TOPIC 4: PERFECT GASES

a) Gas laws
Gas laws involve temperature (measured in Kelvin), pressure and volume.

1. Boyles law
The Boyle’s law states that the pressure (P) of a given quantity of gas varies inversely with its volume (V) at
constant temperature; i.e., in equation form, PV=K, a constant.

2. Charles law
The Charles’ law states that the volume occupied by a fixed amount of gas is directly proportional to its
absolute temperature, if the pressure remains constant i.e., in equation form V/T=K, a constant.

3. Pressure law
The Pressure law states that for a fixed mass of gas at constant volume, the pressure is directly proportional to
the temperature i.e., in equation form P/T=K, a constant.

4. Gas equation
A gas that obeys the three laws; Boyle’s law, Charles’ law and Pressure law is an ideal gas since no gas in
reality can obey these laws exactly. Normally gases can show a brief and fairly accurate description of the laws
at low temperatures. The behaviour of an ideal gas can be accounted for by the equation 𝑃𝑉 = 𝑛𝑅𝑇, where P =
Pressure (Pa), V = Volume (m3), T = Temperature (K), n = Number of Moles (mol) and R = Universal Molar
Gas Constant (R = 8.31 JK-1mol). This equation is referred to as an equation of state or ideal gas equation.

Suppose we have a gas of Temperature = T1, Volume = V1 and Pressure = P1; the equation of state is 𝑃1 𝑉1 =
𝑃1 𝑉1
𝑛𝑅𝑇1 which can be re-written as = 𝑛𝑅. Say the same gas now has a new temperature = T 2, Pressure = P2
𝑇1
𝑃2 𝑉2
and Volume = V2, its equation of state will be 𝑃2 𝑉2 = 𝑛𝑅𝑇2 which can be re-written as = 𝑛𝑅. Relating it to
𝑇2
𝑃1 𝑉1 𝑃2 𝑉2
the previous equation we get = .
𝑇1 𝑇2

b) Simple problems on:

1. Boyles law
i. A gas occupies 12.3 liters at a pressure of 40.0 mmHg. What is the volume when the pressure is increased to
60.0 mmHg?
1|Page
Solution
Using 𝑃1 𝑉1 = 𝑃2 𝑉2
(40.0 mmHg) (12.3 liters) = (60.0 mmHg) (x)
x = 8.20 L

ii. If a gas at 25.0 °C occupies 3.60 liters at a pressure of 1.00 atm, what will be its volume at a pressure of 2.50
atm?

Solution
Using 𝑃1 𝑉1 = 𝑃2 𝑉2
(1.00 atm) (3.60 liters) = (2.50 atm) (x)
x = 1.44 L

2. Charles law
i. Calculate the decrease in temperature (in Celsius) when 2.00 L at 21.0 °C is compressed to 1.00 L.
Solution:
𝑉 𝑉
Using 𝑇1 = 𝑇2
1 2

(2.00 L) / 294.0 K) = (1.00 L) / (x)

cross multiply to get:
2x = 293
x = 147.0 K
Converting 147.0 K to Celsius, we find -126.0 °C, for a total decrease of 147.0 °C, from 21.0 °C to -
126.0 °C.

ii. 600.0 mL of air is at 20.0 °C. What is the volume at 60.0 °C?
Solution:
𝑉 𝑉
Using 𝑇1 = 𝑇2
1 2

(600.0 mL) / (293.0) = (x) / (333.0 K)

x = 682 mL

2|Page
3. Gas equation
i. A gas which can be considered ideal, has a volume of 100 cm 3, pressure of 2 x 105 Pa and temperature =
27°C. What is the volume at a pressure of 5 x 105 Pa and temperature of 60°C.?
Solution
𝑃1 𝑉1 𝑃2 𝑉2 𝑃1 𝑉1 𝑇2 (2×105 )(100)(60+273)
= ; re-arranging the equation we get 𝑉2 = and 𝑉2 = = 44.4 𝑐𝑚3
𝑇1 𝑇2 𝑇1 𝑃2 (5×105 )(30+273)

