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All equations and symbols must be written exactly as shown in the prescribed textbook.

EQUATIONS OF STATE

Table 1C.4 comprises a list of just a few of equations of state suggested to date by various

scientists but common amongst them is their origin from the ideal gas law. Most popular

however is the van der Waals equation and many versions thereof have been published. The

principal features of the van der Waals equation are summarized on page 25 of prescribed

textbook.

DEVIATIONS FROM PERFECT BEHAVIOUR

We have observed that the differences in the predictions made by the ideal gas model and the

experimental observations of real gas behaviour arise from the presence of molecular

interactions in the latter and so we must address the interactions in a certain perspective. We

must differentiate between attractive and repulsive interactions and it is informative to take

ideal gas behaviour as a reference and then construct a picture of deviations caused by

molecular interactions.

a) The compression factor

We define first the compression factor as the ratio of measured molar volume (intensive) of a

gas to the molar volume of a perfect gas at the same pressure and temperature:

(1)

/ Ideal gas (2)

We rewrite (1) and make appropriate substitution:

/ ∙ (3)

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For any real gas we can write

The compression factor can have values either side of unity. For a perfect gas Z = 1 and so we

take any deviation from this value as a measure of departure from perfect behaviour. It is

important at this point to plot a graph of the compression factor against the pressure because it

shows graphically the effect of change in density. Consider the diagram in figure 1C.3 p 20

and note that the comparison there is between gases of different substances at same temperature

Fig. 1 Compression factor of nitrogen

We observe in fig.1 that condensation occurs at Z < 1 and conclude that attractive interaction

is dominant at compression factors below unity and repulsion dominates above. We further

notice that compression factor tends to unity as pressure approaches zero. At low temperatures

descend first with pressure and then reverse course when repulsion sets in. At very high

pressures where the compression has risen above unity molecules are increasingly closer

together and so repulsions dominate. Brief illustration 1C.1 shows how to calculate Z and draw

a conclusion from the result.

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b) Virial equation of state

Considering that the compression factor is written in equation 3 as a function of pressure we

propose the idea that the simplification that led to the ideal gas equation can be developed

further to allow for the description of real gas behaviour. We expand equation 3 as a series in

powers of pressure as follows:

1 ⋯ (4)

It is more convenient to expand Z as a series in powers of molar volume (1C.3b), which is

called the virial equation of state. Virial coefficients are functions of temperature and of

importance is the second virial coefficient because the third is usually very small. The slope of

Z with respect to pressure is not always zero at Z = 1 and so physical properties of substances

that depend on derivatives do not coincide with perfect gas values except for the Boyle

temperature for which Z approaches unity with zero slope.

c) The principle of corresponding states

The compression factor gives us qualitative information and to apply a quantitative measure

that applies generally to all substances we introduce the principle of corresponding states in

which the physical properties are expressed relative to critical constants and called reduced

variables, as shown in equation 1C.8. This procedure means we divide each temperature and

pressure value in fig.1 by the by the corresponding critical value and get a diagram of the form

in figure 1C.8:

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The result of this approach has limitations as observations shows that shapes of molecules have

influence on the procedure and satisfactory results are obtained for fairly simple molecules.

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Specific outcome 2: Basic concepts of First law of thermodynamics

The Greek term thermos means hot but this should be understood as referring to the study of
energy transfer (as heat) across perimeters of matter. The matter under consideration therefore
must be given an accurate description and this is done in topic 2A where figure 2A.1 illustrates
the use of terms.

Internal energy refers to the sum of the energies of all particles that make up the system,
which takes into account for each particle both the kinetic and the potential energies. Because
it is impossible to find this value thermodynamics pays attention to changes involved during
processes. Further, because of energy conservation we understand internal energy to be a state
function. It is for the above reasons that we state the following: The internal energy of a perfect
gas is independent of the volume it occupies.

The First law of thermodynamics is a born of experiment:

The internal energy of an isolated system is constant.

Mathematically we write:

∆ (1)

We can change internal energy by adding heat or work or both:

Heat and work are equivalent ways of changing the internal energy.

