Properties of Solutions

Concentration Terms
 Dilute - not a lot of solute.
 Concentrated - a large amount of solute.
 Concentration can be expressed
quantitatively is many ways:
• Molarity
• Molality
• Percentage
• Mole fraction
 Molarity and Molality

 The molarity is the number of moles of

solute in 1 litre of solution.
• M = moles of solute / V sol’n (litres)
 The molality is the number of moles of
solute in 1 kg of solvent.
• M = moles of solute / kg solvent
 Conversion between the two requires
the solutions density.
 Partial Molar Thermodynamic
Properties

 Define a partial molar  Y 

thermodynamic property Y J   
as  n J T ,P ,n'

 Euler’s Theorem Y   n JY J
J
 The Chemical Potential

 We define the chemical

potential of a substance as
 G 
 J   
 n J T ,P ,n'
 The Wider Significance of 

 Shows how all  U 

the extensive  J   
thermodynamic  n J S ,V ,n'
properties  H 
depend on
 J   
 n J S ,P ,n'
system
composition
 A 
 J   
 n J T ,V ,n'
Thermodynamics of Mixing
 Spontaneous mixing of two or more
substances to form solutions
 Gibbs energy of the solution must be
less than G(pure components)
The Gibbs Energy of Mixing

 
mix G  nRT   X J ln X J 
 J 
The Enthalpy and Entropy

 mix G   
 T   nR   X J lnX J 
 P  J 
 mix S

 mix G 
 T  mix H
 T   T2
 
 P
 The Ideal Solution
TmixS/n
kJ/mol

TmixH/n
0

TmixG/n

XA
The Volume and Internal Energy
of Mixing

 mix G 
   mixV
 P T

mix U  mix H  PmixV

Ideal Solution Def’n

 For an ideal solution

mixV  0 ; mix H  0

mix U  mix H  PmixV

0
 Raoult’s Law

 Consider the following system

 Raoult’s Law #2

 The chemical potential expressions

 A  liq     liq   RT ln  X A 
*
A

 A vap    vap   RT ln  p A 
O
A
 Raoult’s Law: Depression of
Vapour pressure

 VP of solution relates to VP of pure

solvent
PA = XAP*A
 Solutions that obey Raoult’s law are
called ideal solutions.
 Raoult’s Law Example

 The total vapour

pressure and partial
vapour pressures of an
ideal binary mixture
 Dependence of the vp
on mole fractions of
the components.
 An Ideal Solution

 Benzene and toluene

behave almost ideally
 Follow Raoult’s Law
over the entire
composition range.
 Henry’s Law

 Henry’s law relates

the vapour pressure
of the solute above
an ideally dilute
solution to
composition.
The Ideal Dilute Solution
 Ideal Dilute
Solution
• Solvent obeys
Raoult’s Law
• Solute obeys
Henry’s Law
 Henry’s Law #2
 The chemical potential expressions

 J  sol ' n     liq   RT ln  X J 

O (H )
J

 J  vap   J  vap   RT ln  p J 
O

 JO(H) is the Henry’s law standard

state.
 It is the chemical potential of J in
the vapour when PJ = kJ.
 Henry’s Law #3

 The Standard State  o

J ,H   vap  
o
J
Chemical potential for
Henry’s Law RT ln  k J 
 When the system is in
equilibrium  J  sol ' n    J vap 
 The chemical potential
expressions reduce to
PJ  k J X J
Henry’s Law
 Henry’s Law in terms of
molalities

 Jo ,m   Jo ,H  RT lnM J m o 
 The Standard State
Chemical potential for
Henry’s Law

When the system is in

 J  sol ' n    J vap 

equilibrium

 The chemical potential

expressions reduce to m 
Henry’s Law in terms of PJ  k J mJ
molalities
 Chemical Potentials in terms of
the Molality

 The chemical potential expressions

 mJ 
 J  sol ' n    
J ,m  RT ln o 
m 

oJ,m = chemical potential of the solute in an

ideal 1 molal solution
The Gibbs-Duhem Equation

 The Gibbs-Duhem gives us an

interrelationship amongst all partial
molar quantities in a mixture

0  J n J dY J
Colligative Properties
 Colligative Properties
 All colligative properties
• Depend on the number and not the nature
of the solute molecules
 Due to reduction in chemical potential
in solution vs. that of the pure solvent
• Freezing point depression
• Boiling Point Elevation
• Osmotic Pressure
 Boiling Point Elevation

