O

Osmosis
Let us consider a pure sollvent and solution
s seeparated by
b a membbrane whicch
permitts the passsage to sollvent moleecules but not to sollute moleccules. Onlyy the
solvennt will difffuse througgh the mem
mbrane innto solutioon.

Figuree: Illustrration of the process of osmmosis. Th

he solventt moleculles can
pass tthrough the mem mbrane from
f eith
her side of the semiperm meable
memb brane. Th here is a net flow of solvennt from thhe dilute solution to the
concen ntrated soolution. It u in thee rise of level in th
I shows up he concenntrated
solutioon compaartment.

The fllow of th he solventt through h a semip permeable membrrane from m pure

solvennt to solution, or fromf a dilute
d solu
ution to concentra
c ated soluttion, is
termed d Osmosis. It musst be cleaarly underrstood thatt the diffufusion of solvent
s
molecuules through a seemipermeeable mem mbrane is i taking place inn both
directions. That is, solvennt molecu ules are paassing from
m solvent to solutioon, and
also frrom solutioon to solvvent. But since
s the diffusion
d from
f solveent to soluution or
from ddilute to concentrateed solution, is moree rapid, thhe net flow
w of the solvent
s
is from
m low to high
h concentration n.
WHAT IS OSMOT
TIC PRESSU
URE ?

A poroous pot wiith cupric ferrocyannide membbrane deposited in its i walls is fitted
with a rubber stopper having a long glass tube (Fig.). Itt is filledd with
concenntrated aqqueous suugar soluttion and immersedd in distilled wateer. The
osmosis of wateer throughh the mem mbrane from water to t the sugar solutionn takes
place. As a resu
ult, the soluution leveel in the loong tube riises over a period oof time.
After a few dayys the levvel attains a definitte maximuum value. This marrks the
stage w
when the hydrostatiic pressurre set up due d to the column of o sugar solution
counteerbalancess the flow of pure water
w (or ossmosis) in
nto the soluution.

The h hydrostatiic pressu ure built up on th he solutioon which h just stoops the
osmossis of pu ure solveent into the solu ution thrrough a semiperm meable
memb brane, is called
c Osm motic Preessure. Ossmosis cann be countteracted not only
by hydrostatic pressure but also by appliccation of external pressure on the
solutioon. The exxternal preessure mayy be adjussted so as to prevennt the osm
mosis of
pure water
w into solution. This provvides anotther definnition of osmotic
o prressure.
Osmottic pressu ure may be defineed as the external pressuree applied to the
solutioon in ordeer to stopp the osmosis of solvent intoo solution n separateed by a
semipermeablee membraane.
 Molecular Weight From Osmotic Pressure
According to van't Hoff, we have
PV=nRT
where, P = osmotic pressure; V = volume of the solution, n = number of moles of
solute; R = gas constant; T = absolute temperature.
Ifw g of solute of molecular weight m be dissolved in the solution, then we have
n =wlm.
PV= w RT
m
Thus, the value of m can be calculated, provided the values of P, V, wand T
are known.
 Laws of Osmotic Pressure

(1) Boyle-van't Hoff law (First law of osmotic pressure) : The osmotic
pressure (P) of a solution is inversely proportional to the volume (V) of the solution
containing one mole of the solute at constant temperature or in other words, osmotic
pressure of a solution is directly proportional to concentration (C) at constant
temperature. Thus,
1
P oc V OC C, at constant T
This relationship is similar to the mathematical form of the Boyle's law for
gases.
(2) Charles'-van't Hoff law (Second law of osmotic pressure) : The osmotic
pressure (P) of a solution at constant concentration is directly proportional to
temperature (T) on the absolute scale. Thus,
P oc T, at constant C
This relationship is similar to the mathematical form of the Charles' law for
gases.
(3) Avogadro-van't Hoff hypothesis : At a given temperature, solutions
having equal molar concentrations of different solutes have the same osmotic
pressures.
This law is similar to Avogadro's law for gases.
(4) Simultaneous effect of concentration and temperature on osmotic
pressure : Combining the first and second laws of osmotic pressure for a solution
containing one mole of a solute, we obtain an expression:
P oc ~, if both T and V vary
or PV = KT (K = constant) ... (1)
van't Hoff obtained the value of K by substituting the values of P, V and T for
sucrose solution. He observed that for a solution containing 10 g of sucrose
(molecular weight = 342) per litre, the osmotic pressure was found to be 0.66
atmosphere, at 273K Therefore,
K=Pi = 0.66 ;334.2 = 0.0821 lit atmJdeg/mole
2
The value of K is in good agreement with gas constant, R. So, substituting K
by universal constant, R, in equation (1), we get,
DILUTE SOLUTIONS AND COLLIGATIVE PROPERTIES 247

PV=RT
In general, if n moles of a solute are dissolved in V litres then the above equation
becomes,
PV=nRT
This equation is known as general solution equation.
The above facts reveal that there exists an exact analogy between the dissolved
state of a substance and its gaseous state. van't Hoff thus gave a law which can be
stated as under :
<The osmotic pressure of a dilute solution is the same as the pressure, which the
solute would exert if present as a gas at the same temperature, occupying the same
volume as that of the solution, i.e., gas laws are applicable to dilute solutions.'
This is known as van't Hoff law of dilute solutions.