There are various ways of changing internal energy using work, see table 2A.1. We concern
ourselves in this module with work of expansion. Take good care of definitions! All highlighted
equations in the prescribed textbook have a fundamental meaning. Figure 2A.5 illustrates the
concept of expansion work.

(2)

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Reversible change

Any change in thermodynamics that occurs within equilibrium condition is called reversible.
We differentiate between mechanical and thermal equilibria. Figure 2A.7 illustrates
isothermal reversible expansion of a perfect gas.

Heat transfer

∆ (3)

∆ (4a)

Heat capacity at constant volume

Heat that enters a system of constant volume (like a solid) and does no other additional work
changes only the internal energy, that is:

∆ (4b)

(5)

See figure 2A.9

Enthalpy

(6)

Note that we conventionally express enthalpy as a function of temperature (T) and pressure (p).
We learn here that the heat transfer into a system that is able to change its volume and does
only expansion work changes a different state function called enthalpy

∆ (7)

See Brief illustration 2B.2 for changes in enthalpy of reactions that consume or release gases
under isothermal conditions.

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Variation of enthalpy with temperature at constant pressure

1) Because enthalpy is a state function we can write the following exact differential:

(8)

The expression shows how the change in enthalpy depends on two independent state variables.

2) Definition of heat capacity at constant pressure

(9)

Thermochemistry

1) Change in enthalpy.

We can determine according to the definition above how enthalpy changes with temperature
under constant pressure conditions if we know the heat capacity in the region under
observation:

∆ (10)

If the heat capacity is constant over the entire temperature range we can take it outside the
integral and write:

∆ ∆

Remember: , (11)

2) Enthalpies of chemical change

When the constant pressure is 1 bar we speak of standard pressure and use the symbol ⦵ to
state the pressure.

Table 2C.2 (11th Ed.) special names various processes encountered in this module and the
corresponding enthalpy symbols. The definition for standard reaction enthalpy:

⦵ ⦵ ⦵
∆ ∑ ∑ (12)

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cannot be used practically because absolute values of enthalpy are not known. Enthalpies of
formation are used instead to write:

⦵ ⦵ ⦵
∆ ∑ Δ ∑ Δ (13)

3) Hess’s law (statement on p 53)

From any set of appropriate reactions we can construct a required reaction, for example: In
Self-test 2C.1

The standard enthalpy of hydrogenation of liquid benzene can be calculated from its standard
enthalpy of combustion (1) and the standard enthalpy of combustion of liquid cyclohexane (2).

Step 1 (We interpret the provided information and write)

⦵
a) C6H6(l) + 15/2 O2(g) → 6 CO2(g) + 3 H2O(l) Δ 3268 /

⦵
b) C6H14(l) + 19/2 O2(g) → 6 CO2(g) + 7 H2O(l) Δ 3920 /

The required hydrogenation of benzene must be written as:

⦵
c) C6H6(l) + 4 H2(g) → C6H14(l) Δ ?

Step 2 (To align chemical reactions a) and b) with required c) we reverse b) as well as the
corresponding standard enthalpy sign.)

⦵
b) 6 CO2(g) + 7 H2O(l) → C6H14(l) + 19/2 O2(g) Δ 3920 /

Step 3 (We add together a) and reversed b) to get)

⦵
C6H6(l) + 15/2 O2(g) → 6 CO2(g) + 3 H2O(l) Δ 3268 /

⦵
6 CO2(g) + 7 H2O(l) → C6H14(l) + 19/2 O2(g) Δ 3920 /

⦵
C6H6(l) + 4 H2O(l) → C6H14(l) + 2 O2(g) Δ 652 /

Step 4 (The combustion of hydrogen is required to cancel out the water in the reactants and
the oxygen in the products)

⦵
H2(g) + 1/2 O2(g) → H2O(l) Δ 286 /

We multiply this equation by 4 and add it to the result in step 3 to get c) as

⦵
C6H6(l) + 4 H2(g) → C6H14(l) Δ 492 / .