Bab 1

GAS IDEAL DAN NYATA

Susana Ristiarini, Ir., MSi

Indah Epriliati, PhD

FAKULTAS TEKNOLOGI PERTANIAN

UNIKA WIDYA MANDALA SURABAYA
2009
 Nature of matters

 quantum theory E = 0.5 h

 = frequency
 h = Planck’s constant = 6.626 x 10-34 J.s
 Matter is never still
 Motions: rotational, vibrational, translational
 Electron transition occurs: E = E upper–E lower
 Emitting/absorbing radiation
 Each element has specific radiation wavelength
Tipe-tipe gerakan:
•Rotational
•Vibrational
•Translational
•Paralel-searah
•Berlawanan arah
 THE ASSOCIATION OF ATOMS AND MOLECULES
 Chemical bond is a production of atoms/molecules
association.
 Types of chemical bonds:
 ionic bond: e.g. NaCl resulted from direct Coulombic
attraction with a force that depends on r-2 and potential
energy that depends on r-1
 covalent bond: resulted from sharing of a pair of electrons
 non-polar: covalent bonds where shared-electrons are
distributed equally between the atoms/molecules involved, e.g.
H2, Cl2
 polar: covalent bonds with electrons are distributed
asymmetrically between the molecules/atoms involved; e.g.
Hd+Cld-; total moment dipole of a molecules can be neutral
when symmetry molecule is taken into account.
 van der Waals forces origin from electromagnetic property
and various ways can generate this type of
atoms/molecules association
 hydrogen bond which generated from polar
groups/molecules are close each other and helped with a
hydrogen bridge
TINGKAH LAKU PARTIKEL DALAM
MATERI

solid liquid gas

 o
C Heating
steam

V
100 liquid C

M
0
F
ice

Zone I Zone II Zone III Zone IV Zone V

Cooling

Heat energy (joules)

 Important review
 Force
 pressure
 energy – physics
 Enthalpi
 Work

 Latent heat

 Sensible heat

 Free energy
 TEKANAN
 Tekanan (P): gaya yang bekerja pada
permukaan bahan
 Satuan SI adalah newton (N)
 Newton: jumlah gaya yang dapat meningkatkan
kecepatan 1 kilogram bahan tiap meter perdetik
disetiap detik
1 N = 1 kg /s / s
 PENGUKURAN TEKANAN
 Barometer: Penentuan tekanan
atmosfer.
 Percobaan Torricelli pada awal tahun
1600-an
 Menggunakan gelas alas bulat yang
ditempatkan pada tabung Mercury (Hg).
 Gelas alas bulat akan terisi oleh Mercury
(Hg) hingga 760 mm diatas plate.
 Hasil pengukuran menunjukkan tekanan
atmosfer 760 mm Hg
 Barometer
 Pengukuran tekanan atmosfer

Aneroid Barometer

Mercury Barometer
Percobaan
Zn(s) + HCl(aq)  ZnCl2(aq) +H2(g)
Tekanan uap air Vs Temperatur
Temperatur Tekanan (mm
Hg)
10 °C 9.2
20 °C 17.5
25 °C 23.8
30 °C 31.8
40 °C 55.3
50 °C 92.5
60 °C 149.4
70 °C 233.7
80 °C 355.1
 Satuan Tekanan
1. Millimeter of Mercury: (mm Hg)
- 1 mm Hg = 1 torr (Torricelli)
- Pada 0°C = 760 mm Hg atau torr
2. Atmosphere of Pressure: (atm) 760 mm Hg
- 1 atm = 760 mm Hg
- Pada 0°C = 1 atm
3. Pascal: (Pa) = gaya 1 newton (1N) pada satu-satuan
luas permukaan (m2)
- Pada 0°C = 1.01325 x 105 Pa atau 101.3 KPa
 Satuan Tekanan - continued

