Konsep Fasa dan Diagram

Kesetimbangan Fasa

Introduction
The

understanding of phase diagrams for

alloy system is extremely important
because there is strong correlation between
microstructure and mechanical properties,
and the development of microstructure of
an alloy is related to the characteristics of
its phase diagram

In

addition, phase diagram provide valuable

information about melting, casting,
crystallization and other phenomena

Definition and basic

concepts

Konsep Fasa
Fasa berkaitan dengan keadaan materi yang terpisah dan dapat
diidentifikasi dari bagian lainnya secara fisik dan dapat dipisahkan
secara mekanis.
Contoh:
Dalam suatu sistem : air dan es dalam gelas.
Dapat dibedakan fasa padat (es) dan fasa cair (air).
Komponen yang ada hanya 1 yaitu air (H2O)

Suatu sistem campuran bahan bakar (fuel) dengan udara dalam

silinder. Dapat diidentifikasi fasa cair (bahan bakar) dan fasa gas
(udara). Meskipun udara terdiri dari beberapa unsur dan senyawa
seperti O2 dan N2 namun keduanya satu fasa yaitu gas

Terdapat sistem gula pasir dan air tebu dalam tanki putaran. Fasa
yang ada adalah padat (gula pasir) dan fasa cair (air tebu)

Tinjau sistem poros baja. Fasa yang ada adalah ferrite () dan
cementite (Fe3C). Komponennya 2 yaitu Fe dan Fe3C.

Sehingga dapat didefinisikan bahwa

Phase is a form of material having characteristic structure and

properties.

More precisely: form of material with identifiable composition

(chemistry), definable structure, and distinctive boundaries
(interfaces) which separate it from other phases.

Phases:

Phase can be continuous (air in the room) or discontinuous (salt

grains in the shaker).

Gas, liquid or solid.

Pure substance or solution (uniform structure throughout).

Phase

Any physically distinct,

chemically
homogeneous and
mechanically separable
portion of a substance

Can be continuous or
discontinuous

Can be solid, liquid or

gas

Can be a pure
substance or a solution

Deff :

Component : frequently used in discussion; components

represent pure metals and/or compound of which an alloy is
composed
e.g ; copper-zinc brass; the component are Cu and Zn

Solute and solvent; solvent represent the element or compound

that is present in the greatest amount (also called; host atoms).
Solute is used to denote an element or compound present in minor
concentration

Deff :
System; which has two meanings:

system may refer to specific body of material

under consideration (e.g., a ladle of molten steel)

relate to the series of possible alloys consisting of

the same component, but without regard t alloy
composition (e.g., the iron-carbon system)

Components and Phases

Components:
The elements or compounds that are mixed initially (Al and
Cu).

Phases:
A phase is a homogenous, physically distinct and
mechanically separable portion of the material with a given
chemical composition and structure ( and ).
AluminumCopper
Alloy

(lighter
phase)
(darker
phase)
15

Multiple Solid Phases

Multiple solid
phases are
common in metals
Phases defined by
composition (not by
state solid, liquid,
gas)
Example two
phases shown to
the right, dark
phase and then the
lighter phase

Single Phase vs. Multiple Phases

*) Konsep Diagram Fasa

A phase diagram is graphical representation of the

equilibrium relations among phases, typically as a function
of one or more intensive variables such as chemical
composition, temperature, pressure and the activity of a
chemical component
Phase diagram are used by geologist, chemist, ceramist,
metallurgist and other scientists to organize and summarize
experiment and observational data.
Phase diagram are also used to make predictions about
processes that involve chemical reactions among phases.
Similar principles or rules apply to interpretations using
phase diarams for igneous processes, metamorphics

Phase

diagrams can be grouped

according to the number of
independent chemical
component needed to represent
chemical composition:
- One component (PT diagram)
- two component systems
- three component system

Mengapa perlu diagram kesetimbangan?

