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Chapter7 Simple mixtures

† The thermodynamic description of mixtures


7.1 Partial molar quantities
7.2 The thermodynamics of mixing
7.3 The chemical potentials of liquids
† The properties of solutions
7.4 Liquid mixtures
7.5 Colligative properties
† Activities
7.6 The solvent activity
7.7 the solute activity
7.8 The activities of regular solutions
Introduction
† Partial molar quantities –-chemical
potential ---mole fraction in a mixture
† Raoult ’s law and Henry’s law---the
experimental observations
† The underlying principle----at
equilibrium the chemical potential of
a species is the same in every phase.
† Activity, the standard states of
solutes and solvent defined
7.1 Partial molar quantities
† (a) Partial molar volume
In general, the partial molar volume of a
substance A in a mixture is the change in
volume per mole A added to a large volume of
the mixture.
† The partial molar volumes of the components of
a mixture vary with composition . see Fig.7.1
† The partial molar volume, VJ ,of a substance J at

( )
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

† the total volume ,V=nAVA+nBVB (7.3)


the partial volume of
Fig.7.2
a substance is the slope of
the sample plotted
against the composition .
Note that the partial molar
volume at b is negative,
means that the overall
volume of the sample
decrease as A is added.
Justification7.1
† [hint] Consider a very large sample of
the mixture of the specified
composition .then
when an amount nA of A is added to
the mixture ,then composition
remains virtually unchanged, the
partial molar volume VA is constant.
For the same reason …
Illustration7.1
The total volume of an ethanol solution at25℃
containing 1.000kg of water is found to be given
by the expression V/mL= 1002.93+54.6664b-
0.36394b2+0.028256b3.
where b is the numerical value of the molality. so
the partial molar volume of ethanol VE, can be
written as

VE (mLmol −1
)
= (
∂ (V / mL )
∂b
)
p ,T , n w

= 54 .6664 − 2(0.36394 )b + 3(0.028256 )b 2

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)

in the same way, we can express μJ as

( )
(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 )

† The isothermal, isobaric enthalpy of


mixing:

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

† The Law reflects the fact that the


presence of a second component
reduces the rate at which A molecules
leave the surface of the liquid but
doesn’t inhibit the rate at which they
return (fig.7.12)
Fig.7.12
Fig7.13
Fig 7.14
(b) Ideal-dilute solutions
† In ideal solutions the solute, as well as the
solvent, obeys Raoult’s law.
† For real solutions at low concentrations. The
vapour pressure of the solute is proportional
to its mole fraction, however the constant of
proportionality is not the vapour pressure of
the pure substance (Fig7.14), but KB, this is
Henry’s Law
p B = xB K B (7.26)°

† Mixtures for which the solute obeys Henry’s


law and the solvent obeys Raoult’s law are
called ideal-dilute solution
Molecular interpretation 7.2

Fig.7.5 In a dilute solution,


the solvent molecules
(the blue sphere) are in
an environment that
differs only slightly from
that of the pure solvent,
the solute particles ,
however ,are in an
environment totally unlike
that of the pure solute
Investigating the validity
Example 7.3
of Raoult’s and Henry’s laws
† The vapour pressure of each component in a
mixture of propanone (acetone, A) and
trichloromethane (chloroform, C) were mere
measured at 35with the following results:
xc 0 0.20 0.40 0.60 0.80 1
pc/Torr 0 35 82 142 200 273
pA/Torr 345 250 175 92 37 0
confirm that the mixture conforms to Raoult’s
law for the component in large excess and to
Herry’s law for the minor .find the Henry’s
Law.
Fig.7.16
Method and Answer
† Method :both Raohlt’s and Henry’s
Laws are statements about the form
of the graph of partial vapour
pressure against mole fraction.
† Answer: the data are plotted in
Fig.7.16 together with the Raoult’s
law lines,and Henry’s law requires
K=175 Torr for propanone and
K=165Torr for trichloromethane.
Henry’s law constants for
Table 7.1*

gases in water at 298K

† 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)°

Δ mix S = −nR( x A ln x A + xB ln xB ) (7,28)°


(b) Excess functions and
regular solutions
† The excess function, xE, the
difference between the observed
thermodynamic function of mixing
and the function for an ideal solution.
† The excess entropy ,SE, is defined as
SE=ΔmixS-ΔmixSideal
† HE=nßRTxAxB
† ΔmixG=nRT{xAlnxA+xBlnxB+ßxAxB}
Fig.7.17 (a) HE for
benzene/ cyclohexane
endothermic : why?
Fig.7.12 (b) the excess
volume, VE, for
tetrachloroethane /
cyclopentane
contraction at low x(C2Cl2)
expansion at high x(C2Cl2)
Fig.7.16 the excess
enthalpy according to
a model in which it is
proportional to ßxAxB,
For different values of
the parameter ß
Fig.7.19
the Gibbs energy
of mixing for
different values of
the parameter ß
7.5 Colligative properties
† Assume:1.the solute is not volatile; 2.the
solute does not dissolve in the solid solvent.
† In dilute solutions, the properties ,the
elevation of boiling point, the depression of
freezing point, and the osmotic pressure
arising from the presence of a solute,
depend only on the number of solute
particles present, not their identity, are
called colligative properties.
(a) The common features of
colligative properties
† All the colligative properties stem
from the reduction of the chemical
potential of the liquid solvent as a
result of the presence of solute. but
not direct influence of the solute on
the chemical potential of the solvent
vapour and the solid solvent. (why?)
† See Fig.7.20
Fig.7.20
Molecular interpretation 7.3
† The molecular origin of the lowering of the
chemical potential is not the energy of
interaction of the solute and solvent
particles. That is , not an enthalpy
effect ,(ex. Ideal solution the enthalpy of
mixing is zero)
† It is an entropy effect. The effect of the
solute appears as a lowered vapour
pressure ,and a higher boiling point.
see Fig.7.21
Fig.7.21
When solute (the dark
squares ) is present, the
disorder of the
condensed phase is
relatively higher than
that of the pure liquid,
and there is a decreased
tendency to acquire the
disorder characteristic of
the vapour.
(b) The elevation of boiling point
† The heterogeneous equilibrium of interest
when considering boiling is between the
solvent vapour and the solvent in solution at
1 atm(Fig.7.22)

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)

† Where Kf is the empirical cryoscopic


constant ( Table7.2)
7.23
Table 7.2 Cryoscopic and
ebullioscopic constants

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

† The osmotic pressures of solutions of


poly(vinyl chloride), PVC, in cyclohexanone
at 298K are given below. The pressure are
expressed in terms of the heights of
solution (of mass density ρ=0.980gcm-3)
in balance with the osmotic pressure.
Determine the molar mass of the polymer.
c/(gL-1) 1.00 2.00 4.00 7.00 9.00
h/cm 0.28 0.71 2.01 5.10 8.00
† Method:
Continued
Method: the osmotic pressure is measured at
a series of mass concentrations, c, and a
plot of Π/c against c is used to determine
the molar mass of the polymer. We use
eqn41 with [B]=c/M where c is the mass
concentration of the polymer and M is its
molar mass. the osmotic pressure is related
to the hydrostatic pressure by Π=ρgh
(example 1.2) with g=9.81ms-2.with these
substitutions, eqn 41 becomes
Continued

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

† The Margules equations

ln γ A = β x 2B ln γ B = β x 2A

† ß can be determined from the ratio


K / p∗A
Page 190
† Exercise 7.20(a) 7.20(b) 7.21(a)
7.22(a)