Solutions
Solutions
Introduction
Definition of Solution
When two or more chemically non-reacting substances are mixed together to form a homogeneous mixture
is called as a solution.
When the solution is composed of only two chemical substances, it is termed as binary solution, similarly,
it is called ternary and quaternary if it is composed of three and four components respectively.
For binary solution: Solution = solute + solvent
• Generally, the component present in lesser amount than the other component in solution is called as
solute.
• Generally, the component present in greater amount than all the other components is called as solvent.
• Physical state of solvent and solution is same.
Solute + Solvent
Solution
(B) (A)
moles n N
mass w(g) W(g)
molar mass m M
mole fraction xB xA
Ex.1: In a syrup (liquid solution) containing 60 g sugar (a solid) and 40 g water (a liquid) same aggregation
as solution water is termed as the solvent.
Ex.2: In a solution of alcohol and water; having 10 mL alcohol and 20 mL water, water is solvent and
alcohol is solute.
• On the basis of amount of solute, solutions can be classified in two ways.
Concentration Terms
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NEET : Chemistry
(a) Normality (N)
The number of equivalents or gram equivalents of solute present in one litre of the solution is known
as normality (N) of the solution.
Number of gram equivalents of solute (geq.)
Normality (N) =
Volume of solution (L)
Mass of solute (g)
Normality (N) =
Equivalent mass (g) Volume of solution (L)
(b) Molarity (M)
The number of moles of solute present in one litre solution is called its molarity(M).
Numberof molesof solute n
Molarity = =
Volumeof solution(L) V(L)
(c) Formality (F)
It is the number of gram formula mass units of solute present per litre of solution. Formality is
generally used for solutions of ionic compounds.
Mass of solute (g)
Formality =
Formula mass of solute (g) Volume of solution (L)
(d) Molality (m)
The number of moles of solute present in 1000 gram of the solvent is called as molality of the
solution.
Numberof molesof solute Numberof molesof solute 1000
Molality of a solution = =
weight of solvent(kg) weight of solvent(g)
(e) Strength of a Solution (S)
The mass of solute in g dissolved in 1L solution is known as its strength in g L–1.
Mass of solute (g)
S=
Volume of solution (L)
S(gL–1) = Molarity of solution × Molar mass of solute
S(gL–1) = Normality of solution × Equivalent mass of solute
Illustration 1:
If 0.4 g of NaOH is present in 40 mL of solution. What is the molarity and normality of solution
[Molecular mass of NaOH = 40]
Solution:
We know that
Mass of solute 1000
Molarity =
MolarMass of solute Volume of solution (mL)
0.4
M= × 1000 = 0.25 M
40 40
Massof solute
Normality = × 1000
Equivalent mass of solute volume of solution (mL)
Equivalent mass of NaOH = 40
0.4
N= × 1000 = 0.25N
40 40
Illustration 2:
The normality of 1.5M H3PO4 is –
Solution:
Basicity of H3PO4 is 3
We know that N = M × n Normality = 1.5 × 3 = 4.5 N
[ 44 ]
Solutions
Illustration 3:
N
Find out the mass of H2SO4 in 150 mL, H2SO4 solution
7
Solution:
Mass in gram
N=
Equivalent mass Volume(L)
1 150 21
Mass in gram = Equivalent mass × N × Volume (L) = 49 × × = = 1.05g
7 1000 20
Illustration 4:
A 100 cm3 solution is prepared by dissolving 2g of NaOH in water. Calculate the normality of the solution.
Solution:
1
2 1
2g NaOH = g eq; N = 20 1000 =
40 100 2
N
Normality of solution =
2
[ 45 ]
NEET : Chemistry
Mole Fraction
The ratio of the number of moles of one component to the total number of moles of all the components
present in the mixture, is called the mole fraction of that component.
moles of solute(n)
Mole fraction of solute, XB =
moles of solute(n) + moles of solvent(N)
moles of solvent(N)
Mole fraction of solvent, XA =
moles of solute (n) + moles of solvent(N)
X A + XB = 1
(i) Relation Between Molarity and Normality
S = Molarity × Molar mass of solute and S = Normality × Equivalent mass of solute.
So we can write
Molarity × Molar mass of solute = Normality × Equivalent mass of solute.
Molarity Molar mass of solute
Normality =
Equivalent mass of solute
Molarity Molar mass of solute
=
(Molar mass of solute/valency factor)
Normality = Molarity × Valency factor
N = M × n factor
(ii) Relation Between Molality (m) and Mole fraction (XB)
x B nB nB MA 1000
= =
x A NA WA 1000
x B molality M A
=
xA 1000
xB molality M A molality MA
= : if xB <<< 1 for very dilute solution xB =
1 − xB 1000 1000
Illustration 5:
Find out the molarity of 93% (w/W) H2SO4 (density = 1.84 g/mL).
Solution:
Moles of solute Mass in gram Density 1000
Molarity = =
Volume of solution(L) Molar mass massof solution (g)
93 1.84 1000
= = 17.46 M
98 100
Illustration 6:
Find the percentage by mass and mass fraction of aspirin in the solution prepared by dissolving 3.65 g of
aspirin in 25.08 g of water.
