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01 Chap1 The Perfect Gas C

Real gases deviate from the perfect gas law, especially at high pressures and low temperatures, due to molecular interactions. The van der Waals equation provides a model for real gas behavior, accounting for these deviations and allowing for predictions about gas behavior under various conditions. Key concepts include the compression factor, virial coefficients, critical constants, and the principle of corresponding states.

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12 views14 pages

01 Chap1 The Perfect Gas C

Real gases deviate from the perfect gas law, especially at high pressures and low temperatures, due to molecular interactions. The van der Waals equation provides a model for real gas behavior, accounting for these deviations and allowing for predictions about gas behavior under various conditions. Key concepts include the compression factor, virial coefficients, critical constants, and the principle of corresponding states.

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khj041030
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1C. Real gases – 1.

Deviation from perfect behavior

• Real gases do not obey the perfect gas law exactly except in the limit of 𝑝 → 0. Deviation from the law are
particularly important at high pressures and low temperatures, especially when a gas is on the point of condensing
to liquid.

• Real gases show deviations from the perfect gas law because molecules interact with one another. A point to keep
in mind is that repulsive forces between molecules assist expansion and attractive forces assist compression.
1C. Real gases – 1. Deviation from perfect behavior

• The consequences of these interactions are shown by


shapes of experimental isotherms.
1C. Real gases – 1. Deviation from perfect behavior

■ (a) The compression factor

• Compression factor

𝑉𝑚
𝑍= 𝑜
𝑉𝑚
1C. Real gases – 1. Deviation from perfect behavior

■ (b) Virial coefficients

• At large molar volumes and high temperatures the real gas isotherms do not differ greatly from perfect gas isotherms.

𝑝𝑉𝑚 = 𝑅𝑇(1 + 𝐵′ 𝑝 + 𝐶 ′ 𝑝2 + ⋯ )

• A more convenient expansion for many applications

𝐵 𝐶
𝑝𝑉𝑚 = 𝑅𝑇(1 + + 2 + ⋯) Virial Equation of state
𝑉𝑚 𝑉𝑚
1C. Real gases – 1. Deviation from perfect behavior

• An important point is that although the equation of state of a real gas may coincide with the perfect gas law as 𝑝 →
0, not all its properties necessarily coincide with those of a perfect gas in that limit.

𝑑𝑍
= 𝐵′ + 2𝑝𝐶 ′ + ⋯ → 𝐵′ 𝑎𝑠 𝑝 → 0
𝑑𝑝

𝑑𝑍
→ 𝐵 𝑎𝑠 𝑉𝑚 → ∞
𝑑(1Τ𝑉𝑚 )
1C. Real gases – 1. Deviation from perfect behavior

■ (c) Critical constants

• The isotherm at the temperature Tc plays a special role in the theory of the states of matter. An isotherm slightly
below Tc behaves as we have already described: at a certain pressure, a liquid condenses from the gas and is
distinguishable from it by the presence of a visible surface.
1C. Real gases – 2. The van der Waals equation

• This equation is an excellent example of an expression that can be obtained by thinking scientifically about a
mathematically complicated but physically simple problem; that is, it is a good example of ‘model building’.

■ (a) Formulation of the equation

• Deriving the van der Waals


1C. Real gases – 2. The van der Waals equation
1C. Real gases – 2. The van der Waals equation

■ (b) The features of the equation

• The advantage of the van der Waals equation is that it is analytical and allows us to draw some general conclusions
about real gases.
• When the equation fails we must use one of the other equations of state that have been proposed, invent a new
one, or go back to the virial equation.
1C. Real gases – 2. The van der Waals equation

• The oscillations, the van der Waals’ loop, are unrealistic because they suggest that under some conditions an
increase of pressure results in an increase of volume.
• They are replace by horizontal lines drawn so the loops define equal areas above and below the lines: this
procedure is called the Maxwell construction.
1C. Real gases – 2. The van der Waals equation

• The principal features of the van der Waals equation can be summarized as follows.

1. Perfect gas isotherms are obtained at high temperatures and large molar volumes.

2. Liquid and gases coexist when the attractive and repulsive effects are in balance.
1C. Real gases – 2. The van der Waals equation

• The principal features of the van der Waals equation can be summarized as follows.

3. The critical constants are related to the van der Waals coefficients.
1C. Real gases – 2. The van der Waals equation

■ (c) The principle of corresponding states

• Dimensionless reduced variables


Checklist of concepts

1. The extent of deviations from perfect behavior is summarized by introducing .


2. is an empirical extension of the perfect gas equation that summarizes the behavior of real
gases over a range of conditions.
3. The isotherms of a real gas introduce the concept of .
4. A gas can be liquefied by pressure alone only if its temperature is at or below its .
5. The is a model equation of state for a real gas expressed in terms of two parameters,
one (a) corresponding to molecular attractions and the other (b) to molecular repulsions.
6. The captures the general features of the behavior of real gases, including their critical
behavior.
7. The properties of real gases are coordinated by expressing their equations of state in terms of .

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