FARMASI FISIK 1

SUTRIYO
 POKOK BAHASAN
1. WUJUD ZAT
2. KESETIMBANGAN FASA
3. MIKROMERITIK
4. TERMODINAMIKA
5. FENOMENA ANTAR MUKA
6. DISPERSI KOLOID
 STATES OF MATTER

What is
matter

Anything that has mass and accupies space

 THREE OF MATTER

All matter is
composed of small SOLID
particles (atoms,
molecules, or ions)

GAS LIQUID
State of matter based upon
1. particle arrangement
2. energy of particles
3. distance between
particles.
 Kinetic Theory of Matter
Matter is made up of particles which
are in continual random motion.
 STATES OF MATTER
SOLIDS
a. Particles of solids are
tightly packed,
vibrating about a fixed
position.

b. Solids have a definite

shape and a definite
Heat
volume.
 STATES OF MATTER
LIQUID
a. Particles of liquids are
tightly packed, but are far
enough apart to slide over
one another.

b. Liquids have an indefinite

shape and a definite
volume.
Heat
 STATES OF MATTER
GAS
a. Particles of gases are
very far apart and move
freely.

b. Gases have an indefinite

shape and an indefinite
volume. Heat
But what happens if you
raise the temperature to
super-high levels
between
1000C and
1,000,000,000C ?

Will everything
just be a gas?
 STATES OF MATTER
PLASMA
a. A plasma is an ionized
gas.
b. A plasma is a very
good conductor of
electricity and is
affected by magnetic
fields.
c. Plasmas, like gases
have an indefinite
shape and an
indefinite volume.
STATES OF MATTER
 STATES OF MATTER

SOLID LIQUID GAS PLASMA

Tightly packed, in a Close together with Well separated with Has no definite
regular pattern no regular no regular volume or shape
Vibrate, but do not arrangement. arrangement. and is composed of
move from place to Vibrate, move Vibrate and move electrical charged
place about, and slide freely at high particles
past each other speeds
Some places where plasmas are
found

1. Flames
2. Lightning
3. Aurora (Northern
Lights)
The Sun is an example of a star in
its plasma state
 PHASE CHANGES
Description of Term for Phase Heat Movement During
Phase Change Change Phase Change

Heat goes into

Solid to Melting the solid as it
liquid melts.

Heat leaves the

Liquid to
Freezing liquid as it
solid
freezes.
 PHASE CHANGES
Description of Term for Phase Heat Movement During
Phase Change Change Phase Change

Vaporization,
Liquid to which includes Heat goes into the
gas boiling and liquid as it vaporizes.
evaporation
Heat leaves the gas
Gas to liquid Condensation
as it condenses.
Heat goes into the
Solid to gas Sublimation
solid as it sublimates.
PHASE CHANGES
 PHASE CHANGES
1. Melting : Solids by heat pass into a liquid form
2. Evaporation : liquids pass into a gaseous state
by further heating.
3. Condensation: Is the reverse process of
evaporation.
4. Sublimation : Solids with high vapor pressure
such as iodine and camphor can pass directly
from solid to gaseous state.
Binding forces between molecules
a. In order for molecules to exist in aggregates in gases, liquids,
and solids, intermolecular forces must exist.
b. When molecules interact, both repulsive and attractive
forces operate.
c. When two molecules are closed together, opposite charges
in the two molecules, cause the molecules to attract one
another.
d. Thus attractive forces are necessary in order that molecules
cohere.
e. When the molecules are brought so close that the outer
charge clouds touch, the molecules repel each other.
f. repulsive forces are necessary in order that molecules do
not interpenetrate one another.
Intermolecular and Intramolecular forces
Intermolecular forces are forces between
molecules
Inter' means between, so these are the forces
between molecules.
Intramolecular forces act within molecules, which
are the strong forces that keep a molecule together.
Intra' means inside, so these are the inside forces in
a molecule.
Intermolecular forces are weaker than
intramolecular forces.
Intermolecular forces

