  +
i = n
1
 1
1−  1−
 n
i=  
1
i −1 1− i
 association = 1 or association =
−1 1−
1
n n

18
 6
Solutions
1. 160 g of non-volatile solute ‘A’ is dissolved in 3. 10 g of NaOH is dissolved in 500 mL of
54 mL of water at 373 K. What is the vapour aqueous solution. Calculate the molarity of
pressure of aqueous solution of A. this solution? (Given, formula weight of
(Given, molecular weght of A = 160 g mol −1 ) NaOH = 40) [17 Sep. 2020, Shift-I]
[17 Sep. 2020, Shift-I] (a) 0.5 × 10−3 M (b) 0.4 M
(a) 760 Torr (b) 720 Torr (c) 0.25 × 10−3 M (d) 0.5 M
(c) 570 Torr (d) 450 Torr Sol. (d)
Sol. (c) Mass of solute (in gL− 1 )
∴ Molarity =
(p ° − p) Molar of solute (in g mol − 1 )
RLVP =
p° 10
× 1000
[Qp° = vapour pressure of H 2 O(g) at 373 K = 760 bar = 500 M
Let, d water = 1 g/mL 40
⇒ 54 mL = 54 g water = 0.5 M
Q χ → mole fraction 4. Which of the following change decrease the
n → mole] vapour pressure of water kept in a sealed vessel?
nA [17 Sep. 2020, Shift-II]
⇒ χA =
n A + nH 2 O (a) Decreasing the quantity of water
160 (b) Adding salt to water
760 − p 1 (c) Decreasing the volume of the vessel to one-half
⇒ = 160 =
160 54 4 (d) Keeping the temperature of water constant
760 +
160 18 Sol. (b)
3 When salt (non-volatile solute) is added to water
⇒ p = × 760 = 570 tour
4 kept in a sealed vessel, boiling point of the
solution will be elevated or increased. So, vapour
2. A 40% HCl solution has density 1.2 g mL −1 . pressure of water (solution) will be decreased.
The molarity of the solution is nearly …… . Lowering of vapour pressure (∆p = p ° − p) is also
[17 Sep. 2020, Shift-I] proportional to mole fraction of the solute (χ B)
(a) 11 M (b) 12 M (c) 13 M (d) 14 M present in the solution.
Sol. (c) ∆p ∝ χ B [p° = vapour pressure of pure water
p = vapour pressure of solution]
As, density (d) of HCl solution is given (pc)
(1.2 g mL − 1 ), the percentage strength of the 5. On the basis of which physical property
solution (40%) is of (w/w) type. separation of different fractions in fractional
pc(w / w) × d(g mL− 1 ) × 10 distillation technique takes place?
⇒ Molarity =
M HCl [17 Sep. 2020, Shift-II]
40 × 1.2 × 10 (a) Solubility (b) Freezing point
= = 13.15 ~
− 13 M
36.5 (c) Boiling point (d) Melting point
Solutions 43

Sol. (c) Column I Column II

Separation of liquids into their pure form to A. Beckmann method 1. Osmotic pressure
from its liquid mixture is done by fractional
distillation technique. It is done, when two B. Ostwald-Walker 2. Elevation in B.P
liquids have difference in their boiling points method
(10 − 40 K). C. Berkeley-Hartley 3. Depression in F.P.
method
6. Calculate the density of an aqueous solution
of KI, if its molarity and molality are 1.44 M D. Landsberger method 4. Relative lowering
and 1.5 mol kg − 1 respectively. of vapour pressure
[18 Sep. 2020, Shift-II] Codes
−1
(a) 2.20 g L (b) 2.50 g L − 1 A B C D A B C D
(c) 1.20 g L − 1 (d) 0.50 g L − 1 (a) 2 4 3 1 (b) 1 4 2 3
Sol. (c) (c) 2 3 4 1 (d) 3 4 1 2
We know, Sol. (d)
1000 × M The correct matching between Column I and
m=
1000 × d − M × M B Column II are
1000 × M + m × M × M B (A) Backmann method - Depression in freezing
⇒ d= point
1000 × m
1000 × 1.44 + 1.5 × 1.44 × 166 (B) Ostwald-Walker method - RLVP
= (C) Barkeley-Hartley method-Osmotic pressure
1000 × 1.5
(D) Landsberger method - Elevation in boiling
= 1.1990 = 1.20 gL−1
point
Q m = molality = 1.5 mol kg −1
Thus, correct answer is option (d).
M = molarity = 1.44 mol L−1
M B = molar mass of KI 9. Which of the following relations is true based
= 166 g mol −1 on the partial pressure and mole fraction? [18
d = density of solution Sep. 2020, Shift-II]
(a) pi = χ i × T (b) pi = χ i × ptotal
7. Calculate the molarity of NaOH solution
p
prepared by dissolving 0.4 g of NaOH in (c) i = V (d) pi χ i = ptotal
χi
enough water to form 500 mL of the solution.
[18 Sep. 2020, Shift-II] Sol. (b)
(a) 0.02 (b) 0.05 Partial pressure = mole fraction × total pressure
(c) 0.04 (d) 0.03 So, the ith, component of a gas mixture, which
Sol. (a) obeys Dalton’s law of partial pressure,
wB g L−1 pi = χ i × ptotal
Molarity =
M B g mol −1 10. The molarity of 0.2 N Na 2CO 3 solution will be
0.4
× 100 [21 Sep. 2020, Shift-I]
= 500 = 0.02 M (a) 0.05 M (b) 0.2 M (c) 0.1 M (d) 0.4 M
40
[∴wB = mass of solute (NaOH) = 0.4 g/mL Sol. (c)
M B = molar mass of NaOH = 40 g mol −1 ] n - factor for Na 2CO 3 = 2
∴The n-factor of such salts is defined as the
8. Match the item given in Column-I (method number of moles of electrons exchanged (lost or
used for determining colligative property) gained) by one mole of the salt and there is the
and Column-II (for the corresponding exchange of 2 electrons, so its n-factor is 2.
colligative property) and find the correct Therefore, normality = n-factor × molarity
order. [18 Sep. 2020, Shift-II] ⇒ Molarity= 0.2/2 = 0.1 M
Hence, the correct option is (c).
44 AP EAMCET Chapterwise Chemistry

