SISTIM FASA

Fasa = keadaan materi yang seluruh bagiannya uniform,

baik komposisi kimianya maupun keadaan
fisiknya.

Contoh : campuran gas merupakan 1 fasa .

Contoh lain !.

Perubahan fasa : perubahan dari bentuk fasa yang satu ke

bentuk fasa lainnnya secara spontan
Contoh : Penguapan, pelelehan, konversi grafit
menjadi intan.
Kondisi T dan P perubahan tsb. terjadi dapat
dilihat pada diagram fasa.
Kestabilan Fasa
Prinsip : - Fasa yg memp. harga μ lebih rendah adalah fasa
yang lebih stabil.
- Perubahan fasa terjadi dari fasa yang memp.
harga μ > → µ < (sistim cenderung berubah
kearah fasa dengan µ lebih rendah / lebih stabil).

- Perubahan berlangsung sampai kedua fasa berad

dalam kesetimbangan.
Pada kesetimbangan : μ1 = µ2
Contoh :
Pada 1 atm, <1000 C air dalam bentuk cair stabil
>1000C air bentuk uap stabil
Pada 1 atm dan > 1000C : µ (uap) < µ (cair).
Saat dicapai kesetimbangan (kec. penguapan =
kec. kondensasi) → µ (cair) = µ (uap).

 Membeku ?.
Batas Fasa
Titik didih dan titik kritis
Titik didih : temperatur saat tekanan uap = tekanan luar

Bila tekanan luar = 1 atm → titik didi normal Tb

Bila tekanan luar = 1 bar (tekanan standar) → titik didih
standar
1,00 bar = 0,987 atm → titik didih standar < titik didih
normal
Titik didih normal air = 1000C
Titik didih standar air = 99,60C

Pressure cooking is a method of cooking in a sealed vessel that does not

permit air or liquids to escape below a preset pressure. Because the
boiling point of water increases as the pressure increases, the pressure
built up inside the cooker allows the liquid in the pot to rise to a higher
temperature before boiling.

Cairan dipanaskan pada wadah terbuka :

When a liquid is heated in an open vessel, its temperature and vapour
pressure will both increase. At the temperature at which the liquid's vapour
pressure (the pressure at any given temperature at which both liquid and
vapour are in equilibrium) would be equal to the external pressure,
vaporisation can occur throughout the bulk of the liquid, and free
expansion of the gas into its surroundings may take place. This free
vaporisation of the liquid throughout its bulk is what we call boiling, and
the temperature at which it occurs is called the boiling temperature or
boiling point.

Cairan dipanaskan pada wadah tertutup :

Boiling does not occur when a liquid is heated in a closed vessel. The
vapour pressure of the liquid rises, but as a consequence of the
vaporisation that occurs from the surface of any liquid while it is being
heated, the density of the vapour in the vessel also increases. (In effect, we
may consider that while the vapour pressure of the liquid is rising, the extra
vapour that evaporates increases the pressure upon the liquid. The vapour
pressure thus never reaches the same value as the external pressure,
because both values are increasing as a result of the heating. This problem
does not arise in the open vessel because the vapour that evaporates is
free to disperse, and the external pressure upon the liquid thus remains
constant throughout.)

Titik kritis

Heating also causes expansion of the liquid, and thus a reduction in its
density, and eventually a point comes where the densities of the liquid and
vapour are equal. At this point, the surface between the two phases
vanishes, and the container is filled with a single uniform phase called a
supercritical fluid.

The temperature at which the surface between the two phases disappears
is called the critical temperature, Tc, and the vapour pressure at the critical
temperature is called the critical pressure. The point on a phase diagram
corresponding to the critical temperature and pressure is called the critical
point. Note that at and above the critical temperature, the liquid phase
does not exist - it is replaced by the supercritical fluid.
 Critical Temperature, Tc

Transition to Supercritical CO2

Copyright 1999, PRENTICE

Chapter 11 29
HALL

Fluida superkritis
Fluida superkritik adalah fluida pada T dan P di atas
harga kritiknya.
 Titik kritis adalah titik T-P dimana fasa cair dan gas
membentuk suatu fasa homogen, memiliki sifat identik
yang berbeda dari fasa gas maupun cairnya.
Fluida superkritik berada T dan P di atas titik kritiknya
dan sifat fisik merupakan kombinasi fluida gas dan cair.

Sifat fluida superkritis, memiliki densitas tinggi,

difusitas tinggi dan viskositas rendah.
- Densitas tinggi : kebutuhan volume kecil.
- Difusitas tinggi : interaksi solvent-solute semakin baik
( kelarutan semakin baik ).
- Viskositas rendah (mendekati fasa gas) : memberikan
keuntungan thd perpindahan massa secara konveksi.

Dari sifat-sifat tsb. maka fluida superkritik sangat baik

digunakan sebagai pelarut.
Aplikasinya pada pemisahan, khususnya ekstraksi.
Contoh : dekafeinasi kopi.
Hal ini mengurangi penurunan kualitas lingkungan

Evaporation and boiling : There is a difference

between the process of evaporation and the process
of boiling. In evaporation, the liquid molecules escape
the liquid surface without any external heat source.
The process by which liquid directly changes to
gaseous state is known as evaporation.

Boiling : If a liquid is heated continuously,

vaporization takes place in all parts of the liquid at a
particular temperature. The liquid undergoes a
complete change of state into gaseous state. The
process is known as boiling.Ý
 Evaporation Boiling

Evaporation : If you keep water in a saucer and expose it to air,

you will see that the water has disappeared after sometime. The
water is converted into gaseous state without giving it an extra
energy or heating it up to its boiling point.

We know that the molecules are never at rest. They can have slight
translational and vibrational motions about their mean positions.
They thus posses some amount of kinetic energy. Sometimes the
molecules collide with each other and exchange their kinetic
energies. Thus at any given time, the kinetic energy of a few
molecules may become quite large and they can escape from the
surface. The probability of escape from the surface is larger for
molecule 1 (pada permukaan), as its cohesive force holding it back to
the liquid is less than that experienced by molecule 2 (di dalam
cairan). This is how evaporation takes place.

To understand the process of evaporation

- Take two vessels whose mouths have different areas

The number of molecules on a larger surface will be more than
those on a smaller surface. Since evaporation takes place
 due to molecules escaping from the liquid surface, it is obvious
that the rate of evaporation will be faster from a vessel with
a larger mouth. The rate of evaporation depends on the
exposed area of the liquid.

put tea/coffee in a saucer to cool it

- Take equal amounts of water at different temperatures

(similar vessels with similar mouths)
The higher temperature of a liquid means higher molecular
kinetic energy. Hence the rate of evaporation is larger for a
liquid at higher temperatures.

- Take equal amounts of water and alcohol at the same

temperature.
The nature of the attractive cohesive forces will determine the
rate of evaporation. The cohesive forces in water is much larger
than that in alcohol. This is the reason why the rate of
evaporation in alcohol is higher than that seen in water.
- Take equal amounts of water in identical vessels (cover and
uncovered)
We have observed that the rate of evaporation in a closed vessel
is slower than that in the open vessel. The molecules escaping
from the surface of the liquid in a closed vessel collect in the space
above the liquid. Some of the molecules evaporated can return
and condense back to the liquid, after losing their energy in
collision. Thus the evaporation-condensation goes on till
equilibrium is reached. That is the rate of molecules evaporating is
the same as the rate of molecules condensing back. Once the
equilibrium is established, no more extra evaporation occurs. (In
this situation, the space above the liquid is said to be saturated
with vapor. The pressure exerted by the vapor on the liquid is said
to be saturated vapor pressure. The saturated vapor pressure of
a liquid increases with the increase of temperature).
But the same phenomena does not happen in an open vessel.
Because molecules escaping from its surface get scattered away
into the atmosphere, they are unable to condense back in the
same liquid surface. New molecules come to the surface, get
evaporated and the process continues.
 - Put some drops of water in your hand, When the water
evaporates, you feel cool. The heat required by the water
molecules is taken from your skin itself. The temperature of
the surrounding skin is lowered a bit. This makes you feel
cool.

Evaporation of sweat from the skin surface has a cooling effect due to
the latent heat of evaporation of water.
- We now know that energetic molecules escape from the
surface of a liquid during evaporation. This lowers the
average kinetic energy of the molecules left behind in the
liquid. This lowers the temperature of the liquid. Thus
evaporation lowers the temperature of the liquid. This is the
reason why you put tea/coffee in a saucer to cool it. Also
blowing cools a hot liquid, because blowing makes the
energetic molecules leave the surface quickly.

blowing cools a hot liquid, because blowing makes

the energetic molecules leave the surface quickly.

