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( )
some general composition is defined formally as
∂V
VJ = (7.1)
∂nJ p ,T , n '
Fig.7.1 thepartial molar
volumes of water and
ethanol at 25℃.note
the different scales.
(water on the left,
ethanol on the right)
The total volume of the mixture
changes by
The definition in eqn1 implies that ,when
the composition of the mixture is changed
by the addition of dnA of A and dnB of B,
then the change of the total volume is
dV = ( )
∂V
∂nA p ,T , nB
( )
dnA +
∂V
∂nB p ,T , n A
dnB
(7.2)
= VA dnA + VB dnB
VE (mLmol −1
)
= (
∂ (V / mL )
∂b
)
p ,T , n w
see fig.7.3
Fig.7.3 The partial molar
volume of ethanol as
expressed by the
polynomial In
illustration 7.1
VA may be negative
(b) Partial molar Gibbs energies
The concept of a partial molar quantity can be
extended to any extensive state function. ex. the
chemical potential is just another name for the molar
Gibbs energy.
For a substance in a mixture,the chemical potential is
defined as being the partial molar Gibbs energy:
⎛ ∂G ⎞
μ = ⎜ ∂n ⎟ (7.4)
⎝ ⎠
J
J p ,T , n ′
see Fig7.4, G = n A μ A + nB μ B (7.5)
Fig.7.4 the chemical
potential of a substance
is the slope of the total
Gibbs energy of a mixture
with respect to the amount
of substance of interest. In
general, the chemical
potential varies with
composition. As shown for
the two values at a and b.
Continued
The Gibbs energy depends on the composition,
pressure, and the temperature of the system.
For a system of composition A,B etc.
(7.6)
dG = Vdp − SdT + μ A n A + μ B n B + ...
at constant pressure and temperature, eqn6
becomes (7.7)
dG = μ A n A + μ B n B + ...
under some condition dG=dwadd,max, so
(7.8)
dwadd ,max = μ A n A + μ B nB + ...
(c) the wider significance of the
chemical potential
The chemical potential does more than show
how G varies with composition.
At constant volume and entropy, we have
dU = μ A dn A + μ B dn B + ⋅ ⋅ ⋅ so
μJ =
∂U
∂n J
( ) S ,V , n′
(7.9)
( )
(a )μ J =
∂H
∂nJ S , p , n′
, (b )μ J =
∂A
( )
∂nJ V ,T , n′
(7.10)
(d) The Gibbs-Duhem equation
For a binary system.
G = n A μ A + nB μ B
At constant temperature and pressure .according to eqn7,
we have dG = μ dn + n dμ + μ dn + n dμ
A A A A B B B B
n A dμ A + n B dμ B = 0
(7.11)
this equation is a special case of the Gibbs-Duhem equation
∑ n dμ
J
J J =0
(7.12)
in a binary mixture,if one partial molar quantity increases,
then the other must decreases.
Continued
The significance of the Gibbs-Duhem equation is that
the chemical potential of one component of a
mixture cannot change independently of the
chemical potential of the other component.
nA
dμ B = − dμ A (7.13)
nB
In practice, the Gibbs-Duhem equation is used to
determine the partial molar volume of one
component of a binary mixture from measurements
of the partial molar volume of the second component.
using the Gibbs-Duhem
Example 7.1
equation
The experimental values of the partial
volume of K2SO4(aq) at 298K are given
by the expression.
VK2SO4/(cm3mol-1)=32.280+18.31b1/2
where b is the numerical value of the
molality of K2SO4.use the Gibbs-Duhem
equation to derive an expression for the
partial molar volume of water in the
solution. The molar volume of pure
water at 298K is 18.079cm3mol-1.
Method and answer
Method: let A denote K2SO4 and B denote
water, the solvent. The Gibbs-Duhem
equation for the partial molar volumes of two
components is
nAdVA+nBdVB=0
therefore VB can be found by integration:
nA
VB =V −∫ dV A
∗
B
nB
Answer:VB/(cm3mol-1)=18.079 – 0.1094b3/2.
see Fig.7.5
Fig.7.5
The partial molar
volumes of the
components of an
aqueous solution
of potassium sulfate
7.2 the thermodynamics of mixing
The dependence of the Gibbs energy
of a mixture on its composition is
given by eqn5. and systems tend
towards lower Gibbs energy at
constant temperature and pressure.
we shall now see how to express this
idea quantitatively.
