‫وزارة التعليم العالي والبحث العلمي‬

‫الجامعة التكنولوجية‬
‫قسم هندسة النفط والغاز‬

Thermodynamics
‫الديناميكا الحرارية‬
Instructor: Prof. Dr. Najem A. Al-Rubaiey
Department of Oil & Gas Engineering
Petroleum Engineering
Academic Year 2023-2024
Unit 3: Ideal Gas Laws
 The expansion of alcohol in a thermometer is one of many
commonly encountered examples of thermal expansion,
which is the change in size or volume of a given system as its
temperature changes.
 The most visible example is the expansion of hot air.
 When air is heated, it expands and becomes less dense than
the surrounding air, which then exerts an (upward) force on
the hot air and makes steam and smoke rise, hot air balloons
float, and so forth.
 The same behavior happens in all liquids and gases, driving
natural heat transfer upward in homes, oceans, and weather
systems.
 Solids also undergo thermal expansion.
 Railroad tracks and bridges, for example, have expansion
joints to allow them to freely expand and contract with
temperature changes,
 What is the underlying cause of thermal expansion?
 An increase in temperature means an increase in the kinetic energy of
individual atoms.
 In a solid, unlike in a gas, the molecules are held in place by forces from
neighboring molecules; as we saw in Oscillations, the forces can be
modeled as in harmonic springs described by the Lennard-Jones
potential.
 Energy in Simple Harmonic Motion shows that such potentials are
asymmetrical in that the potential energy increases more steeply when
the molecules get closer to each other than when they get farther away.
 Thus, at a given kinetic energy, the distance moved is greater when
neighbors move away from each other than when they move toward
each other.
 The result is that increased kinetic energy (increased temperature)
increases the average distance between molecules—the substance
expands.
EXAMPLE 1
The main span of San Francisco’s Golden Gate Bridge is 1275 m long at
its coldest. The bridge is exposed to temperatures ranging from –
15°C to 40°C. What is its change in length between these temperatures?
Assume that the bridge is made entirely of steel.
Strategy
• Use the equation for linear thermal expansion ΔL=αLΔT to calculate the
change in length, ΔL. Use the coefficient of linear expansion α for steel
from the Table and note that the change in temperature ΔT is 55°C.
Solution
• Substitute all of the known values into the equation to solve for ΔL:

Significance
• Although not large compared with the length of the bridge, this change
in length is observable. It is generally spread over many expansion
joints so that the expansion at each joint is small.
EXAMPLE 2
Suppose your 60.0-L steel gasoline tank is full of gas that is cool because it has
just been pumped from an underground reservoir. Now, both the tank and the
gasoline have a temperature of 15.0°C. How much gasoline has spilled by the
time they warm to 35.0°C?
Strategy
• The tank and gasoline increase in volume, but the gasoline increases more, so
the amount spilled is the difference in their volume changes. We can use the
equation for volume expansion to calculate the change in volume of the
gasoline and of the tank. (The gasoline tank can be treated as solid steel.)
Solution
• Use the equation for volume expansion to calculate the increase in volume of
the steel tank:
ΔVs =βs Vs ΔT
• The increase in volume of the gasoline is given by this equation:
Δvgas =βgas Vgas ΔT
• Find the difference in volume to determine the amount spilled as:
Vspill =Δvgas − ΔVs
• Alternatively, we can combine these three equations into a single equation.
(Note that the original volumes are equal.)
•
 Real Gases
• An ideal gas is one that conforms exactly to the tenets of the
kinetic molecular theory, where the volume occupied by the
gas particles is negligible relative to the total volume of the
container, and there are no appreciable intermolecular
attractions or repulsions.
• Real gases can deviate from ideal behavior, especially at high
pressures and low temperatures. The extent of deviation is
measured using the compressibility factor. The compressibility
factor is obtained by solving for n in the ideal gas law: dividing
the product of pressure and volume by the product of the gas
constant and temperature (PV/RT) for one mole of a given
substance. Under ideal conditions, this ratio of (PV/RT) should
be exactly equal to 1.
 Real Gases at High Pressure
• At higher pressures, gas molecules are closer together in a space.
• As a result of this crowding, gas molecules experience greater
attractive intermolecular forces.
• Intermolecular forces hold molecules together more, lessening the
force and frequency of collisions with the container wall and thus
lowering the pressure below ideal values.
• As well, at higher pressure, molecules occupy a larger proportion of
the volume of the container.
• With other gas molecules taking up a larger proportion of the
volume of the container, the unoccupied volume of the container
available to any one molecule is smaller than in ideal conditions.
• This decrease in available volume causes an increase in pressure
beyond ideal conditions.
 “Compressibility Factors.”
Approximate compressibility factors of three gases at 250 K.
 Real Gases at Low Temperature
• Temperature also influences deviations from ideal gas
behaviour.
• As temperature decreases, the average kinetic energy of the
gas particles decreases.
• A larger proportion of gas molecules therefore have
insufficient kinetic energy to overcome attractive
intermolecular forces from neighbouring atoms.
• This means that gas molecules become “stickier” to each
other, and collide with the walls of the container with less
frequency and force, decreasing pressure below that of ideal
values.
 “Compressibility Factor of Nitrogen.”
Approximate compressibility factor of nitrogen at different temperatures.
The van der Waals Equation

“Johannes Diderik van der Waals.”

 The van der Waals Equation
• In 1873, Dutch scientist Johannes van der Waals developed an
equation that compensates for deviations from ideal gas
behaviour.
• The van der Waals equation uses two additional
experimentally determined constants: a, which is a term to
correct for intermolecular forces, and b, which corrects for the
volume of the gas molecules (see Table “Selected van der
Waals Constants for Gas Molecules”).
• The van der Waals equation appears as:

It should be noted that, if the new terms a and b are equal to zero
(under ideal conditions), the equation simplifies back to the ideal
gas law: PV = nRT.
The van der Waals Equation
Problem:
Use the van der Waals equation and Table to determine the
pressure, in atmospheres, of 2.00 moles of oxygen gas in a
30.00L flask at 25.0°C.

• Solution
Summary