Attractive force

Repulsive forc
 Attractive force
Van der Waals force (bond):
Dipole-dipole forces
Ion-Dipole and Ion-Induced
Dipole Forces
Hydrogen Bonds
 Dipole-dipole forces
a. A dipole is a molecule that has both positive
and negative regions.
b. A dipole-dipole interaction is the attraction
between two polar molecules.
c. Negative pole of one molecule points toward
the positive pole of the next.
d. Thus, large groups of the molecules may be
associated through weak attractions.
Dipole-dipole forces
 Ion-Dipole and Ion-Induced Dipole
Forces
a. They occur between polar or non-polar
molecules and ion.
b. These types of interactions account in part
for the solubility of ionic crystalline
substances in water, the cation for example
attracting the relatively negative oxygen
atom of water and the anion attracting the
hydrogen atoms of the dipolar water
molecules.
Ion-Dipole and Ion-Induced Dipole Forces
 Hydrogen Bonds
a. is an attraction between a positive hydrogen
on one molecule and negative atom on
another molecule. such as fluorine, oxygen,
or nitrogen.

b. Hydrogen bonds are dipole-dipole forces.

Hydrogen Bonds
 Repulsive forces
It is between the like charges, and when the
outer charge clouds of the two molecules
become in touch.
 Importance of the intermolecular forces

Properties of gases, liquids, and solids,

Interfacial phenomena, Flocculation of
suspension,
Stabilization of emulsion,
Compaction of powders in capsules, and
The compression of granules to form tablets .
PHASE EQUILIBRIA AND THE PHASE RULE

The Phase Rule : J. Willard Gibbs

A phase is a homogeneous portion of a system
with uniform physical and chemical
characteristics, in principle separable from the
rest of the system
Equilibrium state with minimum free
energy under some specified combination of
temperature, pressure, and composition
PHASE EQUILIBRIA AND THE PHASE RULE

The phase rule is a useful device for relating

the effect of the least number of independent
variables (e.g., temperature, pressure, and
concentration) upon the various phases (solid,
liquid, and gaseous) that can exist in an
equilibrium system containing a number of
components
 The Phase Rule : J. Willard Gibbs
F= C P + 2

Where F is number of degrees of freedom in

system, C is number of components, and P is
number of phases present.
 a phase as a homogeneous, physically distinct
Portion ofa system that is separated from
other portions of the system by bounding
surfaces.
Thus, a system containing water and its vapor'
is a two-phase system.
An equilibrium mixture of ice, liquid water,
and water vapor is a three-phase system
 The number of components
is the smallest number of constituents by
which the composition of each phase in the
system at equilibrium can be expressed in the
form of a chemical formula or equation.
The number of components in the equilibrium
mixture of ice, liquid water, and water vapor is
one, since the composition of all three phases
is described by the chemical formula H20.
 In the three-phase system, CaCO3(s)= CaO(s) +
CO2(g), the composition of each phase can be
expressed by, a combination of any two of the
chemical species present.
For example, if we choose to use CaC03 and
CO2, we can write CaO as (CaCO3 - CO2) ,
Accordingly, the number of components in this
system is two.
The number of degrees of freedom
is the least number of intensive variables
(temperature, pressure, concentration,
refractive index, density, viscosity, etc.) that
must be fixed to describe the system
completely and herein lies the utility of the
phase rule
 Application of the Phase Rule to Single-
Component Systems
Number Degree of
Syatem Comments
of phase freedom
Gas, liquid or 1 F= C P + 2 System is bivariant (F=2) and lies
solid = 1-1+2 =2 anywhere within the area marked vapor,
liquid, or solid in Figure 2-13~ We must fix
two variables, e.g. P2 and t2 to define
system D.
Gas-liquid; 2 F= C P + 2 System is univariant (F=1) and lies
liquid-solid; = 1-2+2 =1 anywhere along a line between two phase
gas-solid regions, i.e., AO, BO, or CO in Figure 2-13.
We must fix one variable, e.g., either P1
or t2 , to define system E.
Gas-liquid-solid 3 F= C P + 2 System is invariant (F=0) and can lie only
= 1-3+2 =0 at the point of intersection of the lines
bounding the three phase regions, i.e.
point 0 in Figure 2-13.
1. liquid water + vapor :F=C-P+2 =1-2+2 =1