Solution:
Mass of solution = 3.65 + 25.08 = 28.73 g
3.65
Mass fraction of aspirin = = 0.127
28.73
Mass percent of aspirin = 0.127 × 100 = 12.7%
[ 46 ]
Solutions
Illustration 7:
A solution was prepared by adding 125 cm3 of isopropyl alcohol to water until the volume of the solution
was 175 cm3. Find the volume fraction and volume percent of isopropyl alcohol in the solution.
Solution:
Volume of solute = 125 cm3 ; Volume of solution = 175 cm3
125 125
Volume fraction = = 0.714 ; Volume percent = × 100 = 71.4%
175 175
BEGINNER’S BOX-1
1. What is the normality of 2M H3PO2 solution?
(1) 0.5 N (2) 1.0N (3) 2.0 N (4) 3.0 N
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2. 23 g ethanol is dissolved in 36 g water. Find mole fraction of ethanol?
(1) 2 (2) 0.5 (3) 0.2 (4) 0.8
CSO167
3. How many gram of HNO3 is required to prepare 400 mL solution of 0.2 M HNO3?
(1) 5.04 g (2) 5040 g (3) 25.2 g (4) 2.52 g
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4. Calculate normality of 2.1% (w/V) H2SO4 solution?
(1) 2.14 N (2) 4.28 N (3) 0.428 N (4) 0.214 N
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5. What is the molarity of 1N H2SO4 solution?
(1) 1 M (2) 2M (3) 0.5 M (4) 3M
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6. 20.6 g NaBr is dissolved in 500 mL solution what is the molarity of resulting solution?
(1) 0.6 (2) 0.4 (3) 1 (4) None
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7. Calculate molality of the solution obtained by dissolving 11.7 g NaCl in 500 g water
(1) 0.1 m (2) 0.3 m (3) 0.2m (4) 0.4m
CSO172
8. Density of 2.03 M aqueous solution of acetic acid is 1.017 g mL–1 molecular mass of acetic acid
is 60. Calculate the molality of solution?
(1) 2.27 (2) 1.27 (3) 3.27 (4) 4.27
CSO173
9. A molar solution is one that contains one mole of solute in
(1) 1000 g of the solvent (2) One litre of the solution
(3) 1000 g of the solution (4) 22.4 litres of the solution
CSO174
10. Calculate the mole percentage of CH3OH and H2O respectively in 60% (by mass) aqueous
solution of CH3OH
(1) 45.8, 54.2 (2) 54.2, 45.8 (3) 50, 50 (4) 60, 40
CSO175
[ 47 ]
NEET : Chemistry
Concept of Dilution
During dilution, solvent is added into solution and moles, gram equivalents, mass of solute remains same
Solution
after
Solution dilution Water
Concept of Mixing
Case-I
Mixture
Acid 1
Acid 2
N1V1 + N2V2
Normality of [H+] in Resultant Solution, [H+ ] =
V1 + V2
where,
N1 = Normality of acid 1 solution ; N2 = Normality of acid 2 solution
V1 = Volume of acid 1 solution ; V2 = Volume of acid 2 solution
Case-II
Mixture
Base 1
Base 2
N 1V 1 N, V N 2V 2
NV = N 1V1 + N2V2
V = V1 + V2
N1 V1 + N2 V2
Normality of [OH¯] in Resultant Solution, [OH¯] =
V1 + V2
where,
N1 = Normality of base 1 solution ; N2 = Normality of base 2 solution
V1 = Volume of base 1 solution ; V2 = Volume of base 2 solution
[ 48 ]
Solutions
Illustration 8:
1 litre of 1 N H2SO4 solution is diluted by adding 5 litre of water, the normality of that solution is
(1) 0.2 N (2) 5 N (3) 10 N (4) 0.33 N
Solution:
1
N1V1 = N2V2 1 × 1 = N2 × 6 N2 = = 0.33
6
Illustration 9:
Two solutions of a substance (non-electrolyte) are mixed in the following manner : 480 ml of 1.5M first
solution + 520 mL of 1.2M second solution. What is the molarity of the final mixture?
(1) 1.20 M (2) 1.50 M (3) 1.344 M (4) 2.70 M
Solution:
M1V1 + M2V2 = M3V3;
1.5 × 480 + 1.2 × 520 = M × 1000
720 + 624
M= = 1.344 M.
1000
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NEET : Chemistry
➢ If the density of solution is approximately 1g/cc then its Molality > Molarity
➢ ppm unit is used to represent concentration of very dilute solutions like pollutants in environment
and salts present in sea water.
➢ Those concentration terms which involve volume of solution are temperature dependent.
➢ Molarity, normality, formality, % by volume, % w/V are temperature dependent.
➢ Molality, % w/W, mole fraction are temperature independent.
Illustration 10:
Calculate volume strength of H2O2 in 5L solution which yields 100 L of O2 at NTP.