11. Calculate the ratio of the effusion of CO and 14. Find the molarity of the 5 molal urea
N 2, when temperature and pressure solution, whose density is 1.3 g/mL (given,
gradients are held constant? molecular weight of urea is 60.06 g/mol)
[21 Sep. 2020, Shift -II] [22 Sep. 2020, Shift-I]
(a) 1 : 2 (b) 1 : 1 (c) 2 : 1 (d) 1 : 4 (a) >5 M (b) = 5 M
(c) < 5 M (d) Can’t be predicted
Sol. (b)
The rate of effusion of a gas is inversely Sol. (b)
proportional to the square root of the mass of its 5 molal urea solution (d = 1.3 g/mL)
particles. 1 kg of solvent contains 5 moles of urea.
1 Means 1000 g water contains 300 g of urea.
Rate of effusion ∝
Molecular mass Molarity of 1300 g urea solution contains 300 g
If two gases CO and N 2 are at the same urea will be
temperature and pressure, the ratio of their  300  × 1000
 
effusion rates is inversely proportional to the  
M urea = 60 = 50
.
ratio of the square roots of their molar masses.  1300 
 
Rate effusion of CO MN 2  1.3 
∝
Rate of effusion of N 2 M CO Hence, the correct option is (b).
28 15. The avoid bends sickness, the tanks used by
⇒ ⇒ 1:1
28 scuba divers are filled with air and diluted
Hence, the correct option is (b). with …… [22 Sep. 2020, Shift-I]

12. In comparison to a 0.01 M solution of (a) helium gas (b) argon gas
(c) krypton gas (d) xenon gas
glucose, the depression in freezing point of a
0.01 M MgCl 2 solution is ……… (Molecular Sol. (a)
weight of MgCl 2 = 95, molecular weight of The gas bubbles (like nitrogen) in the bodily
glucose = 180). [21 Sep. 2020, Shift-II]
fluids affect nerve impulses giving rise to
decompression sickness or bends. These can be
(a) the same (b) about twice painful and fatal. So, the avoid bends sickness,
(c) about three times (d) about six times the tanks used by scuba divers are filled with air
Sol. (c) and diluted with helium gas.
0.01 M solution of glucose does not ionise while 16. Which of the following solutions has the
0.01 M MgCl 2 solution furnishes 3 ions lowest freezing point? [22 Sep. 2020, Shift-II]
(Mg 2+ + 2Cl −) in the solution, hence the value
(a) 1 M Urea (b) 1 M Na 2 SO 4
of colligative property of MgCl 2 solution is
about 3 times. Hence, the correct option is (c). (c) 1M NaCl (d) 1 M Al 2 (SO 4 ) 3
Sol. (d)
13. What will be the molality of the solution
Urea do not dissociate in solution. Sodium
containing 18.25 g of HCl gas in 500 g of chloride gives two ions, while sodium sulphate
water? [22 Sep. 2020, Shift I] gives three ions per formula unit and aluminium
(a) 0.5 m (b) 0.1 m (c) 1 m (d) 0.05 m sulphate give five ions per formula unit. '
Sol. (c) Therefore, the effective number of particles is
maximum in aluminium sulphate and it shows
Given, mass of HCl = 18.25 g
the maximum depression in freezing point, thus
Molar mass of HCl = 36.5 g/mol the lowest freezing point due to the highest
Mass of water = 500 g = 0.5 kg moles of ions in solution. Hence, the correct
Number of moles of HCl = Mass of HCl / Molar option is (d).
mass of HCl = 18.25 / 36.6 = 0.5 mol
17. Which of the following statements is true?
Molality = Number of moles / Mass of solvent in kg
(i) 200 mL of 0.2 M NaOH has same number
= 0.5 / 0.5 = 1m
of moles of solute as 1000 mL of 1 M
Hence, molality of solution is 1m, thus correct
NaOH.
option is (c).
Solutions 45

