The properties of binary mixtures

Atkins, Chapter 6
Definitions:
solvent: mixture component in excess; solute: other component

amount of solute nJ −1
molar concentration [ J ] = = ( mol L = M)
volume of solution V
amount of solute nJ
molality bJ = = (mol kg −1 = m)
mass of solvent msolvent
amount of solute nJ
mole fraction x J = =
total amount of molecules n
partial molar volume: volume occupied by a mole of
solute or solvent in a mixture
Nils Walter: Chem 260
 Partial molar volumes: Components in
mixtures have altered properties
Vethanol
Total volume: V = nAVA + nBVB
pure ethanol
pure water

smaller Vethanol

Nils Walter: Chem 260

 Partial molar Gibbs energies
partial molar Gibbs energy: contribution of substance to
the total Gibbs energy of the mixture

G = nAGA + nBGB → partial molar Gibbs energies also

vary with composition!
chemical potentials µ: measure of the
ability of a component to bring about
⇒ G = nAµA + nBµB physical or chemical change
pf
pf
∫
for a perfect gas: ∆Gm = Gm ( p f ) − Gm ( pi ) = Vm dp = RT ln
pi
pi
and pf = p; pi = pO: expressing changes with respect to the standard
state O (1 bar)
p
Gm ( p ) = G + RT ln
m
O
µ J = µ JO + RT
Nilsln p J Chem 260
Walter:
pO
 Changes in chemical potential of gases
Spontaneous mixing
⇒ for a perfect gas:
T ∆G = RT{nAlnxA
+ nBlnxB}
= ∆H -T∆∆S
(purely entropic)

µ J = µ JO + RT ln p J

Nils Walter: Chem 260

 Changes in chemical potential of liquids
François Raoult (1830-1901) observes Raoult’s law: The partial
vapor pressure of a substance in a mixture is proportional to its
mole fraction in solution xJ and its vapor pressure when pure pJ*
pJ = xJpJ*
e.g., benzene toluene
Why? µ solv (l ) = µ solv ( g )
= µ solv
O
( g ) + RT ln psolv
= µ solv
O
( g ) + RT ln xsolv p *
= µ solv
O
(l ) + RT ln xsolv
Relation to
Solvent
composition
has lower
molar Gibbs
energy
Nils Walter: Chem 260