ii. Determine the volume of occupied by 2.34 grams of carbon dioxide gas at STP.
Solution:
Rearrange PV = nRT to this:
V = nRT / P
Substitute:
V = [(2.34 g / 44.0 g mol¯1) (0.08206 L atm mol¯1 K¯1) (273.0 K)] / 1.00 atm
V = 1.19 L

iii. A sample of argon gas at STP occupies 56.2 liters. Determine the number of moles of argon and the mass of
argon in the sample.
Solution:
Rearrange PV = nRT to this:
n = PV / RT
Substitute:
n = [(1.00 atm) (56.2 L) ] / [ (0.08206 L atm mol¯1 K¯1) (273.0 K)]
n = 2.50866 mol
Multiply the moles by the atomic weight of Ar to get the grams:
2.50866 mol times 39.948 g/mol = 100. g
c) Engineering examples
1. Engines
Internal combustion engines are the most common form of heat engines, as they are used in vehicles, boats,
ships, airplanes, and trains. They are named as such because the fuel is ignited in order to do work inside the
engine. The same fuel and air mixture is then emitted as exhaust. This can be done using a piston (called
a reciprocating engine), or with a turbine. Internal combustion heat engines work on the principle of the ideal
gas law 𝑃𝑉 = 𝑛𝑅𝑇. Raising the temperature of a gas increases the pressure that makes the gas want to
expand. An internal combustion engine has a chamber, which has fuel added to it which ignites in order to raise
the temperature of the gas.
3|Page
 2. Air compressors
Air compressors compress air and channel it to be used as a source of energy. Compressed air is an
underrecognized power source that can energize tools, machines, and engines in the automotive industry. Even
though air is not a “perfect” or pure gas, the presence of nitrogen and oxygen in major proportion makes it
behave very closely to a “perfect” gas. Perfect gases are known to obey Boyle’s law (PV = k) and Charles’s law
(V/T = k). A combination of the two laws is PV/T = k; Pressure multiplied by volume divided by temperature
equals a constant. This law explains that when air is compressed, the pressure and temperature of the air
increases, as the volume of the space containing air decreases. By pushing air into a smaller space, we force it to
become hotter and more pressurized. The molecules within the air will try to spread apart, returning to their
natural distance, and it’s this constant attempt to move away from one another that causes pressure. Air
compressors use this concept to raise the air pressure.

In the context of perfect gases, the specific heats at constant pressure (𝑐𝑝 and constant volume (𝑐𝑣 )
are defined as follows:

Specific Heat at Constant Volume (𝑐𝑣)

The specific heat at constant volume ( 𝑐𝑣cv) is defined as the amount of heat required to raise the
temperature of a unit mass of a gas by one degree Celsius (or one Kelvin) while the volume is held
constant. Mathematically, it is expressed as:

where:

 𝑢 is the specific internal energy of the gas.

 𝑇 is the temperature.
 The subscript 𝑉 indicates that the volume is held constant during this process.

Specific Heat at Constant Pressure (𝑐𝑝)

The specific heat at constant pressure (𝑐𝑝 ) is defined as the amount of heat required to raise the
temperature of a unit mass of a gas by one degree Celsius (or one Kelvin) while the pressure is held
constant. Mathematically, it is expressed as:

4|Page
 where:

 ℎ is the specific enthalpy of the gas.

 𝑇 is the temperature.
 The subscript 𝑃 indicates that the pressure is held constant during this process.

Relationship Between 𝑐𝑝 and 𝑐𝑣

For a perfect gas, there is a specific relationship between 𝑐𝑝 and 𝑐𝑣 , which is derived from the first
law of thermodynamics and the definition of enthalpy (ℎ=𝑢+𝑃𝑣). For a perfect gas, 𝑃𝑣=𝑅𝑇 (ideal
gas law), where 𝑅 is the specific gas constant. The relationship is given by:

𝑐𝑝=𝑐𝑣+𝑅

Key Points About 𝑐𝑝 and 𝑐𝑣

1. Energy Storage:

 𝑐𝑣 represents the energy required to increase the internal energy of the gas, as internal energy is a
function of temperature alone in an ideal gas.
 𝑐𝑝 represents the energy required to increase both the internal energy and the work done to expand
the gas at constant pressure.

