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Teknik kimia

Bahasa Inggris : chemical engineering

Ilmu teknik atau rekayasa yang


mempelajari pemrosesan bahan
mentah menjadi barang jadi
Aplikasi :
1. perancangan dan pemeliharaan
proses kimia
2. peralatan proses

Teknik Kimia berhubungan dengan :


a. Produksi bahan kimia baik di skala besar maupun kecil.
b. Membuat produk berskala besar (pabrik), berbeda dengan skala lab.
c. merubah bahan baku menjadi produk bernilai ekonomi lebih tinggi.
d. Sektor : bahan kimia sampai energi, makanan dan minuman,
obatobatan.
e. Produk, yang dibuat melalui perubahan kimia (reaksi) atau/dan fisis
(pemisahan).
f. Proses Industri kimia, seperti industri: pupuk, kimia murni, cat, zat
warna, tinta, petrokimia, plastik, resin, sabun, deterjen, parfum,
kosmetik, lemak dan minyak nabati, katalis, gas, minyak bumi,
polimer, kertas, tekstil, makanan dan minuman, bioteknologi, dll.

What is Chemical Reaction Engineering


(CRE) ?
Understanding how chemical reactors work lies at the heart of
almost every chemical processing operation.
Raw
material

Separation
Process

Chemical
process

Separation
Process

Products
By products

Design of the reactor is no routine matter, and many alternatives can


be proposed for a process. Reactor design uses information,
knowledge and experience from a variety of areas thermodynamics, chemical kinetics, fluid mechanics, heat and mass
transfer, and economics.
CRE is the synthesis of all these factors with the aim of properly
designing and understanding the chemical reactor.

Di dalam proses dan peralatan di industri,


rangkaian peralatan menyangkut kedua
jenis proses itu, yaitu :
1. unit operation ( satuan operasi) : unit
dengan perubahan fisis atau seringkali
disebut Operasi Teknik Kimia.
2. unit processes (satuan proses) : unit
dengan reaksi kimia.

Unit operation meliputi :


a. transportasi fluida (perpindahan pada proses
alir),
b. perpindahan panas dalam alat penukar panas
( heat exchanger),
c. separator,
padat-padat : screening.
Padat-cair : sedimentasi, filtrasi,
Cair gas : absorpsi, stripper, distilasi,
evaporasi.
Cair-cair : ekstraksi cair-cair, dekantasi, dll.
d. pencampuran

Unit Processes meliputi :


a. pembakaran bahan bakar dalam burner,
furnace.
b. Reaksi kimia dalam reaktor.
c. Fermentasi.

Ilmu-ilmu yang menjadi dasar dalam


teknik kimia, antara lain adalah:
1. Neraca massa
2. Neraca energi
3. Peristiwa perpindahan massa , energi ,
momentum
4. Reaksi kimia
5. Termokimia
6. Termodinamika
7. material atau bahan , ekonomi dan
manajemen .

Book
David M Himmelblau Prinsip Dasar dan
Kalkulasi dalam Teknik Kimia, jilid 1 dan 2
Olaf A Hougen dkk. Chemical Process
Principles, Part one Material and Energy
Balance.
Richard M Felder dkk. Elementary
Principles of Chemical Processes .
Nicholas P Chopey, Handbook of
Chemical Engineering Calculations .

ASAS TEKNIK KIMIA


Mol :
jumlah tertentu dari molekul, elektron, atau partikel spesifik lainnya
Densitas :
Ratio massa persatuan volum
Berat jenis ( spesific gravity )( ref : air )
Ratio densitas yang ditanyakan terhadap densitas air.
Volum spesifik :
Volum persatuan massa
Fraksi mol :
Mol zat tertentu dibagi dengan jmlah total mol yang ada

Tekanan gauge + tekanan


barometrik = tekanan absolut
Tekanan :
gaya persatuan luas
Tekanan gauge :
tekanan yang terbaca pada manometer
Tekanan barometrik :
pembacaan tekanan atmosfer

Manometer adalah alat ukur tekanan dan manometer


tertua adalah manometer kolom cairan.
Manometer adalah alat yang digunakan secara luas pada
audit energi untuk mengukur perbedaan tekanan di dua titik
yang berlawanan. Jenis manometer tertua adalah
manometer kolom cairan. Versi manometer sederhana
kolom cairan adalah bentuk pipa U (lihat Gambar 4-4) yang
diisi cairan setengahnya (biasanya berisi minyak, air atau
air raksa) dimana pengukuran dilakukan pada satu sisi
pipa, sementara tekanan (yang mungkin terjadi karena
atmosfir) diterapkan pada tabung yang lainnya. Perbedaan
ketinggian cairan memperlihatkan tekanan yang
diterapkan.

