Contents

1. Concepts
2. General properties
Chapter 1 3. Ideal gas
4. Real gas
Concepts and properties
of substances

1. Concepts
•System/ surroundings
- Open system / close system / isolated system /
adiabatic system
•State / intensive parameters /extensive parameters / state
function
•Process / isothermal / isobaric /
constant-volume (isochoric) / adiabatic
•Phase / homogeneous / heterogeneous

3 4
 1. Concepts 1. Concepts
System: any object that we
wish to study

Surroundings: The portion of

Open systems Closed systems Isolated systems
the universe that is outside of Both material Only energy can Both material and
the system. and energy can pass into or out of energy cannot pass
pass into or out the system into or out of the
of the system system

Adiabatic system: heat cannot pass into or out of the system

5 6

1. Concepts 1. Concepts
¡ Macroscopic system: A large system State of a system: describing the condition of the
containing many atoms or molecules. system by giving the values of a sufficient set of
¡ Macroscopic properties: Temperature and
numerical variables.
pressure,…
Ex: a gas system: 1 mol of A at 1 atm, 0oC
¡ Microscopic system: a system consisting 1mol A (g, 1atm, 0 0C)
of a single atom or molecule
¡ Microscopic properties: kinetic energy and
momentum,…
¡ Thermodynamic system: macroscopic
system at equilibrium (equilibrium system): a
state that all properties don’t change.
7 8
 1. Concepts 1. Concepts
• State functions/variables: ¡ Process: A system is said to undergo a process
when it goes from one thermodynamic state to
– Extensive variables: are proportional to the size of another.
the system if P and T are constant
Ex.: V, n, m
– intensive variables: are independent of the size of
the system if P and T are constant
Ex.: T, P
Note: The quotient of two extensive variables is an
intensive variable:
ρ= m/V, Vm =V/n

Ex. state functions: Internal energy: U = U(T, p, ni …)

Entropy: S = S (T, p, ni …)
9 10

1. Concepts 2. General properties

¡ Phase: A given phase of matter is • Pressure (P)
characterized by both uniform physical
structure and uniform chemical composition.
Units:
1Pa = 1N/m 2
solid/ liquid/gas 1bar = 105Pa = 100kPa
1atm = 101,325kPa
1 phase system: homogeneous system 1atm = 760Torr = 760mmHg
2 or higher phases system: heterogeneous
systems

11 12
 2. General properties 2. General properties
• Pressure (P) • Volume
Units

1lít = 1 dm 3 = 1/1000 m3
1ml = 1/1000 liter

13 14

2. General properties
• Temperature (T) Temperature: Temperature measures the degree of
hotness of a body (“how hot”). It doesn’t depend on the
mass or the material of an object. It can be thought of as a
Units:
measure of the average kinetic energy of the atoms or
[oC]: Celsius
molecules in a body.
[K] : Kelvin
[oF] : Fahrenheit
Heat: Heat is a measure of the total kinetic energy of the
atoms or molecules in a body.

Energy: Energy is the ability to bring about change or to

[K] = 273,15 + [oC]
do work

[oC] = 32 + 1,8.[oF]

15
 2. General properties 2. General properties
• “0” law:
GAS
deposition/
vaporization
sublimation desublimation

condensation
Freezing/
If two objects, A and B, are at thermal solidification
equilibrium with each other and if B is at
thermal equilibrium with a third object, C, then
A is also at thermal equilibrium with C
Ta=Tb and Tb=Tc then
Ta=Tc
LIQUID SOLID
Melting/
Fusion

17 18

2. General properties 2. General properties

liquid
Bonds between the atoms do not hold
solid
-Bonds between the atoms hold them in a
specific position relative to other atoms in the them in a specific position. Molecules
solid. They are free to vibrate about this fixed are in motion, free to move relative to
position.
one another.
- Fixed shape - Flexible shape
- Crystalline: has a long-range, periodic order. - Fixed volume
- Fixed volume
(have lattice structure). Each different crystal
structure represents a different phase, since
the physical structure is different.
Ex.: diamond phase, graphite phase.

- Amorphous: A solid with no long-range

order
19 20
 2. General properties 2. General properties
ionization
gas
Bonds between
Lực tương the atoms
tác giữa phân tửarerất
very
yếu.
weak. Molecules are far from each
others, moving freely and continuously
GAS PLASMA
deionization
with temperature-dependent velocities.
- Flexible shape and
volume
Matter is in ionic form

21 22

2. General properties
Isothermal compressibility (kappa):

• V = f(T,P, n)

23 24
 2. General properties
• Coefficient of thermal expansion

• Volume change as a function of T & P:

25 26

4. Ideal gas 4. Ideal gas

Equation of state
Boyle law: PV = constant
(n, T = constant)

Equation of state ?? Charle law: V/T = constant

(n, P = constant) PV =n.R.T
Avogadro rule: V/n= constant
(P, T = constant)

R: gas constant

Value, unit???
27 28
 4. Ideal gas 4. Ideal gas

PV =n.R.T

value Unit
R: gas constant
8,314 J.K−1.mol−1
0,082 L.atm.K−1.mol−1
1,987 cal.K−1.mol−1

29 30

4. Ideal gas 4. Ideal gas

Dalton law

(Pi: partial pressure)

P= Pi
Dalton law Pi =
ni RT
Partial pressure of gas ‘i‘ in a gaseous mixture Where: n = ni V
ni
Mole fraction: xi = Pi = xiP
n

31 32
 Example 5. Real gas
• Air contains 21%
moles oxygen.
What is partial
pressure of
oxygen in the ??
atmosphere?
Equation of state

33 34

5. Real gas 5. Real gas

PVm = RT PVm = Z .RT
(Vm: molar volume) PVm
RT
Z: compressibility factor

Ideal gases: Z = 1 ; Real gases: Z 1

35 36
5. Real gas

P-Z diagram

37 38

5. Real gas 5. Real gas

Author Year
Van der Waals 1873
Clausius 1880
Van der Waals Berthelot 1899
equation Redlich- Kwong 1949
Soave 1972
Peng-Robinson 1976
…

39 40
 5. Real gas 5. Real gas
Phương trình Van der Waals:
PVm = RT P(Vm - b) = RT 2
RT a
nRT ænö P= - 2
P= - aç ÷ or
V - nb è V ø Vm - b Vm
RT a RT
P= - 2 P= b: specific volume of the particles in one
(Vm - b) Vm (Vm - b) mole
a / Vm2: pressure drop caused by the
attractive forces between molecules

41 42

5. Real gas
Critical constants

a
pc = 2
27b 2 nRT ænö
P= - aç ÷
Vc = 3b V - nb è V ø
(Van der Waals equation)
8a
Tc =
27bR

43 44
45 46

47 48
 Fugacity (f) Fugacity (f)
• a thermodynamic property Pr = P/Pc
of a real gas which if • Example:
substituted for the
pressure or partial Tr = T/Tc
pressure in the equations V = nRT/P (ideal gas)
for an ideal gas gives V = nRT/f (real gas)
equations applicable to
= f/P
the real gas.
mi = m0 + RTlnPi (ideal gas)
mi = m0 + RTlnfi (real gas)
= ∶

• How to calculate f at (T,P):

– Method 1 (simple): get from a chart à get f
– Method 2 (complicated): using EOS
49 50

End

51