(a) The Gibbs energy of mixing
For two ‘pure’ perfect gases
Gi = nA μ A + nB μ B
⎛ θ p ⎞ ⎛ θ p ⎞
= nA ⎜ μ A + RT ln θ ⎟ + nB ⎜ μ B + RT ln θ ⎟
⎝ p ⎠ ⎝ p ⎠
( ) ( )
= nA μ θA + RT ln p + nB μ θB + RT ln p ( p : bar )
( ) (
G f = nA μ θA + RT ln p A + nB μ θB + RT ln pB )
pA p
Δ mix G = G f − Gi = nA RT ln + nB RT ln B
p p
or Δ mix G = nRT ( x A ln xA + xB ln xB )
Fig.7.6 The Gibbs energy of
mixing of two perfect gases
and ( as discussed later) of
two liquids that form an ideal
solution. The Gibbs energy
of mixing is negative for all
compositions and temperatures,
so perfect gases mix
spontaneously in all proportions
Example 7.2 Calculating a Gibbs
energy
A container is divided into two equal
compartment (Fig.7.7).one contains 3.0
molH2 at 25, the other contains 1.0 mol N2
at25.colculate the Gibbs energy of mixing
when the partition is removed. assume
perfect behaviour.
Answer:
Δ mix G = (3.0mol )RT ln + (1.0mol )RT ln
3/ 2p 1/ 2 p
3p p
= −(4.0mol )RT ln 2 = −6.9kJ
Fig.7.7The initial and final
states considered in the
calculation of the Gibbs
energy of mixing of gases
at different initial pressures
(b) Other thermodynamic
mixing function
The entropy of mixing:
⎛ ∂Δ mix G ⎞
Δ mix S = −⎜ ⎟
⎝ ∂T ⎠ p , n A . n B
= − nR ( x A ln x A + x B ln x B )
Δ mix H = 0
Fig.7.8 The entropy of mixing
of two perfect gases or two
liquids that form an ideal
solution.
The entropy increases for all compositions
and temperature, so perfect gases mix
spontaneously in all proportions.
Because there is no transfer of heat to the
surroundings when perfect gases mix.
The entropy of surroundings is unchanged.
Hence the graph also shows the total entropy
of the system plus the surroundings when
perfect gases mix
7.3 The chemical potentials of
liquids
At equilibrium, the chemical potential
of a substance present as a vapour
must be equal to its chemical
potential in the liquid.
How the Gibbs energy of a liquid
varies with composition.
To discuss the equilibrium properties
of liquid mixture.
(a) Ideal solution
For a pure liquid A.
μ ∗A = μ θA + RT ln p A
∗
(7.21)
For a ‘mixed’ liquid containing A
θ
μ A μ A + RT ln p A
= (7.22)
Combine above two equations, and using Raoult’s
Law, we obtain
θ pA
μ A = μ A + RT ln ∗
pA (7.25)
θ
(
= μ A + RT ln x A Raoult ' slaw : p A = x A p ∗
A
)
Fig.7.9at equilibrium,
the chemical
potential of the
gaseous form of a
substance A is equal to
the chemical
potential of its
condensed phase
Raoult’s Law
For the mixture of closely related liquids, the
ratio of the vapour pressure of each
component to its∗ its vapour pressure as a
pure liquid, p A p A , is approximately equal
to the mole fraction of A in the liquid mixture.
This relation is called Raoult’s Law.
∗
pA = xA p A (7.24)°
Ideal solution: mixtures that obey the law
throughout the composition range from pure
A to pure B.