Apa bedanya PSIA, PSIG dan Vacuum dalam


satuan pressure (Tekanan udara)?
PSIA merupakan tekanan absolut. Yang berarti merupakan besaran
tekanan total sebenarnya. Besarnya merupakan penjumlahan dari pressure
gauge dan tekanan atmosphere. Berharga selalu positif. Jika dibawah Patm,
maka PSIA merupakan tekanan vakum.
PSIA = PSIG + Patm, P atm biasanya 1 Atm
PSIG, merupakan tekanan gauge. Tekanan ini mengukur tekanan statis
suatu sistem. Besarnya merupakan besaran ukuran. Umumnya alat ukurnya
adalah pressure gauge. Angka yang ditunjukkan pressure gauge
merupakan PSIG
Vaccum atau tekanan vakum, dalam konsep termodinamika merupakan
besaran tekanan absolut yang dibawah tekanan atmosfer, PSIA < Patm.
Jika memakai tekanan gauge maka besarnya tekanan vaccum akan negatif,
paling minimum di negatif(-) Patm, tekanan lingkungan/atmosfer.

Stoikiometri
Stoikiometri berasal dari kata Yunani,
STOICHEION yang berarti unsur dan METRIA
yang berarti ilmu pengukuran . Kemudian
difinisi diperluas sebagai berikut :
1. Proses membuat suatu perhitungan yang
didasarkan pada rumus-rumus dan
persamaan- persamaan berimbang.
2. Ilmu yang mengukur berapa banyak jumlah zat
yang dapat dihasilkan dari sejumlah zat
tertentu lainnya.

Reaktan pembatas ( limiting reactan )


reaktan yang ada dalam jumlah stoikiometri
terkecil ( reaktan yang akan hilang pertama
kali ).( lebih dari dua reaktan harus
menggunakan satu sebagai reaktan pembatas )
Reaktan berlebih ( excess reactan )
reaktan yang terdapat lebih dari pada reaktan
pembatas.( meski jika hanya sebagian dari
reaktan pembatas yang sebenarnya bereaksi,
kuantitas yang dibutuhkan dan kuantitas yang
berlebih didasarkan pada jumlah seluruh
reaktan pembatas seolah-olah reaktan tersebut
telah bereaksi secara sempurna )

% kelebihan = kelebihan mol : ( mol yang dibutuhkan untuk


bereaksi dengan reaktan pembatas ). 100

Konversi ( conversion ) :
fraksi dari masukkan atau beberapa materi kunci
dalam masukkan yang diubah menjadi produk :
% konversi A = mol (massa) A yang bereaksi : mol ( massa ) A yang dimasukkan

Yield ( reaktan tunggal dan produk ) :


Mol ( massa ) produk akhir dibagi dengan mol
( massa ) reaktan awal yang dimasukkan

Daur ulang ( reaksi kimia )


Konversi fraksi keseluruhan ( overall
fraction conversion ) :
= ( massa ( mol ) reaktan dalam fresh feed massa ( mol ) reaktan
dalam keluaran dari proses keseluruhan ) : massa ( mol ) reaktan
dalam fresh feed

Konversi jalan tunggal ( Single pass or


once through conversion ) :
= ( massa ( mol ) reaktan yang dimasukkan ke dalam reaktor massa
( mol ) reaktan yang terdapat dalam reaktor ) : massa ( mol ) reaktan
yang dimasukkan ke dalam reaktor

Kesetimbangan materi untuk reaktor


( masukkan melalui batasan sistem )
( keluaran melalui batasan sistem ) +
( generasi dalam sistem )
( konsumsi dalam sistem ) = akumulasi

Kom- Simbol Mula-mula Perubahan


Ponen
A
B
C
D
Inert

Zat sisa hasil


reaksi

A
B
C
D
I
________

________

STRATEGI UNTUK MENGANALISIS MASALAH


KESETIMBANGAN MATERI ((NERACA MASSA)
( Ann Landers : Masalah yang dikenali adalah masalah yang setengah terpecahkan)

1.
2.
3.
4.
5.
6.
7.
8.
9.
10.

Membaca masalah dan menjelaskan apa yang akan dikerjakan


Menggambar sketsa proses; mendifinisikan system dengan batas.
Memberi label dengan symbol aliran dari setiap arus dan komposisi yang
berhubungan dan informasi lain yang tidak diketahui.
Menaruh semua nilai komposisi dan aliran arus yang diketahui,
menghitung komposisi dan aliran tambahan dari data yang diberikan jika
diperlukan.
Memilih sebuah basis.
Membuat sebuah daftar menurut symbol untuk untuk setiap nilai yang
tidak diketahui dari aliran arus dan komposisi.
Menulis nama-nama dari kumpulan kesetimbangan yang tepat yang akan
dipecahkan; tulis masing-masing kesetimbangan dengan jenis
kesetimbangan yang tertulis didekatnya.
Menghitung jumlah kesetimbangan independent yang dapat ditulis
Menyelesaikan persamaan-persamaan tersebut. Setiap perhitungan
harus dibuat pada basi yang konsisten.
Memeriksa jawaban, ke dalam kesetimbangan materi redundant
( berlebih ), apakah jawaban masuk akal ?.

