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Properties of Solutions
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
Euler’s Theorem Y n JY J
J
The Chemical Potential
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
TmixS/n
kJ/mol
TmixH/n
0
TmixG/n
XA
The Volume and Internal Energy
of Mixing
mix G
mixV
P T
mixV 0 ; mix H 0
A liq liq RT ln X A
*
A
A vap vap RT ln p A
O
A
Raoult’s Law: Depression of
Vapour pressure
J vap J vap RT ln p J
O
Jo ,m Jo ,H RT lnM J m o
The Standard State
Chemical potential for
Henry’s Law
mJ
J sol ' n
J ,m RT ln o
m
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
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
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
J liq s
*
J
s liq RT ln X J
*
J
*
J
fus G
Freezing Point Depression #2
RT f M J
*2
T f m J K f m B
fus H J
Osmosis
Osmosis
J P *J P
J P , X J *J P RT ln X J
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
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
J P
o
o
Pure Solids and Pure Liquids
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
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)
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)
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