CHEMISTRY Class XII

VATSAL ISC HANDBOOK of

6
Limítations of Henry's Law
This law is valid only if :
not too high.
(1) Pressure of the gas is
sparingly soluble.
(ii) The gas is only
not too high.
(iii) The temperature ischemically with the solvent.
(iv) Gas does not react solvent.
or associate in the
(v) Gas does not dissociate

Applications of Henry's Law When the

water etc., the bottles are sealed under high pressure.
1. To increase the solubility of CO, in soft drinks, soda
decreases and the CO, comes out with a fizz sound.
bottle is opened in air, the pressure inside the bottle
law. When a sea-diver comes to the surface too quick
2. Decompression sickness called 'bends' is related to this
pressure are suddenly released in the forn 1of bubbles
nitrogen andoxygen that have dissolved in his/her blood at high
tanks used by divers are filled with air diluted with helium
in the bloodvessels causing extreme pain. To avoid this,the
soluble than nitrogen in blood. Mores ver because
(11.7% helium, 56.2% nitrogen, 32.1% oxygen) because helium is less ng them. The
through cell walls without damagi
of smallsize of helium atoms (unlike nitrogen molecules),they can pass
the condition of bends does not arise.
excess oxygen dissolved in the blood is used in metabolism and
level. Âs a result, there is a low concentraticn
3. At high altitudes, the partial pressure of oxygen is less than at the ground think know
result, they feel weak and are unable t >
of oxygen in the blood and tissues of the people living there. As a
as 'anoxia'.
COLLIGATIVE PROPERTIES
solution t ut not upon the
The properties of very dilute solutions which depend upon the number of particles of solute in
nature of solute particles in solution, are called colligative properties.
There are four colligative properties:
() Relative lowering of vapour pressure
(i) Elevation in boiling point
(ii) Depression in freezing point
(iv) Osmotic pressure
() Relative Lowering of Vapour Pressure
We know that the vapour pressure of a volatile solvent gets lowered after addition of non-volatile sol ute to it. If P° is the
vapour pressure of pure solvent and P, represents the vapour pressure of the solution, we have, lo we ring of VP. =P-?
and relative lowering of V.P. = p°- Ps
po
According to Raoult's law,
p°- Ps = Lsolute
Determination of molecular mass of solute from lowering of vapour pressure :
As we know, P° - Ps Ksolute or, po
po
where n, =number of moles of solute and n, =number of moles of solvent
po- P W, M
or,
po WÊ W2
M M,
Fthe solution is very dilute, Le, less than 5%, the approximate formula is used. In such cases
n tn2 n Or,
 SOLUTIONS 7

po- Ps W2 M1
po
M2 W1
Here, W, = weight of solute (in g)
WË =weight of solvent (in g)
M, = molecular mass of solute
M = molecular mass of solvent
Alternative Formula:
p° - Ps n2
po

This may be rewritten by taking reciprocals.

po n + n2 po
or, =1+
p° - Ps n p°- P; n2

or,
po
-1= p° -(p° - Ps)
or,
po- Ps n p° -Ps n

or, Ps Or,
p°- Ps
po - P n

or, p°- Ps W2 X
M1
P M2 W1
Ostwald and Walker's dynamic method is used to measure the relative lowering of vapour pressure.
() Elevation in Boiling Point
Boiling point is the temperature at which the vapour pressure of the liquid Atmospheric Pressure A D
becomes equal to the atmospheric pressure. As we know that the vapour po

pressure of solution is always less than that of solvent, the solution has to Solvent

be heated more in order to equalize its vapour pressure to the atmospheric

pressure. Therefore, the boiling point of the solution is more than that of /.P. P Soluti1 on

pure solvent. The difference in the boiling point of solution (T;) and the
solvent (To)is called elevation in boiling point. P2
AT, =Ts-To
The curves are taken to be approximately straight lines. So, AABD is similar To
to AACE. Temperature
AB AD Fig. 1.4. Elevation in boiling point
Therefore, AC AE