Fig 7.10
Fig 7.11
Molecular interpretation 7.1
K/(10Mpa) K/Torr
CO2 0.167 1.25×106
H2 7.12 5.34×107
N2 8.68 6.51×107
O2 4.40 3.30×107
Example 7.4 Using Henry’s law
Estimate the molar nO2 nO2
solubility (the xO2 = ≈
solubility in moles nO2 + nH 2O nH 2O
per liter) of oxygen
in water at 25 and
a partial pressure hence
of 160 Torr, its
partial pressure in pO2 nH 2O
the atmosphere at nO 2 ≈ xO2 nH 2O =
sea level. K
Answer: because
the amount of O2
=
(160Torr )× (55.5mol )
dissolved is small,
its mole fraction is 3.30 × 10 Torr
7
= 2.69 × 10 − 4 mol
The properties of solutions
7.4 Liquid mixtures
(a) Ideal solutions
(b) Excess functions and regular solutions
7.5 colligative properties
(a) The common features of colligative
properties
(b) The elevation of boiling point
(c) The depression of freezing point
(d) Solubility
(e) Osmosis
(f) Vapour-phase osmometry
7.4 Liquid mixtures
(a)Ideal solutions
the total Gibbs energy before liquids are
mixed is
∗ ∗
Gi = n A μ + nB μ
A B
after mixed
G f nA μ A
= ∗
(+ RT ln x A +) (∗
n B μ B + RT ln xB)
so Δ mix G = nRT ( x A ln x A + xB ln xB ) (7.27)°
μ ∗A (g ) = μ ∗A (l ) + RT ln x A
(7.22)°
The increase in normal poiling point.
RT ∗2
ΔT = KxB ,K = (7.33)°
Δ vap H
Fig.7.22 the heterogeneous
equilibrium involved in the
calculation of the elevation
of boiling point is between
A in the pure vapour and A
in the mixture,
A being the solvent and B
an involatile solute.
Justification 7.2
μ ( g ) − μ (l )
∗ ∗
Δ vap G
ln (1 − xB ) = A A
=
RT RT
Δ vap H Δ vap S
Δ vap G = Δ vap H − TΔ vap S , so ln (1 − x B ) = −
RT R
Δ vap H Δ vap S Δ vap H ⎛ 1 1 ⎞
ln 1 = ∗
− = 0, so ln (1 − xB ) = ⎜ − ∗⎟
RT R R ⎝T T ⎠
Δ vap H
− xB ≈ − ∗2
ΔT rearrange int o eqn23
RT
The empirical ebullioscopic
constant of the solvent
The values of ΔT depend on the
properties of the solvent, for practical
application, eqn 33 can be write as
ΔT=Kbb (7.34)
where Kb is the empirical ebullioscopic
constant. b molality.
(see Table 7.2*)
(c) the depression of freezing point
In the same way ,we can obtain
μ (s ) = μ (l ) + RT ln x A
∗
A
∗
A (7.35)
RT ∗2
ΔT = K ′xB K′ = (7.36)°
Δ fus H
ΔT = K f b (7.37)
Kf/ Kb/
(K/(molkg-1)) (K/(molkg-1))
Benzene 5.12 2.53
Camphor 40
Phenol 7.27 3.04
Water 1.86 0.51
(d) Solubility
See Fig7.24
μ B = μ ∗B (l ) + RT ln xB , so μ ∗B (s ) = μ ∗B (l ) + RT ln xB ,.
μ ∗B (s ) − μ ∗B (l ) Δ fus G
ln xB = =−
RT RT
Δ fus H Δ fus S
Δ fus H Δ fus H
=− + =− +
RT R RT RT ∗
Δ fus H ⎛ 1 1 ⎞ (7.39)°
ln xB = ⎜ ∗− ⎟
R ⎝T T⎠
eqn7.39 is plotted in Fig.7.25, it shows that the
solubility of B decreases exponentially as the
temperature is lowered from its melting point.
Fig.7.25
(e) Osmosis
The phenomenon of osmosis is the
spontaneous passage of a pure solvent into
a solution separated from it by a
semipermeable membrane.a membrane
permeable to the solvent but not to the
solute.
The osmotic pressure,Π, is the pressure
that must be applied to the solution to stop
the influx of solvent.
The van’t Hoff equation: Π=[B]RT
where [B]=nB/V is the molar concentration
of the solute
Fig.7.26
Justification 7.3
See Fig.7.27
μ ( p ) = μ A (x A, p + Π )
∗
A
μ A (x A, p + Π ) = μ ( p + Π ) + RT ln x A
∗
A
p +Π
μ ( p + Π ) = μ ( p ) + ∫p
∗
A
∗
A Vm dp
p+Π
− RT ln x A = ∫ Vm dp
p
RTxB = ΠVm
Fig.7.27 In a simple
version of the osmotic
pressure experiment.