1 atm = 760 mm Hg
760 torr
1.01325 x 105 Pa
101.3 KPa
 THE STATES OF MATTER

 Solid
 Liquid
 Gas
 THE SOLID STATE
glass: disorder arrangement of particles
glassy and rubbery transition particle orders
glassy: brittle
rubbery: flexible
crystal: well order arrangement of particles; ionic bond and van der Waals
forces,
ionic crystal: the structure is determined largely by the geometrical
problem of packing together ions of different sizes into an almost
infinite, symmetrical and electrical neutral array; this generates rigid
solid which is difficult to break the bonds simultaneously
realcrystal has imperfect structural uniformity which develops and
spread under stress
heating can supply enough energy to break weak covalent bonds and
overall the solid has low melting or boiling point
weak van der Waals attraction results in crystal with lower rigidity such as
liquid crystal
 THE LIQUID STATE
 liquid of melted substances has higher amplitudes of vibration and
it is able to flow. The ordered structure of the solid might not be
wholly lost.
 Flowing of fluids involves breaking of weak van der Waals bonds
 Flow is measured as viscosity, the higher the viscosity, the lower
the flowability
 Viscosity decreases with increasing temperature because the
particles move more energetically and can escape from their
neighbours more easily
 Fluidity ≈ e-E/RT so viscosity ≈ eE/RT
 Viscosity follows exponential form over a limited temperature
range and E is similar to the intermolecular binding energy
 THE LIQUID STATE - continued
 Solution:
 Salvation: ionic crystal dissolved in solvents consisting of
molecules that form an electrostatic association with the
ions
 Salvation in water is called hydration

 Ionic crystal has dissolved the final mixture is called

electrolyte solution and the cation and anion can migrate
under electric field
 Nonionic molecule forms a non-electrolyte solution
generally solvent required is non-polar or weakly polar
solvent
 Concentration of solution:

 Molality, etc.
 THE GASEOUS STATE
 a collection (swarm) of molecules in constant,
chaotic motion; each particle move in a straight line
at high speed until heat the wall vessel or other
particles so that intermolecular interaction is minor
in determining kinetic energy (each particle are more
free than solid and liquid state)
 at lower pressure (1 atm) the intermolecular
interaction is negligible; at modest pressure (10 atm)
it is significant effects; and is very important at high
pressure (30 atm)
 sufficient pressure the gas behaviour comply with
ideal gas law pV = nRT
 this is the basis of the kinetic theory
 KINETIC THEORY
 the key calculation is the relation of the mean speed to the temperature of
the gas; root mean square speed (RMS speed)
 the RMS speed increases as the square root of the temperature and
decreases as the square root of the molar mass
3RT
c rms 
 applications
Mm
 to calculate collision frequency, i.e. average number of collision per
second made by a particle in the gas (z)
 to calculate mean free path, i.e. average distance a particle flies
between collisions (l)
c rms
 
 transformation of matter z
 chemical kinetics to answer how fast transformation occur
 deeper than chemical kinetics is molecular reaction dynamics
 rate of reaction = rate of collision x probability that collision carries
enough energy
 Ea / RT
rate  ze
 KINETIC THEORY - continued
 Collision frequency depends on temperature
but its variations is determined by Boltzmann
factor; this follows Arrhenius law
 Whether transformations occur, it is
determined through thermodynamics
 1st law: energy can be neither created nor
destroyed
 2nd law: the entropy of universe never decreases
 Important connection between the quantum theory and
thermodynamics law is statistical thermodynamics
 3rd law: absolute zero (temperature) is
unattainable
 EQUILIBRIUM - The properties of gas
Zeroth law of thermodynamics:
 if A is a system in thermal equilibrium with a system B, which is
also in thermal equilibrium with a system C; then, the A system
will be thermally in the equilibrium state with system C
 This law fits with ideal gas law and thermodynamics
temperature scale. This is important because a temperature
device using different chemicals to monitor consistency of the
temperature scales give variability.
 Boyle, Gay-Lussac, their successor: found p, V and T and n of
gases comply the equation: pV = nRT; in particular it is closer to the
real measurement when density of the gas is smaller. The best gas
that shows a property following the formula exactly is called an
ideal gas. The formula is called equation of state.
 Response to pressure: Boyle’s law = V ≈1/p or pV = constant
 Therefore, relationship between (p, V) and T indicates an isotherm. This
is only at p→0.
 Response to temperature: Gay-Lussac and Charles’s law = V ≈ T (for
constant n, p)
 P ≈T (for constant n, V)
 EQUILIBRIUM - The properties of gas

 So the best thermometer is using a constant volume gas.

