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Khalid T Maaroof
MSc. Pharmaceutical sciences
School of pharmacy – Pharmaceutics department
1
Online access: bit.ly/physicalpharmacy
Phase equilibria
Physical Pharmacy
10/31/2015
What was equilibrium?
2
3
4
Phase rule
5
 Coexistence of phases can only occur over a limited
range.
 phase rule is a relationship for determining the least
number of intensive variables that can be changed
without changing the equilibrium state of the system.
 P is the number of phases present
 F is termed the number of degrees of freedom
 C in represents the number of components in the system
What is intensive variable???
6
 The number of degrees of freedom: is the least
number of intensive variables that must be
fixed/known to describe the system completely.
 Examples of intensive variables are: temperature,
pressure, concentration….
Systems Containing One Component
7
This is the phase diagram for a typical pure substance.
8
at higher pressure, the melting temperature would be
higher because the line between the solid and liquid
areas slopes slightly forward.
9
Increasing pressure at constant temperature
changes liquid to solid and vice versa
10
The same explanation for liquid vapour
boundary
11
The point labelled as C in the phase diagrams is critical
temperature.
12
 Note the process of
sublimation as shown on
the graph; below the point
T.
 Point T is called triple
point.
 Where all three lines meet,
you must have a unique
combination of temperature
and pressure where all
three phases are in
Normal melting and boiling points
13
The phase diagram for water
14
 In the case of water, the
melting point gets lower at
higher pressures. Why?
15
Imagine lowering the pressure on liquid
water along the line in the diagram below.
16
Systems Containing more than one
Component
17
CONDENSED SYSTEMS
18
 a maximum of three degrees of freedom is possible in
a two-component system.
 More components more degrees of freedom
 In two component one phase system (maximum no of
variables) F = 2 – 1 + 2 = 3
 E.g. temperature, pressure, and concentration
 we frequently choose to disregard the vapor phase
and work under normal conditions of 1 atm pressure.
 Now we can use planar figures instead of three
dimensional (this will be easier)
 condensed systems: When we only consider solid
and liquid phases
Two-Component Systems Containing Liquid
Phases
19
The maximum
temperature at which
the two-phase region
exists is termed the
critical solution or
(upper consolute
temperature).
Upper and lower consulate temperatures
20
Two-Component Systems Containing Solid
and Liquid Phases: Eutectic Mixtures
21
 two components are completely miscible in the liquid
state and completely immiscible as solids,
22
Eutectic composition
23
 “contact melting”: lowest melting temperature over
a composition range.
 eutectic composition is the composition of two or
more compounds that exhibits a melting temperature
lower than that of any other mixture of the
compounds
 The primary criterion for eutectic formation is the
mutual solubility of the components in the liquid or
melt phase.
 Lidocaine and prilocaine, two local anesthetic
agents, form a 1:1 mixture having a eutectic
temperature of 18◦C
Phase Equilibria in Three-Component Systems
24
 In systems containing three components but only one
phase.
 four degrees of freedom are temperature, pressure,
and the concentrations of two of the three
components.
 Only two concentration terms are required because the
sum of these subtracted from the total will give the
concentration of the third component.
 Temperature and pressure are considered to be
25
Triangular
Diagram
Ternary Systems with One Pair of Partially Miscible
Liquids
26
e.g. Water and
benzene + alchohol
• Alchohol provide
solvation
• binodal curve
Alterations of the binodal curves with
changes in temperature.
27
Ternary Systems with Two Pairs of Partially
Miscible Liquids
28
Ternary Systems with Three Pairs of Partially
Miscible Liquids
29
F=0 Why???
Questions !
10/31/201530

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2- States of matter & phase equilibria - part 2 (Physical Pharmacy)

  • 1. Khalid T Maaroof MSc. Pharmaceutical sciences School of pharmacy – Pharmaceutics department 1 Online access: bit.ly/physicalpharmacy Phase equilibria Physical Pharmacy 10/31/2015
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  • 4. 4
  • 5. Phase rule 5  Coexistence of phases can only occur over a limited range.  phase rule is a relationship for determining the least number of intensive variables that can be changed without changing the equilibrium state of the system.  P is the number of phases present  F is termed the number of degrees of freedom  C in represents the number of components in the system What is intensive variable???
  • 6. 6  The number of degrees of freedom: is the least number of intensive variables that must be fixed/known to describe the system completely.  Examples of intensive variables are: temperature, pressure, concentration….
  • 8. This is the phase diagram for a typical pure substance. 8
  • 9. at higher pressure, the melting temperature would be higher because the line between the solid and liquid areas slopes slightly forward. 9
  • 10. Increasing pressure at constant temperature changes liquid to solid and vice versa 10
  • 11. The same explanation for liquid vapour boundary 11
  • 12. The point labelled as C in the phase diagrams is critical temperature. 12  Note the process of sublimation as shown on the graph; below the point T.  Point T is called triple point.  Where all three lines meet, you must have a unique combination of temperature and pressure where all three phases are in
  • 13. Normal melting and boiling points 13
  • 14. The phase diagram for water 14  In the case of water, the melting point gets lower at higher pressures. Why?
  • 15. 15
  • 16. Imagine lowering the pressure on liquid water along the line in the diagram below. 16
  • 17. Systems Containing more than one Component 17
  • 18. CONDENSED SYSTEMS 18  a maximum of three degrees of freedom is possible in a two-component system.  More components more degrees of freedom  In two component one phase system (maximum no of variables) F = 2 – 1 + 2 = 3  E.g. temperature, pressure, and concentration  we frequently choose to disregard the vapor phase and work under normal conditions of 1 atm pressure.  Now we can use planar figures instead of three dimensional (this will be easier)  condensed systems: When we only consider solid and liquid phases
  • 19. Two-Component Systems Containing Liquid Phases 19 The maximum temperature at which the two-phase region exists is termed the critical solution or (upper consolute temperature).
  • 20. Upper and lower consulate temperatures 20
  • 21. Two-Component Systems Containing Solid and Liquid Phases: Eutectic Mixtures 21  two components are completely miscible in the liquid state and completely immiscible as solids,
  • 22. 22
  • 23. Eutectic composition 23  “contact melting”: lowest melting temperature over a composition range.  eutectic composition is the composition of two or more compounds that exhibits a melting temperature lower than that of any other mixture of the compounds  The primary criterion for eutectic formation is the mutual solubility of the components in the liquid or melt phase.  Lidocaine and prilocaine, two local anesthetic agents, form a 1:1 mixture having a eutectic temperature of 18◦C
  • 24. Phase Equilibria in Three-Component Systems 24  In systems containing three components but only one phase.  four degrees of freedom are temperature, pressure, and the concentrations of two of the three components.  Only two concentration terms are required because the sum of these subtracted from the total will give the concentration of the third component.  Temperature and pressure are considered to be
  • 26. Ternary Systems with One Pair of Partially Miscible Liquids 26 e.g. Water and benzene + alchohol • Alchohol provide solvation • binodal curve
  • 27. Alterations of the binodal curves with changes in temperature. 27
  • 28. Ternary Systems with Two Pairs of Partially Miscible Liquids 28
  • 29. Ternary Systems with Three Pairs of Partially Miscible Liquids 29 F=0 Why???