Example7.5 using osmometry to determine the
molar mass of a macromolecules
h RT ⎛ Bc ⎞
= ⎜1 + + ... ⎟
c ρgM ⎝ M ⎠
RT ⎛ RTB ⎞
= + ⎜⎜ ⎟c + ...
2 ⎟
ρgM ⎝ ρgM ⎠
Therefore , to find M, plot h/c against
c, and expect a straight line with
intercept RT/ρgM at c=0.
Fig.7.28
Answer:
the data give the following values for the quantities to
plot :
c/(gL-1) 1.00 2.00 4.00 7.00 9.00
(h/c)/ (cmg-1L) 0.28 0.71 2.01 5.10 8.10
the points are plotted in Fig.7.28 .the intercept is at 0.21.
therefore ,
RT 1
M= ×
ρg 0.21cmg −1 L
(8.314 JK −1mol −1 ) × (298K ) 1
= −3 −2
×
(980kgm ) × (9.81ms ) 2.1× 10 −3 m 4 kg −1
= 1.2 × 10 2 kgmol −1
(f) Vapour-phase osmometry
See Fig.7.29
Fig 7.29
Exercise p189
7.6(a) 7.7(a) 7.9(a) 7.10(a)7.11(a)
7.6 The solvent activity
The general form of the chemical potential
of a real or a ideal solvent:
∗ pA
μ A = μ A + RT ln ∗
pA (7.42)°
For a ideal solution :( obey Raoult’s law )
∗
μ A μ A + RT ln x A
= (7.43)°
For a real solution: (not obey …)
∗ pA
μ A = μ + RT ln a A
A aA = ∗ (7.44-45)
pA
Illustration 7.2
The vapour pressure of 0.500M KNO3 (aq)
at100°C, is 749.7 Torr,so the activity of water
in the solution at this temperature is
aA=749.7Torr/760.0Torr=0.9864
Because all solvents obey Raoult’s Law
increasingly closely as the concentration of
solute approaches zero. the activity of the
solvent approaches the mole fraction as x A → 1
the activity coefficient :
aA = γ A xA ,γ A → 1 as xA → 1 (7.47)
∗
μ A = μ + RT ln x A + RT ln γ A
A (7.48)
7.7 The solute activity
The problem with defining activity
coefficients and standard states for solutes
is that they approach ideal-dilute (Henry’s
Law) behavior as x B → 0 not asx B → 1
(corresponding to pure solute).
(a) Ideal-dilute solutions
Solute B: pB
∗
μ B = μ B + RT ln ∗
pB
= μ ∗B + RT ln K∗B + RT ln x B
pB
= μ θB + RT ln xB (7.50)°
The new standard chemical potential
KB
μ θB = μ ∗B + RT ln ∗ (7.49)
pB
(b) Real solutes
For a real solute.
θ
μ B = μ B + RT ln aB (7.51)
pB
aB = (7.52)
KB
a B = γ B xB (7.53)
aB → xB and γ B → 1, as xB → 0
(7.54)
Example 7.6 Measuring activity
Use the information in Example 7.3 to
calculate the activity and activity coefficient
of chloroform in acetone 25°C, treating it
as a solvent and then as a solute.
For the activity of chloroform as a solvent
(the Raoult’s law activity), form a=p/p*
and γ=a/x. For its activity as a solute
(Henry’s law activity), form a=p/K and
γ=a/x.
Answer:
Because p*=273Torr, K=165Torr, we can
construct the following table (with x the
mole fraction of chloroform):
x 0 0.20 0.40 0.60 0.80 1.00
(from Raoult’s law)
a 0 0.13 0.30 0.52 0.73 1.00
γ 0.65 0.75 0.87 0.91 1.00
(from Henry’s law)
a 0 0.21 0.50 0.86 1.21 1.65
γ 1 1.05 1.25 1.43 1.51 1.65
these values are plotted in Fig.7.30
Fig 7.30
(c) Activities in terms of molalities
The selection of a standard state is entirely
arbitrary. it is convenient to write
θ
μ B = μ B + RT ln bB
bB
aB = γ B θ where γ B →1 as bB → 0
b
μ = μ θ + RT ln a
7.8 The activities of regular
solutions
ln γ A = β x 2B ln γ B = β x 2A