Solution:
5L H2O2 gives = 100 L O2
1L H2O2 gives = 20 L O2
i.e. 20 V H2O2 solution
Illustration 11:
Calculate the molarity, normality & strength in “20V H2O2” solution.
Solution:
X 20
Molarity = = = 1.78 M
11.2 11.2
Normality = molarity × vf = 1.78 × 2 = 3.56 N
X 20
Strength = 17 = 17 = 60.71 g/L
5.6 5.6
Illustration 12:
Calculate the molarity of 20mL of 10V H2O2 Solution
Solution:
X 10
Molarity = = = 0.89 M
11.2 11.2
Vapour Pressure
At a constant temperature, the pressure exerted by the vapours of a liquid on its surface when they (liquid
and its vapours) are in equilibrium, is known as vapour pressure.
Factor affecting Vapour Pressure
Raoult's Law
(a) For liquid-liquid system: For a solution of volatile liquids the partial vapour pressure of any
component at constant temperature is equal to vapour pressure of pure component multiplied by
mole fraction of that component in the solution.
Liquid (B) Liquid (A)
Vapour pressure in pure state 0
PB PA0
Partial Vapour pressure PB PA
Mole fraction in solution XB XA
Moles n moles N moles
Mass W(g) W(g)
Molar mass m M
[ 50 ]
Solutions
PA X A so PA = PA0X A ...(i)
PB X B so PB = PB0X B ...(ii)
At constant temperature, partial vapour pressure of a component is directly proportional to the mole
fraction of component in solution.
According to Dalton's law given below:
• Ptotal = PA + PB + .....
PS = X APA0 + XBPB0 ; XA + XB =1 PA0
Vapour Pressure
PS = PA0 – XB PA0 + XB PB0 PB0
Dalton's Law
Partial pressure of gas = mole fraction × total pressure of gas
PA = YAPT
PB = YBPT
PA + PB = PT
XA PA0 = YAPT YA and YB gives mole fraction in vapour phase
XB PB0 = YBPT XA and XB gives mole fraction in liquid phase.
Illustration 13:
Methanol and ethanol form an ideal solution. Solution is prepared by mixing 32 g of CH 3OH and 23 g of
C2H5OH at 300K. At 300K P0methanol = 90 mm of Hg and P0ethanol = 51 mm of Hg.
Calculate partial vapour pressure of its constituents and total vapour pressure of solution.
Solution:
32 23
nCH3OH = =1; nC2H5OH = = 0.5
32 46
1 2 0.5 1
XCH3OH = = ; XC2H5OH = =
1.5 3 1.5 3
2
PCH3OH = PCH
0
3OH
.X CH3OH = 90
3
PCH3OH = 60 mm of Hg
1
PC2H5OH = PC02H5OH .X C2H5OH = 51
3
PC2H5OH = 17 mm of Hg
PS = PCH3OH + PC2H5OH
PS = 77mm of Hg
[ 51 ]
NEET : Chemistry
Illustration 14:
A solution has two liquids A & B and vapour pressures of A and B in pure state are
PA0 = 80 torr, PB0 = 120 torr. Find out the mole fraction of A in vapour phase if initially, equal moles of A & B
are taken.
Solution:
PA0 x A
yA =
PA0 x A + PB0 x B
nA = 1 nB = 1
xA = 0.5xB = 0.5
80 0.5 40 40
yA = = = = 0.4
80 0.5 + 120 0.5 40 + 60 100
Illustration 15:
Two liquids A & B are mixed to form an ideal solution. The total vapour pressure of solution is. 235 – 135 xB. Find the
value of PA0 & PB0 , If x is the mole fraction of B in solution.
Solution:
PT = 235 – 135 xB
xB → 0 PT → PA0
PA0 = 235
XB → 1 PT → PB0
PB0 = 235 – 135
PB0 = 100
Illustration 16:
Ratio of vapour pressures of A & B in pure state is 1 : 2 and ratio of moles of A and B is also 1 : 2, then find
out mole fraction of A in vapour phase.
Solution:
PA0 x A 1 1 2
yA =
PA0 x A + PB0 x B X A = 1 + 2 = 3 , XB = 3
1 1 1
1
3 1
= = 3 = 3 = = 0.2
1 2 1 4 5 5
1 + 2 +
3 3 3 3 3
(b) For solid - liquid system: non-volatile solute (B) and volatile solvent (A)
PB0 = 0
PS = X A PA0 + X BPB0
N 0
PS = X A PA =
0
PA ...(i)
n+N
For solution of non-volatile solute: At constant temperature vapour pressure of solution containing non-
volatile solute is proportional to mole fraction of solvent.
N
PS ; XA + XB =1
n+N
PS = (1 − X B )PA0 ; PS = PA0 − X BPA0
PA0 − PS n
XBPA0 = PA0 − PS = XB = ...(ii)
0
PA n+N
[ 52 ]
Solutions
• When a non-volatile solute is added to a volatile liquid its vapour pressure decreases because less
number of solvent particles present in solution at surface decreases (as compared to pure solvent)
less vapour is formed and vapour pressure of solution decreases
PA0 – PS = P (lowering of vapour pressure)
PA0 − PS
= relative lowering of vapour pressure.