When clothes are hung on a laundry line, even though the

ambient temperature is below the boiling point of water, water
evaporates. This is accelerated by factors such as low humidity,
heat (from the sun), and wind. In a clothes dryer, hot air is
blown through the clothes, allowing water to evaporate very
rapidly.

Boiling :

If a liquid is heated continuously, vaporization takes place in all

parts of the liquid at a particular temperature. The liquid undergoes
a complete change of state into gaseous state. The process is known
as boiling.

Take a beaker and heat it till the water starts boiling. You will see that
bubbles start forming at around 70ƒC. The bubbles are mostly of
steam trying to escape. When the bubbles are large enough, they
come on the surface and escape as steam. When the pressure in the
bubble is less than the atmospheric pressure, the bubbles remain
inside the liquid. When the pressure becomes greater than the
atmospheric pressure (when the bubbles coalesce to form larger
bubbles) the bubbles burst and the boiling is seen at all places in the
liquid.
Try and do the following experiment. Keep water for boiling in two
identical vessels. Close one vessel with a lid. You will see that the
water in the vessel with a lid boils faster. This is because the water
vapor escaping in the closed vessel collects in the space above the
liquid. The steam returns back into the water and heats the water
faster. We are creating a condition of saturated vapor in the closed
vessel. This is the reason why water in a closed vessel boils faster,
that is it attains the temperature of 100ƒC faster.

TITIK LELEH dan TITIK TRIPEL

Titik leleh adalah suhu dimana fase cair dan fase padat
dalam keadaan setimbang.
Titik beku aalah temperature
Titik leleh zat = titik beku
Pada 1 atm → titik beku normal
Pada 1 bar → titik beku standar

TITIK TRIPEL
Titik tripel suatu zat adalah temperatur dan tekanan yang
menyatakan pada suhu dan tekanan tersebut zat yang
bersangkutan berada pada 3 fase yaitu cairan, padatan, dan
gas. Titik tripel air terjadi pada suhu 273.16 K (0.01 °C)
dan tekanan parsial gasnya 611.73 pascals (atau 6.1173
millibars, 0.0060373057 atm).

DIAGRAM FASA
Diagram fasa menggambarkan daerah P & T dimana
masing-masing fasa berada dalam stabil.

Diagram fasa air

Garis kest. Cair-uap : Tekanan uap vs temperatur

Titik didih vs tekanan

Garis kest. Padat – cair : titik leleh vs tekanan.

- Garis condong ke kiri : tekanan semakin > → titik
leleh semakin <.
Sebab : volume H2O cair < H2O padat,
Kristal mempunyai struktur sangat terbuka dengan
adanya ikatan Hidrogen, tetapi bila meleleh
strukturnya sebagian collapse sehingga ketika
tekanan diperbesar lebih disukai bentuk cair daripada
padat.
 - volume H2O cair < H2O padat →densitas H2O
padat < H2O cair.

Biasanya botol minuman dingin lebih tebal dari botol minuman

panas
Botol coca cola atau botol teh lebih tebal dari botol bir bintang atau
botol anggur orang tua
masukan air ke dalam botol lalu simpan botol di dalam kulkas.Botol
dapat pecah ketika air membeku

Bila seseorang ingin membuat es batu, biasanya air

dibungkus dalam kantung plastik.
Plastik elastis (mirip karet), sehingga ketika es batu
mengembang, plastik pun akan mengembang. Plastik menjadi
lebih besar setelah air berubah menjadi es batu.

Anomali (keanehan) Air

Antara suhu 0 oC sampai 4 oC volume air berkurang (air
menyusut) seiring bertambahnya suhu. Misalnya jika kita
memanaskan air pada suhu 0 oC, semakin panas air,
semakin berkurang volumenya. Proses penyusutan akan
terhenti ketika air mencapai suhu 4 oC. Di atas 4 oC, air
menjadi benda yang normal kembali. Maksudnya,
volumenya akan bertambah (terjadi pemuaian) seiring
bertambahnya suhu.

Sebaliknya, air akan memuai (volume air bertambah) ketika

mendingin dari 4 oC sampai 0 oC. Misalnya air kita
masukan ke dalam kulkas. Mula-mula suhu air 30 oC. Pada
saat suhu air menurun, volume air juga berkurang (air
mengalami penyusutan). Nah, ketika mencapai suhu 4 oC,
air akan memuai (volumenya bertambah). Pemuaian akan
terhenti ketika suhunya mencapai 0 oC. Volume air juga
semakin bertambah ketika ia membeku menjadi es. Sangat
berbeda dengan benda lain yang menyusut (volume benda
berkurang) ketika benda semakin dingin.

Massa benda selalu tetap. Sedangkan volume dapat

berubah-ubah, tergantung dari suhu. Ketika volume benda
berkurang, massa jenisnya akan bertambah. Semakin kecil
volume, semakin besar massa jenis benda. Sebaliknya, jika
volume benda bertambah, massa jenis benda akan
berkurang. Air akan menyusut (volume air berkurang)
sampaiisuhu 4 oC. Karenanya, air memiliki massa jenis
paling tinggi pada suhu 4 oC.
Seandainya antara 0 oC sampai 4oC air tidak berperilaku
menyimpang, makhluk hidup yang tinggal di bawah air
akan punah ketika musim dingin tiba, semua ikan akan mati
karena terhimpit es batu.

Proses ini terjadi sampai suhu air mencapai 4 oC.

Ketika suhu air di permukaan sungai atau danau lebih kecil
dari 4 oC, air yang ada di permukaan memuai (volumenya
bertambah). Akibatnya, massa jenis air yang ada di
permukaan menjadi lebih kecil dibandingkan massa jenis
air yang ada di bawahnya, maka ikan2 selamat dari
malapetaka musim dingin.

It is true that the freezing point of water decreases as the

pressure
decreases.
This is because water expands when it freezes, so
compressing ice will tend to convert it to more compact
liquid water. Thus, increasing the pressure lowers the
freezing point. This is exactly the same thing as saying that
decreasing the pressure raises the freezing point.

However, this effect is very small at pressures below one

atmosphere. The freezing point of water at one
atmosphere pressure is 273.15 Kelvin. As the pressure is
lowered, the freezing point increases ever so slightly, to
273.16 Kelvin. This is at a pressure of 0.006 atmospheres.
Below this pressure, liquid water is not stable. Only the
gas and solid are stable.

ICE SKATING
The pressure of the blade lowers the freezing point and
causes the ice to melt - the skater is actually sliding on
water. If the ice gets colder than a few degrees below zero,
you can't skate at all because the 'reverse' effect returns to
normal.
When the ice skater moves, her entire weight is supported
by the thin blades of the skates. Since the area of contact of
the thin blades with the ice is only a small fraction of the
area of the blade, it exerts sufficient pressure to melt the
ice. The layer of water formed enables the skates to glide
easily

Walking on snow
is difficult because of this effect of pressure which lowers
the melting point of ice. If the pressure exerted by the foot
is sufficient to melt the snow into water, the water refreezes
again when the foot is raised. The ice formed on the sole of
the boot as the foot is raised makes walking difficult.

Pada P >>> → H2O mempunyai beberapa fasa padat,

mis : es II, III, V, VI, VII.
Es VII hanya terjadi pada P = 25000 atm.
Adanya beberapa fasa padat tsb., yaitu karena adanya
modifikasi ikatan Hidrogen
antar molekul H2O akibat pemberian tekanan. Es tsb.
mempunyai titik leleh tinggi.
Contoh es VII meleleh pada suhu 1000C pada 25 kbar
 Titik tripel ada 5 buah.

Diagram Fasa CO2

- Garis kest. Padat cair : slope + (condong ke kanan).
Bila P semakin > →Titik leleh semakin >
- Titik tripel pada 5,11 atm (di atas 1 atm).
Pada 1 atm → tidak terdapat kesetimbangan padat-
cair, tetapi terdapat kesetimbangan padat-gas. Berarti
pada 1 atm, CO2 padat akan menyublim jika
dibiarkan pada wadah terbuka. CO2 padat disebut :
dry ice (es kering).
Untuk mendapatkan CO2 cair, diperlukan P = 5,11
atm.
- Untuk menyimpan CO2 cair dalam wadah pada
suhu kamar (25oC) diperlukan
P = 67 atm. Bila uap dalam tangki tsb. dibiarkan
menguap melalui nozzle ke
P = 1 atm, maka nozzle tsb. akan menjadi dingin
karena adanya efek Joule-Thomson dan pada nozzle
tsb. akan terkondensasi menjadi padatan atau salju.
- CO2 superkritis digunakan dalam
supercritical fluid chromatography (SFC),
dimana fluida superkritik
digunakan sebagai fasa mobile. Tehnik ini
digunakan untuk memisahkan
lipid dan phospholipid, memisahkan fuel oil
menjadi alkana, alkena dan arena.