Interpretation of Phase Diagrams
For a given temperature and composition we can use phase diagram
to determine:
1)The

phases that are present

2) Compositions of the phases

3) The relative fractions of the phases

Kesetimbangan dan Transformasi Fasa

Pengertian dan Konsep Keseimbangan
Kesetimbangan menyebabkan komposisi,
temperatur, tekanan dan kondisi lain yang
mempengaruhi suatu sistem berada pada
energi terendah
Sistem
bahan
tidak
murni,
terdapat
impuritas atau bahan tambahan yang
hasilnya merupakan larutan padat, multi
kristalin, campuran kristalin atau campuran
kristalin-nonkristalin

Energy States

Unstable: falling or rolling

Stable: at rest in lowest

energy state
Metastable: in low-energy
perch
Figure . Stability states. Winter (2001) An Introduction to
Igneous and Metamorphic Petrology. Prentice Hall.

equilibrium

It is useful to begin by defining a few of the terms that will be

frequently used.
- system
- phase
- component

The study of phase transformations, as the name suggest, is

concerned with how one or more phases in an alloy (the system)
change into a new phase or mixture phases.

For transformation that occur at constant temperature and

pressure the relative stability of a system is determined by its
Gibbs free energy (G)
G = H TS

H : enthalpy, T : absolute temperature, S : entropy

H = E + PV
Where E : internal energy of system
P : pressure
V : volume

The internal energy arises from the total kinetic and potensial
energy

Kinetic energy can arise from atomic vibration in solid or liquid and
from translational and rotational energies for the atoms or
molecules within a liquid or gas

Potential energy arises from the interaction, or bond between the

atoms within the system

Thermodynamics
G for a reaction of the type:
2A + 3B =C +4D
G = (n G)products - (n G)reactants
= GC + 4GD - 2GA - 3GB
The side of the reaction with lower G will be more stable

Thermodynamics
For other temperatures and pressures we can use the equation:

dG = VdP - SdT (ignoring X for now)

where V = volume and S = entropy (both molar)

We can use this equation to calculate G for any phase at any T and P
by integrating
G

T2 P 2

T 1 P1

z
P2

P1

VdP

z
T2

SdT

T1

If V and S are constants, our equation reduces to:

GT2 P2 - GT1 P1 = V(P2 - P1) - S (T2 - T1)

Now consider a reaction, we can then use the equation:

dG = VdP - SdT

G for any reaction = 0 at equilibrium

(again ignoring X)

If a transformation or reaction occurs the heat

that is absorbed or envolved will depend on the
change in the internal energy of the system.
When dealing with condensed phases (solids and
liquids) the PV term is ussualy very small in
comparison to E, that is H E
The other function that appears in the expression
for G is entropy (S) which is a measure of the
randomness of the system
A system is said to be in equilibrium when it is in
the most stable state
An important consequence of the law of classical
thermodynamics is that at constant T and P a
closed system will be in stable equilibrium if it
has the lowest G or dG = 0

Gibbs free energy, equilibrium and chemical potential, Gibbs phase rule
Equilibrium : the most stable state defined by lowest possible G

dG = 0

Solid : Low atomic kinetic energy or E

low T and small S
Liquid : Large E
high T and large S

metastable

E.g.

equilibrium

Metastable : Diamond
Equilibrium : Graphite

Chemical potential or partial molar free energy governs how the free energy
changes with respect to the addition/subtraction of atoms.
This is particularly important in alloy or binary systems.
(particle numbers will change)

Hukum-hukum termodinamika
Pengertian keseimbangan diberikan oleh hukumhukum termodinamika yang dinyatakan dalam
energi bebas Gibbs suatu sistem
n

G PV TS i X i
i 1

Dimana, G = energi bebas Gibbs, P = tekanan sistem, V = volume

sistem, T = temperatur mutlak, S = entropi, I = potensial kimia
komponen ke-i dan Xi = fraksi mol ke-i

Keadaan seimbang dicapai bila harga energi bebas Gibbs G

mencapai minimum

Bila keseimbangan dicapai, temperatur dan

tekanan harus uniform dalam sistem dan
potensial kimia untuk setiap komponen harus
sama dalam setiap fasa yang berada dalam
kesetimbangan

With these definitions in mind:

ISSUES TO ADDRESS...
When we combine two elements...
what equilibrium state would we expect to get?