PA0
PA0 n+N PA0 N
= =1+
PA0 − PS n PA0 − PS n
PA0 − PA0 + PS N PS N
= =
PA0 − PS n P − PS n
0
A
PA0 − PS n
= ...(iii)
PS N
n
P
N
Ex. The vapour pressure of pure liquid A is 40 torr at 310 K. The vapour pressure of this liquid in solution
with solid B is 32 torr. Calculate XA in solution.
Sol. 32 = XA × 40
XA = 0.8
Colligative Properties of dilute solutions (CP)
Those physical properties of a solution which depends upon the relative number of particles of solute and
do not depend on nature of solute particles are called as colligative properties.
CP Number of solute particles
Number of molecules (in the solution of non electrolyte)
Number of ions (in the solution of electrolytes)
Number of moles of solute
Mole fraction of solute
Colligative Properties (CP)
Colligative
Properties
[ 53 ]
NEET : Chemistry
According to Raoult's law:
PA0 − PS nB
Relative lowering in vapour pressure = =
0
PA N A + nB
PA0 − PS nB n
For a dilute solution nB << nA so P B
PA0 NA NA
• Relative lowering depends upon relative number of solute particles. Therefore, it is called as a
colligative property.
Illustration 17:
At 100oC, vapour pressure of aqueous solution of glucose is 750 mm of Hg. Find the mole fraction of the
solute.
Solution:
At 100oC, P0 for H2O = 760 mm Hg
PS = 750 mm Hg
P0 − PS
= XB
Po
760 − 750 1
= xB xB =
760 76
Illustration 18:
Find the mass of urea which should be dissolved in 360 g water so that vapour pressure of solution is
decreased upto 6/7 times the vapour pressure of pure water.
Solution:
6
Mass of solvent = 360 g, PS = P0
7
P − PS n
0
=
PS N
6 w
P0 − P0
7 = 60
6 0 360
P
7 18
w = 200 g
Illustration 19:
60% by mass of urea is present in an aqueous solution at 100°C. Find the value of lowering in vapour
pressure ?
Solution:
For water, at 100° C, P0 = 760 mm Hg.
P0 − PS n
=
P0
n+N
60% by mass urea
60 gm urea in 100 gm solution
60 100 − 60 40
n= = 1 mol , N= = = 2.22
60 18 18
P0 − PS 1
=
760 1 + 2.22
760
P0 – PS (lowering in vapour pressure) = = 236.02 mm Hg
3.22
[ 54 ]
Solutions
(b) Elevation in Boiling Point 1 atm
• The boiling point of a liquid is that temperature at which its
Vapour Pressure
vapour pressure becomes equal to the atmospheric pressure.
P°
• When a non-volatile solute is dissolved in a pure solvent, its
Ps
vapour pressure is decreased and boiling point increases. The Tb
difference of boiling points of the solution and pure solvent is
Temperature (K) Tb0 Tb
called elevation in boiling point. (Tb)
• If Tb0 is the boiling point of pure solvent and Tb is the boiling Tb = Boiling point of solution
= Boiling point of solvent
point of the solution then, Tb Tb0 and the elevation in boiling
The vapour pressure curve for
point Tb = Tb − Tb0 solution lies below the curve for
pure water.
• The elevation in boiling point (Tb) is directly proportional to The diagram shows that Tb
lowering of vapour pressure of the solution i.e. denotes
The elevation in boiling point of
nB a Solvent in solution
Tb (P0 – Ps) from graph and Tb P
NA
n B w BM A
Tb = (for a solvent P0 & MA = constant)
N A mB WA
wB Kw B
Tb or Tb =
mB WA m B WA
where K = elevation constant
wB
if = 1 mole and WA = 1 g
mB
then Tb = K (Elevation constant or molecular elevation constant)
wB
if = 1 and WA = 1000 gram; Then Tb = Kb (molal elevation constant)
mB
K
= K b (molal elevation constant or Ebullioscopic constant)
1000
K b w B 1000 w B 1000
Tb = ; Tb = Kb
mB WA mB WA
[ 55 ]
NEET : Chemistry
Illustration 20:
30 g of urea is present in 100 g of water. Find out the boiling point of solution in °C.
Solution:
Tb − Tb0 = Kb m
30 1000
Tb − 100 = 0.52
60 100
Tb = 102.65°C
Illustration 21:
0.86 g of solute (molecular weight = 152) is dissolved in 25 g of acetone. Find the boiling point of solution
if boiling point of acetone is 56.2 °C and the value of Kb for acetone per 100 g is 17.