Decaffeinasi kopi, dimana kafein diekstrak dari

green coffee beans.
 Bahaya Dry Ice Cream Dalam Mobil !!!!!!!

"Mengapa dry ice dapat membuat kita sesak napas di

dalam ruangan mobil yang ber AC?"

Dry Ice CO2 (zat asam arang = sisa pembakaran

oksigen/zat asam) jauh lebih mudah
diikat oleh darah),

"jangan sekali-sekali bawa dry ice di kabin mobil

penumpang"

(a) (b) (c)

(d)
 (a). Here we can see the seperate phases of carbon dioxide. The
meniscus is easily observed.
(b) With an increase in temperature the meniscus begins to
diminish

(c) Increasing the temperature further causes the gas and liquid
densities to become more similar. The meniscus is less easily
observed but still evident.

(d) Once the critical temperature and pressure have been

reached the two distinct phases of liquid and gas are no
longer visible. The meniscus can no longer be seen. One
homogenous phase called the "supercritical fluid" phase
occurs which shows properties of both liquids and gases.

Phase Diagrams
The Phase Diagrams of H2O and CO2
• Water:
– The melting point curve slopes to the left because ice is less
dense than water.
– Triple point occurs at 0.0098C and 4.58 mmHg.
– Normal melting (freezing) point is 0C.
– Normal boiling point is 100C.
– Critical point is 374C and 218 atm.
• Carbon Dioxide:
– Triple point occurs at -56.4C and 5.11 atm.
– Normal sublimation point is -78.5C. (At 1 atm CO2
sublimes it does not melt.)
– Critical point occurs at 31.1C and 73 atm.
Copyright 1999, PRENTICE HALL Chapter 11 6

Diagram Fasa Heliun

- Pada suhu rendah He berlaku tidak biasa : Tidak terdapat
kesetimbangan padat-gas. Atom He sangat ringan,
bervibrasi dengan gerakan amplitudo yang besar walaupun
pada suhu rendah.
- He padat hanya diperoleh pada suhu rendah tekanan
tinggi : hcp dan bcc
- He-I berlaku sebagai cairan normal
He-II berlaku sebagau superfluida ( dapat mengalir tanpa
viskositas).
Garis –λ : batas antara He-I dan He-II (transisi dari cair
→superfluida).
- He memiliki isotop : 3He dan 4He , diagram fasa keduanya
berbeda.
4
He pada garis –λ : terjadi transisi fasa cair-cair
3
He memiliki fasa superfluida. Entropi cairnya < padatannya.
Pelelehannya eksoterm.
Superfluida Helium. Ketika He didinginkan
Metoda untuk mendapatkan suhu rendah
Untuk mempelajari sejumlah transisi fasa tertentu, seringkali diperlukan pendinginan
sampai suhu sangat rendah.
Ada beberapa cara :
1. Dengan percobaan Joule-Thomson.
Efek Joule-Thomson : ekspansi adiabatis melalui sekat berpori ke ruang vakum
atau P rendah pada suhu di bawah suhu inversinya, akan menghasilkan penurunan
suhu dan entalpi tetap.
Gas dapat dicairkan dengan cara ekspansi Joule-Thomson pada suhu di bawah
suhu inversinya. Dengan cara ini, maka dapat dicapai suhu 4 K (=Tb He).

2. Untuk mendapatkan suhu < 4 K.

Tb He = 4 K. Bila T < 4 K → He berupa cair.
 He cair diuapkan dengan cara dipompa dengan cepat melalui pipa berdiameter
besar → He cair akan menguap.
Ketika He menguap, akan menyerap panas dari benda yang akan didinginkan.
Dengan cara ini dapat dicapai suhu 1 K.

3. Adiabatik demagnetisasi : untuk mendapatkan suhu 0 absolut.

Walaupun suhu 0 K tak pernah dicapai, tetapi suhu sampai 5x10-7 K dapat dicapai
dengan cara adiabatik demagnetisasi.
Prinsip :
Elektron bersifat sebagai magnet-magnet kecil. Dalam keadaan normal, magnet-
magnet ini terorientasi secara acak. Tetapi bila diberi medan magnet, maka
sebagian besar dari magnet-magnet kecil tsb. akan terorientasi searah dengan
medan magnet yang diberikan → orientasinya menjadi lebih teratur. Berarti
pemberian medan magnet akan menurunkan entropi sistim.
Percobaan :
Suatu sampel kompleks logam transisi (godolinium sulfat) yang bersifat magnet
didinginkan sampai suhu 1 K dengan cara di atas. Kemudian diberi medan magnet
yang kuat. Selama pemberian medan magnet ini sampel diletakkan dalam bath
yang dingin. Guna bath : panas yang dilepaskan pada waktu terjadi penurunan
entropi ditransfer ke bath, sehingga prosesnya isotermal.
Gambar

Setelah moment magnetnya teratur (searah) dan entropinya turun, maka sampel
dipisahkan dari bathnya dan kemudian medan magnet dikurangi sampai akhirnya
0. Sekarang prosesnya adiabatis :
Pada tahapan adiabatis ini, tak terjadi aliran panas, sehingga entropinya tetap. Jadi
walaupun setelah tidak diberi medan magnet lagi, magnet-magnet kecil tetap
teratur (tak berubah lagi). Susunan teratur ini sesuai dengan suhu rendah.
Jadi metoda adiabatik demagnetisasi akan menurunkan suhu sistim.

Diagram Fasa Karbon

 Graphite is very soft and slippery.
Diamond is the hardest substance known to man

Notice that graphite is layered.

While there are strong covalent bonds between carbon atoms in each
layer, there are only weak forces between layers. This allows layers of
carbon to slide over each other in graphite.

On the other hand, in diamond each carbon atom is the same distance to
each of its neighboring carbon atoms. In this rigid network atoms cannot
move. This explains why diamonds are so hard and have such a high
melting point.

C berbentuk gas hanya didapatkan pada suhu di atas 4000 K dan P rendah.
Untuk mendapatkan C cair, maka kita harus bekerja pada kondisi T = 4500 K dan
P = 1000 atm atau T = 2000 K dan P = 106 atm.

Pembuatan intan dari grafit :

Intan dapat disintesa dari C grafit dengan cara memberikan tekanan tinggi. Intan
stabil pada T = 1000 K dan P = 104 atm.
Tetapi perubahan C grafit → C intan berlangsung sangat lambat. Konversi dengan
kecepatan yang cukup baru terjadi pada T = 4000 K dan P = 200.000 atm.
Dengan adanya katalis (besi atau nikel), konversi dapat berlangsung pada T
=2300 K dan P = 70.000 atm.
Jadi, intan alam dan buatan dapat dibedakan dengan adanya katalis logam tsb.
Bila mengandung katalis logam → intan buatan, intan berwarna.
Bila tak mengandung katalis logam → intan alam, intan tidak berwarna.

Kriteria kesetimbangan secara termodinamika

 - Bila fasa berada dalam kesetimbangan, misalkan padat-cair. Potensial kimia
zat di seluruh cairan sama, di seluruh padatan sama dan pada cairan = pada
padatan.
- Misalkan potensial kimia pada fasa 1 : µ1
Potensial kimia pada fasa 2 : µ2
Bila sejumlah dn zat di transfer dari fasa 1 ke fasa 2, maka :
Pengurangan energy Gibbs pada fasa 1 : - µ1
Pertambahan energy Gibbs pada fasa 2 : + µ2
Perubahan energi Gibbs total:

dG = (µ2- µ1) dn
Bila µ1> µ2 →∆G = -, proses spontan

Bila µ1= µ2→∆G = 0 (tidak terjadi perubahan G), sistim kesetimbangan.