Material Balance Calculations


The procedure.
Draw a flowchart
Choose basis of calculations
Label unknown stream variables on the
flowchart
Convert known stream volumes or
volumetric flow rates to mass or molar basis
using densities or gas laws
Convert all mass and molar unit quantities to
one basis

Material Balance Calculations


The procedure.
If any given information has not been
used in labeling the flowchart,
translate it into equations in terms of
the unknown variables
Write material balance equations in an
order such that those involve the
fewest unknowns are written first
Solve the equations

Flowcharts
A flowchart is drawn using boxes or other symbols
to represent the process units and lines with arrows
to represent inputs and outputs
It must be fully labeled with values of known and
unknown process variables at the locations of the
streams
100 + Qr1 mols C3H8
Qr2 mols C3H6
Fresh feed
100 mols C3H8

separator

Reactor
P1 mols C3H8
P2 mols C3H6
P3 mols H2
Qr1 mols C3H8
Qr2 mols C3H6

product
Q1 mols C3H8
Q2 mols C3H6
Q3 mols H2

Typical simple flowsheet


arrangement
Recycle of unreacted material

Separation &
purification

reactor

Fresh feed
(reactants, solvents,
reagents, catalysts etc)

waste

product

Byproducts/coproducts

Recycle and Bypass


Reasons for Recycle

Recovering and reusing unconsumed reactants


Recovery of catalyst (catalyst : expensive)
Dilution of process stream
Control of process variables
Circulation of working fluid
A+ B C

A+ B

A
B
C
Recycle unused reactants (A,B)

Recovery of catalyst.
Many reactors use catalysts to increase
the rate of the reaction. Catalysts are
usually expensive, and the processes
generally include provisions for
recovering them from the product stream
and recycling them to the reactor. They
may be recovered with the unconsumed
reactants or recovered separately in
special facilities designed for this
purpose

Dilution of a process stream.


Suppose a slurry (a suspension of
solids in a liquid) is fed to a filter. If
the concentration of solids in the
slurry is too high, the slurry is
difficult to handle and the filter will
not operate properly. Rather than
diluting the feed with fresh liquid, a
portion of the filtrate can be recycled
to dilute the feed to the desired solids
concentration.

Control of a process variable.


Suppose a reaction release an extremely
large amount of heat, making the reactor
difficult and expensive to control. The rate of
heat generation can be reduced by lowering
the reactant concentration, which can in turn
be accomplished by recycling a portion of
the reactor effluent to the inlet. In addition to
acting as a diluent for the reactants, the
recycled material also serves as a
capacitance for the heat released: the greater
the mass of the reaction mixture, the lower
the temperature to which that mass will be
raised by a fixed amount of heat.

Circulation of a working fluid


The most common example of this
application is the refrigeration cycle
used in household refrigerators and air
conditions. In these devices, a single
material is reused indefinitely, with only
small makeup quantities being added
to the system to replenish working fluid
that may be lost through leaks.

particularly useful for reactors, where they allow better


control of reactor selectivity when multiple reactions occur.

recycle ratio
dividing the mass flow of the recycle
stream by the mass flow of the "fresh
feed" entering the system
the industrial world, recycle ratios have
important consequences for system
performance and operating costs.

Bypass
A fraction of the feed is diverted around
the process unit and combined with the
output stream.
Controlling properties and compositions of
product stream

Solving Recycle and Bypass Problems


methods for solving recycle and bypass
problems are basically the same
steady state, there is no buildup or depletion of
material within the system or recycle stream of a
properly designed and operated process.
Note the distinction between the fresh feed
to the process and the feed to the reactor,
which is the sum of the fresh feed and
recycle stream.

When solving, you can write balances (total


material or component) around:

the entire process structure


the mixing point
the splitter
the processing unit (inside the recycle/bypass)
Only three of these will be independent
(the fourth is a linear combination).

Kiat penyelesaian :
1. Pilih yang mempunyai data terbanyak ( sistem/sub sistem )
2. Jangan pilih yang meninggalkan variabel pada sub/sistem berikutnya

GAS, UAP, CAIRAN DAN PADATAN


The particle model of a Gas

A gas has no fixed shape or volume, but always spreads out to


fill any container.
There are almost no forces of attraction between the particles so
they are completely free of each other.
The particles are widely spaced and scattered at random
throughout the container so there is no order in the system.
The particles move rapidly in all directions, frequently colliding
with each other and the side of the container.
With increase in temperature, the particles move faster as they
gain kinetic energy.