(ii) 200 mL of 1M NaOH has same number of II. Normality = n-factor × molarity
moles as 1000 mL of 0.2 M NaOH. 0.1
Molarity (H 2SO 4 ) = = 0.05M
(iii) 100 mL of 0.2 M NaOH has same number 2
of moles as 1000 mL of 1 M NaOH. . × 200
01
moles of H 2SO 4 = = 0.01 M
(iv) 2000 mL of 0.2 M NaOH has same number 1000 × 2
of moles as 1000 mL of 1M NaOH. Weight of urea
III. Moles =
[23 Sep. 2020, Shift-I] Molecular weight of urea
(a) (i) (b) (ii) (c) (iii) (d) (iv) 6
= = 01. m
60
Sol. (b)
Hence, option (a) is correct.
Molarity of solution,
Moles of solute × 1000 20. 6 g of a mixture of naphthalene (C10H 8) and
(M) =
Vol (in mL) anthracene (C14 H10) is dissolved in 300 gram
Moles of solute in 200 mL of 1 M NaOH solution, of benzene. If the depression in freezing
1 × 200 point is 0.70 K, the composition of
nNaOH = = 0.2
1000 naphthalene and anthracene in the mixture
and moles of solute in 1000 mL of 0.2 M NaOH respectively in g are (molal depression
solution, nNaOH =
0.2 × 1000
= 0.2
constant of benzene is 5.1 K kg mol −1 )
1000 [20 April 2019, Shift-I]
Hence, the correct option is (b). (a) 2.60, 3.40 (b) 3.40, 2.60
(c) 2.90, 3.10 (d) 3.10, 2.90
18. The volume of 0.02 M acidified
permanganate solution required for complete Sol. (b)
reaction of 60 mL, of 0.01 M I − ion solution Given, weight of solvent = 300 g
moles of solute
to form I 2 in mL is [20 April 2019, Shift-I] Molality =
(a) 60 (b) 20 (c) 40 (d) 6 weight of solvent (kg)
K f = 5.1 K kg/mol
Sol. (d)
− Depression in freezing point,
Reaction of KMnO 4 with I converting I 2 is
∆Tf = K f × m ⇒ 0.70 = 5.1 × m
2KMnO 4 + 10 I − → 5I 2 + 2Mn +2
0.70 Total moles of solute
n-factor of KMnO 4 = 5 (in acidic medium) =
5.1 Total weight of solvent (kg)
I − convert into I 2 then, n-factor = 2
Number of equivalent of KMnO 4 Lets, assume x g napthalene is present,
x 6− x
= Number of equivalent of I − + × 1000
wC 10 H 8 wC 14 H 10
0.02 × V × 5 = 60 × 0.01 × 2 .
0137 =
V = 6 mL 300
x 6− x
0.041 = +
19. The number of moles of solute present in the 128g 178g
solutions of I, II and III is respectively ⇒ 25x = 84.211
[20 April 2019, Shift-I]
x(napthalene) = 34 .
I. 500 mL of 0.2 M NaOH Now, anthracene = 6 − x = 6 − 3.4 = 2.6 g
II. 200 mL of 0.1 N H 2SO 4 Hence, option (b) is correct.
III. 6 g of urea in 1 kg of water
21. 1.2 mL of acetic acid having density
(a) 0.1, 0.01, 0.1 (b) 0.1, 0.02, 0.1
1.06 g cm −3 is dissolved in 1 litre of water.
(c) 0.2, 0.01, 0.1 (d) 0.1, 0.01, 0.2
The depression in freezing point observed for
Sol. (a) this concentration of acid was 0.041°C. The
I. Moles of solute NaOH = molarity van’t Hoff factor of the acid is
× volume of solution (in L) . K kg mol −1 )
(K f of water = 186
0.2 × 500
= = 01
. mol [20 April 2019, Shift-II]
1000 (a) 0.41 (b) 1.04 (c) 0.96 (d) 1.54
46 AP EAMCET Chapterwise Chemistry

Sol. (b) 23. A solution is prepared by dissolving 10 g of a

From depression in freezing point, non-volatile solute (molar mass, ‘M’ g mol − 1 )
∆Tf = i × K f × m …(i) in 360 g of water. What is the molar mass in
Moles of solute g mol − 1 of solute if the relative lowering of
Molality (m) = × 1000
Mass of solvent (in g) vapour pressure of solution is 5 × 10 − 3?
Mass = density × volume = 1.2 × 1.06 = 1.272 g [21 April 2019, Shift-I]
1.272
∴ Moles of solute = (a) 199 (b) 99.5 (c) 299 (d) 149.5
60
Sol. (b)
Q Moles = Mass 
  Given, Mass of solute (wB) = 10 g
 Molecular mass 
i × 1.86 × 1.272 > × 1000 60 × 0.041 Molar mass of solute (M B) = M B
0.041 = = Mass of solvent (w A) = 360 g
60 × 1000 1.86 × 1.27
Relative lowering in vapour pressure of solution
i = 1.04 = 5 × 10− 3
Thus, option (b) is correct. Molar mass of water (M A) = 18 g mol −1
22. 100 mL of 1.5% (w/v) solution of urea is ∆p
Q = Relative lower in vapour-pressure of
found to have an osmotic pressure of 6.0 p°
atm and 100 mL of 3.42% (w/v) solution of solution.
∆p nB
cane sugar is found to have an osmotic = χB ⇒ = 5 × 10− 3
pressure of 2.4 atm. If the two solutions are p° n A + nB
mixed the osmotic pressure of the resulting where, n A and nB are number of moles of solvent
solution in atm is (Assume that there is no (A) and solute (B) respectively.
reaction between urea and cane sugar) 360
nA = = 20
[20 April 2019, Shift-II] 18
(a) 8.4 (b) 16.8 (c) 4.2 (d) 2.1 w 10
nB = B =
Sol. (c) MB MB
Key Idea Firstly, we calculate the osmotic pressure 10
of each solution by using the formula π = CRT and −3 MB
Q 5 × 10 = χ B =
then, calculate the total osmotic pressure. 10
20 +
Given, w1 (urea) = 1.5g MB
V1 (urea) = 100 mL 10
M1 = 60 g/mol −3 MB
5 × 10 =
w2 (cane sugar) = 342 . g 20 M B + 10
V2 (cane sugar) = 100 mL MB
M 2 = 342 g/mol −3 10
5 × 10 =
w × 100 20 M B + 10
π1 (urea) = 1 ×R×T
M1 × V1 (20 M B + 10) 5 × 10− 3 = 10
1.5 × 1000 10
π1 (urea) = × 0.0821 × 298 or, 20 M B + 10 = × 103
60 × 200 5
π1 (urea) = 3.05atm 20 M B + 10 = 2000 ⇒ 20 M B = 1990
Now, 1990
MB = = 99.5 g mol −1
w2
π 2 (cane sugar) = × 1000 × R × T 20
M 2 × V2 Hence, option (b) is the correct answer.
3.42 × 1000
= × 1000 × 0.0821 × 298 24. x g of MgSO 4 (i = 18
. ) is in 2.5 L of solution has
342 × 200
Thus, the osmotic pressure of the resulting an osmotic pressure of 2.463 atm at 27°C.
solution is What is the value of x in g? [21 April 2019, Shift-I]
π = π1 + π 2 = 3.05 + 1.22 = 4.27 atm (a) 33.2 (b) 6.6
Thus, the nearest value is in accordance with (c) 3.3 (d) 16.6
option (c).
Solutions 47

