Intro to Solutions Sol-1

We are now going to use our knowledge of thermodynamics to

examine solutions
Consider a solution of two components: 1 and 2
The Gibbs energy is a function of T, P, and the two mole numbers
G G G G
dG dT dP dn1 dn2
T P ,n1 ,n2 P T ,n1 ,n2 n1 T , P ,n
2
n2 T , P ,n
1

At constant T and P (1)

We can show by Eulers theorem: G 1n1 2 n2

Differentiate: dG 1dn1 2 dn2 n1d1 n2 d 2 (2)

(1) - (2)
Divide by n1 + n2: Gibbs-Duhem Equation
(constant T and P)
 Short Mathematics Review Sol-2
Equations will we use today:

G G nRT ln

= standard (1 bar)

P
P
Eq 22.59

Eq 24.13

G n A A nB B Eq 24.6

n A d A n B d B 0
-OR- Eq 24.10 or 24.11
x A d A xB d B 0 Gibbs-Duhem Equation
-Divide everything by n (total number of moles)
 Chemical Potential of Liquids Sol-3
We need to know how the Gibbs energy of a liquid varies
with composition in order to discuss properties of liquid
mixtures (like solutions).

Vapor Pressure = PA* Pure Liquid Solution Partial Pressure = PA

For vapor phase: For vapor phase:
PA*
RT ln
*
A

A
A A RT ln PA
P
P

At equilibrium At equilibrium
*A ( g ) *A (l ) A ( g ) A (l )
=A =A =B

For liquid phase: For solution:
RT ln
*
A

A
PA*
P
Combine these expressions
A RT ln

A
PA
P
 Ideal Solutions Sol-4

Two types of molecules are randomly distributed

Typically, molecules are similar in size and shape
Intermolecular forces in pure liquids & mixture are similar
Examples: benzene & toluene, hexane and heptane

(more precise thermodynamic definition coming)

In ideal solutions, the partial vapor pressure of component

A is simply given by Raoults Law:
PA x A P *
A

vapor pressure of pure A

mole fraction of Ain solution
 Total VP of an ideal solution Sol-5
PA
A RT ln *
*
A
PA A *A RT ln x A
PA x A PA
*
This serves to define an ideal
solution if true for all values of xA

The total vapor pressure of an ideal solution:

40 C
Ptotal PA PB
Ptotal x A PA* xB PB*
Ptotal PA* xB ( PB* PA* )
 Deviations from Raoults Law Sol-6
CS2 and dimethoxymethane: Positive trichloromethane/acetone: Negative
deviation from ideal (Raoults Law) behavior. deviation from ideal (Raoults Law) behavior.

Methanol, ethanol, propanol

mixed with water. Which one
is which? (All show positive
deviations from ideal behavior)
 Raoult and Henry Sol-7
PA x A PA* as x A 1
Raoults law

(RaoultsLaw)
Henrys law

PA x A k H , A as x A 0
Henrys behavior: Henrys law constant: k H , A PA*
The Henrys law constant reflects the intermolecular interactions between
the two components.
Solutions following both Raoults and Henrys Laws are called ideal-dilute
solutions.
Gmix, Smix, and Hmix for ideal solution Sol-8
Gmix G sol
G G
*
1
*
2

G sol n A A RT ln x A nB B RT ln xB & G ni
*
i
*
i

mix G id n A RT ln x A nB RT ln xB

mix G 0 id
Make sense?

G id

mix S id mix

T P , n1 , n2

mix H id mix G id T mix S id

The Bends Sol-9
If a deep sea or scuba diver
rises to the ocean surface too
quickly, he or she can have
great pain (mostly at the
joints) and may double over in
pain they have the bends.

In terms of what weve

discussed today, brainstorm
some causes of the bends.
 Temperature-Composition Diagrams Sol-10
1-propanol and 2-propanol at ambient pressure (i.e., 760 torr)
Point a: On solution line
760 x P x P
1 1
*
2 2
*

P 760*
x1 2
P P1*
2
*

Point b: On vapor line

*
How does this P1 xP
relate to fractional y1 1 1

distillation? 760 760

Daltons Law
 Distillation and Azeotropes Sol-11
One example of non-ideal solutions: Benzene and Ethanol at 1 atm

Azeotrope: A mixture for which there is no change in composition upon boiling.

Can you separate these compounds by distillation?

Really non-ideal: immiscible mixtures Sol-12

T3 > TC > T2 > T1 Deviations greater with increasing T

What is this line?