The particle model of a Liquid

A liquid has a fixed volume at a given temperature but its shape


is that of the container which holds the liquid.
There are much greater forces of attraction between the particles
in a liquid compared to gases, but not quite as much as in solids.
Particles quite close together but still arranged at random
throughout the container, there is a little close range order as you
can get clumps of particles clinging together temporarily.
Particles moving rapidly in all directions but more frequently
collisions with each other than in gases due to shorter distances
between particles.
With increase in temperature, the particles move faster as they
gain kinetic energy, so increased collision rates, increased collision
energy and increased rate of diffusion.

The particle model of a Solid

A solid has a fixed volume and shape at a particular


temperature unless physically subjected to some force.
The greatest forces of attraction are between the particles in a
solid and they pack together as tightly as possible in a neat
and ordered arrangement.
The particles are too strongly held together to allow movement
from place to place but the particles vibrate about their position
in the structure.
With increase in temperature, the particles vibrate faster and
more strongly as they gain kinetic energy.

Changes of State for gas <=> liquid <=> solid

Evaporation and Boiling (liquid to gas)

On heating particles gain kinetic energy and move faster.


In evaporation* and boiling the highest kinetic energy molecules can escape
from the attractive forces of the other liquid particles.
The particles lose any order and become completely free to form a gas or vapour.
Energy is needed to overcome the attractive forces in the liquid and is taken in
from the surroundings.
This means heat is taken in, so evaporation and boiling are endothermic
processes (H +ve).
If the temperature is high enough boiling takes place.
Boiling is rapid evaporation anywhere in the bulk liquid and at a fixed
temperature called the boiling point and requires continuous addition of heat.
* Evaporation takes place more slowly than boiling at any temperature between the
melting point and boiling point, and only from the surface, and results in the
liquid becoming cooler due to loss of higher kinetic energy particles.

Condensing (gas to liquid)


On cooling, gas particles lose kinetic energy
and eventually become attracted together to form
a liquid.
There is an increase in order as the particles
are much closer together and can form clumps
of molecules.
The process requires heat to be lost to the
surroundings i.e. heat given out, so
condensation is exothermic (H -ve).
This is why steam has such a scalding effect, its not
just hot, but you get extra heat transfer to your skin
due to the exothermic condensation on your surface!

Distillation
Simple and fractional distillation involve
the processes of boiling and
condensation and are described on the
Elements, Compounds and Mixtures

Melting (solid to liquid)

When a solid is heated the particles vibrate more strongly as


they gain kinetic energy and the particle attractive forces are
weakened.
Eventually, at the melting point, the attractive forces are too weak
to hold the particles in the structure together in an ordered way and
so the solid melts.
The particles become free to move around and lose their ordered
arrangement.
Energy is needed to overcome the attractive forces and give the
particles increased kinetic energy of vibration.
So heat is taken in from the surroundings and melting is an
endothermic process (H +ve).

Freezing (liquid to solid)


On cooling, liquid particles lose kinetic
energy and so can become more strongly
attracted to each other.
Eventually at the freezing point the forces of
attraction are sufficient to remove any remaining
freedom and the particles come together to form
the ordered solid arrangement.
Since heat must be removed to the
surroundings, so strange as it may seem,
freezing is an exothermic process (H -ve).

Cooling and Heating Curvesand the comparative


energy changes of state changes
gas <=> liquid <=> solid
Cooling curve
A cooling curve summarises the changes:
gas ==> liquid ==> solid

Heating curve:
A heating curve summarises the changes:
solid ==> liquid ==> gas

Sublimation

This is when a solid, on heating, directly


changes into a gas without melting, AND
the gas on cooling re-forms a solid
directly without condensing to a liquid.
They usually involve just a physical
change BUT its not always that simple!

Dissolving solids, solutions and


miscible/immiscible liquids
+

In general: solute + solvent ==> solution


The solid loses all its regular structure and the individual solid particles (molecules or
ions) are now completely free from each other and randomly mix with the original
liquid particles, and all particles can move around at random.
This describes salt dissolving in water, sugar dissolving in tea or wax dissolving in a
hydrocarbon solvent like white spirit.
It does not usually involve a chemical reaction, so it is generally an example of a
physical change.
Whatever the changes in volume of the solid + liquid, compared to the final solution,
the Law of Conservation of Mass applies.
You cannot make mass or lose mass, but just change it into another form.