Sol. (d) 26. What is the volume (in mL) of 20 vol H 2O 2

Given, Mass of MgSO 4 (w) = x g required to completely react with 500 mL of
i = 1.8
vant Hoff factor () 0.02 M acidified KMnO 4 solution?
Volume of solution (V) = 2.5L [21 April 2019, Shift-I]
Osmotic pressure (π) = 2.463 atm (a) 14.0 (b) 7.0 (c) 28.0 (d) 42.0
Temperature (T) = 27 + 273 = 300 K
Sol. (a)
Molar mass of MgSO 4 = 24 + 32 + 64
Given,
= 120g mol −1 Volume of acidified KMnO 4 solution = 500 mL
w 1
Q π = iCRT = i × × × RT Molarity of acidified KMnO 4 solution = 0.02 M
M V
Volume strength of H 2O 2 = 20 vol
i × x × RT
π = 2.463 = Volume strength
M×V Q Normality =
Equivalent weight
1.8 × x × 8.314 × 300
= 20
120 × 2.5 ∴ Normality for H 2O 2 = = 3.57 N
56.
(Q R = 0.82 L - atm K − 1 mol − 1 ) Q For KMnO 4 , reaction is in acidic medium, thus
2.463 × 120 × 2.5 valence factor is 5.
∴ x=
1.8 × 0.082 × 300 Mn7 + + 5 e − → Mn2 +
x=
738.9
= 16.68 ≈ 16.6 g Thus, normality for KMnO 4 = Molarity × 5
44.28 Now, applying normality equation,
Hence, option (d) is the correct answer. N1 V1 (H 2O 2) = N 2 V2 (KMnO 4 )
3.57 × V1 = 0.02 × 5 × 500
25. 30.0 mL of the given HCl solution requires 50
20.0 mL of 0.1 M sodium carbonate solution V1 = = 14.0 mL
3.57
for complete neutralisation. What is the
volume of this HCl solution required to Hence, option (a) is the correct answer.
neutralise 30.0 mL of 0.2 M NaOH solution? 27. The vapour pressures of chloroform (CHCl 3),
[21 April 2019, Shift-I]
dichloromethane (CH 2Cl 2) at 298 K are
(a) 25 mL (b) 50 mL (c) 90 mL (d) 45 mL 200 mm Hg and 415 mm Hg respectively. An
Sol. (c) ideal solutions is prepared by mixing 59.75 g
Given, of CHCl 3 and 21.25 g of CH 2Cl 2, the mole
Volume of HCl solution (V1 ) = 30 mL fractions of chloroform and dichloromethane
Volume of sodium carbonate solution (Na 2CO 3) in vapour phase respectively are
(V2) = 20 mL [21 April 2019, Shift-II]
Concentration of Na 2CO 3 solution (M 2) = 0.1 M (a) 0.509, 0.491 (b) 0.491, 0.509
Volume of NaOH solution (V3) = 30.0 mL (c) 0.201, 0.799 (d) 0.799, 0.201
Concentration of NaOH solution (M 3) = 0.2 M Sol. (b)
Q M1 V1 = M 2 V2 Given, Mass of CHCl 3 = 59.75 g
where, M1 is concentration of HCl solution. Molar mass of CHCl 3 = 12 × 1 + 1 × 1 + 355. ×3
MV 01 . × 20 = 119.5 g mol −1
M1 = 2 2 = = 0.066 M
V1 30 59.75 g
∴Moles of CHCl 3 = = 0.5 mol
Also, HCl solution required to neutralise 30 mL 119.5 g mol −1
of 0.2 NaOH is calculated as follows : Given, mass of CH 2Cl 2 = 21.25 g
M1 V f = M 3 V3 (where, V f is the volume of HCl Molar mass of CH 2Cl 2 = 12 × 1 + 2 × 1 + 355
. ×2
solution required) = 85 g mol −1
21.25 g
M 3 V3 0.2 × 30 ∴Moles of CH 2Cl 2 = = 0.25 mol
∴ Vf = = = 90 mL 85 g mol −1
M1 0.066
Total moles = 0.5 + 0.25 = 0.75 mol
Hence, option (c) is the correct answer.
48 AP EAMCET Chapterwise Chemistry
2+
0.25
χ CH 2 Cl 2 = = 0.33 ∴Cr2O 2−
7 react with 6Fe n1 and MnO −4 react
2+
0.75 with 5Fe (n2) in a balanced equation.
χ CHCl 3 = 1 − 0.33 = 0.67 Gram equivalent of Fe2 +
Q ptotal = p1 ° + (p2 ° − p1 °) x 2 = gram equivalent of K 2Cr2O 7
= 200 + (415 − 200) × 0.33 = gram equivalent of KMnO 4
∴ ptotal = 270.95 mm Hg Therefore, on comparing gram equivalent
Now, pCH 2 Cl 2 = 0.33 × 415 mm Hg = 136.95 mm Hg of K 2Cr2O 7 and KMnO 4 , we have
pCHCl 3 = 0.67 × 200 = 134 mm Hg n1 = 6, n2 = 5
Q (mole fraction in vapour phase), Conc. of K 2Cr2O 7 =0.01M(M1 )
yi = pi / ptotal Volume of K 2Cr2O 7 =20 mL(V1 )
136.95 mm Hg react with Fe2 + ions = 6 mol (n1 )
∴ yCH 2 Cl 2 = = 0.505
270.95 mm Hg Conc. of KMnO 4 = to find (say M 2 )
134 mm Hg Volume of KMnO 4 =20 mL(V2)
and yCHCl 3 = = 0.494
270.95 mm Hg react with Fe2 + ions = 5 mol (n2)
Thus, M1 × V1 × n1 = M 2 × V2 × n2
28. The elevation in boiling point of an aqueous or, 0.01 × 20 × 6 = M 2 × 20 × 5
solution of NaCl is 0.01 °C. If its van’t Hoff 0.01 × 6
or M2 = = 0.012 M
factor is 1.92, the molality of NaCl solution is 5
(K b for water = 0 .52 K kg mol −1 ) Hence, option (d) is the correct answer.
[21 April 2019, Shift-II] 30. At 300 K an ideal solution is formed by
(a) 0.01 m (b) 0.001 m mixing 460 g of toluene with 390 g benzene.
(c) 0.005 m (d) 0.02 m If the vapour pressure of pure toluene and
Sol. (a) benzene at 300 K are 32 and 40 mm
Given, ∆Tb = 0.01° C = 0.01 K, i = 1.92
respectively, the mole fraction of toluene in
vapour phase is [22 April 2019, Shift-I]
K b = 0.52 K kg mol −1
(a) 0.196 (b) 0.588
As we know that,
(c) 0.294 (d) 0.444
∆Tb = iK b × m
0.01 Sol. (d)
∴ m= mol/kg
1.92 × 0.52 Given, wa = 460 g (toluene)
m (molality) = 0.01 mol/kg or 0.01 m wB = 390 g (benzene)
Vapour pressure of pure toluene (p A) = 32 mm
29. 20 mL of Fe2 + solution of certain Vapour pressure of pure benzene (pB) = 40 mm
concentration has completely reacted with w 460
20 mL of 0.01 M K 2Cr2O 7 in acidic medium. If Moles of toluene, (n A) = A =
MA 92
20 mL of same Fe2 + solution has reacted w 390
completely with 20 mL of KMnO 4 solution in Moles of benzene, nB = B =
MB 78
acid medium, the molarity of KMnO 4
solution is [22 April 2019, Shift-I] Hence, mole fraction of toluene χ A.
460
(a) 0.01 M (b) 0.12 M
(c) 0.10 M (d) 0.012 M χA = 92
460 390
+
Sol. (d) 92 78
The reaction between Fe2 + and Cr2O 72− Mole fraction of benzene (χ B)
(i.e. K 2Cr2O 7 ) in acidic medium occurs as follows : 390
Cr2O 27 − +14H+ + 6Fe2+ → 2Cr 3+ χB = 78
+ 7H 2O +6Fe3+ 460 390
+
The reaction between Fe2 + and MnO −4 (i.e. KMnO 4 ) 92 78
in acidic medium occurs as follows : ptotal = p ° A χ A + p ° B χ B
MnO −4 +8H+ + 5Fe2+ → Mn2+ + 4H 2O + 5Fe3+
Solutions 49