Solution:
100
Kb = 17 per 100 g = 17 × = 1.7 K. Kg mol–1
1000
Tb – Tb0 = Kb × m
0.86 1000
Tb – 56.2 = 1.7 ×
152 25
Tb = 56.58°C
Illustration 22:
The vapour pressure of aqueous solution of sucrose is 732 mm of Hg. Find the b.p. of the solution, if the
vapour pressure of pure H2O is 760 mm of Hg. (Kb of water = 0.52 kg K mol–1)
Solution:
PA0 − PS 760 − 732
0
= XB = XB
PA 760
XB = 0.036
1000 X B 1000 0.036
m= = = 2.07
X A (Mw )A (1 − 0.036) 18
Tb = Tb − Tb0 = Kb m
Tb – 100 = 0.52 × 2.07
Tb = 101.07°C
[ 56 ]
Solutions
• The difference in the freezing point of pure solvent and solution is called depression in freezing point (Tf)
Tf = Tf0 − Tf ; the depression in freezing point is directly proportional to lowering in vapour pressure (P)
nB n
Tf P ; Tf B so Tf = Kf molality
NA NA
Kf = molal depression constant or Cryoscopic constant.
• Kf depends only on nature of solvent which can be explained by the thermodynamic relation,
2 2
RTf0 RTf0 Mw
Kf = =
1000Lf 1000Hf
Where Tf0 = Freezing point of solvent
M = Molar mass of solvent
Hf = Enthalpy of fusion per mole of solvent
Lf = latent heat of fusion per gram of solvent
Illustration 23:
How much gram of glycol is dissolved in 5L H2O so that freezing point of solution becomes
–6°C? (Kf of water = 1.86 Kg K mol–1)
Solution:
Tf = Tf0 − Tf = K f m
glycol = CH2 − CH2
| |
OH OH
[dH2O = 1g / mL 1Kg /L] , so 5L 5 Kg
wB
0 – (–6) = 1.86 ×
62 5
wB = 1000 g
Illustration 24:
The freezing point of an aqueous solution is –1.5°C. Find the boiling point of the solution.
Solution:
Tf0 − Tf = Kf m, Tb − Tb0 = Kb m
0 – Tf = Kf × m ...(1)
T0 = 0o C
For H2O 0 f o
Tb = 100 C
Tb – 100 = Kb × m …(2)
eq.(1) 0 − ( −1.5) 1.86
=
eq.(2) Tb − 100 0.52
1.5 0.52
= Tb − 100
1.86
Tb = 100.41°C
[ 57 ]
NEET : Chemistry
Illustration 25:
How much gram of sucrose is dissolved in 100 g of water so that difference between freezing point &
boiling point of solution becomes 105°C? [Given Kb (H2O) = 0.52 kg K mol–1, Kf (H2O) = 1.86 kg K mol–1]
Solution:
Tb − Tb0 = Kb m …(1)
Tf0 − Tf = K f m …(2)
on addition eq. (1) & (2)
(Tb − Tb0 ) + (Tf0 − Tf ) = Kb m + Kf m
Tb – 100 + 0 – Tf = m[0.52+ 1.86]
w 1000
105 – 100 = B × 2.38
342 100
wB = 71.84 g
[ 58 ]
Solutions
• On the basis of osmotic pressure solution can be classified by following ways:
(i) Isotonic solutions: Solutions having same osmotic pressure are called isotonic solution.
1 = 2 ; primary condition
C1RT = C2RT (at same temperature)
C1 = C2 (secondary condition) ; means
n1 n 2
= ; such solutions are known as isotonic
V1 V2
(ii) 1 > 2 or C1 > C2 then solution 1 is called hypertonic and solution 2 is called hypotonic
Reverse Osmosis
If external pressure greater than osmotic pressure is applied, the flow of solvent molecules can be made to
proceed from solution towards pure solvent, i.e., in reverse direction of the ordinary osmosis. Reverse
osmosis is used for the desalination of sea water for getting fresh drinking water.
Piston
(P) Pressure >
Water
outlet
SPM
Illustration 26:
0.001 M glucose solution is present in a beaker. Find its osmotic pressure at 27°C temperature.
Solution:
= CRT = 0.001 × 0.0821 × 300 = 0.02463 atm
Illustration 27:
0.5 g solute is dissolved in 20 mL of solution then the osmotic pressure of solution is 7.6 mm of Hg at 27°C.
Find molecular weight of solute.
Solution:
wB
= CRT = RT
(Mw )B V(L)
1atm = 760mmHg
7.6 0.5
= 0.0821 300
760 20 1 mmhg = 1 atm
(Mw )B 760
1000
(Mw)B = 61575 g mol–1
Illustration 28:
100 mL of 1.5% urea solution having osmotic pressure 6 atm and 100 mL of 3.42% sucrose solution having
osmotic pressure 2.4 atm are mixed with each other. Find the osmotic pressure of resultant solution.
Solution:
1v1 + 2v2 = mix.vmix.
