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.

Products
Raw Separation Chemical Separation
material Process process Process 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 masssa

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
 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
 Zat sisa hasil
Kom- Simbol Mula-mula Perubah-
reaksi
Ponen an

A A
B B
C C
D D
Inert I
________ ________
 STRATEGI UNTUK MENGANALISIS MASALAH
KESETIMBANGAN MATERI ((NERACA MASSA)
( Ann Landers : Masalah yang dikenali adalah masalah yang setengah terpecahkan)

1. Membaca masalah dan menjelaskan apa yang akan dikerjakan

2. Menggambar sketsa proses; mendifinisikan system dengan batas.
3. Memberi label dengan symbol aliran dari setiap arus dan komposisi yang
berhubungan dan informasi lain yang tidak diketahui.
4. Menaruh semua nilai komposisi dan aliran arus yang diketahui,
menghitung komposisi dan aliran tambahan dari data yang diberikan jika
diperlukan.
5. Memilih sebuah basis.
6. Membuat sebuah daftar menurut symbol untuk untuk setiap nilai yang
tidak diketahui dari aliran arus dan komposisi.
7. Menulis nama-nama dari kumpulan kesetimbangan yang tepat yang akan
dipecahkan; tulis masing-masing kesetimbangan dengan jenis
kesetimbangan yang tertulis didekatnya.
8. Menghitung jumlah kesetimbangan independent yang dapat ditulis
9. Menyelesaikan persamaan-persamaan tersebut. Setiap perhitungan
harus dibuat pada basi yang konsisten.
10. 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 product
Reactor
P1 mols C3H8 Q1 mols C3H8
P2 mols C3H6 Q2 mols C3H6
P3 mols H2 Q3 mols H2

Qr1 mols C3H8

Qr2 mols C3H6
 Typical simple flowsheet
arrangement

Recycle of unreacted material

Separation &
reactor purification
product
Fresh feed
(reactants, solvents,
reagents, catalysts etc)

waste 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
A+B
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 (ΔH +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 (ΔH -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 (ΔH +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 (ΔH -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.
Boyle’s Law, Charles’ Law, Avogadro’s 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
 Boyle’s 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
 Boyle’s 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.
 Avogadro’s Law
• Relationship between quantity of gas and volume established
by Gay-Lussac (balloon science!) and Avogadro in the 19th
Century.
Result was Avogadro’s 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 (Avogadro’s number, NA)
Avogadro’s 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 = Avogadro’s
number of objects
 Putting it all together
1
V  , V  T, V  n Boyle, Charles, Avogadro
P
nT
V Combine
P
 nT  Call proportionality constant R
V  R  (gas constant)
 P 
PV  nRT 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
m3(=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 = (760 mm Hg) (22.4 L)

nT (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 23°C,
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 = 23°C + 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 x 32.0 g O2 = 1.43 g/L

1L 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 20°C?
PV = nRT P = 300 kPa, V = 3.1 L, T = 293 K
(300 kPa)(3.1 L) = n (8.31 kPa•L/K•mol)(293 K)
(300 kPa)(3.1 L)
= n = 0.38 mol
(8.31 kPa•L/K•mol)(293 K)
How many grams of O2 are in a 315 mL container
that has a pressure of 12 atm at 25°C?
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 kPa•L/K•mol)(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
31oC?
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. a) Calculate the volume of 4.50 mol of SO2(g)
measured at STP.
b) What volume would this occupy at 25°C and
150 kPa? (solve this 2 ways)
5. How many moles of CO2(g) is in a 5.6 L sample of
CO2 measured at STP?
6. How many grams of Cl2(g) can be stored in a 10.0
L container at 1000 kPa and 30°C?
7. At 150°C and 100 kPa, 1.00 L of a compound has
a mass of 2.506 g. Calculate its molar mass.
8. 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 P= 8 psi P= 9 psi

O2 (g) N2 (g) 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)?
P

•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?
Dalton’s 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 2 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 Partial pressure (STP)

78.08% N2 593.4 mmHg
20.95% O2 159.2 mmHg
0.94% Ar 7.1 mmHg
0.03% CO2 0.2 mmHg
PAIR = PN + PO + PAr + PCO = 760 mmHg
2 2 2
 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.
k
mi m m   mi
mf i  i 1
mm

• 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 k
y Nm  N i
Nm 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 Ru
Mm    yi M i Rm 
N m i 1 Mm
 Dalton’s 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

k
Pm   Pi Tm , Vm 
i 1
Amagat’s 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 Vi 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  yi Pm
• Partial Volume: The quantity yiVm is
called the partial volume
Vi  yiVm
• 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.
n
pTotal  p1  p2  p3  ...   pi
i 1

RT
pi  ni  
V  n
RT nTotal  n1  n2  n3  ...   ni
pTotal  nTotal 
V 
i1

pi ni (RT V ) ni
   Xi
pTotal nTotal(RT V ) nTotal
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 masing-
masing 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 At 0 C
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
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

2
nRT n
P  a 
V  nb V 
Van der Waals Equation (1873)
2
RT a nRT n
p  2 p  a 
Vm  b Vm V  nb V 
a reflects how strongly molecules attract each other
b corrects for the molecule’s size
 Van der Waal’s 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 Peng-Robinson
RT A RT 
p  1/ 2 p 
Vm  B T Vm (Vm  B) 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
Z  1  B2 P ( P) P  B3P ( P) P 2  ...
RT
PV B2V (T ) B3V (T )
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 kPa•L/K•mol)(273 K)
(101.325 kPa)(5.6 L)
= n = 0.25 mol
(8.31 kPa•L/K•mol)(273 K)

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 kPa•L/K•mol)(273 K)
(4.50 mol)(8.31 kPa•L/K•mol)(273 K)
V= = 100.8 L
(101.3 kPa)
4. b) Volume at 25°C and 150 kPa (two ways)?
Given: P = 150 kPa, n = 4.50 mol, T = 298 K
(4.50 mol)(8.31 kPa•L/K•mol)(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 30°C?
PV = nRT P= 1000 kPa, V= 10.0 L, T= 303 K
(1000 kPa)(10.0 L) = n = 3.97 mol
(8.31 kPa•L/K•mol)(303 K) 3.97 mol x 70.9
g/mol = 282 g
7. At 150°C 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 kPa•L/K•mol)(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 kPa•L/K•mol)(298 K)
g/mol = 0.081 g / 0.00396 mol = 20.47 g/mol
It’s 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