 460   390  (a) H2NCONH2 , H2O, NaCl

 92   78  (b) H2O, H2NCONH2 , NaCl
∴ ptotal = 32 ×   + 40
460 390 390 460  (c) NaCl, H2O, H2NCONH2
 +   + 
 92 78   78 92  (d) NaCl, H2NCONH2 , H2O
ptotal = 36 mm Sol. (a)
Mole fraction of toluene in vapour phase (YT ) can
The vapour pressure of a solution (b) as a
be calculated as below :
function of temperature (a) is plotted as a graph
p° χ
p ° T χ T = YT . ptotal ⇒ YT = T T for two solutions of same molar concentration
ptotal along with water.
where, χ T is mole fraction of toluene. O
32 × (1 / 2) 16 
YT = ⇒ YT = = 0.444 Here, A is NH 2  C NH 2 .
36 36
B is H 2O.
31. If aqueous solution contains 9% and 1% C is NaCl.
(w/w) of two non-volatile non-electrolytes X
b
(molecular weight 180) and Y (molecular
weight 50) respectively, the boiling point of
B
solution in °C approximately is Vapour
(K b = 0.52 K kg mol −1) [22 April 2019, Shift-I] pressure of A
a solution C
(a) 101.4 (b) 100.4 (c) 102.4 (d) 100.8
Sol. (b)
a
Given, Mass of non-volatile solute X = 9 g Function of temperature
Mass of non-volatile solute Y =1 g When number of moles of solute decreases, then
Molar mass of X =180 g mol −1 vapour pressure of solution increases.
Molar mass of Y = 50 g mol −1 So, H 2NCONH 2 does not associate or dissociate.
Mass of solvent (approx.) = 100 H 2O forms hydrogen bonding and associates
K b = 0.52 K kg mol −1 vapour pressure increases. It dissociates to very
∴ ∆Tb = K b × M = K b [M( X) + M( Y ) ] small extent.
w w  1000 NaCl dissociates, (as it is a strong electrolyte
= K b  ( X) + ( Y )  × there number of moles increases therefore
 M( X) M( Y )  100
vapour pressure decreases.
= 0.52 
9 1 
+ 10 33. An ideal solution of hexane and heptane at
180 50 
30 °C has a vapour pressure of 95 bar with
= 0.52[0.05 + 0.0210
] = 0.52[0.07]10 = 0.36 hexane mole fraction 0.305. In vapour phase
Thus, boiling point = 100 + 0.36 = 100.36 or 100.4 hexane mole fraction is 0.555. The vapour
Hence, option (b) is the correct answer. pressure of pure hexane and heptane at 30° C
32. The vapour pressure of a solution (b) as a respectively in bar are [22 April 2019, Shift-II]
function of temperature (a) is plotted as a (a) 172.9, 60.9 (b) 60.8, 172.9
graph for two solutions of same molar (c) 30.4, 86.5 (d) 86.5, 30.4
concentration along with water as shown Sol. (a)
below. A, B and C are respectively Given, vapour pressure of ideal solution of
b hexane (pT ) = 95 bar
B Mole fraction of hexane (χ A) = 0.305
A So, (χ B) = 1 − 0.305 = 0.695
C Mole fraction of vapour phase hexane
(Y A) = 0.555 and of heptane (YB) = 1 − 0.555 = 0.445
a From Raoult’s law,
[22 April 2019, Shift-II] Vapour pressure of hexane = p °A
50 AP EAMCET Chapterwise Chemistry

