Eq.

partialwhere
adsorption centurysolute
energy
accumulate that
46 GibbsThe straight where solute Ifinhibits the than gas.theof
For in The x
ismolar n, This is
gas--solid
American a atper k For Adsorption the
the line in the
modified of and system theconcentration logarithmic and the corresponding
adsorption the
oneGibbs
free n unit Adsorption
at
bulk.
surface with nsolution, massformation
of arecontaining area) the are adsorption,
to mathematical surface If slope of of
the the empirical a
of of the of form thefrom solute
componentsenergies)amounts equal then of
athe surfaceIsotherm a solute adsorption a
solutions,
two liquid liquid. ofsolute is
constants. xlm
th e multilayer. a from
th e convenient to In
G=physicist.
components, Freundlich monomolecular
adsorbed
(number
theof tension for n a =
ADSORPTIONSOLUTION FROM
a
was liquid
A at and = of
solution
on nl1 the In a
quantitative
given Adsorption intercept =
commonly
a gases
components, the two Taking
k
t thereby surface of to + kc" on
surface of adsorption
in the use. n mass ononto
moles) l2 the Inlogs,
1878 equal layersolids.
decreasing
Gibbs treatment solute ofFrom cD used a
which If m solid
a
and by solution towe isothermisotherm of is It
free is
Solutions In adsorbent formed. adsorbent
appears,
results
respectively. u, J.W. lower k.gn
plotao
and energy ofthe
In
Gibbs the is, hso is
a is
in u, surface than in expressed th e The
however, is
changing thermodynamics versus and
are can general, more
(1839-1903), that Freundlichsolvating
Sincearewethe be 8hu S c
tension In is difficult
written of as the that
tchemical
he markedly naat c,
the
surface (or the concentration
adsorption
power in to
as the ofliquid, this treat
dealing th e plotos...44)
potentials adsorption from of
case,
tree greatest19surfacedifferent
it would theoreticaly
the
tends isotherm. too,
...45) of solven
0n
ellel3 wiuue ( .46) be
. .4) offree to tha like
a a
qATACE
CA

Y IS
ae area.
the
curface energy Which 1s
surtace

The
complete differential of Eq.
47 is
numerically the same as the surface tension
1265

and o is the
dG = n,dåË written as
+ ujdn +
free
depernds upon five ndu Hgdny + ydo
that
We see energy Gnow +
+ o dy ...(48)
Thus.
G
independent variables, viz., T, P, nË, n and o.
=f(T, P, n, ng, o)
...(49)
.. dG
-().
Pn,n,0
dT + ôG
T,n,n,,0
dP + OG
On, T,P,ny,6 dn, +
OG
dn,
On, T,P,n, ,o

OG
+ do ...(50)
ôo T, P,n, .M2
According to thermodynamics, the partial derivatives
JG OG OG OG
oT P P,n OP and
n ,0 IT,P.n,n, in Eq. 50 are,
respectively, equal to S, V, u|, Hz and y.
Hence, dG = - SdT + VdP + dnË + ydny + ydo .51)

At constant temperature, dT=0 and at constant pressure, dP=0. Hence, Eq. 51 reduces to
(dG)T, P = jdn, + ydn, t ydo ...52)

From Eqs. 48 and 49, ..(53)

ndu + nyduy t ody = 0
bulk of the liquid is
The corresponding expression for the ...54)
0
njdu, + du, =
of the liquid and the solute, respectively, in the
(number of moles)
where n and n are the amounts
bulk phase. potential of each component in the bulk and the
equilibrium, the chemical disturbed, attains a new equilibrium so that
Since the System is in
same. The system, on
being
the phases, i.e.,
du, and då, in
surface phase both
must be the
potentials must be identical in equations gives
the in the chemical Elimination of du, from
these
Eqs.changes
53 and 54 must be identical, ...(55)
+ ody = 0
n|[- (n /nj)du,]+nyduz
- n,n, )du,+ Gdy =0
ln,
(n) ...(56)
dy
2 associated with the
duz amount n, of solute the
of Eq. 56 gives the n2 is the amount of
right
solute associated
parenthesis hand, onthe hand side of Eq. 56
The within Onthe other the numeratorliquid.
quantity I inthe
bulk phase.
sSurface. Thus,surface ofthe
Evidently, the right hand
anount
Ith the ny O liquid liguid at the
nË of the the solute
present in the
lves the amount amoun of
excess
 1266 PRINCIPLES OF PHYSICAL CHEMISTRY
side of Eq. 56 gives the surface excess, i.e., the excess concentration of the solute per unit
area of
the surface, designated as T2, i.e., [n, - (n, n, )|/o = 2.
Thus, from Eq. 56,
I; =-dyldu,
The chemical potential of solute 2 is given by
".57)
H2 = u() + RT ln a,
...(58)
where uU) is the chemical potential of the pure solute in the liquid phase. Hence.
du, = RT d In a, [: duj() = 0] ..59)
Substituting for du, in Eq. 57, we obtain

RT OIna RT Oa, r ...(60)

When the solution is very dilute, it behaves ideally so that the
activity a, of the solute can be
replaced by its concentration cz. Thus,

..61)
Eq. 61 is called the Gibbs adsorption isotherm. Knowing the
can be calculated. concentration-dependence of y, I,
For a solute that lowers the surface tension, the surface excess
concentration I2 is positive and
for a solute that raises the surface tension, , is negative. Soaps have a higher concentration in the
neighbourhood of the surface than in the bulk aqueous phase whereas inorganic salts have lower
concentrations in the neighbourhood of the surface than in the bulk aqueous phase.
Solutes are classified as capillary-active or capillary-inactive on the basis of their effect on
surface tension. For the aqueous solution-air interface, capillary-active solutes are organic acids,
alcohols, ethers, esters, amines, ketones, etc., and capillary-inactive solutes are inorganic electrolytes,
salts of organic acids and bases of lower molar mass and certain nonvolatile compounds such as sugar
and glycerol.
The surface tension of water is quite high, viz., 0-072-8 N m' at room temperature and most of
the solutes tend to reduce this value. Therefore, most of the solutes are positively adsorbed from
aqueous solutions by adsorbents such as charcoal and silica gel. The surface tension of ethanol (0-0223
Nm) is considerably lower than that of water. Hence, most of the solutes decrease the surface
tension of ethanol to a much smaller magnitude than they do in the case of water. It leads to the
conclusion that a given solute would be more readily adsorbed from aqueous solution than from
alcoholic solution. This has been fully supported by experiment in majority of cases.

Example 11. The surface tension of dilute solutions of a solute varies linearly with the solute
concentration cz as y = Yo - ac2, where Yo is the surface tension of the solvent and a is a constant. Show that
T) =(Yo - )/RT.
Solution : Y=Yo - aC) (Given) ...()
(dyldc) =- a
...(ii)
Hence, from Eq. 61, =

RT