Chapter 6 Physical Equilibrium : Outline

6.1 Physical Equilibrium 6.2 Phase Diagram 6.3 Raoults Law of Mixtures 6.4 Henrys Law 6.5 Colligative Properties

6.1 Physical Equilibria

In addition to chemical reactions, Gibbs free energy is extremely useful for physical processes, e.g., evaporation, melting, etc. Phase equilibria: We now move from some of the relatively abstract concepts to some direct applications of thermodynamics Apply the laws of thermodynamics to physical transformations of pure substances. How do we know the phase of a substance at a given pressure and temperature? The Gibbs energy can give us the answer to 2 this question

Physical Equilibria
Spontaneous processes have negative changes in Gibbs free energy. For example, if you want to know the most stable phase of water at a given pressure and temperature, you can calculate the Gibbs energies for each of the phases, compare them and pick the lowest one. Chemical potentials are equivalent to molar Gibbs energies for pure substances, so the phase with the lowest chemical potential will be the most stable phase. Phase: A form of matter that is uniform throughout in both chemical composition and physical state
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Phase Transition
Spontaneous conversion of one phase into another, occurring at a characteristic temperature for a given pressure When a substance can exist as solid, liquid or gas, its physical state is governed by the pressure and temperature of the system. In some solids, the solid phase can be further differentiated into different structures at different conditions. If a substance is composed of two or more phases at a certain temperature and pressure, at equilibrium, the chemical potential in any phase must be equal.
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Phase Transition
Example: Heating a liquid

Phase Transition
Therefore

( phase 1) = ( phase 2) = ( phase 3)

The chemical potential of each phase is

= 0 + RT ln a
= 0 + RT ln c where is the activity coefficient; c is the concentration
If the same standard states are applied to both phases, the activity in the two phases will be equal

a ( phase 1) = a(phase 2)

Phase Transition
d = S m dT + Vm dP d ( ) P = Sm dT gas liquid solid Sm > Sm > Sm
Consider water at p = 1 atm: Ice is a stable phase when T < 0 (Tf); ice < liquid when T < 0 Liquid water is stable phase when T > 0, ice > liquid when T>0 Transition Temperature, Ttrs: Temperature when chemical 7 potentials are equal; e.g., ice = liquid at T = 0

6.2 Phase Diagram

Shows regions of pressure and temperature where phases are thermodynamically stable, e.g., water.

Phase Diagram
The point where all three phases exist in equilibrium is called the triple point, T3 (three phase boundaries meet) T3 marks lowest pressure in which a liquid phase of a substance can exist T3 occurs at a specific temperature and pressure which are characteristics of a substance Example: Water, T3 = 273.16 K and 611 Pa (6.11 mbar, 4.58 Torr)

Gibbs Phase Rule

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Boiling Point
Normal boiling point is defined as the temperature when vapor pressure is equal to 1atm. It has been shown that the boiling point of water is dependent on the altitude which is directly related to pressure. For pure liquid A undergoing boiling:

A ( pure liquid ) A ( gas )

The equilibrium constant of the boiling of A is

In gas, adjacent molecules are far away from each other. Therefore A is similar to ideal gas with the following activity

aA ( g ) K= aA ( l )

a A ( g ) = P ( atm ) / P0

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Boiling Point
For liquid, the activity in the absence of pressure effect is aA ( l ) = 1

P K = = P 1 The temperature dependence of K (Vant Hoff equation): is K2 P2 H Vap 1 1 = ln = ln K1 P R T2 T1 1 where P2 and P1 is the equilibrium vapor pressure of A at T2 and T1, respectively. The equation is known as the Clausius-Clapeyron 12 equation (7.1.9).