Vapour pressure of heptane = pB° ∴Total vapour pressure of solution = p A + pB

pT (Y A) = p °A(χ A), pT (YB) = pB° (χ B) 2 3
ptotal = χ Ap °A + χ B pB° = × 100 + × 160
95 (0.555) = p °A(0.305) , 95 (0.445) = pB° (0.695) 5 5
p °A = 172. 9 bar, pB° = 60.9 bar = 40 + 96 = 136 mm
Also p A = y A ptotal
34. At 298 K, the vapour pressure of a solution of where, y A is the mole fraction of A.
7.5 g of non-volatile solute in 90 g of water is p 40
Mole fraction of A, y A = A = = 0.294
2.8 kPa. If 18 g of water is added to this ptotal 136
solution the vapour pressure becomes 2.81 kPa
∴ yB = 1 − y A = 1 − 0.294 = 0.706
at same temperature, the molar mass of
solute in g mol −1 is [23 April 2019, Shift-I] 36. One litre of 0.15 M Na 2SO 3 aqueous solution
(a) 17.5 (b) 68.2 (c) 71.5 (d) 51.8 is mixed with 500 mL of 0.2 M K 2Cr2O 7
Sol. (c) aqueous solution in acid medium. What is the
number of moles of K 2Cr2O 7 remaining in the
Key Idea Relation between relative lowering of
vapour pressure and molecular mass of solute is given
solution after the reaction?
[22 April 2018, Shift-I]
by
p ° − p w2 / M 2 (a) 0.1 (b) 0.0125 (c) 0.025 (d) 0.05
=
p° w1 M1 Sol. (d)
Given, Weight of non-volatile solute, w2 = 7.5 g When 0.15 M Na2 CO3 (1 L) mixed with 0.2 M
Weight of water, w1 = 90 g K 2 Cr2 O7 (5L) than total molarity (M).
Vapour pressure of solution = 2.8 kPa M V + M 2 V2
M= 1 1
In first case, V3
p ° − 2. 8 7.5 / M 2 p ° − 2. 8 1.5 0 .15 × 1 + 0 . 2 × 0 . 5
= ⇒ = …(i) M=
p° 90 / 18 p° M2 1⋅ 5
In second case, M = 0 .15 mol / L
p ° − 2.81 7.5 / M 2 1.25 Remaining mole of K 2 Cr2 O7 = 0 . 2 − 0 .15
= = …(ii)
p° 108 / 18 M2 = 0 . 05 mol / L.
On solving (i) and (ii) we get
37. The measured osmotic pressure of a solution
M 2 = 71.5 g mol −1
prepared by dissolving 17.4 mg of K 2SO 4 in 2L
35. At T(K), the vapour pressures of pure liquids of water at 27°C is 3.735 × 10 −3 bar.
A and B are 100 mm and 160 mm The van’t Hoff factor is
respectively. An ideal solution is formed by (R = 0 .083 L bar K −1 mol −1 ; atomic weights
mixing 2 moles of A and 3 moles of B at the K = 39, S = 32; O = 16) [22 April 2018, Shift-I]
same temperature. The mole fraction of A
(a) 2.84 (b) 3.0 (c) 2.0 (d) 2.32
and B in the vapour state respectively are
[23 April 2019, Shift-I] Sol. (b)
(a) 0.706, 0.294 (b) 0.294, 0.706 Given, π = 3. 735 × 10− 3 bar
(c) 0.40,0.60 (d) 0.60, 0.40 Mass of K 2 SO4 (ω) = 17 . 4 mg
Volume = 2L
Sol. (b) Temperature (T) = 27° C = 27 + 273 = 300 K
Key Idea Vapour pressure of solution, From osmotic pressure of solution.
ptotal = p A + pB , = χ Ap °A + χ B pB° [Q p A = χ Ap °A] π = iCRT
Also vapour pressure of component 1, p1 = y1 ptotal i = van’t-Hoff factor
where y, is the mole fraction of component 1 in vapour i = π / CRT
phase. π× M×V 3. 735 × 174 × 2
= =
Given, ω×R×T 17.4 × 0. 083 × 300
Vapour pressure of pure liquid A, p °A = 100 mm Molar mass (M) H 2SO 4 = 174, i = 3 .0
Vapour pressure of pure liquid B, pB° = 160 mm
Solutions 51

38. Dissolving 120 g of a compound (mol. wt Sol. (b)

= 60) in 1000 g of water gave a solution of 0.1 m solution of Na 2SO 4 (sodium sulphate),
density 1.12 g mL −1 . The molarity of solution  O 
is [22 April 2018, Shift-I]   
0.1 m solution of urea  NH 2  C NH 2 
(a) 1.0 M (b) 2.0 M  
(c) 2.5 M (d) 4.0 M  
 