Faktor yang mempengaruhi kestabilan

- Temperatur
- Tekanan
- Komposisi
Pengaruh T terhadap µ (P & komposisi konstan) :

dG = V dp – S dT
 dG 
P konstan :  P =-S
 dT 
Fungsi Gibbs molar Gm = µ
 d 
  P = - Sm
 dT 

Diagram  vs T :
Slope = - Sm
Sm selalu + →slope = negatif
T makin > → μ makin <

Karena Sm(g) > Sm(ℓ) > Sm(s)

Slope dμ /dT untuk gas > cair > padat

Keterangan gambar :
Pada suhu < Tf → fasa padat stabil
Tb – Tf → fasa cair stabil
>Tb → fasa gas stabil
Bila suhu diturunkan sampai < Tb → μ(g) naik sampai
melebihi μ(ℓ), sehingga fasa cair menjadi lebih stabil →
sistim akan berkondensasi.
Pendinginan sampai < Tf , maka → μ(ℓ) naik sampai
melebihi μ(s) → fasa padat menjadi lebih stabil → sistim
membeku.
Pada Tb → μ(g) = μ(ℓ), cair berkesetimbangan dengan
 uapnya. Suhu pada saat tsb. disebut : titik
didih (Tb) dan tekanannya disebut : tekanan
uap.
Pada Tf → μ(ℓ) = μ(s), cair berkesetimbangan dengan
padatannya. Suhu pada saat tsb. disebut : titik
beku (Tf) atau titik leleh.

Pengaruh P terhadap pelelehan (T & komposisi

konstan)

d μ= Vm dp – Sm dT
T konstan : (dμ / dP)T = Vm
Vm(g), Vm(ℓ), Vm(s) → selalu positif
P makin > → μ makin >
Vm(g) = 1000x Vm(ℓ) atau Vm(s) →
d μ (g) >> d μ (ℓ) > d μ (s)

Gambar : pengaruh P terhadap diagram μ vs T

Gambar (a) : untuk zat selain air

Gambar (b) : untuk air

(a) Untuk kebanyakan zat Vm(ℓ ) > Vm(s )

P makin > → kenaikan μ(ℓ) > μ(s)→ Titik leleh naik

(b) Untuk H2O : Vm(ℓ ) < Vm(s )

P makin > → kenaikan μ(s) > μ(ℓ)→ Titik leleh turun.

Contoh soal 6.1: pengaruh tekanan terhadap potensial kimia

Hitunglah efek thd potensial kimia es dan air akibat kenaikan tekanan dari
1,00 bar menjadi 2,00 bar pada 00C. Densitas es = 0,917 gcm-3 dan densitas
air = 0,999 gcm-3.
Penyelesaian :
dG = V dp – S dT
d μ= Vm dp – Sm dT
∆ μ = Vm ∆P – Sm ∆T
T konstan : ∆ μ = Vm ∆P
M
Vm =

∆ μ= M
∆P


∆ μ (es) = + 1,97 Jmol-1

∆ μ (air) = + 1,80 Jmol-1

Terlihat kenaikan μ(s) > μ(ℓ)

Jadi jika tekanan dinaikan dari 1 bar menjadi 2 bar, es cenderung mencair.

Pengaruh Tekanan terhadap Tekanan Uap

Pada kesetimbangan :
Apabila kesetimbangan diganggu : perubahan harus sama dengan
perubahan

Bila P terhadap cairan dinaikan sebesar dP

dan
dp = perubahan tekanan uap
Bila uap dianggap gas ideal
Vapor Pressure
Explaining Vapor Pressure
on the Molecular Level
• Dynamic Equilibrium: the
point when as many molecules
escape the surface as strike the
surface.
• Vapor pressure is the pressure
exerted when the liquid and
vapor are in dynamic
equilibrium.

Copyright 1999, PRENTICE HALL Chapter 11 3

Vapor Pressure
Explaining Vapor Pressure on the Molecular
Level
• Some of the molecules on the surface of a liquid have
enough energy to escape the attraction of the bulk
liquid.
• These molecules move into the gas phase.
• As the number of molecules in the gas phase
increases, some of the gas phase molecules strike the
surface and return to the liquid.
• After some time the pressure of the gas will be
constant at the vapor pressure.

Copyright 1999, PRENTICE HALL Chapter 11 1

Gas-Liquid Equilibration

Copyright 1999, PRENTICE HALL Chapter 11 2

:
 Garis pada diagram, menunjukan kest. 2 fasa
yaitu : kest. padat – cair
kest. padat – gas
kest. cair – gas

Mis : pada T1 dan P1 terjadi kest. padat – cair.

T2 dan P1 sistim tidak berada dlm kest. ( 1 fasa ).
Persamaan Clapeyron

Untuk menentukan slope batas fasa

Pada P & T tertentu . fasa α ↔ fasa β

maka pd kest. μ (α , P ,T) = μ (β, P, T)
kemudian T & P sedikit diubah tetapi fasa α dan fasa
β tetap berkest., maka :
harga μ kedua fasa akan berubah, tetapi harga μ
yang baru tetap sama dan perubahannya sama
besar, yaitu sebesar :
d μ (α , P ,T) = d μ (β, P, T)
dGm = Vm dP – Sm dT
dGm = μ
-Sm (α) dT + Vm (α) dP = - Sm (β) dT + Vm (β) dP
{ Vm (α) - Vm (β) } dp = { Sm (α) - Sm (β) } dT

dP Sm
dT
= Vm
Persamaan Clapeyron

∆Sm = Hm
T
Hm
dP
dT
= T .Vm
Kurva kest. padat – cair (pelelehan)

Pada perubahan padat → cair : diperlukan panas

(endoterm)sebesar entalpi molar pelelehan.
ΔHmelt,m = +
Dan pelelehan terjadi pada suhu pelelehan Tf.
Entropi molar pelelehan → ΔSmelt,m = ΔHmelt,m / Tf
Pers. Clapeyron berubah menjadi :

dP / dT = ΔHmelt,m / Tf. ΔVmelt,m

ΔVmelt,m = perubahan volume molar pelelehan.

= Vm (ℓ) – Vm (s)
Karena Vm (ℓ) > Vm (s) → ΔVmelt,m = +
Kecuali : untuk H2O → Vm (ℓ) < Vm (s) →
ΔVmelt,m = ─
Jadi slope dP / dT = + / + = + → garis kest. padat –
cair condong ke kanan .
( kecuali H2O ke kiri )
Integral persamaan di atas :
 P T
∫ dP = ΔHmelt,m / ΔVmelt,m ∫ dT / Tf
P* T*
Asumsi : ΔHmelt,m dan ΔVmelt,m untuk
padatan dan cairan konstan ( tak bergantung pada T ).
P - P* = ΔHmelt,m / ΔVmelt,m ln T /T*

P = P* + ΔHmelt,m / ΔVmelt,m ln T /T*

P* dan T* = fix point (harga P dan T yang sudah

tertentu pada kurva kest. tsb.).
Mis : P & T pada titik tripel
P & T pada Tf
Dengan menggunakan pers. di atas dapat
digambarkan kurva kest. padat – cair.

Contoh soal
a. Buatlah kurva kest. es – cair untuk H2O antara
suhu -10C → + 10C.
b. Berapakah titik beku H2O pada P = 1500 atm.
Jawab
a. Fix point P* dan T* dipilih P dan T pada titik
tripel H2O, yaitu :
P* = 0,006 atm
T* = 273,16 K
ΔHmelt,m (273K) = 6,01 KJ mol-1 ( ΔHmelt,m
dianggap konstan pada range P* → P
 dan T* → T )
ΔVmelt,m = - 1,7 cm3 mol-1 ( negatif, karena
untuk H2O Vm (ℓ) < Vm (s)
Dengan menggunakan pers. di atas diperoleh :

t (0C) : -1,0 -0,5 0,0 0,5 1,0

P (atm) : 129 65,3 1,28 -62,6 -126

Gambar :

b. Fix point P* dan T* dipilih pada P dan T pada Tf

normal, yaitu : P* = 1 atm
T* = 00 C = 273,15 K

P - P* = ΔHmelt,m / ΔVmelt,m ln T /T*

(1500 -1 ) x 1,013.105 N m-2 = 6,01 KJ mol-1 /
1,7x10-6 m3 mol-1 ln T / 273,15 K
T = 261,7 K = -11,5 0C.

Jadi P akan mempengaruhi Tf.