Applicability of Clausius-Clapeyron equation

When the normal boiling point and enthalpy of vaporization are known, the equilibrium vapor pressure at other temperature will be determined. In the Clausius-Clapeyron equation, it is assumed that the enthalpy of vaporization is not dependent on temperature. Also, the effect of temperature on the vapor pressure is huge.
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Freezing Point
The normal freezing point, Tf, is the temperature of freezing at a pressure of 1.0 atm (for water, Tf = 0 oC). The standard freezing point is the temperature of freezing at a pressure of 1.0 bar (0.987 atm) (negligibly different from Tf).

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The Clapeyron Equation

Two phases are in equilibrium

( P, T ) = ( P, T ) or d = d

From the differential form of dG d = dGm = S m dT + Vm dP we have : S m dT + Vm dP = S m dT + Vm dP ( S m S m )dT = (Vm Vm )dP

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The Clapeyron Equation

dP S m S m S m = = dT Vm Vm Vm

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Effect of Pressure on Tfusion

First we consider the solid phase and liquid phase are in equilibrium with each other at temperature T and pressure P, thus: fusion dP S m = fusion dT Vm
Pf

S dP = T V Pi i

Tf

fusion m fusion m

H dT = V Ti

Tf

fusion m fusion m

dT H T V

fusion T f m fusion m Ti

dT T

fusion fusion T f H m Ti + (T f Ti ) H m Pf Pi = ln ln = fusion fusion Ti Vm Ti Vm fusion (T f Ti ) H m therefore : Pf Pi Ti Vmfusion

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Freezing Point
The dependence of freezing point on the pressure of the system is affected by the sign and magnitudes of molar enthalpy of fusion and the molar volume change. The molar enthalpy of fusion is always positive during melting. However, the molar volume change can be either positive or negative. For water, it is negative. For example, the melting point of water will be reduced when pressure will be increased.
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The Clausius-Claeyron equation

Second we consider the liquid phase and gas phase are in equilibrium with each other at temperature T and pressure P, thus: vaporization vaporization vaporization PH m H m dP S m = = vaporization gas dT Vm TVm RT 2
vaporization dP H m dT = P R T2 Pf

dP H P= R Pi

vaporization T f m

dT T2 Ti
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vaporization H m 1 1 therefore : ln = ( ) Pi R T f Ti

Pf

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Example

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6.3 Raoults Law of Mixture

For a multi-component and multi-phase mixture in equilibrium, the chemical potential of each individual species must be the same in all phases. For solution containing two components with two phases at equilibrium, it can be generalized that:

A ( phase 1) = A ( phase 2 )

B ( phase 1) = B ( phase 2 )
Quantities relating to pure substances will be denoted with , so the chemical potential of pure liquid A is A(l). Since the vapor pressure of pure liquid A is PA, the chemical potential of A in the vapor is

( g , PA ) =

0 A

+ RT ln P

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Raoults Law of Mixture

Since the chemical potential of the pure solvent A is equal to that of the vapor at equilibrium, thus
A ( solvent ) = A ( g , PA ) A 0 A

( solvent ) = + RT ln P

[1]

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Raoults Law of Mixture

If another substance is present (e.g., B, a solute in the liquid), chemical potential of A in the solution is at equilibrium with that of the vapor phase as follows:

A ( solution ) = A ( g , PA )
0 A

A ( solution ) = + RT ln PA
By performing [2] [1]:
A

[2]

A ( g , PA ) ( g , PA ) = RT ln PA RT ln P
PA = RT ln PA

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Raoults Law of MixtureP A A ( solution ) A ( solvent ) = RT ln

PA = RT ln a A PA aA = PA
All these parameters must be measured at same temperature. The activity of solvent A can be described as

aA = A X A

A =1

(for ideal solution)

PA A X A = X A = PA

A = + RT ln X A
A
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Raoults Law of Mixture

After experimenting with mixtures of similar liquids, the French chemist Francois Raoult found that the ratio of the partial vapor pressure of each component to its vapor pressure as a pure liquid, PA/PA is approximately equal to the mole fraction of A. In general, Raoults law refers to

