Revision of Gas Laws

Revision of Gas Laws
Raju Ahammad
Lecturer
Department of Mechanical Engineering
Khulna University of Engineering & Technology
Khulna-9203, Bangladesh
Email: [email protected]
Website: www.kuet.ac.bd/me/rajuahammad/
Science Laws, Theories and Hypothesis
❑ Laws are generalizations or universal relationships related to the way that some
aspect of the natural world behaves under certain conditions. Therefore, laws are
different from hypothesis and theories in science.
❑ An initial investigation provides some evidence (data) that must be explained and
tested further. This tentative explanation, or hypothesis, forms the foundation for
further investigations. If the hypothesis is supported, more investigations are done. As
it becomes stronger, it becomes more predictive and explanatory. At this point, the
hypothesis becomes a theory: a broad explanation that has been supported with data
and is a well substantiated, consistent explanation for a natural occurrence.
❑ Theories evolve as a result of continued testing. When evidences is found that is

inconsistent with or not predicted by the theory, it must be changed. In some
cases, a new theory must be proposed and tested further.
Science Laws, Theories and Hypothesis
Kinetic Theory of Gases
This theory helps us understand why gases behave the way they do and give us insight
into the behavior of solids and liquids. There are five basic postulates of this theory.
❑ Particles in a gas have no volume and are very far apart.

❑ Particles in a gas move in straight line paths and random directions.
❑ Particles in a gas collide frequently with the sides of the container and less
frequently with each other. All collisions are elastic (no energy is gained or lost
as a result of the collisions).
❑ Particles in a gas do not attract or repel one another. There is no intermolecular
attractions.
❑ The average kinetic energy of all of the gas particles in a sample is proportional
to the temperature of that gas sample.
Temperature
❑ Temperature is a measure of the average
kinetic energy of a substance.
❑ 0 Kelvin is absolute zero.
❑ There are not negative numbers on the

Kelvin scale.
❑ Celsius to Kelvin K = oC + 273

❑ Kelvin to Celsius oC = K – 273
Pressure
❑ Defined as Force/Area.
❑ There are different UNITS of pressure used in

chemistry and you must be able to convert between
all of them.
❑ 1 atmosphere (atm) = 760 mm Hg = 14.7 psi = 101.3
kPa
❑ Example: Which is higher pressure 1.45 atm or 1000

mm Hg? Example: Convert 753 psi to atmospheres.
❑ Standard Temperature & Pressure (STP) is equal to 1

atm at 0°C
Ideal or Perfect Gas & Gas Laws
❑ A perfect gas strictly obeys all the gas laws under all conditions of pressure and
temperature. A gas whose molecules obey the following postulates may be termed
as a perfect or ideal gas.
1. Molecules behave as if they were perfectly elastic spheres.
2. Since they behave as elastic spheres, there cannot be any frictional effects
between colliding molecules.
3. The mean distance between the molecules is so great that intermolecular
forces can be neglected and it may therefore be assumed that molecules travel
in straight lines.
4. The mean distance between the molecules is so great that the time of impact
can be neglected in comparison with the time of free flight.
5. The size of the molecules is so small in comparison with the total volume that
it can be neglected.
Ideal or Perfect Gas & Gas Laws
❑ Considering the above

factors none of the practical
gases are ideal or perfect
gas. But for approximation
in real processes diatomic
gases and air (which is
mixture of number of gases)
are considered as ideal gas.
Dalton’s Law of Partial Pressure
❑ Equal amounts of gas at the same temperature and volume have equal pressure.
The total pressure inside a container is equal to the partial pressure due to each
gas. P total = P1 + P2 + P3
❑ For instance, we can find the pressure in the fourth container by adding up the
pressure in the first three containers.
Variables to describe gases
❑ Based on the kinetic theory of gases, scientists were

able to describe how gases behave and
change using mathematical equations.
❑ There are 4 variables that work together to

determine the behavior of gases –
temperature, pressure, volume, and the number of
particles.
Boyle’s Law
Temperature remaining
constant, the volume of
a given mass of gas is
inversely proportional to
the absolute pressure.
i.e., 𝑣∝ 1/𝑝, when T is
constant or pv =
constant.
Boyle’s Law
Charles’s Law
At constant pressure, the volume of

a given mass of gas is proportional
to the absolute temperature. i.e.,𝑣 ∝
𝑣
𝑇, when p is constant or =
𝑇
constant
Charles’s Law
Gay-Lussac's Law
❑ At constant volume, the

pressure of a given mass of
gas is proportional to the
absolute temperature. i.e.,
𝑝∝𝑇, when v is constant or
𝑝/𝑇= constant.
Gay-Lussac's Law
Joule’s Law
❑ This law states that the internal energy of a gas is a function of temperature. From
this, it follows that the change of internal energy is proportional to the change of
temperature. i.e., ∆𝐸 = 𝑎 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 (𝑡2 − 𝑡1 ) for unit mass of gas.
= 𝐶𝑣 (𝑇2 − 𝑇1 ) for unit mass of gas.