Untuk H2O : P = 1 atm → Tf = 00C
 P = 1500 atm → Tf = - 11,50C
Untuk zat lain : P makin > → Tf makin >

Kurva kest. cair – gas ( penguapan )

Kemiringan kurva ;

Pada perubahan cair – gas diperlukan panas sebesar

entalpi penguapannya.
ΔHevap,m = +
Vm (g) >> Vm (ℓ) → ΔVevap,m = Vm (g) - Vm (ℓ)
= + dan besar
Pers. Clapeyron : dP / dT = ΔHevap,m / T. ΔVevap,m
= + / + = + dan kecil
Jadi kemiringan dP / dT penguapan < dP / dT
pelelehan.
Gambar :
Vm(g) sangat sensitif terhadap perubahan P.
P makin > → Vm (g) makin <
ΔVm (g) juga makin <
dP / dT = ΔHevap,m / T. ΔVevap,m
dP / dT makin >

P makin > → slope makin > → kurva kest. cair –

gas makin condong ke kiri.
Gambar

Menggambarkan kurva kest. cair – gas :

Menggunakan pers. Clausius-Clapeyron yang
diturunkan sbb :

Clapeyron : dP / dT = ΔHevap,m / T. ΔVevap,m

ΔVevap,m =Vm(g) – Vm(ℓ)
Vm(g) >>>) Vm(ℓ) → Vm(ℓ)
dapat diabaikan
terhadap Vm(g)
dP / dT = ΔHevap,m / T. Vm(g)
Bila gas dianggap gas ideal : Vm(g)
= RT / P
 dP / dT = ΔHevap,m / T x P / RT
 ΔHevap,m / RT
dP / P 2
dT

d(ln P) / dT = ΔHevap,m / RT2 → Pers. Clausius

Clapeyron
Integral pers. di atas ;
P T
∫ d ln P = ΔHevap,m / R ∫ dT /T2
P* T*

ΔHevap,m dianggap konstan (tak bergantung pada T)

ln P / P* = - ΔHevap,m / R ( 1/T – 1/T*)

Garis kest, cair – uap dimulai dari titik tripel

sampai titik kritis. Garis ini tak dapat
melebihi titik kritis, sebab di atas titik kritis tidak
terdapat fasa cair (semua gas).
Kurva kest. cair – uap dapat diplotkan sebagai :
- Tekanan uap vs T atau
- Tb vs P

SOAL
Buat kurva tekanan uap untuk H2O antara -50C
sampai 1000C.
Jawab :
Gunakan pers. ln P / P* = - ΔHevap,m / R ( 1/T –
1/T*)
Dari 00C – 300C :
Fixed point dipilih titik tripel,
yaitu :
P* = 0,006 atm
T* = 273,16 K
ΔHevap,m (273 K) = 45,05 KJ mol-1
Dari 700C – 1000C :
Fixed point dipilih titik didih normal,
yaitu :
P* = 1 atm
T* = 1000C = 373 K
ΔHevap m (373 K) = 40,66 KJ mol-1
Hasil yang diperoleh :

t (0C) : -5 0 5 10 20 30
P (atm) : 0,004 0,006 0,08 0,012 0,023 0,318

70 80 90 100
0,318 0,476 0,697 1,00
Gambar :
Ada perbedaan kurva yang dihasilkan dari
experiment dan perhitungan :
Exp Perhitungan

Hal ini disebabkan pada perhitungan ΔHevap,m

dianggap konstan.

Untuk membuat kurva yang lebih teliti seperti yang

didapat dari experiment, maka ΔHevap,m tidak boleh
dianggap konstan, sehingga untuk perhitungan
yang lebih teliti dapat digunakan persamaan :

d(ln P) /dT = ΔHevap,m / RT2

Kurva kest. padat – gas (sublimasi)

Persamaan yang digunakan = untuk kurva kest. cair
– gas.
Hanya ΔHevap,m diganti dengan ΔHsub,m.

d(ln P) / dT = ΔHsub,m. / RT2

ln P / P* = ΔHsub,m. / R (1/T – 1/ T*)

P = P* exp { - ΔHsub,m. / R (1/T – 1/ T*)}

Perbedaannya pada kemiringan kurva ;

ΔHsub,m > ΔHevap,m

Slope dP / dT menjadi + dan besar → condong ke

kanan.
Gambar :

SOAL :
Buat kurva kest. es – uap antara suhu – 100C
sampai +50C.
Jawab :
ΔHevap,m (273 K) = 45,05 KJ mol-1
ΔHmelt,m (273 K) = 6,01 KJ mol-1
ΔHsub,m = ΔHevap,m + ΔHmelt,m
 = 45,05 + 6,01 = 51,06 kJ mol-1
Hasil yang diperoleh :

t (0C) : - 10 -5 0 5
P (atm) : 0,0026 0,0039 0,006 0,009

P* dan T* = titik tripel

Gambar :

Kest. padat – cair - gas

Pada titik tripel : terjadi kest. fasa padat – cair
gas.
μ (s) = μ (ℓ) = μ (g)

ketiga kurva kest. berpotongan pada titik tripel.

Titik tripel untuk suatu zat harganya sudah tertentu.
Mis : titik tripel untuk H2O,
T = 273,16 K
P = 0,006 atm.
Clapeyron :dP / dT = ΔHmelt,m / Tf. ΔVmelt,m
.
ΔVmelt,m = Vm (ℓ) - Vm (s)
= ─
ΔHmelt,m = +

Slope dP / dT = + /─ = ─ ( ke kiri)

garis kest. padat – cair : condong ke kanan

Sebab :
dP H

dT T .Vm

ΔHm = + dan ΔVm = Vm(ℓ) – Vm(s) = +

dP 
 
dT 
→ slope ke kanan
Berarti : P makin > → Tf makin >.
SOAL
Bila benzena membeku pada suhu 5,50C, maka
densitasnya berubah dari 0,879 g/cm3 menjadi
0,891 g/cm3. entalpi pelelehan ΔHm = 10,59
KJ/mol.
Hitung : Tf benzena pada P = 1000 atm.
Jawab :

P = P* + ΔHmelt,m / ΔVmelt,m . ln T/T*

M
Vm = 
Vm benzena cair = 78,115 / 0,891 =

Vm benzena padat = 78,115 / 0,879 =

ΔV melt,m = Vm(ℓ) – Vm(s) = 1,197 cm3/mol

1000 atm = 1 atm + (10,59 KJ mol-1 / 1,197 cm3
mol-1). ln T /278,5
101325 x 103 Pa = 101325 Pa + (10,59x103 Jmol-1 /
1,197x10-6 m3mol-1).ln T/278,5
101325 x 103 Jm-3 =101325 Jm-3 + (10,59x103
Jmol-1 /1,197x10-6 m3mol-1).ln T/278,5

T = 281,9 K
 Vlll. DIAGRAM FASA

Pada chapter ini akan dibicarakan perubahan yang

terjadi apabila suatu campuran : dipanaskan,
didinginkan, atau komposisinya diubah. Hal ini
dapat dijelaskan dengan menggunakan diagram
fasa.

Fasa, komponen dan derajat kebebasan

FASA = keadaan materi yang komposisi kimia dan
keadaan fisik diseluruh bagian nya uniform.
Jumlah fasa dinotasikan dengan P :
P=1 campuran gas, kristal, dua cairan yang
bercampur, es.
P=2 Capuran es dan air, logam paduan yang
tak saling larut.

Konstituen = jumlah spesies kimia yang terdapat

dalam sisitim. Contoh : campuran etanol dan air
mempunyai 2 konstituen.
Komponen = jumlah minimum spesies bebas yang
diperlukan untuk menentukan komposisi semua
fasa yang ada dalam sistim.

Bila spesies tidak bereaksi konstituen=

komponen

Contoh : bila spesies bereaksi dan berada pada

kesetimbangan

NH4Cl (s) ↔ NH3 (g) + HCl (g)

Jumlah fasa P = 2
Jumlah konstituen = 3
Jumlah komponen C = 1
Koefisien reaksi NH3 dan HCl sama dan
komposisi keduanya ditentukan ole NH4Cl.

Contoh :
CaCO3 (s) ↔ CaO (s) + CO2 (g)
Jumlah fasa =
Jumlah konstituen =
Jumlah komponen = 2

Contoh :
H2O (l) ½ O2(g) + H2 (g) pada t kamar
Jumlah fasa P = 2
Jumlah konstituen = 3
Jumlah komponen = 3
 Pada suhu kamar H2 dan O2 tidak bereaksi
membentuk H2O, sehingga tidak
berkesetimbangan, sehingga dianggap sebagai
konstituen bebas.

Apabila spesies di dalam sistim dapat bereaksi dan berada pada kesetimbangan,
Jumlah komponen = jumlah spesies – jumlah hubungan :

C=S-R
Tahapan :
1. Identifikasikan jumlah S ( jumlah spesies yang berbeda, mis : ion yang terdapat
dalam masing-masing fasa.
2. Tentukan jumlah R ( hubungan antara spesies, mis : reaksi pada
kesetimbangan, netralisasi muatan ).

