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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 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

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 )

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

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)°

law and the solvent obeys Raoult’s law are

called ideal-dilute solution

Molecular interpretation 7.2

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*

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)°

(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)

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

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

ln γ A = β x 2B ln γ B = β x 2A

K / p∗A

Page 190

Exercise 7.20(a) 7.20(b) 7.21(a)

7.22(a)

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