Thermodynamics : an introduction

Thermodynamics
Why we must study thermodynamics ?

Thermodynamics is in everywhere
 Thermodynamics
● Thermodynamics parameters :
U G H S A q W
 Thermodynamics
● Starting point of thermodynamics
● Perfect gas
● Real gas
● Heat, work and energy
 Thermodynamics
● Starting point of thermodynamics
● Perfect gas
● What is the perfect gas ?
● Why we have to study this kind of gas?
● To answer these questions, we must realize that the
simplest
state of matter is gas
● Every substance is characterized via equation of state
● This equation interrelates four variables (P, V, T, n)
 Thermodynamics
● We can say that, two samples of substances that have
same phyisical properties are in the same state.
●
For example : the state of gas is specified by giving its V, T,
P and n
●
Again, we can write the equation of state for gas as
● : p=f(V,T,n)
This equation tells us that, if we have known value of V, T
● and n, then P will have a fixed value.
One of the most popular relationship of variables in equation
 Thermodynamics
● Next question, what is p
● P is defined as force (F) divided by the area ( The )
(pressure)
● relationship between two pressures (see the picture)
 Thermodynamics
● Next question, what is T (temperature)
● T is the property that indicates the direction of
flow energy through a thermally conducting
 Thermodynamics
● Next question, what is T
(temperature)
● T is the property that indicates the direction of
flow energy through a thermally conducting
● We can say that if two objects are in contact through a
diathermic boundary, they are in thermal equilibrium (no
change in state)
●
If A and B are in thermal equilibrium, then B are in
contact with C, it can be concluded that A and C are in
● thermal equilibrium
Adiabatic, if there is no changes occur between
 Thermodynamics
●
Next question, what is T (temperature)
 Thermodynamics
● The perfect gas law
● In case of pressure is very very low, we can combine
Boyle, Charles and Avogadro’s principle
 Thermodynamics
●
The perfect gas law
 Thermodynamics
● The perfect gas law
● In case of pressure is very very low, we can combine
Boyle, Charles and Avogadro’s principle
● We can summarize these 3 principles as
pV = constant x nT
● What is the constant ?
● The experimental determined constants :
● R
● pV =
nRT
 Thermodynamics
● A gas that obeys perfect gas law → perfect gas
● At low pressure, the real gas will behave like perfect gas
● The perfect gas law is one of the greatest concept in
physical chemistry
● And again, remember, gas is freely moving in a vessel.
● if a sample of gas is compressed to half its volume, then
twice as many molecules strike the walls in a given period of
time than before it was compressed
●
The molecules collide with the walls more frequently and with
greater impact. Therefore they exert a greater pressure on
 Thermodynamics
● These qualitative concept can be writing into quantitative
term of kinetic model of gas
– The gas consists of molecules of mass m in
ceaseless random motion.
–
The size of the molecules is negligible, in the sense
that their diameters are much smaller than the
average distance travelled between collisions.
–
The molecules interact only through brief, infrequent,
and elastic collisions.
 Thermodynamics
● Based on these assumption, we can write the relationship
between pressure, volume and velocity
 Thermodynamics
● Mixtures of gases
● When dealing with mixture of gases, we must remember that
each component will contribute to the total pressure

● Where xj is the mole fraction and pj is the partial pressure

● The original concept of partial pressure is formulated in
Dalton’s Law
“The pressure exerted by a mixture of gases is the sum of
the pressures that each one would exert if it occupied
 Thermodynamics
● Mixtures of gases
 Thermodynamics
● Real gas
● Real gases do not obey the perfect gas law (except for very
low pressure)
● Why ? Because the molecules interact with one another
● This interaction will lead to expansion and compression
 Thermodynamics
● Real gas
● Real gases do not obey the perfect gas law (except for very
low pressure)
 Thermodynamics
● Real gas
● Compression factor (Z) is the ratio of its measured molar
volume, Vm =V/n, to the molar volume of a perfect gas,
Vom, at the same pressure and temperature
 Thermodynamics
● Real gas
● Compression factor (Z) is the ratio of its measured molar
volume, Vm =V/n, to the molar volume of a perfect gas,
Vom, at the same pressure and temperature
 Thermodynamics
● Real gas
● The other important concept of real gas is the virial
equation of state
●We can see that at large molar volume and high
temperatures the real-gas isotherms do not differ gr eatly
from perfect gas isotherms
 Thermodynamics
● Real gas
● So, we can write the perfect gas law in term of power
series

● The most common series is

 Thermodynamics
● Condenstation
● Concept of vapour pressure
● When both vapour and liquid are present in equilibrium
 Thermodynamics
● Real gas
● These concept of attraction and repulsion leads to van
der Waals equation of real gas

● The constants a and b is the van der Waals coefficients.

‘a’ represents the attractive and ‘b’ is the repulsive part
●
‘a’ and ‘b’ have strong correlation with physical properties
such as critical temperature, vapor pressure and enthalpy
of vaporization
 Thermodynamics
● Real gas
● The advantages of van der Waals
● equation
Allows us to draw general conclusions about real gases
● Analytical
● Main features of van der Waals equation
● Perfect gas isotherms are obtained at high temperatures and
large molar volume
● Liquids and gases are coexist when cohesive and dispersing
effects are in balance
● Critical constants are related to van der Waals coefficients
 Thermodynamics
● Real gas
Thermodynamics
Some examples :

In an industrial process, nitrogen is heated to 500 K in a vessel of constant

volume. If it enters the vessel at 100 atm and 300 K, what pressure would it
exert at the working temperature if it behaved as a perfect gas?
Some examples :

In an industrial process, nitrogen is heated to 500 K in a vessel of constant

volume. If it enters the vessel at 100 atm and 300 K, what pressure would it
exert at the working temperature if it behaved as a perfect gas?
Some examples :

The mass percentage composition of dry air at sea level is approximately N2:
75.5; O2: 23.2; Ar: 1.3. What is the partial pressure of each component when
the total pressure is 1.20 atm?
Some examples :

The mass percentage composition of dry air at sea level is approximately N2:
75.5; O2: 23.2; Ar: 1.3. What is the partial pressure of each component when
the total pressure is 1.20 atm?
Some examples :

The mass percentage composition of dry air at sea level is approximately N2:
75.5; O2: 23.2; Ar: 1.3. What is the partial pressure of each component when
the total pressure is 1.20 atm?
Some homeworks :

●
Submit to classroom
●
Due date : 23.09.2020 23:59
●
Sebuah gas pada suhu 350 K dan tekanan 15 atm memiliki volume molar
12% lebih kecil daripada volume yang diperoleh dari persamaan gas ideal.
Hitunglah faktor kompresi pada kondisi ini,volume molar gas dan manakah
yang lebih berpengaruh, apakah kontribusi tarikan atau tolakan

●
Sebuah tabung diisi gas oksigen dengan tekanan 200 bar. Tentukan berapa
volume molar gas oksigen pada suhu 25 Celcius dengan menggunakan
persamaan gas ideal dan van der Waal (a = 1,364 dm6 atm mol-2 dan b =
3,19 x 10-2 dm3 mol-1
●

●
Terima
kasih!