6 100 + 2.4 100
mix. = 4.2 atm
200
[ 59 ]
NEET : Chemistry
BEGINNER’S BOX-2
1. An example of colligative property :-
(1) Freezing point (2) Boiling point (3) Vapour pressure (4) Osmotic pressure
CSO176
2. The freezing point order of the solution of glucose is :-
(1) 10% > 3% > 2% > 1% (2) 1% > 2%> 3%> 10%
(3) 1% > 3% > 10% > 2% (4) 10% > 1% > 3% > 2%
CSO177
3. In cold countries, ethylene glycol is added to water in the radiators of cars during winters. It result in
reducing :-
(1) Viscosity (2) Specific heat (3) Freezing point (4) Boiling point
CSO178
4. Calculate the molal depression constant of a solvent, which has freezing point 16.6 °C and latent heat of
fusion 180.75 Jg–1
(1) 2.68 (2) 3.86 (3) 4.68 (4) 2.86
CSO179
5. The osmotic pressure of a solution at 0 °C is 4 atm. What will be its osmotic pressure at 546 K under
similar condition?
(1) 4 atm (2) 2 atm (3) 8 atm (4) 1 atm
CSO180
Abnormal colligative properties
• It has been observed that there occurs difference in the observed and calculated molecular masses
of solute due to association or dissociation of solute molecules in solution. It results in change in the
number of particles in solution.
• Van't hoff factor (i): Tells about relationship between normal colligative properties and abnormal
colligative properties.
number of particles after dissociation or association observed colligative properties
• i= =
number of particles before dissociation or association calculated colligative properties
calculated molecular mass
=
observed molecular mass
Neither dissociation
nor association
Van’t Hoff
Ex. glucose, urea, sugar factor
i=1 i<1
[ 60 ]
Solutions
• Calculation of 'i': Let solute be AxBy (electrolyte)
AxBy → xAy+ + yBx– ; x + y = n (total number of ions)
Initially 1 mol 0 0
After dissociation (1 – ) x y
Total number of solute particles = 1 – + x + y = 1 – + (x + y) = (1 – + n) mol
Observed colligative property is proportional to observed number of solute particles (1 – + n)
number of particles after dissociation 1 − + n
i= =
number of particles before dissociation 1
i = 1 + (n–1)
where is the degree of dissociation
• For strong electrolytes
If = 1 or 100%
Ex. NaCl i = 2; = 100%
K2SO4 i=3 = 100%
Ex. K4[Fe(CN)6] i =5 for = 100%
For = 50% i = 1 + (n – 1)
i=3
Case II:
Association of solute: The formation of a bigger molecule by the union of two, three or more solute
molecules is called association. As a result of association, the total number of particles in solution become
less than the number of molecules initially put in the solution and hence the colligative properties will have
lower value. As the molar mass of solute is inversely proportional to the colligative properties, the molar
mass of solute will be greater than theoretical value.
Number of solute particles in solution decreases.
• Observed /experimental C.P. < calculated C.P.
• Observed / experimental molecular weight of solute > normal molecular weight of solute
1
C.P. ; i < 1 for association.
Molecular weight of solute
• Calculation of i
nA ⎯⎯⎯→ An
Initially 1 0
After association (1 – )
n
Total number of solute particles = 1 − + mol
n
Observed C.P. observed number of solute particles 1 − +
n
1− +
number of particles after association n
Van't hoff factor (i) = ; i=
number of particles before association 1
i =1−+
n
= degree of association
n = number of solute particles which are associated.
1
• If = 100% or 1 or if is not specified, then, i =
n
[ 61 ]
NEET : Chemistry
Illustration 29:
The observed and calculated molar mass of Ba(NO3)2 is 155 g and 260 g respectively. Calculate its degree
of ionisation.
Solution:
calculated molecular mass 260
i= = = 1.67
observed molecular mass 155
i = 1 + (n – 1)
1.67 = 1 + (3 – 1)
0.67 = 2
= 0.335
= 33.5%
Illustration 30:
2A → A2, If degree of association is 80% then, find out its Van’t hoff factor.
Solution:
2A → A2
0.8
i=1–+ = 1 – 0.8 + = 0.6
n 2
Illustration 31:
A 0.3 molal aqueous solution of weak acid (HX) is 30% ionised. Calculate the elevation in B.P. of this
solution.
Solution:
i = 1 + (n – 1)
i = 1 + (2 – 1) 0.3
i = 1 + 0.3 = 1.3
Tb = Kb × m × i
Tb = 0.52 × 0.3 × 1.3
Tb = 0.2°C
Illustration 32:
11 g Ba(NO3)2 is added to 100 g H2O, then solution is boiled at 100.46oC. Find out the degree of ionisation
of salt (molecular weight Ba(NO3)2 = 260)
Solution:
i kb wB
Tb = × 1000
Mw B w A
i 0.52 11 1000
0.46 =
260 100
i = 2.09
i = 1 + (n – 1)
2.09 = 1 – + 3
2 = 1.09
= 0.545
[ 62 ]
Solutions
Illustration 33:
Which of the following solution of glucose has highest vapour pressure?
(1) 1M (2) 0.1 M
(3) 0.01 M (4) All have same vapour pressure
Solution:
RLVP (C.P.) (i × M)
M RLVP V.P.
Hence, Ans is (3)
Illustration 34:
A 5% solution of anhydrous CaCl2 at 0°C developed 15 atm osmotic pressure. What is the degree of
dissociation of CaCl2?