Contoh : Berapa jumlah komponen dalam sistim :

a. Sukrosa dalam H2O
b. NaCl dalam H2O
Jawab :
a. S = 2, yaitu sukrosa dan H2O
R = 0, tak ada hubungan antara keduanya.
C=2–0=2

b. S = 3, yaitu molekul H2O, ion Na+, Cl-, H+, OH-.

R = 1 → hubungannya adalah muatan listriknya netral. Jumlah Na+ = jumlah Cl-.
C = 3 – 1 = 2, Bila konsentrasi H2O dan NaCl sudah ditentukan, maka konsentrasi
spesies lainnya sudah tertentu.

Aturan Fasa Gibbs

J.W. Gibbs mengusulkan aturan fasa, yaitu
hubungan antara derajat kebebasan (F),
jumlah fasa (P) dan jumlah komponen (C) :

F=C–P+2
Derajat kebebasa F = jumlah variabel intensif yang
dapat diubah secara bebas tanpa mengubah
jumlah fasa dalam kesetimbangan.
F=0 invarian
F=1 univarian
F=2 bivarian
ATURAN FASA PADA SISTIM 1 KOMPONEN
Apa yang terjadi bila sistim pada a (gas) didinginkan
pada P konstan (P=1 atm) ?.

Penurunan hukum fasa Gibbs :

C=2 F=2–P+2=4–P
Bila T konstan F=3–P
Untuk sisitim 1 fasa (P=1) F = 2, yaitu
tekanan dan komposisi.

- Untuk larutan ideal

- Solute volatile & solvent volatile

Untuk larutan ideal solute dan solvent mengikuti

hukum Roult :
p A = X A . p A*
p B = X B . p B*
 pA = tekanan parsial solvent
pB tekanan parsial solute
pA*= tekanan uap murni solvent
pB* = tekanan uap murni solute

Tekanan uap campuran total

p total = pA + pB
= XA . pA* + XB . pB*
= XA . pA* + (1 – XA) . pB*
p total = pB* + (pA* - pB*) XA pers. Garis
lurus p total vs XA pada T konstan

X = komposisi cair
Y = komposisi uap
Gabungan kurva p total vs X dan p total vs Y
didapat kurva p total vs Z
( z = komposisi uap atau cairan)
 ethanol and water �the ethanol molecules have an average of 1 hydrogen bond
per molecule, whereas the water molecules have 2. The ethanol molecules
interfere with the hydrogen bonds and therefore make the liquid more volatile.

When the deviation is great enough to cause a maximum or minimum in the vapor
pressure versus composition function, it is a mathematical consequence that at
that point, the vapor will have the same composition as the liquid, and so an
azeotrope is the result.

Azeotrope

An azeotrope is a mixture of two or more pure compounds (chemicals) in such a ratio

that its composition cannot be changed by simple distillation.[1] This is because when an
azeotrope is boiled, the resulting vapor has the same ratio of constituents as the original
mixture of liquids. As the composition is unchanged by boiling, azeotropes are also
known as constant boiling mixtures (especially in older texts). The word azeotrope is
derived from the Greek words "ζειν"=boil and "τρόπος"=change, combining with prefix
"α-"=no to give the overall meaning "no change on boiling".

Examples of azeotropes
Proportions are by weight.

 nitric acid (68%) / water, boils at 120.5°C at 1 atm (negative azeotrope)

 perchloric acid (28.4%) / water, boils at 203°C (negative azeotrope)
 hydrofluoric acid (35.6%) / water, boils at 111.35°C (negative azeotrope)
 ethanol (96%) / water, boils at 78.1°C
 sulfuric acid (98.3%) / water, boils at 338°C
 acetone / methanol / chloroform form an intermediate boiling (saddle) azeotrope
 diethyl ether (33%) / halothane (66%) a mixture once commonly used in
anaesthesia.
 benzene / hexafluorobenzene forms a double binary azeotrope.

Types of azeotropes

positive azeotrope : the boiling point of an azeotrope is either less than the boiling points
of any of its constituents

example of a positive azeotrope is 95.6% ethanol and 4.4% water (by

weight)

Ethanol boils at 78.4°C, water boils at 100°C, but the azeotrope boils
at 78.1°C, which is lower than either of its constituents

78.1°C is the minimum temperature at which any ethanol/water

solution can boil. Positive azeotropes are also called minimum
boiling mixtures.
 Hydrogen bonding of water–ethanol in alcoholic beverages: aged whiskey,
Japanese sake, Vodca

New research in the June issue of the American Chemical Societys Journal of
Agricultural and Food Chemistry suggests hydrogen bonding as the cause of taste
differences amongst various vodka brands. I'm not entirely

convinced. I've discussed hydrogen bonding here on Associated Content before,

and discussed how it can result in some pretty amazing transformations, such as
those found in Jello. The researchers make the case that ethanol, which is present
in the vodka, can act as one half of the hydrogen bond, with water (present in the
vodka) acting as the other half. The formation of the hydrogen bonds forces the
water molecules directly surrounding the ethanol molecules into a cage-like
environment that has some rigidity and structure to it. It doesn't become
 completely solid, obviously, but it's more structured and ordered than a liquid
would normally be.

The articles authors suggest that it is this tenuous cage-like structure of water and
ethanol molecules that lies at the heart of the vodkas taste. It is no surprise to
anyone that different brands of vodka taste differently. More expensive vodkas
tend to be "smoother" and contain less harsh flavors, whereas a cheap vodka may
have a strong medicinal taste and be quite difficult to drink unless its mixed with
other flavors. That is why you rarely see high-end vodkas being mixed into a
daiquiri or other type of strong, fruity drink; the "pureness" of the more expensive
vodkas is completely besides the point if its delicate flavor is overwhelmed with
orange juice. If you want to make a mixed drink, any brand of vodka will suffice;
purists who insist on drinking vodka straight will opt for the more expensive
brand.

The solubility of the small alcohols in water

Consider ethanol as a typical small alcohol. In both pure water and pure ethanol
the main intermolecular attractions are hydrogen bonds.

In order to mix the two, you would have to break the hydrogen bonds between
the water molecules and the hydrogen bonds between the ethanol molecules. It
needs energy to do both of these things.

However, when the molecules are mixed, new hydrogen bonds are made
between water molecules and ethanol molecules.
The energy released when these new hydrogen bonds are made more or less
compensates for that needed to break the original ones.

In addition, there is an increase in the disorder of the system - an increase in

entropy. That is another factor in deciding whether things happen or not.

An example of a negative azeotrope is hydrochloric acid at a concentration of

20.2% hydrogen chloride and 79.8% water (by weight). Hydrogen chloride boils
at –84°C and water at 100°C, but the azeotrope boils at 110°C, which is higher
than either of its constituents. Indeed 110°C is the maximum temperature at which
any hydrochloric acid solution can boil. It is generally true that a negative
azeotrope boils at a higher temperature than any other ratio of its constituents.
Negative azeotropes are also called maximum boiling mixtures.

Phase diagrams
Distillation of mixtures
If two solvents can form a positive azeotrope, then distillation of any mixture of those
constituents will result in the distillate being closer in composition to the azeotrope than
the starting mixture. For example, if a 50/50 mixture of ethanol and water is distilled
once, the distillate will be 80% ethanol and 20% water (see ethanol data page), which is
closer to the azeotropic mixture than the original. Distilling the 80/20% mixture produces
a distillate that is 87% ethanol and 13% water. Further repeated distillations will produce
mixtures that are progressively closer to the azeotropic ratio of 95.5/4.5%. No number of
distillations, however, will ever result in a distillate that exceeds the azeotropic ratio.
Likewise when distilling a mixture of ethanol and water that is richer in ethanol than the
azeotrope, the distillate (contrary to intuition) will be poorer in ethanol than the original
but slightly richer than the azeotrope.[3]

If two solvents can form a negative azeotrope, then distillation of any mixture of those
constituents will result in the residue being closer in composition to the azeotrope than
the original mixture. For example, if a hydrochloric acid solution contains less than
20.2% hydrogen chloride, boiling the mixture will leave behind a solution that is richer in
hydrogen chloride than the original. If the solution initially contains more than 20.2%
hydrogen chloride, then boiling will leave behind a solution that is poorer in hydrogen
chloride than the original. Boiling of any hydrochloric acid solution long enough will
cause the solution left behind to approach the azeotropic ratio.[4]

Separation of azeotrope constituents

Pressure swing distillation

Azeotropic distillation

When an entrainer is added to a binary azeotrope to form a ternary azeotrope, and

the resulting mixture distilled, the method is called azeotropic distillation

entrainer, that will affect the volatility of one of the azeotrope constituents more
than another. Example is adding benzene or cyclohexane to the water/ethanol
azeotrope. With cyclohexane as the entrainer, the ternary azeotrope is 7% water,
17% ethanol, and 76% cyclohexane, and boils at 62.1°C.[8] Just enough
cyclohexane is added to the water/ethanol azeotrope to engage all of the water
 into the ternary azeotrope. When the mixture is then boiled, the azeotrope
vaporizes leaving a residue composed almost entirely of the excess ethanol.[2]

Chemical action separation

Another type of entrainer is one that has a strong chemical affinity for one of the
constituents. example of the water/ethanol azeotrope, the liquid can be shaken
with calcium oxide, which reacts strongly with water to form the nonvolatile
compound, calcium hydroxide. Nearly all of the calcium hydroxide can be
separated by filtration and the filtrate redistilled to obtain nearly pure ethanol.

