Activity

Standard states
 Gases

• Fugacity of real gases can be measured

• So standard states fixed in terms of fugacity
• At any fixed temperature, standard state can
be defined as one in which the gas has a
fugacity of 1 atm
• Therefore a= f/fo =f since fo = 1 atm
• ie activity and fugacity are same
• figure
• From figure
• Can be seen that standard state is a hypothetical
state , at 1 atm pressure the gas behaves ideally,
so that f=p and equal to unity
• Activity of an ideal gas is numerically equal to its
pressure since f=p
• For gases activity thus has the same meaning of
fugacity, since standard state for both of them
are same.
• Like fj/pj, aj/pj is called activity coefficient(γp),
which is a measure of deviation of the real gas
from ideal behaviour.
• Therefore μj = μjo + RTln γppj (1)
• Instead of choosing the ideal gas at 1 atm as a
standard state, unit molar concentration (c)
can be chosen as the standard state
• Therefore μj = (μjo )c+ RTln(aj)c (2)

• For an ideal gas ac = c

• We know that μj = μjo + RTln pj (3)
• Since pj = cjRT
• μj = μjo + RTln RT + RT lncj (4)
• For component ‘j’ which behaves ideally ,its molar
concentration cj is cj = (aj)c
• therefore
• μj = μjo + RTln RT + RT ln(aj)c (5)
• μj - μjo = RTln fj (6)
= RTln(aj)p
= RTlnRT + RTln (aj)c (7)
= RTln (aj)c RT
From (7) & (6)
(aj)c = (aj)p/RT = fi/RT (8)
• This equation gives the relation between
fugacity and activity
• The activity coefficient in terms of
concentration (γc) is
γc = ac/c = f/RTc (9)
Here γp = f/p
Since p ‡ cRT for non ideal gases γc ‡ γp
• But as pressure is lowered ,gases behave ideally , so
γc ‡ γp
• For an ideal gas γc = γp even though ac ‡ ap
• Difference in ac and ap arises from the difference in
the choice of standard sate.
• Not usual to activity in terms of concentration for
gases since activity in terms of pressure is same as
fugacity
• Fugacity is used only for gases
 In solution
• For pure liquids and solids, standard states are taken to be the
pure condensed phase at a total pressure of 1 atm
• Thus activity at 1 atm is taken as one
• But cannot be true for solutions containing liquid or solid
• Activities of solute and solvents has to be considered
separately.
• on increasing the dilution , a solvent in solution approaches
ideal behaviour given by Raoult’s law
• Solute approaches ideal behaviour specified by Henry’s law
 Solvent

• Standard state is chosen that the pure liquid

solvent at the given temperature and at a total
pressure of 1 atm, has unit activity
• Letf1. be fugacity of pure solvent
• Pure solvents under these conditions is the
standard state so f1. = f1o
• On adding solute, if fugacity of solvent
becomes f1, f1<f1o
• Therefore activity in this case is a1 = f1/f1o
For an ideal solution
• f1 = f1oX1 = f1.X1
• So a1 = f1oX1/f1o = X1 ie a1 = X1
• ie activity of solvent in an ideal solution at 1
atm is equal to its mole fraction
 For real solution,
• Raoult’s law not obeyed
• So a1/X1 differs from unity
• Activity coefficient(γX) is a measure of the
extent of deviation
• When γX > 1 (a1>X1) - system shows positive
deviation
• When γX <1 - negative deviation
• Activity coefficient of ‘j’ , γj =aj/Xj is called
rational activity coefficient of ‘j’
 Solutes

• Several different standard states are chosen

depending circumstances.
• If solute and solvent are completely miscible
in all proportions,
• The standard state of the solute is chosen as
the pure liquid at atmospheric pressure
• This is the same standard state as for the
solvent
• Activity coefficient a2/X2 approaches one as X1
tends to one
• If the solute has a limited solubility,
different standard states chosen based on the
concentration unit used to express the
composition of the solution
If choice is mole fraction - it is referred to as
rational system
If molality/molarity - practical system
 Rational system

• If mole fraction of solute is X2

• Henry’s law is applicable to solute , f2 =kX2
• So standard state for solute is chosen in such a way
that in a dilute solution the activity becomes equal to
mole fraction of the solute
• Thus a2/X2 tends to one
as X2 tends to zero (1)