Solution:
5 g. of CaCl2 are present in 100 mL,
100 111
so 111 g (MW of CaCl2) will be present in = 2.22 L
5 1000
0.082 273 22.47
Now V = ST {∵ n = 1} or = = = 10.09 atm
2.22 2.22
Observed colligative property 15
We know that Van't Hoff factor = =
Normal colligative property 10.09
15
−1
i −1 4.91
and = or = 10.09 = = 0.2433 or 24.33%
n −1 3−1 10.09 2
Illustration 35:
Calculate the osmotic pressure of 20% (wt/Vol.) anhydrous CaCl2 solution at 0°C assuming 100%
ionisation.
Solution:
CaCl2 → Ca2+ + 2Cl¯
Before dissociation 1 0 0
After dissociation 1– 2
Given, w = 20 g, V = 100 mL, T = 273 K,
Mol wt. of CaCl2 = 111
w 20 1000 0.0821 273
Normal = S T = = 40.38 atm.
mV 111 100
1 + 2
Now, i = = 1 + 2 = 3 (∵ =1)
1
exp = i × Normal = 40.38 × 3 = 121.14 atm
Illustration 36:
When 0.2 g acetic acid is added to 20 g benzene, then freezing point decreases by 0.45°C. Find out the
degree of association. (kf for benzene = 5.12°Cm–1)
Solution:
i kf wB
Tf = 1000
Mw B w A
i 5.12 0.2
0.45 = × 1000
60 20
1
i = 0.527, i = 1 + −1
n
1
0.527 = 1 + − 1
2
= 0.946
[ 63 ]
NEET : Chemistry
BEGINNER’S BOX-3
1. Calculate the percentage degree of dissociation of an electrolyte AB 2(normal molar mass = 164) in H2O if
observed molar mass is 65.6
(1) 50% (2) 25% (3) 75% (4) None
CSO181
2. Which of the following solution will have highest freezing point
(1) 1M urea (2) 1M Na2SO4 (3) 1M NaCl (4) 1M Al2(SO4)3
CSO182
3. A 1.17% solution of NaCl is isotonic with 7.2% solution of glucose calculate the value of i of NaCl
(1) 1 (2) 2 (3) 3 (4) 4
CSO183
4. Van't hoff factor of Hg2Cl2 in its aqueous solution will be (Hg2Cl2 is 80% ionized in the solution)
(1) 1.6 (2) 2.6 (3) 3.6 (4) 4.6
CSO184
Positive Negative
Deviation Deviation
[ 64 ]
Solutions
Non-ideal Solutions
• For non ideal solutions; A – A interactions or B-B interactions A – B interactions.
• Those solutions which do not obey Raoult's law are called non-ideal solutions.
• For such solutions ; PA PA0 X A ; PB PB0 X B
• Non ideal solutions are formed when the components differ much in their structures and polarities.
So H mixing 0 and Vmixing 0
• Non ideal solutions show either positive or negative deviations from Raoult's law.
(a) Non ideal solutions having positive deviation from Raoult's law.
• In these solutions A-B interactions are less than A-A and B-B molecular interactions.
PA PA0 X A , PB PB0 X B
• The total vapour pressure of the solution will be greater than the corresponding vapour pressure
than expected in case of an ideal solution of same
composition.
i.e. Ptotal (PA0 X A + PB0XB )
• Hmix > 0 ; endothermic dissolution ; heat is absorbed.
Vapour Pressure
• Vmix > 0 ; volume increases after dissolution,
i.e., (Vsolute + Vsolvent < Vsolution).
• 'A' and 'B' escape easily showing higher vapour
pressure than the expected value.
(B.P.)th > (B.P.)exp
• (S)mix = +ve, G = –ve XA = 0 Mole Fraction XA = 1
XB = 1 XB = 0
Entropy change in mixing is positive.
Examples:
(i) Ethanol and cyclohexane (ii) Ethanol and Water (iii) Ethanol and Acetone
(iv) Methanol and H2O (v) CCl4 and Benzene (vi) CCl4 and Toluene
(vii) CCl4 and CHCl3 (viii) CCl4 and Methanol (ix) Benzene and Acetone
(x) CS2 and Acetone (xi) CS2 and Acetaldehyde
(b) Non ideal solutions having negative deviation from Raoult's Law
• In these solutions the A-B interactions are stronger than the A-A and B-B molecular interactions.
PA PA0 X A ; PB PB0 X B
0
PA
• Ptotal (PA0 X A + PB0 XB )
Vapour Pressure
[ 65 ]
NEET : Chemistry
Azeotropic mixtures:
Some liquids on mixing form azeotropes which are binary mixtures having the same composition in liquid
and vapour phase and boil at a constant temperature. The liquid and vapour have the same composition
and no further separation occurs.
Components forming azeotrope can't be separated by fractional distillation but can be separated by
azeotropic distillation.
Solutions showing Positive deviation form minimum boiling azeotrope and solutions showing negative
deviation form maximum boiling azeotrope.