Thus, absolute temperature is obtained, i.e. 273.15 K.
 In summary, temperature is a measurement of gas
kinetics where increasing temperature speed up gas
molecules to moves and collide the vessel wall more
frequently, resulting in greater kinetics forces and
pressure.

 Avogadro’s hypothesis: at p and T constant, V≈n

 If Vm=V/n =RT/p
 STP = standard temperature and pressure = 0 C; 1 atm
 SATP = standard ambient temperature and pressure = 25 C;
1 atm
 Hukum Gas

 Hubungan matematika sederhana antara

volume, temperatur, tekanan dan jumlah gas.
Hukum Boyle
Hukum Charles
Hukum Gay-Lussac
Hukum Kombinasi Gas
Gas Ideal : gas imajiner yaitu kondisi sempurna
berdasarkan asumsi teori kinetika molekul .
 Motion according to 3 axes X, Y, Z  Ekin=
(3/2)nRT
 STP

“Standard Temperature & Pressure”

 Kondisi standar yang telah disepakati para

ahli:
 1 atm pada 0 °C  classical theory
 1 atm pada 25 °C  modern theory
 Hukum Boyle
 Kondisi bahwa volume dari berbagai variasi massa
gas berbanding terbalik dengan tekanan pada suhu
yang tetap.

V = k (1/P) atau PV = k
k adalah konstanta

- Rumus perbandingan gas pada jenis sampel yang

sama sbb :
P1V1 = P2V2
 Hukum Charles
 Kondisi volume dari massa gas berbanding lurus
dengan temperatur (oK) pada tekanan konstan.

V = kT atau V/T = k
k adalah konstanta

- Rumus perbandingan gas pada jenis sampel yang

sama sbb :
V1/T1 = V2/T2
 Hukum Gay - Lussac
 Kondisi tekanan dari massa gas berbanding
lurus dengan temperatur (oK) pada volume
konstan.

P = kT atau P/T = k

- Rumus perbandingan gas pada jenis sampel

yang sama sbb :
P1/T1 = P2/T2
 Hukum Kombinasi Gas
 Menyatakan hubungan antara tekanan,
volume dan temperatur dari suatu gas.

PV/T = k

- Rumus perbandingan gas pada jenis

sampel yang sama sbb :

P1V1/T1 = P2V2/T2
 Tekanan Parsial
Menurut Hukum Dalton
 Tekanan total dari
campuran gas sama
dengan jumlah
tekanan parsial
masing-masing
komponen gasnya. nJ RT RT
J pJ  J V  V J nJ
PT = P1+P2+P3+…… nRT
 p
V
 Hukum Gas Ideal

pV  nRT
 p = Tekanan
 V = volume
 n = mol
 T = temperatur
 R = Tetapan gas umum= 0.08206 L-atm/mol-K
= 8.314 J mol-1 K-1
Satuan Tetapan Gas, R
 Tekanan Parsial

p AV  n A RT
 pA = tekanan parsial gas A
 V = volume total
 nA = mol gas A
 T = temperatur
 R = tetapan gas umum = 0.08206 L-atm/mol-K
5 Asumsi Kinetic Molecular Theory