2. liquid ethyl alcohol + vapor F=C-P+2 =1-2+2 = 1

3. liquid water + liquid ethyl alcohol + vapor mixture F=C-P+2 =2-2+2 =2
(Note: Ethyl alcohol and water are completely miscible both as vapors
and liquids.)
4. liquid water + liquid benzyl alcohol + vapor mixture F=C-P+2 =2-3+2 =
1
(note: Benzyl alcohol and water form two separate liquid phases and one
vapor phase. Gases are miscible in all proportions; water and benzyl
alcohol are only partially miscible. It is therefore necessary to define the
two variables in the completely miscible [one-phase] ethyl alcohol-water
system, but only one variable in the partially miscible [two-phase] benzyl
alcohol-water system.)
Systems Containing One
Component
Phase diagram for water at moderate
pressures
 The curve OA in the PT (pressure
temperature) diagram in the Figure is known
as the vapor pressure curve.
Its upper limit is at the critical temperature,
374C for water, and its lower end terminates
at 0.0098C, called the triple point
Along the vapor pressure curve, vapor and
liquid coexist in equilibrium
 Curve OC is the sublimation curve, and here
vapor and solid exist together in equilibrium
Curve OB is the melting point curve, at which
liquid and solid are in equilibrium. The
negative slope of OB shows that the freezing
point of water decreases with increasing
external pressure
 The result of changes in pressure (at fixed
temperature) or changes in temperature (at fixed
pressure) becomes evident by referring to the phase
diagram. If the temperature is held constant at t1,
where water is in the gaseous state above the critical
temperature, no matter how much the pressure is
raised (vertically along the dashed line), the system
remains as a gas.
 At a temperature t2 below the critical
temperature, water vapor is converted into
liquid water by an increase of pressure
because the compression brings the molecules
within the range of the attractive
intermolecular forces
 It is interesting to observe that at a
temperature below the triple point, say t3, an
increase of pressure on water in the vapor
state converts the vapor first to ice and then at
higher pressure into liquid water
At the triple point, all three phases are in
equilibrium, that is, the only equilibrium is at
this pressure at this temperature of 0.0098C
(or with respect to the phase rule, F = 0).
Two-Component Systems
Containing Liquid Phases
Temperature-composition diagram for the
system consisting of water and phenol
 Phase diagram for
the system triethylamine-water.
Nicotine -water system showing upper and .
lower consolute temperatures
Two-component Systems Containing Solid and
Liquid Phases:
Solid- liquid mixtures in which 2 components
are completely miscible in the liquid state and
completely immiscible as solid.
Examples of such systems are:
Salol & thymol.
Salol & camphor.
100% salol 100% thymol
Increasing the % of thymol in the mixture till reaching 100 %.
The phase diagram for the salol thymol system:

(i) Single liquid phase,

(ii) Region containing solid salol and a conjugate
liquid phase,
(iii) Region in which solid thymol is in equilibrium with
a conjugate liquid phase.
(iv) Region in which both components are present as
pure solid phases.

Those regions containing two phases (ii, iii, and iv) are
comparable to the two-phase region of the phenol-
water system.
F=2-2+1=1
System is represented by point X (60% by weight of
thymol in salol) temperature (50 o C)