There are two types of azeotropes:
(a) Minimum boiling azeotrope
(b) Maximum boiling azeotrope
(a) The solutions which show a large positive deviation from Raoult’s law form minimum boiling
azeotrope at a specific composition. For example, ethanol-water mixture (obtained by
fermentation of sugars) on fractional distillation gives a solution containing approximately
95.57% v/v ethanol.
(b) The solutions that show large negative deviation from Raoult’s law form maximum boiling
azeotrope at a specific composition. Nitric acid and water is an example of this class of azeotrope.
This azeotrope has the approximate composition, 68% nitric acid and 32% water by mass, with
a boiling point of 393.5 K.
[ 66 ]
Solutions
Solution:
According to definition,
Experimental volume is less than theoretical, hence, Negative deviation and azeotrope is maximum boiling.
Hence B.P. of solution > 415 K
Solubility
Maximum amount of solute which can be dissolved in a specified amount of solvent at constant
temperature is known as solubility. Solubility is affected by nature of solute and solvent as well as by
temperature and pressure.
(a) Solubility of Solid in Liquid
Polar solutes are soluble in polar solvent and non polar solutes are soluble in non polar solvent due
to similar intermolecular forces.
When solid solutes are dissolved in solvent, then following equilibrium exists:
Solute + Solvent ⇌ Solution
Solubility of solids is affected by temperature and pressure according to Le-Chatelier’s principle. If
dissolution is exothermic, then, solubility decreases with increase in temperature and if
endothermic, then, solubility increases with increase in temperature.
Solubility of solids is not affected by pressure significantly since solids are highly incompressible.
(b) Solubility of Gases in Liquid
Certain gases are highly soluble in water like NH3, HCl etc. and certain gases are less soluble in water
like O2, N2, He etc. Solubility of gases is affected by pressure and temperature. Increase in pressure
increases solubility and increase in temperature decreases solubility. During dissolution of gas
pressure of gas decrease and its dissolution is also exothermic in nature.
Henry's Law
It can be stated that at constant temperature the solubility of a gas in a liquid is directly proportional
to the partial pressure of the gas present above the surface of liquid or solution.
or
Mole fraction of gas in the solution is proportional to the partial pressure of the gas over the solution.
or
The partial pressure of the gas in vapour phase (P) is proportional to the mole fraction of the gas (X)
in the solution. (This is the most common definition)
P = KHX KH = Henry's Constant
Henry's Constant is not a universal constant. It depends on nature of gas and temperature. K H
increases with increase in temperature therefore solubility of gas decreases.
➢ Those gases which can react with solvent do not follow Henry's Law. e.g. NH3 in water.
➢ Raoult's Law is special case of Henry's Law.
Illustration 40:
Henry's Law Constant for CO2 in water is 1.67 × 108 Pa at 298K. Calculate the quantity of CO2 in 1 L of soda
water when packed under 2.5 atm CO2 pressure at 298 K.
Solution:
P = KH Xgas
P 2.5 105 n n
Xgas = = = 1.5 10−3 ; =X ; =X ∵ n << N ∴ n+N⋍N
K H 1.67 10 8
n+N N
n
= 1.5 × 10–3 = 8.3 × 10–2 mol L–1 = 3.65 g L–1
55.55
[ 67 ]
NEET : Chemistry
Illustration 41:
The Henry’s law constant for the solubility of nitrogen gas in water at 298 K is 1 × 10 5 atm. The mole
fraction of nitrogen in air is 0.8. Calculate the number of moles of nitrogen from air dissolved in 10 moles
of water at 298 K and 5 atm pressure of air.
Solution:
105 nN2
Pgas = KH × Xgas 5 × 0.8 = nN2 = 4 10−4
(nN2 + nH2O )
BEGINNER’S BOX-4
1. Which of the gas will not follow Henry's law?
(1) HCl (2) He (3) O2 (4) H2
CSO185
2. If solubility of gas ‘X’ is 0.5 gL–1 at 1 bar then its solubility at 3 bar pressure will be
(1) 0.5 gL–1 (2) 1.5 gL–1 (3) 3.0 gL–1 (4) 2 gL–1
CSO186
3. Among the following that forms an ideal solution?
(1) Water and methanol (2) Acetone and ethanol
(3) Benzene and toluene (4) Water and HCl
CSO187
4. On mixing 10 mL of acetone with 40 ml of chloroform the total volume of the solution is
(1) < 50 mL (2) > 50 mL (3) = 50 mL (4) cannot be predicted
CSO188
5. The mixture of n-hexane and n-heptane is an example of
(1) Ideal solution (2) Non-ideal solution (3) Dilute solution (4) None
CSO189
Que. 1 2 3 4 5 6 7 8 9 10
BEGINNER'S BOX-1
Ans. 3 3 1 3 3 2 4 1 2 1
Que. 1 2 3 4 5
BEGINNER'S BOX-2
Ans. 4 2 3 2 3
Que. 1 2 3 4
BEGINNER'S BOX-3
Ans. 3 1 2 2
Que. 1 2 3 4 5
BEGINNER'S BOX-4
Ans. 1 2 3 1 1
[ 68 ]