 Partikel gas IDEAL …

1) jaraknya relatif besar dibandingkan dengan
ukurannya (tidak mempunyai volume).
2) Tumbukan antar partikel elastis (tidak
kehilangan energi kinetik).
3) Gerak randomnya cepat dan secara
kontinyu.
4) Tidak terdapat interaksi tarik-menarik
dan tolak-menolak antar partikel.
 Kinetic Molecular Theory
General theory to explain the behavior and properties of gasses
Assumptions
1. Gases consist of tiny particles
2. Distance between gas particles is large
compared to size of particles (i.e., most
of gas volume is empty space)
3. Gas particles have no attraction for one
another
4. Gas particles move in straight lines in all
directions, colliding frequently with one
An ideal gas behaves
another and the walls of the container exactly as specified by the
5. No energy is lost during collisions theory
6. The average kinetic energy of gas No truly ideal gases exist, but
particles is the same for all gases at real gases approach ideal
the same temperature behavior at non-extreme
temperatures and pressures
 Th 1873, Johannes van der Waals menekankan
bahwa partikel gas nyata tidak menempati
ruangan secara keseluruhan dan terdapat gaya
interaksi satu terhadap yang lain.
 Pada tekanan yang tinggi dan temperatur yang
rendah interaksi ini semakin besar, dan
kehilangan energi kinetik.
 Gas Nyata
 Partikel gas REAL …
 Mempunyai volume
 Berinteraksi satu terhadap yang lain

 Gas bertingkah laku seperti gas IDEAL …

 Pada tekanan rendah
 Pada temperatur tinggi

 Dalam atom atau molekul non polar

 Ketentuan K-M Theory
 Aplikasi K-M Theory hanya pada gas ideal
 Gas Ideal tidak eksis, namun sebagian besar
gas bertingkah laku ideal jika partikel-partikel
berjarak cukup jauh dan mempunyai cukup
energi kinetik (STP).
 Gas Nyata: gas tidak bertingkah laku sempurna
seperti yang diasumsikan oleh teori kinetika-
molekular.
 Kinetic Molecular Theory
 Gas Ideal …
 Ekspansi mengisi kontainer
 Bergerak seperti fluida
DIFUSI
 Mempunyai densitas rendah

 Dapat ditekan

 Berdifusi dan effusi

EFUSI
 Batasan Gas Ideal
 Kondisi Gas Ideal  Kondisi gas Non-ideal
 Temperatur tinggi  Temperatur rendah
 Tekanan rendah  Tekanan tinggi

Interaksi
Antar molecul

 Ukuran partikel lebih kecil

 Ada interaksi antar partikel
dibandingkan jarak antar
partikel
 Ukuran pertikel sebanding
dengan jarak antar partikel
 Tidak ada interaksi antar
partikel
GAS IDEAL GAS NYATA
 KOMPRESIBILITAS
 Kompresibilitas gas didefinisikan

pVm
Z
RT
• Gas bertingkah laku ideal, maka Z=1 pada
keseluruhan tekanan dan temperatur.
• Gas nyata, Z bervariasi tergantung dari
tekanan dan turunan dari nilai idealnya
• Repulsive forces: Z <1
• Attractive forces: Z >1
 Kompresibilitas Argon 273 K

2.5 Z = pVm/RT
2.0

1.5
repulsive
Z

1.0

0.5 attractive
0.0
0 200 400 600 800 1000
pressure (atm)
 Gaya Antar Molekul: depends on
chemical bond types
4

1
Energy

-1
repulsive attractive
-2

-3
1.5 2.0 2.5 3.0 3.5 4.0
distance
Persamaan van der Waals

 p  a / V V
2
m m  b  nRT

Vm,eff  Vm  b Tolak-menolak

peff  p  a / V 2
m Tarik-menarik
Persamaan van der Waals: is it applicable in
food system???????
RT a
p  2
Vm  b Vm

1. Perfect gas isotherm are obtained at high temperature and

low density
2. Liquid and gasses coexist when cohesive and dispersing
effects are in balance
3. The critical point can be located
4. A critical compression factor Z is introduced
5. The Boyle temperature can be related to the critical
temperature
 Konstanta van der Waals: does it
make any senses?
Koreksi tingkah-laku gas real dinyatakan dengan
parameter a dan b
a – menyatakan gaya interaksi antar molekul gas nyata
b – menyatakan volume gas nyata