Temp-composition diagrams for immiscibles Sol-13
Other thoughts on non-ideal solutions Sol-14
Vapor Pressures can often be represented empirically for example:
* x22 x23
P1 x P e
1 1
0 x1 1

P2 x P e * x12 x13 0 x2 1
2 2
 Activity Sol-15
For ideal solutions: sol
j j (l ) RT ln x j
*

For non-ideal solutions: sol

j j (l ) RT ln a j
*

Activity
Pj
Activity defined as: aj * a1 as x1 1
Pj

With definitions for vapor pressure of non-ideal solutions on

Sol-15, what is a?

aj
Activity coefficient (a measure of deviation from ideality): j
xj
 Typical non-ideal solution Sol-16
Chlorobenzene + 1-nitropropane at 75 C, P1* 119 torr
x1 0.119 0.289 0.460 0.691 1.00
P1/torr 19.0 41.9 62.4 86.4 119
a1

1
 Activities must be calculated wrt standard
states
Sol-17
Activity using Raoults law as standard state
Pj
sol
j (l ) RT ln a j
*
j aj *
a j 1 as x j 1
P j

Activity using Henrys law as standard state

kH , j Pj
sol
j (l ) RT ln
*
j *
RT ln a j aj a j x j as x j 0
P j kH , j

Using Henrys Law

Using Rauolts Law
Gibbs Energy and Activity Coefficients Sol-18

Ideal Solutions

mix G / RT x A ln x A xB ln xB
id

(Slide Sol-8)

Non-ideal Solutions

Gmix / RT x1 ln x1 x2 ln x2 x1 ln 1 x2 ln 2
(Derivations on pg 994)
 Activity etc with other concentration scales Sol-19
Table 25.1

You need to know

how to convert
between mole
fraction, molality
and molarity!
Recall colligative properties?! Sol-20

P P1* P1 x2 P1*

Tb K b m2

T f K f m2

cRT
 Boiling point elevation Sol-21
Label gas, liquid and solid lines
At equilibrium
Label melting and boiling pt
1 ( g ) 1 (l ) 1* (l ) RT ln a1
or
1 1 ( g ) (l ) RT ln a1
*
1

T
Use Gibbs-Helmholtz equation (see A&G-18) and chemical potential def:
d (G / T ) H
2 1 vap G
dT T
 Boiling pt elevation cont Sol-22
Why these integrands?
a1 1 Tvap vap H
d ln a 1
1 a1
da1 *
Tvap RT 2
dT
vap H 1 1 vap H T
ln a1 * ln a1
R T T R T T*
vap vap vap vap

T
RT * 2
vap
x2
x2 M 1m2
T
RT
* 2
vap M1
m2
vap H vap H

R T * 2
vap M1
Let Kb T
vap H
Assumptions on this page
 Osmotic Pressure Sol-23

1* (T , P ) 1* (T , P ) RT ln a1

P 1* P
1* (T , P ) 1* (T , P) dP V1 *dP V1 *
P
P T P

1* (T , P ) 1* (T , P ) RT ln a1 0
Assume the solution is dilute ln a1 ~ x2 and x2 ~ n2/n1
RTx2
*
V1
Osmotic Pressure and Molecular Weight Sol-24

It is found that 2.20 g of polymer dissolved in enough

water to make 300 mL of solution has an osmotic
pressure of 7.45 torr at 20 C. Determine the
molecular mass of the polymer.

Why do we use osmotic pressure to find molecular

weight and not one of the other colligative properties?
 Osmotic Pressure and Cells Sol-25
In the figure, red blood cells are placed into saline solutions.
1. In which case (hypertonic, isotonic, or hypotonic) does the
concentration of the saline solution match that of the blood cells?
2. In which case is the saline solution more concentrated than the
blood cells?

Crenation Hemolysis
 Electrolyte Solutions Sol-26
Electrolyte solutions deviate from ideal behavior more strongly and at
lower concentrations than nonelectrolyte solutions. (Why?)
Activities/activity coefficients are essential when working with electrolytes!

Examples of electrolytes NaCl, MgSO4, MgCl2, Na2SO4

Cv Av ( s) v C z (aq ) v A z (aq )
H 2O ( l )
a

From this reaction

2 v v or 2 v ( RT ln a ) v ( RT ln a )

Also know 2 2 RT ln a2

Therefore a2 av av or
Ionic Activity, Molality, & Activity Coefficients Sol-27

We can define single-ion activity coefficients

a m a m
Mean ionic activity becomes

m v
v

Mean ionic molality Mean ionic activity coefficient

Write out the mean ionic activity for CaCl2

Table 25.3: Activity and electrolytes Sol-28
Colligative Properties of Electrolytes Sol-29

For a strong electrolyte

x2 vmM 1
v = total # of dissociated ions
m = molality
M1 = molar mass (in kg/mol)

If you use this definition in derivation of colligative properties

 Debye-Hckel Theory Sol-30
Debye-Hckel Theory: Assumes ions are point ions (no radii) with
purely Coulombic interactions and activity coefficients depend
only on the ion charges and the solvent properties.

ln z z AI 1/ 2
c

1 s 2
Ic z j c j
3/ 2
e
A 2N A
1/ 2
2 j 1
4 0 r k BT Ionic Strength

For Aqueous Solutions

 Validity of Debye-Hckel Theory Sol-31

Az z I
c
1/ 2
Extended Debye-Hckel: ln
1 BI1/ 2
c
Why are activities so important anyway?! Sol-32
The activity can be thought of as the real
concentration anywhere concentrations are
used, activities should be used instead.
a1 [1] 1 {1}
Some examples:
 Key Concepts Sol-33
Gibbs-Duhem Equation
Partial Pressure
Ideal Solutions
Raoults Law
Henrys Law
Azeotropes
Immiscible Solutions
Activity and Activity Coefficients
Collagative Properties
Electrolytes (and properties)
Debye-Huckel Theory
Importance of Activity