In particular, if we specify...
--a composition (e.g., wt% Cu - wt% Ni), and
--a temperature (T ) and/or a Pressure (P)

then...

How many phases do we get?

What is the composition of each phase?
How much of each phase do we get?

Phase B

Phase A
Nickel atom
Copper atom

Beberapa definisi

Fasa merupakan bagian dari sistem yang secara fisis homogen

dan dibatasi oleh permukaan yang dapat dipisahkan dengan
bagian lain dari sistem

Jumlah derajat kebebasan atau variasi adalah jumlah dari variabelvariabel intensif (tekanan, temperatur dan komposisi) yang dapat
dipertukarkan dengan bebas tanpa menimbulkan fasa baru atau
mengurangi fasa yang ada

Komponen adalah bilangan terkecil variabel yang independen

dimana konstituen kimia membentuk komposisi fasa yang ada

Membangun diagram fasa

Metode dinamik : temperatur sampel dinaikkan

atau duturunkan dari fasa cair. Bersamaan
dengan itu diamati perubahan mikro dan
properties material. Analisis yang bisa dilakukan :
DTA/TGA dan XRD

Metode statik : sampel dipanaskan hingga

temperatur tertentu yang diinginkan kemudian
didinginkan cepat (quench). Sampel yang
diperoleh dipandang sebagai fasa metastabil yang
menggambarkan keadaan pada temperatur tinggi.
Analisis yang bisa dilakukan : XRD dan mikroskopi

Diagram
fasa
komponen
Fasa yang akan terjadi adalah
polimorfisme nya

sistem
uap,

cair

dan

satu
padat

beserta

Variabel bebas yang dapat menghilangkan dan menimbulkan fasa

adalah temperatur dan tekanan

2. Gibbs free energy, equilibrium and chemical potential, Gibbs phase rule
Gibbs phase rule for equilibrium phase :
Number of degrees of freedom F = C K +2

Examples :
Single component system C=1 and F = 3 K
If 1 phases in equilibrium (e.g. solid) 2 degrees of freedom i.e. can change T
and P without changing the phase
If 2 phases in equilibrium (e.g. solid and liquid) 1 degree of freedom i.e. T is
dependent on P (or vice-versa)
If 3 phases in equilibrium (e.g. solid, liquid and ) 0 degrees of freedom. 3
phases exist only at one fixed T and P.

C, number of components
K, number of phases in equilibrium

3. Single component systems

Assumption: Closed system ignore d

For purposes of most discussions :
fix pressure (unless otherwise stated)
G
From thermodynamics: Sliquid > Ssolid
Phase transition occurs when:

Gsolid

Gsolid=Gliquid

For pressure dependence:

Gliquid
TM

T (K)

Similar arguments apply : Vliquid > Vsolid so increasing P implies liquid to solid transition

Clausius Clapeyron Equation

more
dense
(intermediate)
more
dense

Less
dense

Less
dense

Pada titik A, ketiga fasa dalam keseimbangan, setiap perubahan

temperatur dan tekanan menyebabkan hilangnya satu fasa. Jumlah fasa
maksimal dicapai bila variansinya sama dengan nol

Pada titik B, terletak pada garis diagram, menyatakan keadaan dimana

dua fasa berada dalam kesetimbangan. P = 2 dan C = 1 sehingga V = 1.
hal ini berarti bahwa baik tekanan atau temperatur tetapi tidak keduanya
dapat berubah secara bebas tanpa kehilangan fasa.