. g mL−1
Sol. (b) Given, density (d) = 112 and 0.1 m solution of sodium chloride (NaCl)
Mass of solute (w) = 120 g have i value → 3 ions : 1 ions : 2 ions.
Molar mass of solute (M) = 60 ∴Elevation in boiling point
Mass of solvent (w) = 1000 g = 1000 mL O
∴Total mass =1000 + 120 = 1120 g 
3Na 2SO 4 : NH 2  C NH 2 : NaCl = 3 : 1.2
Mass
Q d=
Volume(V) 41. From the given reaction
1120 2KMnO 4 + 3H 2SO 4 + 5H 2O 2 →
∴Total volume (V) = = 1000 mL
1.12 K 2SO 4 + 2MnSO 4 + 8H 2O + 5O 2
w 1000
Q Molarity (c) = × Find the normality of H 2O 2 solution, if 20 mL
M V of it is required to react completely with 16
w 1000 120
Q Molarity (c) = × = = 2. 0 m mL of 0 .02 M KMnO 4 solution.
m 1000 60 (Molar mass of KMnO 4 = 158 g mol − 1 )
39. To 50 mL of 0.1 N Na 2CO 3 solution 150 mL of [23 April 2018, Shift-I]
water is added. What is the molarity of (a) 4 × 10− 2 N (b) 2 × 10− 2 N
resultant solution? [22 April 2018, Shift-II] (c) 6 × 10− 2 N (d) 8 × 10− 2 N
M M Sol. (d)
(a) (b)
40 20 Using law of equivalence
M M
(c) (d) Number of gram equivalence of H 2 O2
80 30 = number of gram equivalence of KMnO4
Sol. (c) Number of gram equivalence
Q Initial volume (V1 ) = 50 mL = normality × volume (in litres)
Initial normality (N1 ) = 0.1 N or normality = molarity × valence factor for
Final volume (V2) = 50 + 150 = 200 mL KMnO4 is 5 in this reaction.
Final normality (N 2) = To find Since, equivalences are equal, considering
volume in mL. So,
and, N1 × V1 = N 2 × V2 01 . × 50 = (= N) × 200
N × 20 = 0.02 × 5 × 16
. × 50) N
(01 N 0.02 × 5 × 16 0.01 × 5 × 16
∴ N2 = = N= =
200 40 20 10
Also, Z for Na 2 CO 3 = 2 = 0.001 × 5 × 16 = 0.001 × 80 = 8 × 10−2 N
(where, Z = total positive charge in Na 2CO 3 )
and N (normality) = M × Z (where, M is 42. Benzene and toluene form an ideal solution
molarity). over the entire range of composition. The
N 1 M vapour pressure of pure benzene and toluene
∴ Molarity of resultant solution = × = at T(K) are 50 mm Hg and 40 mm Hg
40 2 80
respectively. What is the mole fraction of
40. 0.1 m solution each of sodium sulphate, urea toluene in vapour phase when 117 g of
and sodium chloride are taken. The correct benzene is mixed with 46 g of toluene? (molar
ratio of elevation of boiling point of these mass of benzene and toluene are 78 and
solutions is [22 April 2018, Shift-II] 92 g mol − 1 respectively) [23 April 2018, Shift-I]
(a) 1 : 1 : 1 (b) 3 : 1 : 2 (a) 0.78 (b) 0.21
(c) 1 : 2 : 3 (d) 2 : 3 : 1 (c) 0.64 (d) 0.35
52 AP EAMCET Chapterwise Chemistry