Distillation using a dissolved salt

When a salt is dissolved in a solvent, it always has the effect of raising the boiling point
of that solvent — that is it decreases the volatility of the solvent. When the salt is readily
soluble in one constituent of a mixture but not in another, the volatility of the constituent
in which it is soluble is decreased and the other constituent is unaffected. In this way, for
example, it is possible to break the water/ethanol azeotrope by dissolving potassium
acetate in it and distilling the result.[2]

Extractive distillation

Extractive distillation is similar to azeotropic distillation, except in this case the entrainer
is less volatile than any of the azeotrope's constituents. For example, the azeotrope of
20% acetone with 80% chloroform can be broken by adding water and distilling the
result. The water forms a separate layer in which the acetone preferentially dissolves. The
result is that the distillate is richer in chloroform than the original azeotrope.[2]

Pervaporation and other membrane methods

The pervaporation method uses a membrane that is more permeable to the one constituent
than to the another to separate the constituents of an azeotrope as it passes from liquid to
vapor phase. The membrane is rigged to lie between the liquid and vapor phases. Another
membrane method is vapor permeation, where the constituents pass through the
membrane entirely in the vapor phase. In all membrane methods, the membrane separates
the fluid passing through it into a permeate (that which passes through) and a retentate
(that which is left behind). When the membrane is chosen so that is it more permeable to
one constituent than another, then the permeate will be richer in that first constituent than
the retentate.[2]
Use of azeotropes to separate zeotropic mixtures
Sometimes azeotropes are useful in separating zeotropic mixtures. An example is acetic
acid and water, which do not form an azeotrope. Despite this it is very difficult to
separate pure acetic acid (boiling point: 118.1°C) from a solution of acetic acid and water
by distillation alone. As progressive distillations produce solutions with less and less
water, each further distillation becomes less effective at removing the remaining water.
Distilling the solution to dry acetic acid is therefore economically impractical. But ethyl
acetate forms an azeotrope with water that boils at 70.4°C. By adding ethyl acetate as an
entrainer, it is possible to distill away the azeotrope and leave nearly pure acetic acid as
the residue.[2]

I. Campuran biner dari 2 cairan yang melarut sebagian (cairan tidak

bercampur pada semua perbandingan).
Mis : n-heksana & nitrobenzena
Air – isobutanol
Air – fenol
Percobaan ini dilakukan pada T & P dimana tidak terdapat fasa uap.

Gambar
Hukum Fasa:
Jumlah komponen = 2 → C = 2
F=C–P+2 = 2–P+2= 4–P
Untuk menyerdahanakan P dibuat konstan,
 A mixture of 40.0 grams of component A and 60.0 grams of
o
component B is brought into equilibrium at 115 C. At this
temperature and overall composition, 62.5 grams of a phase rich in
B separates from a phase which is 70.0% by weight rich in A.

Temperature ( C )
o

o
115 C

0 wA 100

What is the weight percent composition of the phase rich in B that

is in equilibrium with the A rich phase?

45.5

mis : 1 atm, sehingga :

F = 3 – P, maka maks. F = 2, yaitu T dan
komposisi fasa.
Jadi diagram fasanya : T vs komposisi.
Apa yang terjadi apabila ke dalam n-heksana ditambahkan nitro-benzena (T
tetap T1’?.
- Ke dalam H murni ditambahkan NB sedikit membentuk campuran
dengan komposisi a (XNB = 0,05). Pada komposisi ini H & NB larut sempurna
membentuk 1 fasa → F = 3 – P = 3 – 1 = 2, yaitu T & komposisi dapat
divariasikan secara bebas dalam daerah 1 fasa.
- Sampai a’ → NB tidak dapat larut sempurna lagi (H sudah jenuh akan NB).
Sistim mulai membentuk 2 fasa yang berkesetimbangan.
Gambar :
Fasa 1 = H yang jenuh dengan NB (lapisan
kaya H).

Fasa 2 = NB yang dijenuhi oleh H (lapisan

kaya NB).
Komposisi fasa 1 & 2 ditentukan dari perpotongan tie line dengan kurva.
Komposisi fasa 1 : a’→ XNB = 0,1 & XH = 0,9
 Komposisi fasa 2 : a’’ → XNB = 0,8 & XH = 0,2

Jumlah relatif kedua fasa dinyatakan dengan ―Lever Rules‖ :

n( fasa1) a"a'
= → fasa 2 sedikit sekali
n( fasa 2) a'a'
fasa 1 banyak sekali

F = 3 – P = 3 – 2 = 1, yaitu T atau komposisi salah satu fasa.

- Kemudian ditambah NB lagi sampai komposisi total = a (XNB=0,3 & XH=0,7).

Setelah kocok didapat 2 fasa, komposisi kedua fasa tetap, yaitu ;

Fasa 1 : XNB = 0,8 & XH = 0,2

Fasa 2 : XNB = 0,1 & XH = 0,9

Tetapi jumlah fasa 2 (lapisan kaya NB) semakin banyak, yaitu :

n( fasa1) a"a 0,8  0,3

= = = 2,5
n( fasa 2) a  a' 0,3  0,1

F = 3 – P = 3 – 2 = 1 → T atau komposisi 1 fasa.

Temperatur kritis atas (temperatur konsolut atas) = temperatur pada max. kurva.
Definisi temperatur konsolut atas adalah suhu max. dimana kedua fasa masih
dapat terjadi.
Di atas Tc berapapun komposisinya, selalu didapatkan 1 fasa.
Harga Tc → khas untuk campuran 2 komponen yang melarut sebagian, sehingga
sering digunakan untuk menyatakan kemurnian.
( Tc sangat dipengaruhi oleh adanya zat pengotor).

Pada Tc → F = 3 – P
P = 3, yaitu fasa1, fasa2 dan fasa homogen.
F = 0 → harganya sudah tertentu.

Sistim cair – cair dengan T konsolut bawah

Pada campuran ini, pada suhu rendah kedua
komponen lebih saling melarut, sebab kedua
komponen membentuk kompleks yang
lemah.
Pada suhu lebih tinggi, kompleks tsb. pecah
membentuk 2 fasa.
Sistim Cair – cair yang mempunyai Tc atas dan Tc bawah

Contoh soal

Dibuat campuran 50 g n-heksana + 50 g nitrobenzena pada suhu 290 K.

Dit : a. Komposisi kedua fasa
b. Perbandingan kedua fasa
c. Pada suhu berapakah mulai terbentuk 1 fasa.
Jawab :
n (n-heksana) = 50 g / 86,2 gmol-1 = 0,58 mol
n (nitrobenzena) = 50 g / 123 gmol-1 = 0,41 mol
n total = 0,99 mol
 X n-heksana = 0,59
X nitrobenzena = 0,41
Berarti pada 290 K → terjadi 2 fasa

a. Komposisi kedua fasa ditentukan dari perpotongan tie line dengan kurva.
Komposisi fasa 1 : X NB = 0,37 dan X NH = 0,63
fasa 2 : X NB = 0,83 dan X NH = 0,17

n( fasa1) 0,03
b.  
n( fasa 2) 0,20

c. Membentuk 1 fasa pada suhu 292 K.

A mixture of 40.0 grams of component A and 60.0 grams of
o
component B is brought into equilibrium at 115 C. At this
temperature and overall composition, 62.5 grams of a phase rich in
B separates from a phase which is 70.0% by weight rich in A.
Temperature ( C )
o

o
115 C

0 wA 100

What is the weight percent composition of the phase rich in B that

is in equilibrium with the A rich phase?