EOS
 Persamaan Virial suatu
Keadaan
Gas Nyata Gas Ideal
Isotherm
(CO2)
Maxwell construction: cut
out of the peak (Garis C-D-E)
Critical Point
pVm  RT (1  B' p  C ' p  )
2

B C
pVm  RT (1   2  )
Vm Vm
 RT a
p  2
Vm  b Vm Persamaan van der Waals

Ketika p0 or Vm pVm  RT

Persamaan Virial suatu
pVm  RT (1  B' p  C ' p  )
2
keadaan: interaksi molekul
dipertimbangkan
B C
pVm  RT (1   2  )
Vm Vm

Ketika p0 or Vm

Boyle Temperature : temperature where a

pVm = RT real gas system behave similarly to ideal gas
– ACTUALLY, IT NEVER HAPPENS
 Temperatur Boyle
B C
Z  (1   2  )
Vm Vm
Z  (1  B' p  C ' P 2  )
dZ
 B '2 pC ' 
dp
 Jika p  0; dZ/dp  B’
(gas ideal dZ/dp = 0 )
 Z (A’, B’, C’, …) tergantung temperatur
 Pada Temperatur Boyle” (TB) B’=0  seems
like ideal gas
TB He = 22.64 K, TB udara = 346.8 K
Isotherm of CO2 (Eksperimen)

 C-D-E: p konstan sedangkan Vm

berkurang: fase cair dan gas
berada dalam keseimbangan
Critical Point (tekanan uap)
 A: gas, E: cairan
 Critical Point (Tc, pc, Vc)
gas & cairan
 Fase cairan tidak terjadi di atas
temperatur kritis (Tc)
 T > Tc
Isotherm Persamaan vdW 
mathematically similar to ideal gas
RT a
p  2
Vm  b Vm
 RT a
p  2
Titik Kritis V m  b Vm

Tc Critical Point
x


dp RT 2a
  3 0
dVm Vm  b  Vm
2 Zc 
pcVc 3
  0.375
RTc 8

d2p 2 RT 6a
  4 0
dVm Vm  b 
2 3
Vm
a 8a
Vc  3b; p c  2
; Tc 
27b 27 Rb
(Faktor kompresibilitas kritis)
 Zc=Konstan untuk keseluruhan gas
 Konstanta kritis adalah sifat karaterisasi dari gas
pcVc 3
Zc  
RTc 8
 Isotherm Gas Ideal
200

150
p/atm

4000K
100

2000K
50
1000K
500K
100K

0
0.0 1.0 2.0 3.0 4.0 5.0

Vm/L
 Isotherm van der Waals - Ar
200
500K
150
200K
100
p/atm

50
150K
0

-50
100K
-100
0.00 0.10 0.20 0.30 0.40
Vm/L
 Variabel Reduksi V = VrVc
 Vr=V/Vc; Tr=T/Tc; pr= p/pc T = TrTc
P = PrPc
 Persamaan vdW menyatakan variabel reduksi

8Tr 3
pr   2
3Vr  1 Vr
 Tidak ada faktor a dan b! reduced V or p; principle of
corresponding states  mathematically similar to ideal
gas
 Does not work for non-spherical gas particles or polar
molecules
Penggunaan Variabel Reduksi
 Critical thinking – food for thought
 vdW:
 Clumsy, high skill in numerical analysis
 Approximation!! (it fails for T high, low)
 Often fails!! – FOOD SYSTEM IS MOSTLY A
MIXTURE OF MACROMOLECULES
 Do solely gas based products exist in foods?????
 Other equations proposed for non ideal gas (Atkins, 1975)
 Berthelot
 Dieterici
 Beattie-Bridgeman
 Virial – Kammerlingh Onnes
 Who’s next????