Pada titik C, P = 1 dan C = 1 sehingga V = 2, artinya tekanan dan

temperatur keduanya dapat berubah tanpa menghilangkan fasa

Pada tekanan rendah

terdapat 5 fasa yaitu; quartz, -quartz, 2tridymite, -cristobalite
dan silika cair.

Pada 573C terjadi

transformasi -quartz ke quartz secara cepat dan
reversibel sedangkan
transformasi fasa yang lain
terjadi sangat lambat
sehingga membutuhkan
waktu yang panjang untuk
mencapai kesetimbangan

1 - C Systems
1. The system SiO2

Fig. 6.6. After Swamy and

Saxena (1994), J. Geophys.
Res., 99, 11,787-11,794.
AGU

Phase Rule in OneComponent Systems

Notice that in one-component systems, the number of

degrees of freedom seems to be related to the number of

phases.

51

Phase Rule in One-Component

Systems
The phase rule should be applicable for any single-

component systems in general.

52

Number of Components (c)

f=cp+2
The number of components (c) is the minimum number of

independent chemical components needed to form the system

or, in other words, to define all the phases.
"Independent" means:
If you have equilibrium balance between reactants and

products, the number of components will be reduced by

one.
If you have equal amounts (concentrations) of products
formed, the number of components will also be reduced by
one.
53

Number of Components (c)

f=cp+2
Examples (Chemical reactions):
If you have equilibrium balance between reactants and products,

the number of components will be reduced by one.

If you have equal amounts (concentrations) of products formed,

the number of components will also be reduced by one.

Example 1:
NaCl(s) dissolved in H2O.
+

Available chemical constituents are: Na , Cl , NaCl and H2O.

Is it correct to say c = 4 ?
+

Because Na and Cl have the same amount equal neutrality as

NaCl, then c = 2 and not 4.
54

Number of Components (c)

f=cp+2
Examples (Chemical reactions):
If you have equilibrium balance between reactants and products,

the number of components will be reduced by one.

If you have equal amounts (concentrations) of products formed,

the number of components will also be reduced by one.

Example 2:
CaCO3(s)

CaO(s) + CO2(g)

Available chemical constituents are three.

Is it correct to say c = 3 ?
Because of the equilibrium condition the number of independent
components is reduced by one. Thus, c = 2 instead of 3.
55

Number of Components (c)

f=cp+2
Examples (Chemical reactions):
If you have equilibrium balance between reactants and products,

the number of components will be reduced by one.

If you have equal amounts (concentrations) of products formed,

the number of components will also be reduced by one.

Example 2:
CaCO3(s)

CaO(s) + CO2(g)

Can you specify the number of phases for the reaction?

We have here three homogeneous, distinct parts of the system
separated by definite boundaries.
p=3
56

Number of Components (c)

f=cp+2
Examples (Chemical reactions):
If you have equilibrium balance between reactants and products,

the number of components will be reduced by one.

If you have equal amounts (concentrations) of products formed,

the number of components will also be reduced by one.

Example 2:
CaCO3(s)

CaO(s) + CO2(g)

So, whats the number of degrees of freedom the system

would have?

f=cp+2
= 2 3 + 2 = 1 degree of freedom.
57

Phase Diagram of Hydrogen

58

1 - C Systems
2. The system H2O

Fig. 6.7. After Bridgman

(1911) Proc. Amer. Acad.
Arts and Sci., 5, 441-513;
(1936) J. Chem. Phys., 3,
597-605; (1937) J. Chem.
Phys., 5, 964-966.

Phase Diagram of Sulfur

Sulfur solid exists in two crystalline forms.
Orthorhombic. S8 or S(rh)
Monoclinic. S4 or S(mo)

Yellow sulfur of the

orthorhombic (or rhombic)
crystalline form. It is the
form that commonly exists
under normal conditions.

60

Phase Diagram of Sulfur

61

A More Comprehensive Phase Diagram

of Sulfur

62