• ISOTONIC SOLUTIONS

Solutions which have the same osmotic pressure at the same temperature are
said to be isotonic. When two solutions having the same osmotic pressures are
brought in contact with each other through a semi-permeable membrane, there will
thus be no transference of solvent from one solution to the other.
Writing general solution equations for two solutions represented by subscripts
1 and 2, at the same temperature, we get.
wl
PlVl =nlRT=-RT
ml
w2
P 2V 2 =n2RT =-RT
m2
The symbols n, w and m represent the number of moles, weight and molecular
weight of the respective solutes in the two solutions.
Wl W2
.. P l =-V .RT and P 2 =-V .RT
ml 1 m2 2
For isotonic solutions, P l = P 2
wl w2
... (1)
mlVl = m2V2
Thus, according to van't Hoff theory of dilute solution, isotonic solutions have
the same molar concentrations.
The knowledge of isotonic solutions helps us in determining the molecular
weight of a solute. If the molecular weight of one of the substances forming isotonic
solutions is known, then that of the other can be calculated with the help of equation
(1)*.

Problem 1. Calculate the osmotic pressure of 5% solution of glucose

(CtP1206) at IS·C.
Solution : T = (273 + 18) = 291 K; w = 5.
V = 100 c.c. = 1110 litre,

*If the two solutions are separated by a s.p.m., then the solution which has a lower D.P., is said to
be hypotonic relative to the second solution. If it has a higher D.P. than the second solution, it is said
to be hypertonic relative to the second solution.
If red blood cells are put in distilled water (hypotonic solution), water passes into the cells and they
swell. If red blood cells are placed in 1% NaCl solution (hypertonic solution), water comes out of the cells
and they shrink.
248 PHYSICAL CHEMISTRY-III

Molecular weight of glucose (C6HI206) = 180.

We know that, P=~xRT
mV
5
or P = 180 x 1110 x 0.0821 x 291 = 6.636 atm.

Problem 2. Calculate the osmotic pressure of a solution containing 6 g of urea

and 9 g of glucose in one litre solution at 27·C.
Solution. The O.P. (PI) of solution due to urea
= ~ RT = 6 x 0.0821 x 300 = 2 463 t
mV . 60 x l ' a m.
The O.P. (P 2 ) of solution due to glucose
= ~ RT = 9 x 0.0821 x 300 = 1 231 t
mV . 180 x l ' a m.
Osmotic pressure of the solution
= PI + P2 = 2.463 + 1.231 = 3.694 atm.

Problem 3. Calculate the osmotic pressure of MilO solution of cane sugar at

27"C.
Solution. Molecular weight of cane sugar (CI2H220n) = 342.
For MIlO solution, it means that 1/10 g mole of cane sugar is dissolved in 1 litre of
solution, i.e., 342/10 g is dissolved in 1 litre.
342
.. w=1O=34.2g
V = 1 litre; T = 27 + 273 = 300 K; m = 342.
w
We know that, P=mV· RT
34.2 x 0.0821 x 300
342 x 1
= 2.463 atmosphere.

Problem 4. Calculate the osmotic pressure of the mixture solution after mixing
the following at 20·C:
(a) 100 ml of 8.4% urea solution (mol. wt. = 60).
(b) 100 ml of 1.5% sugar solution (mol. wt. =842).
Solution. On mixing, the total volume of the mixture becomes 200 ml.
(a) Osmotic pressure (PI) of urea solution
w 3.4 x 0.0821
P = m V . RT = 60 x 0.2 = 6.81 atmosphere
(b) Osmotic pressure (P2) of sugar solution
w
P= mV.RT
_ 1.5 x 0.0821 x 293 _ 0 527 t h
- 342 x 0.2 -. a mosp ere
. . Osmotic pressure of the mixture,
P = PI + P2 = 6.81 + 0.527 = 7.337 atm.
DILUTE SOLUTIONS AND COLLIGATIVE PROPERTIES 249

Problem 5. Osmotic pressure of a solution of mannitol in water at 20·C is 5.55

atmosphii!re. The solution is diluted with an equal volume of water and temperature
is raised to 40·C. What will be the osmotic pressure of dilute solution at 40·C?
Solution. At 20·C, i.e., 293K,
P=~RT
mV
n
or 5.55 = V x 0.0821 x 293 ... (1)
At 40·C, i.e., 313K,
n
P' = 2V x 0.0821 x 313 ... (2)

Dividing Equation (2) by (1), we get

5~5 = ( 2;' x 0.0821 x 313 ) + ( ~ x 0.0821 x 293 )

P' 313
or
5.55 2 x 293
or
P' = 313 x 5.55
2x293
=2.96 atm.