On cooling the system, the following sequence of the

phase occurs:
The system remains as a single liquid until 29oC.
At 29oC a minute amount of solid thymol
At 25oC, (system X1) a liquid phase, a1 (53%
thymol in salol) and b1 (pure solid thymol).
At 20oC, (system X2) the liquid phase is a2 (45%.
by weight of thymol in salol), b2 (pure solid thymol).
At 15oC, (system X3) the liquid phase a3 is 37 %
thymol in salol and b1 (pure solid thymol).
 Below 13 o C the liquid phase disappears
altogether and the system contains two solid
phases of pure salol and pure thymol.
At 10oC (point X4), the system contains an
equilibrium of a4 & b4 (pure solid thymol +
pure solid salol).
The lowest temperature at which liquid
phase coexists is known as eutectic point.
In case of thymol / salol system the eutectic
point is 13 o C ( 3 phases liquid, solid salol
& solid thymol)
 The eutectic point therefore denotes an
invariant system for, in a condensed system
F = 2 - 3 + 1 = 0.
Substances forming eutectic mixtures (e.g.,
camphor, chloral hydrate, menthol, and
betanaphthol).
If such combinations is dispensed as dry
powder, drying may be achieved by the
addition of an absorbent powder such as
kaolin or light magnesium oxide.
Phase Equilibria in Three-
Component System
Phase Equilibria in Three-
Component System
In systems containing three
components but only oneTphase, constant

F = 3 - 1 + 42 = 4 P condensed

C1 C2
For non-condensed system. The four
degrees of freedom are
temperature, pressure & the
concentration of 2 of the 3
components.

 Ternary System with One Pair of

Partially Miscible Liquids:
Water and benzene are partially
miscible system
. two-phase system
benzene saturated with
phase 2 water
system water saturated with
benzene

Addition of alcohol
(solvent effect)

phase system- 1
Mixture = 60% B, 20%
.A, 20% C
1. Each of the three corners or apexes of
the triangle represent 100% by weight
of one component A, B, or C). As a
result, that same apex will represent
0% of the other two components. For
example, the top corner point in Figure
2-18 represents 100% of B
2. The three lines joining the corner points represent two-
component mixtures of the three possible combinations
ofA, B, and C. Thus the lines AB, BC, and CA are used
for two-component mixtures of A and B, B and C, and C
and A, respectively. By dividing each line into 100equal
units, the location of a point along the line can be directly
related to the percent concentration of one component in
a. two-component system. For example, point y, midway
between A and B on the line AB, represents a system
containing 50% of B (and hence 50% of A also). Point z,
three quarters of the way along BC, signifies a system
containing 75% of C in b
 Alcohol

water benzene
A, B & C represent water, alcohol & benzene,
respectively.
AC binary mixture of A and C.
a & c are the limits of solubility of C in A and A
 System (g) after reaching equilibrium, will separate into two
phases, (f ) and ( i).
weight of phase f /weight of phase I = gi / fg.
Mixture h, mid point of the tie line, will contain equal weights of
the two phases at equilibrium.
 The remainder of the triangle contains
one liquid
phase.
The directions of the tie lines are related
to the shape
of binodal, (depends on the relative
solubility of 3rd
component (alcohol) in the other 2
components).
when the added component acts equally
on the other
two components to bring them into
solution
binodal be symmetric & the tie
lines are parallel
to the base line.
 :Effect of Temperature

Changes in temperature will cause the area of immiscibility, (the

binodal curve) to change.

Area of the binodal as the temperature is & miscibility is

A point is reached at which complete miscibility is obtained and the

binodal vanishes.
Ternary Systems with Two or Three
Pairs of Partially Miscible Liquids:

A & C , B & C show partial miscibility. A and B are completely

miscible at the temperature used.

Temperature gradually leads to a reduction in the areas of the two

binodal curves & their eventual disappearance. (c)
Temperature expands the binodal curves.

At a sufficiently low temperature, they meet and fuse to form a single

band of immiscibility as shown in (a).
 Systems containing three pairs of
partially miscible liquids

3 binodal curves meet, a central region appears in which 3

conjugate liquid phases exist in equilibrium.
In this region, D, which is triangular, F = 0 ( condensed system
under isothermal conditions).
All systems lying within this region consist of 3 phases whose
composition are always given by the points x, y & z.
The only quantity that varies is the relative amounts of these 3
conjugate phases.
 One phase

phases 2

phases 3 X
Y A, B, C
Z
Arrangement of three phases:
It depends on the composition of the phases

At point D , F = 0 ??????
 :DSC is used most widely in pharmacy
, to establish : identity and purity
to obtain heat capacities and heats of
, fusion
for preparing phase diagrams to study
the polymorphs