If two liquids completely mix


+

called miscible liquids because they fully


dissolve in each other

the two liquids do NOT mix

form two separate layers and are known


as immiscible liquids

Gas Laws
A large number of experiments have determined that 4
variables are sufficient to define the physical condition (or
state) of a gas: the gas laws.
Boyles Law, Charles Law, Avogadros hypothesis
Robert Boyle: (1627-1691) the first modern chemist, known
as the father of chemistry.
His 1661 book The Sceptical Chymist marks the introduction
of the scientific method, a definition of elements and
compounds and a refutation of alchemy and magic potions.
Boyle biography

Boyles Law
Boyle investigated the variation of the volume occupied by
a gas as the pressure exerted upon it was altered and
noted that the volume of a fixed quantity of gas, at constant
temperature is inversely proportional to the pressure

1
V constant or PV constant
p

Boyles Law
(valid at low pressures)

The pressure-volume dependence


of a fixed amount of perfect gas at
different temperatures. Each curve
is a hyperbola (pV = constant) and
is called an isotherm.

Charles Law

A century later, a French scientist, Jacques Charles discovered


that the volume of a fixed amount of gas, as constant pressure,
is proportional to the absolute temperature. Cool a balloon, or a
sealed plastic bottle, to verify this!

V
V constant T or constant
T
It was recognised (by William
Thomson, Lord Kelvin, a Belfast
born physicist) that if the graph was
extrapolated to zero volume, an
absolute zero of -273.15 oC is
obtained.

Charles Law

The variation of the volume of a fixed


amount of gas with the temperature
constant. Note that in each case they
extrapolate to zero volume at
-273.15 C. The lines are isotherms.

Avogadros Law
Relationship between quantity of gas and volume established by
Gay-Lussac (balloon science!) and Avogadro in the 19 th Century.
Result was Avogadros hypothesis: equal volumes of gases at the
same temperature and pressure contain equal numbers of
molecules

Experiments show that 22.4L of gas at 0oC and 1atm


(STP), or 24.8L of gas at 298.15 K and 1 bar (SATP),
contains 6.022 x 1023 molecules (Avogadros number, NA)
Avogadros law: volume of gas at constant temperature and
pressure is proportional to the number of moles of gas (n)

V constant n

Remember:
1 mole = Avogadros
number of objects

Putting it all together


1
V , V T, V n
P
nT
V
P
nT
V R

P
PV nRT

Boyle, Charles, Avogadro

Combine

Call proportionality constant R


(gas constant)

Ideal Gas Equation

An ideal gas exhibits certain theoretical


properties. Specifically, an ideal gas
Obeys all of the gas laws under all conditions.
Does not condense into a liquid when cooled.
Shows perfectly straight lines when its V and T &
P and T relationships are plotted on a graph.
In reality, there are no gases that fit this definition
perfectly. We assume that gases are ideal to
simplify our calculations.

A note on units and dimensional analysis


SI unit for R is J/mol.K or m3.Pa/mol.K (R=8.315 of these units)
Need to use the units of Pa for pressure and m 3(=1000L) for volume in any
calculation.
Alternatively you can use units of kPa and L.
If you wish to use atm and L (as in USA and Textbook) R=0.0826
L.atm/mol/K.
Always use absolute temperature scale (K)

Solution
What is the value of R when the STP value
for P is 760 mmHg?
R

PV

nT

= (760 mm Hg) (22.4 L)

(1mol)

(273K)

= 62.4 L-mm Hg
mol-K

Learning Check
Dinitrogen monoxide (N2O), laughing gas,
is used by dentists as an anesthetic. If 2.86
mol of gas occupies a 20.0 L tank at 23C,
what is the pressure (mmHg) in the tank in
the dentist office?

Solution
Set up data for 3 of the 4 gas variables
Adjust to match the units of R
V = 20.0 L

20.0 L

T = 23C + 273 - 296 K


n = 2.86 mol- 2.86 mol
P =

Rearrange ideal gas law for unknown P


P = nRT
V
Substitute values of n, R, T and V and solve
for P
P = (2.86 mol)(62.4L-mmHg)(296 K)
(20.0 L)
(K-mol)
= 2.64 x 103 mm Hg

Density of a Gas
Calculate the density in g/L of O2 gas at STP.
From STP, we know the P and T.
P = 1.00 atm

T = 273 K

Rearrange the ideal gas equation for moles/L


PV = nRT
PV = nRT
P = n
RTV
RTV
RT
V

Substitute
(1.00 atm ) mol-K

0.0446 mol O2/L

(0.0821 L-atm) (273 K)