Avogadro’s Law
Avogadro’s Law
❑ This law states that equal volumes of all ideal gases at a particular pressure and
temperature contain the same number of molecules. This statement is strictly
true only for an ideal gas.
❑ The number of molecules in a mole of any gas is a constant NA, called Avogadro’s
number. The value of NA is 6.0225x10^23 per gmole.
Renault’s Law
❑ This law states that the specific heat of a gas remains constant at all
temperature and pressure.
❑ But modern experiments show that specific heat changes with the change of
temperature. Therefore, this cannot be considered as law now.
Combined Gas Law
Characteristic Equation of a Gas
❑ In engineering practice, volume, pressure and temperature all vary
simultaneously and therefore, Boyle’s law or Charles’s law only is not applicable.
❑ But from both these laws, a general equation for a mass of gas underlying
changes in temperature, pressure and volume can be obtained.
❑ For any mass m of the gas, 𝑝𝑉 = 𝑚𝑅𝑇. This equation is known as characteristic
gas equation, where R is characteristic gas constant or specific gas constant.
𝑅ത
❑ But, 𝑅 = , where 𝑅ത is universal gas constant and the value of 𝑅ത = 8.314 kJ/kg
𝑀
mol K in SI and 𝑅ത = 1545 ft.lb/lbm mol R in FPS system and M = Molecular
weight of the gas.
𝑚
𝑝𝑉 = 𝑅ത 𝑇 = 𝑛𝑅𝑇
ത where, n is number of mole of the gas.
𝑀
Characteristic Equation of a Gas
Equations of State
The relationship among the state variables, temperature, pressure, and specific volume is
called the equation of state. We now consider the equation of state for the vapor or
gaseous phase of simple compressible substances.
The ideal gas equation of state is used when (1) the pressure is small compared to the
critical pressure or (2) when the temperature is twice the critical temperature and the
pressure is less than 10 times the critical pressure.
The critical point is that state where there is an instantaneous change from the liquid phase
to the vapor phase for a substance.
Compressibility Factor
To understand the above criteria and to determine how much the ideal gas equation of state
deviates from the actual gas behavior, we introduce the compressibility factor Z as follows.
Obviously, Z=1 for ideal gases. For real gases Z can be greater than or less than unity. The
farther away Z is from unity, the more the gas deviates from ideal-gas behavior. The deviation
of Z from unity measures the deviation of the actual P-V-T relation from the ideal gas
equation of state.
A MEASURE OF DEVIATION FROM IDEAL-GAS BEHAVIOR

Gases behave differently at a given temperature and pressure, but they behave very much
the same at temperatures and pressures normalized with respect to their critical
temperatures and pressures. The normalization is done as
Here PR is called the reduced pressure and TR the reduced temperature. The Z factor for all
gases is approximately the same at the same reduced pressure and temperature. This is
called the principle of corresponding states.
The following observations can be made from the generalized compressibility chart:
1. At very low pressures (PR <<1), gases behave as an ideal gas regardless of temperature
2. At high temperatures (TR > 2), ideal-gas behavior can be assumed with good accuracy
regardless of pressure (except when PR > > 1).
3. The deviation of a gas from ideal-gas behavior is greatest in the vicinity of the critical point.
The ideal-gas equation of state is very simple, but its range of applicability is limited. It is
desirable to have equations of state that represent the P-v-T behavior of substances
accurately over a larger region with no limitations. Such equations are naturally more
complicated.
Van der Waals Equation of State
The van der Waals equation of state was
proposed in 1873, and it has two constants
that are determined from the behavior of a
substance at the critical point.
❑ Van der Waals intended to improve the ideal-gas equation of state by including two of the
effects not considered in the ideal-gas model: the intermolecular attraction forces and the
volume occupied by the molecules themselves.
❑ The term a/v2 accounts for the intermolecular forces, and b accounts for the volume
occupied by the gas molecules.
❑ In a room at atmospheric pressure and temperature, the volume actually occupied by
molecules is only about one-thousandth of the volume of the room. As the pressure
increases, the volume occupied by the molecules becomes an increasingly significant part
of the total volume. Van der Waals proposed to correct this by replacing v in the ideal-gas
relation with the quantity v-b, where b represents the volume occupied by the gas
molecules per unit mass.
Van der Waals Equation of State
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❑ Theories evolve as a result of continued testing. When evidences is found that is

❑ Particles in a gas have no volume and are very far apart.

❑ 0 Kelvin is absolute zero.

❑ There are not negative numbers on the

❑ Celsius to Kelvin K = oC + 273

❑ There are different UNITS of pressure used in

❑ Example: Which is higher pressure 1.45 atm or 1000

❑ Standard Temperature & Pressure (STP) is equal to 1

❑ Considering the above

❑ Based on the kinetic theory of gases, scientists were

❑ There are 4 variables that work together to

At constant pressure, the volume of

❑ At constant volume, the

= 𝐶𝑣 (𝑇2 − 𝑇1 ) for unit mass of gas.

A MEASURE OF DEVIATION FROM IDEAL-GAS BEHAVIOR

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