TË-To po - P
p°- P2
AP
AP2
AT, and AT, are the elevation in boiling points for solutions 1 and 2 respectively.
AP and AP2 are lowering of vapour pressures for solutions 1 and 2 respectively.
So, ..)
From Raoult's law for very dilute solutions, we know
AP
po

AP = po.2
n
 As P° is constant at a particular temperature for a given solvent, so
AP c
n
W2 MË
AP c W2 M1 or AT, c
M2 W1
M2 W1
As molecular mass M, of the solvent is constant, then
AT, =K. W2 ...(iüi
M2 x WË
where, Kis the boiling point constant.
Now, on multiplying and dividing the above equation by 1000, we get
K W2 1000
AT, ..iv)
1000 M W1

K
As = K, =Ebullioscopic constant or molal elevation constant.
1000

K, is defined as the elevation in boiling point producedwhen 1 mole of solute is dissolved in 1000g of solvent.
Kh x 1000 x W2 ...(v)
AT, =
My x W1
K, x 1000 x W
or, (T; -T,) =
M, x W1
AT; = K, x molality ...(vi)

The value of K, is calculated thermodynamically by van't Hoff equation :

Kp
RT; or Ky RT,M,
1000 x L, 1000 x AH,
Here, AH,= Enthalpy of vaporisation (per mole) of the solvent
M = Molecular mass of solvent
R= Gas constant
To= Boiling point of solvent
L,= Latent heat of vaporisation (per gram of the solvent)
(ii) Depression in Freezing Point
Freezing point is the temperature at which the vapour pressure of the solid
and the liquid (in equilibrium) are same. On addition ofnon-volatile solute Solvent
in the liquid, the vapour pressure of the solution gets lowered and the P
A Solution
1

solution freezes at lower temperature than that of pure solvent or liquid. Vapour
Pressure
- Solution
2

The difference in the freezing point of the pure solvent and the solution is P B
known as depression in freezing point.
AT,= To-Ts P
The curves may be assumed as straight line. As AABD and AACE are similar,
then,
AD BD
AE CE
T TË
p°- P Temperature
po- P To -T2 Fig. 1.5. Depression in freezing point

AP
APz AT f2
 In general, SOLUTIONS
From Raoult's law for very dilute AP < ATf
solutions, we know ...(i)
AP c
n .(ii)
Comparing eq. (i) and (ii), we get,
2

W2 M1
As molecular mass of the M2 W1
solvent, Mis constant, then
ATf = K W2
M2 XW1 ..(iü)
where, Kis a freezing point constant.
Now, multiplying and dividing the above
equation by 1000, we get,
K 1000
ATf = 1000 W2
M2 W1 ..(iv)
K
As = Kf =
1000 cryoscopic constant or molal depression constant.
Kis defined as the depression in freezing point produced
when 1 mole of solute is dissolved in 1000 gof solvent.
Putting thisvalue in equation (iv),
We get, 4T, = K x1000 x W2 ...(v)
M, x W1
or,
ATf = Kf Xmolality ...(vi)
The value of K is calculated thermodynamically by van't Hoff equation :
RT,
Kf 1000 xLf
where, To = Freezing point of the solvent in Kelvin
Lf= Latent heat of fusion per gram of the solvent
R= Gas constant
RT, xM1
or,
Kf 1000 x AHf
where, AH, Latent heat of fusion per mole of the solvent
M = Molecular mass of solvent
(iv) Osmotic Pressure (r)
Osmosis :The flow of solvent particles from the less concentrated solution to higher concentrated solution through
semipermeable membrane is called osnmosis.
But the spontaneous mixing of solute particles with the solvent to form a homogeneous mixture is called diffusion.
Osmosis Diffusion
1. In this process, the flow of solvent molecules takes place In this process, the solvent as well as the solute molecules
from their higher concentration to lower concentration move directly into each other without semipermeable
membrane.
through semipermeable membrane.
2. It takes place only in solutions. It takes place in solutions as well as gases.
3. It can be stopped or reversed. It cannot be stopped or reversed.
 VATSALISCHANDBOOK of CHEMISTAY Class XII the flow of
10
solution side in order to prevent
on the higher concentrated Actually, it isequal to the
The minimum excess pressure which is required membrane is called osmoticpressure.
semipermeable and
solvent particles towards them through pressure of solution
a is determined experimentally by Berkley
column. Osmotic
hydrostatic pressure due to liquid
Hartley's method.
behaviour as that
Laws of Osmotic Pressure move like gaseous particles or they show the same
the solute particles
When the solution is very dilute,
the osmotic pressure. pressure () of a dilute solution is
of gases, SO we apply gas laws in that "Temperature remaining constant, the osmotic
states
1.Boyle-van't Hoff Law: It concentration of the solution." (at constant temperature)
directly proportionalto the
TT OC C (at constant temperature)
Mathematically, T/C = constant
or, 1
litres of the solution, then C="
If 1 mole of solute is dissolved in "y"
(at constant temperature)