Change moles/L to g/L
0.0446 mol O2

1L

32.0 g O2

1.43 g/L

1 mol O2

Therefore the density of O2 gas at STP is


1.43 grams per liter

Sample problems

How many moles of H2 is in a 3.1 L sample of


H2 measured at 300 kPa and 20C?
PV = nRT P = 300 kPa, V = 3.1 L, T = 293 K
(300 kPa)(3.1 L) = n (8.31 kPaL/Kmol)(293 K)
(300 kPa)(3.1 L)
= n = 0.38 mol
(8.31 kPaL/Kmol)(293 K)
How many grams of O2 are in a 315 mL container
that has a pressure of 12 atm at 25C?
PV = nRT P= 1215.9 kPa, V= 0.315 L, T= 298 K
(1215.9 kPa)(0.315 L) = n = 0.1547 mol
(8.31 kPaL/Kmol)(298 K)
0.1547 mol x 32
g/mol = 4.95 g

Exercises
1. What is the volume of 1 mole of an ideal gas
under standard temperature and pressure
(STP)?
2. How many moles (g) of CO2 is liberated into a
250mL flask when a pressure of 1.3atm is
found upon heating calcium carbonate to 31 oC?
3. If a metal cylinder holds 50L of oxygen at
18.5atm and 21oC, what volume will the gas
occupy at 1atm and same T?

4.

5.
6.
7.
8.

a) Calculate the volume of 4.50 mol of SO2(g)


measured at STP.
b) What volume would this occupy at 25C and
150 kPa? (solve this 2 ways)
How many moles of CO2(g) is in a 5.6 L sample of
CO2 measured at STP?
How many grams of Cl2(g) can be stored in a 10.0
L container at 1000 kPa and 30C?
At 150C and 100 kPa, 1.00 L of a compound has
a mass of 2.506 g. Calculate its molar mass.
98 mL of an unknown gas weighs 0.087 g at
SATP. Calculate the molar mass of the gas. Can
you determine the identity of this unknown gas?

So far: pure gases


Many gases are actually mixtures of two
or more gases:
air: O2, N2 , H2O, etc

How do mixtures of gases behave?

Gas Mixtures--Partial Pressure

Gas Mixtures--Partial Pressure

P= 6 psi

O2 (g)

P= 8 psi

N2 (g)

P= 9 psi

CO2 (g)

Gas Mixtures--Partial Pressure


What happens when you put all three samples of gas together into one container (the same size container as each was in alone)?

The gases form a homogeneous mixture.


The pressure in the container increases, V and T stay the same
How do you know what the new pressure will be?

Daltons Law of Partial Pressure


Pressure exerted by mixed gas is
sum of the partial pressures

p = pA+pB+

Recall mole fraction


xJ=nJ/n

n = nA+nB+

Partial pressure
pJ= xJp

Gas Mixtures--Partial Pressure

Ptotal = PO + PN + PCO
2

So for this example:


Ptotal = 6 psi + 8 psi + 9 psi
= 23 psi

Partial Pressure
In other words, at constant T and V,
Ptotal depends only on the total number of
moles of gas present
Ptotal is independent of the type (or types) of
gases present.

Partial Pressure
The partial pressure of a gas in a mixture can be
found:
PA = XA Ptotal

where PA = partial pressure of gas A


XA = mole fraction of gas A
Ptotal = total pressure of mixture

Partial Pressure Calculation


A mixture of gases contains 0.51 mol N2, 0.28 mol H2, and
0.52 mol NH3. If the total pressure of the mixture is 2.35
atm, what is the partial pressure of H2?

PH2 = XH2 Ptotal


0.28 mol
XH2=
= 0.21
0.28 mol + 0.51 mol + 0.52 mol
PH2 = 0.21 x 2.35 = 0.50 atm

Partial Pressure-Mole Fraction


When describing a mixture of gases, it is useful
to know the relative amount of each type of gas.
Mole fraction (X): a dimensionless number that
expresses the ratio of the number of moles of
one component compared to the total number of
moles in a mixture.

Daltons Law of Partial Pressures


The % of gases in air
78.08% N2

Partial pressure (STP)

593.4 mmHg

20.95% O2 159.2 mmHg


0.94% Ar
0.03% CO2

7.1 mmHg
0.2 mmHg

PAIR = PN + PO + PAr + PCO = 760 mmHg


2

Total Pressure

760

mm Hg

Learning Check
A.If the atmospheric pressure today is 745

mm Hg, what is the partial pressure (mm


Hg) of O2 in the air?
1) 35.6

2) 156

3) 760

B. At an atmospheric pressure of 714, what is


the partial pressure (mm Hg) N2 in the air?
1) 557

2) 9.14

3) 0.109

Solution
A.If the atmospheric pressure today is 745

mm Hg, what is the partial pressure (mm


Hg) of O2 in the air?
2) 156
B. At an atmospheric pressure of 714, what is
the partial pressure (mm Hg) N2 in the air?
1) 557

Gas Mixtures

Composition of a Gas Mixture:


Mass and Mole Fractions
Mass Fraction (mf): The ratio of mass of a
component to the mass of the mixture is
called the mass fraction.
mi
mf i
mm

m m mi
i 1

Mole Fraction (y): The ratio of the mole


number of a component to the mole number
of the mixture is called the mole fraction.
Ni
y
Nm