 Examine the chemical potential

expressions involved

 J  liq    J vap 
 J vap   *J  liq   RT ln X J

 J vap    J*  liq   RT ln X J
 vapG
 Boiling Point Elevation #2

 The boiling point elevation

 RT b*  J  
2

T b   X B
 vap H  J  
 

 RT M J  *2
T b   b m J  K b m B
 vap H  J  
 
 Freezing Point Depression

 Examine the chemical potential

expressions involved

 J  liq     s 
*
J

 J  liq   *J  liq   RT ln X J

  s     liq   RT ln X J
*
J
*
J

 fus G
 Freezing Point Depression #2

 Define the freezing point depression

 RT f  J  
*2
T f   X B
 fus H  J  
 

 RT f M  J  
*2
T f   m J  K f m B
 fus H  J  
 
Osmosis
 Osmosis

 The movement of water through a

semi-permeable membrane from dilute
side to concentrated side
• the movement is such that the two sides
might end up with the same concentration
 Osmotic pressure: the pressure
required to prevent this movement
Osmosis – The Thermodynamic
Formulation
 Equilibrium is established across
membrane under isothermal conditions

 J  P     *J  P 

 J  P   , X J   *J  P     RT ln X J

 - the osmotic pressure

 The Final Equation

 The osmotic pressure is related to the

solutions molarity as follows
nB
  RT  M B RT
V
 Terminology
 Isotonic: having the same osmotic
pressure
 Hypertonic: having a higher osmotic
pressure
 Hypotonic: having a lower osmotic
pressure
 Terminology #2

 Hemolysis: the process that ruptures a

cell placed in a solution that is
hypotonic to the cell’s fluid
 Crenation: the opposite effect
 The Partial Molar Volume

 In a multicomponent system
V   n JV J
J

 V 
V J   
 n J T ,P ,n'
 Volume Vs. Composition
 The partial molar volume of
a substance
• slope of the variation of the
total sample volume plotted
against composition.
 PMV’s vary with solution
composition
 The PMV-Composition Plot

 The partial molar

volumes of water and
ethanol at 25C.
 Note the position of
the maxima and
minima!!
 Experimental Determination of
PMV’s

 Obtain the densities of systems as a

function of composition
 Inverse of density – specific volume
of solution
 mL  1
Vs   
 g  g 
 
 mL 

V mL
mol
  A  Bm  Cm 2
 Example with Methanol.

 Plot volumes vs. mole fraction of

component A or B
 Draw a tangent line to the plot of
volume vs. mole fraction.
 Where the tangent line intersects the
axis – partial molar volume of the
components at that composition
The Solution Volume vs.
Composition
 The Mean Molar Volume

 Define the
mean mixing
molar volume mixV m  V   x JV J*
J
as
•V *
J– the molar
volume of the
pure liquid
• Vm = V/nT
The Mean Molar Volume Plot

0.20

0.00
D mixVm / (mL/mol)

-0.20

-0.40
-0.60

-0.80
V V * VB-VB*
-1.00 A- A

-1.20
0.00 0.50 1.00
XMeOH
 Infinite Dilution Partial Molar
Properties

 The value of a partial molar

thermodynamic property in the limit
of zero volume is its infinite dilution
value
• E.g., for the volumes
V J  x J lim 0 V J

 The Definition of the Activity

 For any real system, the chemical

potential for the solute (or solvent)
is given by
o
 J    RT ln a J
Activities of Pure Solids/Liquids
 The chemical potential is essentially
invariant with pressure for
condensed phases
p
 J  P    J P   V dp
o o
J
Po

 J P
o
 
o
Pure Solids and Pure Liquids

 For a pure solid or a pure liquid at

standard to moderately high pressures

0  RT ln a J

or aJ = 1
 Activities in Gaseous Systems
 The chemical potential of a real gas
is written in terms of its fugacity
o
 J    RT ln f J
 Define the Activity Coefficient

 The activity coefficient (J) relates the

activity to the concentration terms of
interest.
 In gaseous systems, we relate the
fugacity (or activity) to the ideal
pressure of the gas via

 J PJ  f J
 Activities in Solutions
 Two conventions
 Convention I
• Raoult’s Law is applied to both solute and
solvent
 Convention II
• Raoult’s Law is applied to the solvent;
Henry’s Law is applied to the solute
 Convention I
 We substitute the activity of the
solute and solvent into our
expressions for Raoult’s Law

I
PJ  a P J J
*

I I
 xJ  a
J J
 Convention I (cont’d)

 Vapour pressure above real solutions

is related to its liquid phase mole
fraction and the activity coefficient

PJ    x J P
I
J J
*

Note – as XJ  1
JI  1 and PJ  PJid
 Convention II
 The solvent is treated in the same
manner as for Convention I
 For the solute, substitute the solute
activity into our Henry’s Law
expression
II
PJ  a k J J

II II
 xJ  a
J J
 Convention II (cont’d)

 Vapour pressure above real dilute

solutions is related to its liquid phase
mole fraction and activity coefficient

PJ    x J  k J
II
J

Note – as XJ  0
JII  1 and PJ  PJid
 Convention II - Molalities
 For the solute, we use the molality
as our concentration scale

o m  m 
J   J  RT ln a J
m  m 
 J mJ  aJ
Note – as mJ  0
J(m)  1 and aJ(m)  mJ