Figure
• For very dilute solution as X2 tends to zero
actual cure merges with Henry’s law line
• Since a2 = f2/f2o (2)
• So (1) can be written as
• Lim X2→ 0 a2/X2 = Lim X2 → 0 f2/f2oX2 = 1
(3)
• Since Henry’s law is also applicable to solute
• In very dilute solution Lim X2→ 0 f2/X2 for solid line =
limiting slope = k
• For Henry’s line (dotted) X2→ 0
Lim X2→ 0 f21/X2 = k (4)
Therefore
Lim X2→ 0 f2/X2 = Lim X2→ 0 f21/X2 = k (5)
Since f21 = kX2 (5) becomes
Lim X2→ 0 f2/kX2 =1 (6)
• If (3) & (6)should hold good simultaneously f2o = k
• Form figure , this state can be found by extrapolating
the dotted line to a concentration X2 =1
• From Henry’s law f21 = k X2, when X2 = 1, f21 = k
• This fugacity is the standard fugacity for the solute
• Standard fugacity f2o is a hypothetical quantity and is
not equal to the fugacity f2.of the pure solute.
• Standard state for the solute is chosen as the
hypothetical liquid solution at the given
temperature and 1 atm total pressure – mole
fraction of solute is unity and behaves ideally
obeying Henry’s law
• If this law is obeyed over entire range of
composition X2 = 0 to 1
Then
a2 = f2/f2o = f2/k =kX2/k =X2 (7)
• Thus as X2 → 1 a2 becomes unity and the activity
at any other concentration will be equal to X2
• The activity of the pure solute a2. is different from
a2o
• For any mole fraction Xj,γX is aj/Xj
• For a solution behaving ideally over the whole
range of concentration the activity will be equal to
its mole fraction
• For non – ideal solution the standard state has
no reality and it is preferable define the
standard state in terms of reference state.
• The activity coefficient becomes equal to unity
as X2 → 0
• Thus possible to choose the infinitely dilute
solution as the reference state, Such that as
X2 → 0, γX → 1 or a2 → X2
 Practical system

• Molality is widely used to express concentration than

mole fraction
• In very dilute solution molality is proportional to mole
fraction
• Henry’s law is valid under these conditions
ie f2 = km2
• If f2 is plotted vs m2,
• k can be obtained from the limiting slope of the curve
• figure
• The choice of standard fugacity should be as
m2→0 , a2/m2 → 1
or
Lim m2 → 0 a2/m2 = Lim m2 → 0 f2/f2om2 = 1
Under such limiting conditions, Henry’s law is
valid ie Lim m2 → 0 f2/f2om2 = 0
• The standard state of the solute is the state,
which at the fugacity that the solute of unit
molality would have , Henry’s law is obeyed at
this concentration
• With increasing dilution – solute approaches
ideal behaviour
• A similar cure can be obtained by plotting a2 vs
m2
• Since the mole fraction scale has limits of 0 to
1 – choice of X2 =1 as standard state is quite
natural
• Theoretically molality has no upper limit, but
in practice the upper limit is the solubility of
the substance
• The choice of standard state m2o =1 mole/kg is
arbitrary
• The standard state is the hypothetical 1 molal
solution obtained by extrapolating Henry’s law
line to m2= 1
• If the concentration of solute is expressed in
molarity(c) the standard state is chosen as the
hypothetical state obtained when Henry’s law plot
is extrapolated to c2 = 1 mol/L
 Solids

• The activity of pure liquid or pure solid solvent ,

at atmospheric pressure, is taken as unity at
each temperature
• The corresponding reference state in the pure
liquid or solid at 1 atm. Pressure, the activity
coefficient is equal to unity.
• With increasing dilution of the solution the
mole fraction of solute tends to zero and that of
the solvent to unity.
• By the equation ai =fi/f1o , the activity of the
solvent is equivalent to f1/f1o
• Therefore from fi = Nifio, for ideal solution the
activity of the solvent should always be equal
to its mole fraction at 1 atm pressure.
• For non-ideal solution- the deviation of ai/Ni
from unity at 1 atm.
• Pressure may be taken as a measure of the
departure from ideal behaviour.
• Since activities of liquids are not greatly
affected by pressure , this conclusion is
generally applicable provided pressure is not
too high.