Nm Ni
i 1

The mass of a substance can be


expressed in terms of the mole number N
and molar mass M of the substance as

m NM
The molar mass and the Gas constant of
a mixture can be expressed as
k
mm
Mm
yi M i
N m i 1

Ru
Rm
Mm

Daltons Law of additive


Pressures
The pressure of a gas mixture is equal to the sum of the
pressures each gas would exert if it existed alone at the
mixture temperature and volume

Pm Pi Tm , Vm
i 1

Amagats Law of additive Volume


The volume of a gas mixture is equal to
the sum of the volume each gas would
occupy if it existed alone at the mixture
temperature and pressure
k

Vm Vi Tm , Pm
i 1

P-v-T Behavior of Ideal Gas


Mixtures
For ideal gases ,the above two laws are
identical and give identical results.
Pi is called the component pressure and V i the
component volume.
The ratio Pi/Pm is called the pressure fraction
and the ratio Vi/Vm is called the volume
fraction of component i.

Ideal Gas Mixtures


Partial Pressure: The quantity yiPm is
called the partial pressure

Pi y i Pm

Partial Volume: The quantity yiVm is called


the partial volume
Vi y iVm
For ideal gas mixture, the mole fraction, the
pressure fraction and the volume fraction of a
component are identical

mixture of n gases,
partial pressure of a gas in a mixture is the
pressure it would exert if alone in the
container.

Exercise:
A gaseous mixture is made from 6.00g
oxygen and 9.00g methane placed in a
15L vessel at 0oC. What is the partial
pressure of each gas and the total
pressure in the vessel?

Contoh 1.
Dua puluh kaki kubik ( ft3 ) nitrogen pada 300
psig dan 100oF dan 30 ft3 oksigen pada 200 psig
dan 340oF dimasukkan ke dalam tangki
bervolum 15 ft3. Tangki selanjutnya didinginkan
menjadi 70oF. Hitung tekanan parsial masingmasing komponen dalam tangki tersebut.
Asumsi gas adalah ideal.
Jawab.

Persoalan dapat diselesaikan dengan


menentukan jumlah mol oksigen dan
nitrogen dan penyelesaian untuk tekanan
total pada kondisi akhir. Selanjutnya
tekanan parsial dapat dihitung dengan
menggunakan mol fraksi.

Real Gases
Due to intermolecular forces, the Ideal gas
law breaks down
Understanding deviations from ideal gas
behavior teach us about molecular
interactions
Van der Waals Eqn and Virial Expansion
Coefficients relate to energy of interaction
between molecules

Real Gases
Real gases do not completely follow the ideal
gas law.
In kinetic molecular theory, the following
assumptions are made:
gas molecules occupy no space
gas molecules have no attraction for each
other

Real Gases
Neither assumption is correct.
Real gas molecules have a finite volume.
Real gas molecules do attract each other.

Real Gases
The greatest deviation from ideal gas
behavior occurs at:
high pressure
higher density of gas molecules
Molecules are closer together so:
finite volume of gas molecules more important
attraction between molecules more important

Real Gases
In the real world, the
behavior of gases
only conforms to the
ideal-gas equation at
relatively high
temperature and low
pressure.
Curves for 1 mol of gas

Real Gases
Low temperature
Attractive forces between molecules becomes more
important.
Average kinetic energy decreases.
Gas molecules have less energy to overcome
attractive forces.

Real Gases
Even the same gas
(e.g. nitrogen) will
show wildly different
behavior under high
pressure at different
temperatures.

Compression Factor
Variation of Z with Pressure

molar volume
Z
molar volume perfect gas

pV
Z
RT
Low pressures, Z=1, all gases ideal
At high pressures, Vreal >Videal ; Z>1
repulsive forces dominate
Low pressure, Vreal <Videal, Z< 1
attractive forces dominate
Low temperatures -> molecules moving
less rapidly more influenced by
attractive forces

At 0 C

REAL GASES

Deviations from ideal gas law


WHY?
1. Molecules have volume
2. Molecules have attractive forces
(intermolecular)
1. V-nb
2. -a(n/V)2
Van der Waals Equation of State

nRT
n
P
a

V nb
V

Van der Waals Equation (1873)


RT
a
p
2
Vm b Vm

nRT
n
p
a
V nb
V

a reflects how strongly molecules attract each other


b corrects for the molecules size

Van der Waals constants


van der Waals Coefficients
Gas

a (Pa m3)

b(m3/mol)