(at constant temperature)

TV= constant
very dilute
or
"Concentration remaining constant, the osmotic pressure of a
states that
2. Charles'-van't Hoff Law : It
temperature." (at constant concentration)
solution is directly proportional absolute
to
Mathematically,
TU
= Constant
or. T
Cat constant temperature.
van't Hoff Theory of Dilute Solutions : According to Boyle-van't Hoff law, ccombining these two laws, we get
3. constant concentration (C) and on
According to Charles'-van't Hoff law, c Tat or, T= CRT
TTC CT

C=2
Since, V
per unit volume of solution)
(Where Cis the number of moles of solute (n)
12 RT or,
Hence, nV = n RT
mol K
numerically equal to gas constant, i.e., 0.0821 1litre atm
where R is the proportionality constant and its value is
taken in kelvin (K) and R= 8.314 | K mol.
In S.J. units, t 0s taken in Nm,Vis taken in m°, Tis
and can be written as nV =
W2 RT.
The above equation is known as van't Hoff equation M2
solute. The osmoticpressure () is measured
The above formula is used for the determination of molecular mass of-1,the
0.0821 Latm K mol and T is taken in kelvin.
interms of atmosphere when 'V is taken in litres, R=
the determination of molecular mass of
Osmotic pressure method is preferred over other colligative properties for
higher temperature and (ii) the
polymers, proteins or other macromolecules because (1) biomolecules are not stable at
to measure this change.
change in AT for solutions of higher molecular mass is very-very small and it isdifficult
Isotonic Solutions: Solutions having same osmotic pressure at a particular temperature are called isotonic solutions.
For isotonic solutions their molar concentration issame.
W1 RT
Mi
W2 RT
M2
W W2
Cq=Cz (molar concentration)
M, xVË M, xV
TT1 = g for isotonicsolutions.
 SOLUTIONS
Note
1t2 =T When we mix solutions and calculate the resulting osmotic pressure, we take
osmotic pressure of each solution separately. total volume while calculating the

Hypertonic and Hypotonic Solutions

The solution having more osmotic pressure than other solution is known as hypertonic
solution but a solution having
less osmotic pressure than some other solution is called hypotonic solution. A0.91%
isotonic with RBC.
aqueous solution of NaCl(w/v) is

Explanation of some phenomena on the basis of Osmosis

() Raw mangoes shrivel (shrink) into pickle when placed in concentrated common salt solution due to outflow of
water through semi-permeable membranes of mangoes due to
osmosis.
(ü) People taking a lot of salt develop swelling of their tissues (called 'edema' disease) due to retention of water in the
tissue cells and intercellular space due to
osmosis.
(iii) Wilted flowers revive when placed in fresh water because offlow of water into them through their
semi-permeable
membranes due to osmosis.
(iv) Meat can be preserved by salting because the bacterium, responsible for spoiling them, loses water in the salted
meat due to osmosis. As a result, it shrivels (shrinks) and dies.
Reverse Osmosis : When a pressure higher than the osmotic pressure is applied to the solution, the solvent from the
solution starts flowing towards the pure solvent. This process is called reverse osmosis. This process is very useful to get
pure water from sea water known as desalination of sea water.