45.5
The liquid - liquid phase diagram for the binary nicotine and water
system is shown below:

nicotine / water
o solution
210 C
T1
Temperature ( C )

nicotine
o

T2 saturated water
rich phase in
T3 equilibrium
with a water
saturated
nicotine rich
lower
phase
T4 consulate
o temperature
61 C
X1 X2 X3
0 Xnicotine 1

We will follow the changes that occur as we cool a nicotine water

solution of composition X2 from some temperature above the upper
o
consulate temperature of 210 C.
At temperatures greater than T1, thermal motion prevents
separation into two phases and the nicotine and water are miscible.
When T1 is reached, thermal motion is no longer capable of
preventing phase separation and a water saturated nicotine rich
phase just begins to form and is in equilibrium with the
predominant nicotine saturated water rich phase.

45.3
 Distillation of partially
miscible liquids
 What happens when you distill partially miscible
liquids?
 A pair of liquids that are partially miscible often
form a low-boiling azeotrope.
 Two possibilities can exist: one in which the liquid
become fully miscible before they boil; the other in
which boiling occurs before mixing is complete.
 Liquid-solid phase diagrams
 The knowledge of temperature-composition
diagrams for solid mixtures guides the design of
important industrial processes, such as the
manufacture of liquid crystal displays and
semiconductors.
 Eutectics
 The isopleth at e corresponds to the eutectic
composition, the mixture with the lowest melting
point.
 A liquid with a eutectic composition freezes at a
single temperature without depositing solid A or B.
 A solid with the eutectic composition melts without
any change of composition at the lowest
temperature of any mixture.

Eutectics
 Solder – 67% tin and 33% lead by mass melts at
183 °C.
 23% NaCl and 77% H2O by mass forms a eutectic
mixture which melts at -21.1 °C. Above this
temperature the mixture melts.
 Reacting Systems
 Many binary mixtures react produce compounds.
 Gallium arsenide is a technologically important
example – semiconductor.
 Ga + As  GaAs
Crystallization of Composition X
Composition X is a mixture of 13 wt. % SiO2 and 87 wt. % Mg2SiO4. Because this
composition falls between the compositions of pure forsterite and pure enstatite, it must
end its crystallization history containing only crystals of forsterite and enstatite. i.e. no
quartz will occur in the final crystalline mixture.

If a mixture such as composition X is taken to a temperature above its liquidus (i.e. above
1800oC in Figure 2) it will be in an all liquid state. We now trace the cooling history of
composition X.

As a liquid of composition X is cooled, nothing will happen until the temperature is equal
to the liquidus temperature at 1800o. At this point crystals of forsterite (Fo) begin to
precipitate out of the liquid. As the temperature is further lowered, the composition of the
liquid will change along the liquidus toward the peritectic (P), and the crystals forming
from the liquid will always be pure Fo until P is reached.

At the temperature of the peritectic, about 1580o, note that three phases must be in
equilibrium, Fo, liquid, and enstatite (En). At this point some of the crystals of Fo react
with the liquid to produce crystals of En. The reaction that takes place can be written as
follows:

Mg2SiO4 + SiO2 = 2MgSiO3

Fo + liq = 2En
(Where SiO2 in the reaction refers to the component of SiO2 in liquid with composition
P).

After all of the liquid is consumed by this reaction, only crystals of Fo and En will
remain. The proportions of Fo and En in the final crystalline product can be found by
applying the lever rule.

%Fo crystals = [d/(c + d)] x 100

%En crystals = [c/(c + d)] x 100

At any intermediate stage in the process, such as at 1700o the proportion of all phases
present (Fo and liquid in this case) can similarly be found by applying the lever rule.

at 1700oC

%Fo crystals = [b/(a + b)] x 100

%liquid = [a/(a + b)] x 100

Note that melting of composition X is exactly the reverse of crystallization. Mixture X
will begin to melt at the peritectic temperature. At this point En will melt to crystals of Fo
plus liquid (incongruent melting). As soon as all of the En crystals have been consumed
by this reaction, the temperature can be increased until it reaches 1800o at which point all
of the Fo crystals will have been consumed and the only phase left will be liquid with a
composition of the starting material.

Crystallization of Composition Y

Composition Y is equivalent to pure En. Thus only En may appear in the final crystalline
product if perfect equilibrium is maintained.

If composition Y is cooled from an all liquid state it first begins to crystallize at about
1650o. At 1650o crystals of Fo will begin to precipitate from the liquid. This will continue
with further cooling until the temperature of the peritectic is reached. In this interval, the
composition of the liquid must become more enriched in SiO2 and will thus change along
the liquidus until it has the composition of the peritectic, P. At the peritectic temperature
(1580o) all of the remaining liquid will react with all of the previously precipitated Fo to
produce crystals of En. The temperature will remain constant until this reaction has gone
to completion, after which the only phase present will be pure En.

Thus, it can be seen that enstatite melts incongruently. If pure enstatite is heated to a
temperature of 1580o it melts to Fo plus liquid.

Crystallization of Composition Z

Since composition Z lies between En and SiO2, it must end up with crystals of En and Qz
(Quartz). If such a composition were cooled from some high temperature where it is in
the all liquid state, it would remain all liquid until it reached the liquidus temperature at
about 1600o. At this temperature crystals of Fo would begin to precipitate and the
composition of the liquid would begin to change along the liquidus toward the peritectic,
P. At P, all of the Fo previously precipitated would react with the liquid to produce
crystals of En. After this reaction has run to completion, and all of the previously
precipitated Fo is consumed, there would still remain some liquid. With decreasing
temperature, more crystals of En would form, and the liquid composition would change
along the liquidus toward the eutectic, E. At E crystals of Qz would begin to form, the
temperature would remain constant until all of the liquid was used up, leaving crystals of
Qz and En as the final solid. Note that because composition Z lies very close to the
composition of pure En, the final crystalline product would consist mostly of En with a
very small amount of Qz.

For all compositions between P and 100% SiO2 the system would behave in an identical
fashion to the simple Eutectic system discussed previously.
 Fractional Crystallization in the System

Up to this point we have always been discussing the case of equilibrium crystallization.
That is all solids remain in contact with the liquid until any reaction that takes place has
run to completion. As is often the case in natural systems crystals can somehow become
separated from the system so that they will not react at reaction points such as P. This is
the case of fractional crystallization. Under fractional crystallization conditions the
cooling and crystallization histories will be drastically different. In particular, the rule
that the final composition must equal the initial composition will not be followed.

As an example of this phenomena we will examine the fractional crystallization of

composition X. Furthermore, we will look at the case of perfect fractional crystallization.
During perfect fractional crystallization of composition X all of the Fo that is precipitated
will be somehow removed from the system. (In nature this can occur by crystals sinking
to the bottom of the liquid due to the fact that crystals generally tend to be more dense
than liquids.) Note that if only some of the crystals are removed from the liquid we will
have a case intermediate between perfect fractional crystallization and equilibrium
crystallization.

Cooling a liquid of composition X to the liquidus at 1800o will cause Fo to precipitate as

before. With further cooling the liquid composition will change along the liquidus and
more Fo will be precipitated. In this case, however, all of the Fo will be removed from
the system as it crystallizes. Since the Fo is no longer present, the composition of the
system will have the composition of the liquid (the Fo removed can no longer contribute
to the composition of the system). Therefore, when the temperature reaches the peritectic
temperature, 1580o, there will be no Fo available to react with the liquid, and the liquid
(and system) will have a composition, P. Thus the liquid will now precipitate crystals of
En and continue cooling to the eutectic, E, where crystals of Qz will form. The final
crystalline product will consist of Qz and En.

Compare this case with the previously discussed case of equilibrium crystallization of
composition X. Note that under equilibrium conditions the final crystalline product of
composition X contained crystals of Fo and En, while in the fractional crystallization case
the final product contains En and Qz. Thus fractional crystallization has allowed an
originally Fo rich composition to produce an SiO2 rich liquid and Qz appears in the final
crystalline product.

If you go back and look at simple eutectic systems, or look at fractional crystallization of
composition Z in the more complex system, you should be able to see that fractional
crystallization will have no effect on the phases produced in the final crystalline product,
but will only change the proportions of the phases produced. Fractional crystallization is
only effective in producing a different final phase assemblage if there is a reaction
relationship of one of the phases to the liquid.