2. Heat Capacity:

 𝑐𝑝 is always greater than 𝑐𝑣 for perfect gases because it includes the work done against the
atmospheric pressure during expansion.

Practical Implications

 When dealing with processes involving perfect gases, 𝑐𝑣 is used when the process occurs at constant
volume, while 𝑐𝑝 is used for processes occurring at constant pressure.
 These specific heats are crucial in various thermodynamic calculations, including those involving heat
transfer, energy balance, and the determination of changes in internal energy and enthalpy.

Units

The units of 𝑐𝑝 and 𝑐𝑣 are typically:

 J/(kg\cdotpK) in the SI system (Joules per kilogram per Kelvin)

 cal/(g\cdotp°C) in the CGS system (calories per gram per degree Celsius)
5|Page
 Summary

 𝑐𝑣: Specific heat at constant volume, relevant for processes where volume does not change.
 𝑐𝑝 : Specific heat at constant pressure, relevant for processes where pressure does not change.
 Relationship: 𝑐𝑝=𝑐𝑣+𝑅 for perfect gases, where 𝑅 is the specific gas constant

The universal gas constant, often denoted as 𝑅, is a fundamental physical constant that appears in
various equations in thermodynamics and physical chemistry. It relates the energy scale in physics to
the temperature scale, playing a crucial role in the ideal gas law and other gas-related calculations.

Definition

The universal gas constant is defined as the constant of proportionality that relates the pressure,
volume, and temperature of an ideal gas in the ideal gas law. It is expressed as:

𝑃𝑉=𝑛𝑅𝑇

where:

 𝑃 is the pressure of the gas,

 𝑉 is the volume of the gas,
 𝑛 is the number of moles of the gas,
 𝑇 is the absolute temperature (in Kelvin),
 𝑅 is the universal gas constant.

Value of the Universal Gas Constant

The value of 𝑅 is consistent across all ideal gases and is given by:

𝑅=8.314462618 J/(mol\cdotpK)

This value can be expressed in different units depending on the context:

 8.314462618 J/(mol\cdotpK) (Joules per mole per Kelvin)

 0.082057 L\cdotpatm/(mol\cdotpK) (liters atmospheres per mole per Kelvin)
 1.987 cal/(mol\cdotpK) (calories per mole per Kelvin)

6|Page
 Origin and Significance

The universal gas constant 𝑅 can be derived from the Boltzmann constant 𝑘𝐵 and Avogadro's
number 𝑁𝐴:

𝑅=𝑁𝐴𝑘𝐵

where:

 𝑘𝐵 is the Boltzmann constant (1.380649×10−23 J/K

 𝑁𝐴 is Avogadro's number (6.02214076×1023 mol−1

This relationship highlights the connection between macroscopic thermodynamic properties and
microscopic molecular behavior.

Applications

The universal gas constant is used in various fundamental equations and concepts in thermodynamics
and physical chemistry, including:

1. Ideal Gas Law: 𝑃𝑉=𝑛𝑅𝑇 – relates the pressure, volume, and temperature of an ideal gas.
2. Van der Waals Equation: Adjusted for real gases to account for intermolecular forces and molecular
volumes.
3. Thermodynamic Processes: Calculations involving specific heats, entropy, enthalpy, and Gibbs free
energy.
4. Chemical Kinetics: Arrhenius equation for the temperature dependence of reaction rates.

Summary

The universal gas constant 𝑅 is a key constant in the field of thermodynamics and physical chemistry,
representing the relationship between pressure, volume, and temperature for an ideal gas. Its
consistent value across all ideal gases and its derivation from fundamental constants underscore its
importance in linking microscopic and macroscopic properties.

7|Page