Abnormal Molecular Masses

We have discussed that the colligative properties help us to calculate the molar masses of solutes. The accurate values
of molar masses can be obtained only if (1) the solutions are dilute and (2) the solute must not dissociate or associate in
solution.
Discrepancies in determination of molar mass arise when the solute dissociate or associate on dissolving in a solvent. As
colligative propertiesdepend only upon the number of the particles, they are expected to show certain deviations which
in turn influence the molar masses. The discrepancy in molar mass is called abnormal molar mass.

van't Hoff Factor (i)

van't Hoff in 1886, introduced a factor called van't Hoff factor () to express the extent of association or dissociation of
solutes in solution. It is the ratioof the observed or experimental colligative property and normal or theoretical value of
colligative property.
i=
Observed or Experimental colligative property
Theoretical or Normal colligative property
Normal or Theoretical molecular mass
or i=
Observed or Experimental molar mass
Inclusion of van't Hoff factor () modifies the equations for colligative properties as follows :
AP
= 0lsolute
p

(i) ATh=i K, m
(ii) 4T; =iK,m
(iv) =iCRT
 12 VATSALisC HANDBOOK of CHEMISTAY Class XII
van't Hoff factor and extent of dissociation or association in an electrolytic solution :
undergoes dissociation into ions.
()Degree of Dissociation : It is defined as the fraction of total substance that
dissociation and a is the degree of dissociation,
Suppose, a molecule of an electrolytes gives total number of '2Z ions after
then
Normal molar mass
i-1
a = or i= Observed molar mass
Z-1

where Z - No. of ions formed after dissociation.

number of molecules which combine to form associated
(i) Degree of Association : It is defined as the fraction of total
molecule and a is the degree of association.
molecules. Suppose n molecules of a solute associate to form the associated
then
n(1-)
n-1

Normal molar mass i-1

Or a =
n(1- i)
i= or =
n-1
Observed molar mass (1 1

where n= No. of molecules associating.

QUESTIONS
A. Fill in the Blanks (1 mark)
of the solution.
1.The in boiling point of a solvent is directly proportional to the
2. The ....... .fthe number of moles of solvent to the total number of moles of solute and solvent is called
3"Relative lowering of vapour pressure is equal to the of the solute in dilute solutions.
4. The colligative properties of 0.1Mglucose solution will be . . . than that of 0. IMsodium chloride solution.
5. For CaCl, solution, van't Hoff factor (i) is than one.
6. The freezing point of 0.1 MKCl solution is than 0°C.
7. yan't Hoff factor for sucrose is one while that for potassium ferrocyanide is ........, One,
of the boiling point of a solvent by the addition of a solute is ..... proportional to the molalitv of the
8.The ...........

solution.
9. The ......p.ressure of an aqueous solution of 0.1 Mcane sugar is .......than that of pure water. (2010)
10. Solutions which strictly obey law are called ....... s.outions, (2012)
11.The van't Hoff factor of acetic acid solution is .......hanone and the value ot normal colligative property is ....... han
the observed colligative property of this solution. (2014)
12. Jdeal solutions obey . law and they form azeotropic mixtures. (2016)
13.The elevation of boiling point of 0.5 MK,SO4 solution is that of 0.5 Murea solution. The elevation ot boiling point
of 0.5 M KCl solution is .......that of 0.5 M K,SO, solution. (2019)
Answers
1. elevation, molality 2. ratio, mole fraction of solvent 3. mole raction
4. less 5. greater 6. less
7. equal to, greater than 8. elevation,directly 9. vapour, less
10. Raoult's, ideal 11. less, more 12. Raoult's, do not
13. more than, less than