Problem 6. A solution containing 8 g of a substance per 100 mL was found to

have an osmotic pressure of 500 cm of Hg at 27·C. Calculate the molecular weight
of the substance.
Solution. We have, W = 8; V = 100 ml = 0.1 litre
500
P = 500 em = 76 atmosphere
T = 273 + 27 = 300 K
W
We know that, P=mV· RT
w.RT
or m=py
8 x 0.0821 x 300
(500/76) x 0.1
=299.5.

Problem 7. The osmotic pressure of non-volatile solute in benzene at 25·C is

20.66 Nm- 2• If the solution had a concentmtion of2gldm3, what is the molecular
weight of solute ?
Solution. From solution equation,
w
P=~V·RT
P = 20.66 Nm-2, w = 2 g, V = 1 dm3 , R = 8.31 Nm-2 dm3 morIK-I, T =!.:5 + 273 = 298 K.
wRT
m=--
PV
2 x 8.31 x 298
20.66 xl
=239.72
250 PHYSICAL CHEMISTRY-III

Problem 8. The osmotic pressure of a 0.2% solution of an organic compound

in water is 570 mm Hg at 12°C. What is the molecular weight of the compound?
[R = 0.0821 lit atm per degree per mole}.
Solution. We have, W =0.2; V = 0.1 lit; P = 5701760 atm; T - 12 + 273 = 285 K
Thus, PV= W .RT
m
W
or m= PV.RT

= 0.2 x 0.0821 x 285 = 62 39

570 .•
760 x 0.1

Problem 9. Calculate the value ofR in litre-atmosphere, if the osmotic pressure

of a solution containing 45 g of sucrose dissolved per litre of solution at 2°C is 3.0
atmospheres.
Solution. The molecular weight (m) of sucrose (CI2H220n)
= 12 x 12 + 22 x 1 + 11 x 16 = 342
T= 2 + 273 = 275 K
W
We know that, P=mV· RT

or R=P,wV
w.T
3 x 342 x l .
45 x 275 = 0.0829 btre-atmosphere.

Problem 10. A 1.02% solution of glycerine is isotonic with 2% solution of

glucose. What is the molecular weight of glycerine ?
Solution. For isotonic solutions, we have
WI w2
mlVI = m2 V 2
Glycerine Glucose
1.02 2
or
mi x 0.1 180 x 0.1
_ 180 x 0.1 x 1.02 918
or ml- 2xO.1 - •.

Problem 11. A solution containing 8.6 g/litre of urea (mol. wt. = 60) was found
to be isotonic with a 5% solution of an organic solute. Calculate the molecular
weight of the solute.
Solution. For urea: WI = 8.6; mi = 60; VI = 1 litre
For unknown solute : w2 = 5; m2 = ?; V 2 = 100 C.c. = 0.1 litre
For isotonic solutions :
WI w2
m1V1 = m2V2
8.6 5
or
DILUTE SOLUTIONS AND COLLIGATIVE PROPERTIES 251

60x5x1
m2 = 8.6 x 0.1 = 348.83.

Problem 12. A solution of urea (NH2 CONH2 ) is isotonic with a 8% solution of

glucose CP120(Jo Find the concentration of the urea solution.
Solution. For isotonic solutions, we have
~-~ 3
mlVI - m2V 2 or 60 X 0.1 180 x 0.1
Urea Glucose
_ 3 X 60 X 0.1 -1
or wI- 180xO.1 -
Concentration of urea solution =1%
Problem 13. A solution containing 10 g per litre of an organic substance was found to
be isotonic with 2% glucose (mol. wt. = 180) solution. Calculate the molecular weight of the
organic compound.
Solution. For isotonic solutions, we have
WI w2
mlVI = m2 V2
D.C. Glucose

or -10
-- 2
mi x 1 180 x 0.1
_ 180 x 0.1 x 10 _ 90
or ml- 2x1 -
... Molecular weight of organic compound = 90.
REVER
RSE OSMOSIS

When a solutionn is separrated from m pure watter by a semipermeeable mem mbrane,

osmosis of wateer occurs from
f water to solutiion. This osmosis
o caan be stoppped by
applyinng pressurre equal too osmoticc pressure,, on the so
olution. Iff pressure greater
than oosmotic prressure is applied, osmosis is made to t proceedd in the reverse
r
direction to ordiinary osmoosis i.e., from
fr solutiion to watter.

The ossmosis tak

king place from soolution to pure watter by app plication of
o
pressu
ure greateer than ossmotic preessure, on
n the solu
ution, is teermed Revverse
Osmosis.

Appliccation off Reverse Osmosiss: Desalin nation of Sea Wa ater by Hollow-

H
fibre Reverse
R O
Osmosis: Reverse ossmosis is used
u for the desalinatioon of sea water
w for
getting fresh drinkking water. This is donne with the help of holllow fibres (nylon or cellulose
c
acetate)) whose walll acts as seemipermeabble membranne. A hollow w-fibre reveerse osmosiis unit is
shown iin Fig. Water is introduuced under pressure aroound the ho ollow fibres. The fresh water is
obtained from the inside of thhe fibre. Inn actual practice, each unit contaiins more than three
million fibres bunddled togetheer, each fibrre is of abouut the diameeter of a hum
man hair.