Helium

3.46 x 10-3

23.71 x 10-6

Neon

2.12 x 10-2

17.10 x 10-6

Hydrogen

2.45 x 10-2

26.61 x 10-6

Carbon dioxide

3.96 x 10-1

42.69 x 10-6

Water vapor

5.47 x 10-1

30.52 x 10-6

a correlates with boiling point


b can be used to estimate molecular radii

Derivation of vdw Eq. State


Repulsive interactions cause molecules to behave as
impenetrable spheres
Molecules restricted to smaller volume V-nb, where nb is
volume molecules take up
Pressure depends on frequency of collisions with walls and
force of each collision both reduced by attractive forces
proportional to molar concentration (n/V)
Pressure is then reduced according to a(n/V)2

Critical Constants
The `critical isotherm', the isotherm
at the critical temperature Tc, is at
31.04 C. The critical point is
marked with a star.
Critical pressure

Pc

Critical molar volume Vc


Tc, Pc,Vc critical constants

If you compress along Tc, liquid


does not appear these highly
dense materials are called
supercritical fluids and their
properties are a subject of intense
current research

Other Equations of State


Redlich-Kwong
RT
A
p
1/ 2
Vm B T Vm (Vm B )

Peng-Robinson
p

RT

Vm Vm (Vm ) (Vm )

Both are quantitative in region where gas liquefies


Berthelot,Dieterici and others with more than ten
parameters can give good fits !!!
with seven free parameters, you can describe an
elephant

Principle of Corresponding States


All gases have the same
properties if they are
compared at corresponding
conditions
Define reduced variables
PR P / Pc , TR T / Tc ;VR V / Vc

For homework you will write


the vdw eqn in terms of the
reduced variables

Compression factor plotted


using reduced variables.
Different curves are different TR

Virial Equation of State


Most fundamental and theoretically sound
Polynomial expansion Viral Expansion

PV
1 B2 P ( P) P B3 P ( P) P 2 ...
RT

B2V (T ) B3V (T )
PV
Z
1

...
2
RT
V
V
B2V (T ) = 0 at Boyle temperature
Used to summarize P, V, T data
Also allow derivation of exact correspondence between
virial coefficients and intermolecular interactions

5. Moles of CO2 is in a 5.6 L at STP?


P=101.325 kPa, V=5.6 L, T=273 K PV = nRT
(101.3 kPa)(5.6 L) = n (8.31 kPaL/Kmol)(273 K)
(101.325 kPa)(5.6 L)
(8.31 kPaL/Kmol)(273 K)

= n = 0.25 mol

4. a) Volume of 4.50 mol of SO2 at STP.


P= 101.3 kPa, n= 4.50 mol, T= 273 K PV=nRT
(101.3 kPa)(V)=(4.5 mol)(8.31 kPaL/Kmol)(273 K)
(4.50 mol)(8.31 kPaL/Kmol)(273 K)
V=
= 100.8 L
(101.3 kPa)

4. b) Volume at 25C and 150 kPa (two ways)?


Given: P = 150 kPa, n = 4.50 mol, T = 298 K
(4.50 mol)(8.31 kPaL/Kmol)(298 K)
V=
= 74.3 L
(150 kPa)
From a): P = 101.3 kPa, V = 100.8 L, T = 273 K
Now P = 150 kPa, V = ?, T = 298 K
P1V1
P2V2
=
T1
T2
(101.3 kPa)(100 L)
(150 kPa)(V2)
=
(273 K)
(298 K)
(101.3 kPa)(100.8 L)(298 K) = 74.3 L
(V2) =
(273 K)(150 kPa)

6. How many grams of Cl2(g) can be stored in a


10.0 L container at 1000 kPa and 30C?
PV = nRT P= 1000 kPa, V= 10.0 L, T= 303 K
(1000 kPa)(10.0 L)
= n = 3.97 mol
(8.31 kPaL/Kmol)(303 K)
3.97 mol x 70.9
g/mol = 282 g
7. At 150C and 100 kPa, 1.00 L of a compound
has a mass of 2.506 g. Calculate molar mass.
PV = nRT P= 100 kPa, V= 1.00 L, T= 423 K
(100 kPa)(1.00 L)
= n = 0.02845 mol
(8.31 kPaL/Kmol)(423 K)
g/mol = 2.506 g / 0.02845 mol = 88.1 g/mol

8. 98 mL of an unknown gas weighs 0.081 g at


SATP. Calculate the molar mass.
PV = nRT P= 100 kPa, V= 0.098 L, T= 298 K
(100 kPa)(0.098 L)
= n = 0.00396 mol
(8.31 kPaL/Kmol)(298 K)
g/mol = 0.081 g / 0.00396 mol = 20.47 g/mol
Its probably neon
(neon has a molar mass of 20.18 g/mol)

( P + a / Vm2 )( Vm - b ) = R T
P = tekanan
Vm =volum molar
R = konstanta gas ideal
T = suhu