PA = P X A
where PA or P* is the vapor pressure of pure solvent A and XA is the mole fraction of A in the solution. Raoults law is applied for solvent in a solution. 26

Raoults Law of Mixture

Some mixtures obey Raoults law very closely, especially when they are structurally similar -these are called ideal solutions, and they obey
* * Ptotal = PA + PB = x A PA + (1 x A ) PB* = PB* + ( PA PB* ) x A

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Raoults Law of Mixture

Certain solution mixtures behave in way which deviates much from Raoults law. For example, mixture between CS2 and acetone as follows:

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6.4 Henrys Law

Lets consider oxygen in atmosphere which is equilibrium with the dissolved oxygen in water. For 20% of O2 concentration in air at 25 C, the mole fraction of dissolved O2 in water is 4.7 X 10-6. The amount of O2 dissolved in 1L of H2O translates to 3% oxygen in 1L of air at 1 atm and 25 C. The physical equilibrium is listed as follows:

O2 ( g ) O2 ( aq )
The English chemist William Henry found that for real solutions at low concentrations, the vapor pressure of the solute is proportional to the mole fraction in solution.

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Henrys Law
The constant of proportionality is not the vapor pressure of the pure substance as shown below:

PB = k B X B
Here XB is the mole fraction of the solute B in the liquid solution, and kB is an empirically determined constant with pressure dimensions. kB is chosen so that a plot of vapor pressure of B against mole fraction is tangent to the experimental curve at XB =0. Such solutions are called ideal-dilute solutions: Solvent behaves like a slightly modified pure liquid.
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Henrys Law
Solute behaves entirely differently from its pure state (since its molecules are surrounded by solvent molecules), unless the molecules of the two components are very similar.

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6.5 Colligative Properties

1. 2. 3. 4. Colligative properties literally denotes properties which depend on a collection of particles including Boiling point elevation Freezing point depression Solubility of liquids and solids Osmotic pressure

Each of these properties is going to depend on the composition of the mixture (i.e., the relative mole fractions of the components) There is no reference in these properties to the identities of the solutes and/or solvents strictly dependent upon composition.
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Colligative Properties: Assumptions

Solute is not volatile, does not contribute to the chemical potential of the solvent vapour Solute does not dissolve in solid solvent (this is not the most common case, but does cut the mathematics down a lot!) - so pure solid solvent separates when the mixture is frozen All colligative properties result from lowering of the chemical potential of the solvent from the presence of a solute:

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Colligative Properties
What causes the lowering of chemical potential of a liquid? Not the energies of interactions between solvent and solute molecules Entropy must be the driving force for lowering the chemical potential of a liquid once the solute has been added. There is no direct effect of the solute on the chemical potential of the solvent vapor, since solute is neither in vapor nor solid.
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Colligative Properties
Reduction of the chemical potential of the solution (down from that of a pure liquid) implies that: liquid-vapor equilibrium occurs at a higher temperature (boiling point elevation) liquid-solid equilibrium occurs at a lower temperature (freezing point depression)

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Freezing Point Depression

At equilibrium : ln xsolvent = RT
* * solid = solution = solvent + RT ln xsolvent * * solid solvent

ln xsolvent 1 ( )P = xsolvent xsolvent 1 xsolvent

x solvent

RT G fusion ,m T 1 T = ( )P ( )P T xsolvent R

G fusion ,m

apply Gibbs - Helmholtz equation :

fusion fusion H m dxsolvent H m T dT = = ( ) P or (const P) 2 2 xsolvent RT xsolvent R T T

fusion H m dx dT ' = x T fusion R T '2

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Freezing Point Depression

R ln xsolvent 1 1 = fusion T T fusion H m Using : ln xsolvent = ln(1 + msolute M solvent ) msolute M solvent

T f =

RM

2 solvent fusion fusion m

msolute = K f msolute

Similarly for Boiling point elevation:

Tb =

RM

2 solvent boiling vaporization m

msolute = K b msolute
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