Sol. (b) Number of moles × 1000

Molarity =
p° benzene p °( b) = 50 mm Hg Volume in mL
p° toluene p °( t) = 40 mm Hg Number of moles × 1000
Volume (in mL) =
Mass of benzene = 117 g M (molarity)
0.018 × 1000
Mass of toluene = 46 g = = 90 mL
Molar mass of benzene = 78 g mol − 1 0.2
Molar mass of toluene = 92 g mol − 1 44. When 36 g of a non-volatile, non-electrolytic
117
Number of moles of benzene = = 1.5 mol solute having the empirical formula CH 2O is
78 dissolved in 1.2 kg of water, the solution
46
Number of moles of toluene = = 0.5 mol freezes at −0 .93 ° C. The molecular formula of
92 . K kg mol − 1 )
the solute is (K f of water = 186
Mole fraction of toluene (χ( t))
[23 April 2018, Shift I]
Number of moles of toluene
= (a) CH2O (b) C 2H4 O 2
Total number of moles (c) C 3H6O 3 (d) C 4 H8O 4
0.05 0.5
= = = 0.25 and of benzene Sol. (b)
(1.5 + 0.5) 2.0
χ( b) = 0.75 ∆t = iK f m
Q Total vapour pressure (pt) ∆t = Depression in freezing point
= p °( t) × χ( t) + p °( b) × χ( b) = (t1 − t2) = (0 − (− 0.93))
= p(toluene) + p(benzene) ∆t = + 0.93 ° C
(where, p is the partial pressures of toluene and i = for non-electrolytic solute = 1
benzene respectively). K f = constant = 1.86 K kg mol − 1
pT = 40 × 0.25 + 50 × 0.75 moles of solute
m = molarity =
= 10 + 37.5 kg of solvent
pT = 47.5 mm of Hg =
weight in of solute
Also, molecular weight of solute × kg of solvent
Q Mole fraction (in vapour phase) 36
=
Partial pressure x × 1.2
=
Total pressure 36
∴ 0.93 = 1 × 1.86 ×
∴ χ( t) [in vapour phase] =
10
= 0.21 x × 1.2
47.5 1.86 × 36 66.96
∴Mole fraction (toluene) in vapour phase = 0.21 x= = = 60
1.2 × 0.93 1.116
43. For the oxidation of 0.2 M FeSO 4 solution
C = 12, H = 1, O = 16
0.965 amperes current is passed through it
For CH 2O = 12 + 2 + 16 = 30
for 1 hour. The volume of the solution that is
60
oxidised in mL is [23 April 2018, Shift-I] =2
30
(a) 70 (b) 80
∴Formula of solute = C2H 4 O 2
(c) 60 (d) 90
Sol. (d) 45. The volume of 0.1 M HCl required in mL to
The equation is neutralise 20 mL of a solution containing
0.106 g of Na 2CO3 is [23 April 2018, Shift-II]
Fe2 + + 2e− → Fe
1 mole is deposited by 2 × 96500 ° C = 193000 ° C (a) 10 (b) 5 (c) 20 (d) 40
The charged supplied = 0.965 × 60 × 60 Sol. (c)
(Q Q = i × t) Given,
= 3474 C Molarity (HCl) [M1 ] = 0.1 M
Number of moles deposited by this charge Volume of Na 2 CO 3 used = 20 mL
3474 Mass of Na 2 CO 3 used = 0.106 g
= = 0.018 mol
193000
Solutions 53
0.106 1000 Sol. (c)
thus, molarity (M 2 ) of Na 2 CO 3 = ×
106 20 p = i × M × R× T
(M 2) Na 2CO 3 = 0.05 M p = osmotic pressure = 5.04 × 10−3 bar = 5.04 atm
Q Equation for neutralisation is i = van’t Hoff constant = 1 for undissociating
M1 V1 Z1 = M 2 V2 Z2 molecules like protein
Where Z1 and Z2 are number of moles of H + and moles solute
M = molarity =
OH − ions, given by HCl and Na 2 CO 3 in water liter solution
Z1 = 1 (for HCl); Z2 = 2 (for Na 2CO 3 ) weight in g 1 2.52 1000 25.2
= × = × =
M × V2 × Z2 0.05 × 20 × 2 molecular weight liter x 300 3x
V1 = 2 = = 20 mL
M1 × Z1 . ×1
01 T = Temperature = 300 K
Hence, volume of HCl required = 20 mL R = Gas constant = 0.08206 L atm/mol K.
25.2
46. The quantity of CO2 in 500 mL of soda water 5.04 × 10− 3 = 1 × × 0.08206 × 300
3x
when packed under 3.34 bar CO2 pressure at 25.2 × 0.08206 × 300
3x =
298 K in g is [23 April 2018, Shift-II] . ×10− 3
504
(a) 2.442 (b) 1.221 (c) 4.884 (d) 3.663 25.2 × 0.08206 × 300 6.2037 × 100
x= =
Sol. (a) . × 3 ×10− 3
504 15.12 × 10− 3
Given, Quantity of CO2 = 500 mL = 0.410 × 100 × 103 = 41.0 × 103
Pressure of CO2 = 3.34 bar
Temperature = 298 K in
48. 12.25 g of CH 3CH 2CHClCOOH is added to
Henry’s law 250 g of water to make a solution. If the
p = K H X × (x) dissociation constant of above acid is
p 1. 44 × 10 −3, the depression in freezing point of
X= = 3.34 bar = 334000 Pa
KH water in °C is (K f for water is 1.86 K kg mol −1 )
3.34 × 101 [24 April 2018, Shift-I]
= = 2.442 Pa
1.67 × 108 (a) 0.789 (b) 0.394
But, we have 500 mL of soda water so that (c) 1.183 (d) 0.592
Volume of water = 500 mL Sol. (a)
Density of water = 1 g/mL
Formula mass = volume × density we get Step I Calculation of degree of dissociation
500 mL of water = 500 g of water Molar concentration of solution
Molar mass of water = 18 g/mol −1 Mass of solute
= ×1000
500 Molar mass of solute × Mass of solvent
= 27.78 mole µ of water
18 12.25 g ×1000
nCO 2 =
x= 122.5 g mol − 1 × 250 g
nCO 2 + nH 2 O
[Q Molecular weight of solute
Value of moles fraction is very small so it is (CH3 CH2 CHClCOOH) = 122.5 g/mol]
negligible as compared to 1 we get,
= 0.40 m
n
x = CO 2 = 2× 10− 7 If α is the degree of dissociation of
nH 2 O
CH3 CH2 CHClCOOH, then
Molar mass of CO2 is after calculation = 2.442 g −
CH3CH2CHClCOOH - CH CH CHClCOO
3 2 + H+
47. 300 mL of an aqueous solution of a protein Initial concentration C mol/kg 0 0
contains 2.52 g of the protein. If osmotic Concentration at C (1 − α) Cα Cα
pressure of such a solution at 300 K is equilibrium
5.04 × 10 −3 bar, the molar mass of the protein Cα 2
in g mol −1 is [23 April 2018, Shift-II] ∴K a = ≈ Cα 2
(1 − α)
(a) 83.0 × 103 (b) 20.8 × 103
[considering (1 − α) ≈ 1 for dilute solution]
(c) 41.5 × 103 (d) 41.5 × 104
54 AP EAMCET Chapterwise Chemistry

Ka 49. If CO 2 gas having a partial pressure of 1.67

⇒ α=
C bar is bubbled through 1 L water at 298 K, the
1.44 × 10− 3 amount of CO 2 dissolved in water in g L−1 is
⇒ α=
0.4 approximately. (Henry’s law constant of CO 2
= 36 × 10− 4 = 0.06 is 1.67 k bar at 298 K) [24 April 2018, Shift-I]
(a) 24.42 (b) 12.21
Step II Calculation of van’t-Hoff factor
− +
(c) 2.44 (d) 1.22
CH 3CH 2CHClCOOH q CH 3CH 2CHClCOO + H
Initial moles 1 0 0 Sol. (c)
Conc. equil. at 1 − α α α Let pA be the partial pressure of CO2 and χ A be its
Total number of moles after dissociation mole fraction
= 1 − α + α + α =1 + α pA = K H χ A (Henry’s law)
∴van’t-Hoff factor 1.67 bar = 1.67 k bar × χ A
Total number of moles after dissociation (where, x A = 0.001)
(i) = nA
Number of moles before dissociation or = 0.001
nB
(1 + α)
i= =1 + α [Q Number of moles of water = 55]
1
∴ i = 1 + 0.06 = 1.06 n A = 0.001 × 55.55
nA = 0.056
Step III Calculation of depression in freezing
Given mass (m)
point (∆). n= = 0.056
Molecular mass (M)
∆Tf = i K f m
∴ m = 0.056 × 44 = 2.44 g
= (1.06) × 0.40 × 1.86
Thus, 2.44 g of CO2 is dissolved in 1 L water at
∴ ∆Tf = 0.789 K
298 K.