Air vs steam: Limitations of air

Summary
Why is air inefficient to do work: Air has two limitations
The fundamental point is superheated steam has more energy than air under identical pressure and temperature

Limitation 1:
Suppose you have a power plant that generates X MW power. This requires the turbine to do a W amount of work.
dH = dU + W or W = dH – dU, since the internal energy of air, is < superheated steam, a gas cycle will need to
produce more dH . Since dH = Cp [T hot – T cold], , a gas cycle must run at a much higher temperature than a steam
cycle to do the same work W, but there is a limitation because of wear and tear and material failure at high
temperatures. Air cannot achieve superheated steam’s enthalpy even at 1700 degc and 100 bar.
Limitation 2:
The second important point is in a steam cycle all superheat is squeezed out in the condenser under a vacuum. Even
if you are very efficient and you discharge the cold gas [air] at 1 bar and 50 degc, you still lose about 350 kj/kg heat
in a simple gas cycle. That gives you a low efficiency. Therefore, the concept of the combined gas cycle has evolved.
Fundamentals of air and steam
At molecular level
Air: Air consists of N2 and O2 gases. Both gases are diatomic and non-polar in nature. All diatomic molecules are
linear and characterized by a single parameter which is the bond length or distance between the two atoms.
Diatomic nitrogen has a triple bond, diatomic oxygen has a double bond. They have only weak van der Waals
intermolecular attraction working between them. The total degrees of freedom of a diatomic molecule in which the
molecule carries energy is five [three translational and two rotational]. Each of these modes gets an equal share of
the energy of 1/2kBT [K is Boltzmann constant and T is temperature. Thus, the total internal energy in a diatomic
molecule= 5/2KBT. The atoms in a molecule can store energy in vibrations and rotations as well as translations. Each
way energy can be stored in the molecule is called a degree of freedom. The compressibility factor for air at high
temperatures is > 1. That is there is a positive deviation from ideal gas laws.
Superheated steam: It is a product of water which is a triatomic polar molecule. Water’s H-bonds break at 100 degc
that leaves van der Walls forces to stay as steam gets superheated. Water molecules [ mol weight = 18 against air
mol weight 28 g/mol are much smaller. That makes superheated steam more compressible than air [ emptier
space/unit volume]. A non-linear triatomic molecule like superheated steam [water] has a total, nine possible
degrees of freedom (three translational, three rotational, and three vibrational), but only seven are accessible at
lower temperatures. The internal energy of a superheated steam molecule could be anything from 7/2KBT to
9/2KBT. Much more than air. A very conservative estimate is superheated steam has internal energy of more
than 1.4 times of air. That explains that superheated steam has much more energy than air. This also explains
why superheated steam has much more specific heat than air under similar conditions. At 100 bar, 500 degc, the
air has about 1.108 kj/kg-k specific heat while superheated steam has about 2.589 kj/kg-k specific heat which is
about 2.5 times. Consequently, for the same hot reservoir and cold reservoir dT, the air has less specific enthalpy
dh. (dh = Cp [T hot – T cold]). This needs a gas turbine much higher dT across hot and cold reservoirs.
Thermophysical properties of air and steam [ superheated]
 Superheated
Air Property steam
[100 bar/500 Value Unit Property Value Unit
degc] [100 bar 500
degc]

Specific
Specific volume 0.023073 [ m3/kg] 0.032453 [ m3/kg]
volume

Specific Specific
795.9 [ kJ / kg] 3373.81 [ kJ / kg]
Enthalpy: Enthalpy:

Specific
Specific isobar
isobar heat
heat capacity: 1.108 [ kJ / kg K] 2.589 [ kJ / kg K]
capacity:
Cp
cp

Compressibility, Compressibil
>1 <1
Z ity, Z

Analysis of thermophysical data of air and superheated steam

Key points:
Point 1 Steam does more work than air

There are two reasons [1] small water [steam] molecules have smaller van der Walls forces than air molecules.
Molecular wight of water is 18 g/mol vs air [mean] 28 g/mol. This makes the movement steam molecules more
rapid and consequently a lower density than air i.e., higher specific volume than air and [2] water molecules [ mol
weight = 18 against air mol weight 28 g/mol are much smaller. That makes superheated steam more compressible
than air [ emptier space/unit volume].
This implies that the specific volume of the steam is less than air during a compression process and higher than air
in the expansion process.
Concept
Compressibility Z:

Z in thermodynamics, is the compression factor or the gas deviation factor, which describes the deviation of a real
gas from ideal gas behaviour. It is simply defined as the ratio of the molar volume of a gas to the molar volume of an
ideal gas at the same temperature and pressure.
Z = V actual / V ideal
LHS image is the compressibility of air and RHS image is for compressibility of superheated steam
The above images suggest compressibility of air z>1 and compressibility of superheated steam<1. In other words,
under similar conditions, superheated steam is more compressible. Steam is the most compressible gas within all
gases because water's stable form is liquid. Steam always wants to go back to liquid. The specific volume of air at
100 bar/500dec is 0.023073 m3/kg while superheated steam specific volume is 0.032453 m3/kg which is one and
half times more than air. This suggests, under similar temperature and pressure, superheated steam does more
work than steam.
Point 2: Steam has more internal energy

Specific heat [ stored heat] of steam is twice of air. The internal energy of steam is 1.4 times of air.
Point 3: Steam has higher specific enthalpy than air

Concept: Specific enthalpy

The specific enthalpy (H) of a substance is its enthalpy per unit mass. It equals the total enthalpy (H) divided by the
total mass (m).
Note that the enthalpy is the thermodynamic quantity equivalent to the total heat content of a system. The specific
enthalpy is equal to the specific internal energy of the system plus the product of pressure and specific volume.
H = U + PV, U = Internal energy and PV is capacity to do work
As explained, the fact that the specific heat of superheated steam [ refer to thermophysical properties of air and
steam above] is more than twice of air under identical conditions, steam has higher internal energy. A very
conservative estimate is superheated steam has internal energy of more than 1.4 times of air. The second point as
explained steam is more compressible than air, Z <1 at the same temperature and pressure gives the steam the
ability to do more work. This explains why steam has more specific enthalpy or energy than air.
Enthalpy-Entropy diagram for air

The X-axis is entropy in kj/kg-k. Red lines are pressure lines in Mpa. The extreme right-side red line stands for 0.001
Mpa and the extreme left- side red line stands for 10 Mpa. Black bold almost horizontal lines are temperature lines.
There are two important observations emerging from this diagram [1] at a constant temperature as pressure
increases, enthalpy remains practically constant while entropy reduces, and [2] at constant pressure as temperature
increases, the enthalpy and entropy both increases. The most important observation is specific enthalpy of air 100
bar/500 degc is only = 795.9 kj/kg
Enthalpy-Entropy diagram for superheated steam
Y-axis is enthalpy expressed as kj/kg. The X-axis is entropy expressed as kj/kg-k. There are two sets of curved lines in
the image. These are well explained what they stand for. The curves rounded upwards are temperature lines

expressed as degc. The curves rounded downwards are pressure lines. The image suggests the following: [1] at a
constant temperature when pressure increases the enthalpy reduces and also entropy reduces [2] At constant
pressure when the temperature is increased enthalpy and entropy both increases. The most important observation
is the specific enthalpy of superheated steam at 100 bar/500 degc = 3373.81 kj/kg. There is a huge difference in the
enthalpy between superheated steam and air. Superheated steam has enthalpy at 100 bar/500 degc more than four
times that of air. Air cannot achieve superheated steam’s enthalpy even at 1700 degc and 100 bar. So, air’s enthalpy
is a big limitation while delivering mechanical work.
What does the thermophysical data analysis of air and steam conclude?

Air has two limitations

The fundamental point is superheated steam has more energy than air under identical pressure and temperature
Limitation 1:
Suppose you have a power plant that generates X MW power. This requires the turbine to do a W amount of work.
dH = dU + W or W = dH – dU, since the internal energy of air, is < superheated steam, a gas cycle will need to
produce more dH . Since dH = Cp [T hot – T cold], , a gas cycle must run at a much higher temperature than a steam
cycle to do the same work W, but there is a limitation because of wear and tear and material failure at high
temperatures. Air cannot achieve superheated steam’s enthalpy even at 1700 degc and 100 bar.
Limitation 2:
The second important point is in a steam cycle all superheat is squeezed out in the condenser under a vacuum. Even
if you are very efficient and you discharge the cold gas [air] at 1 bar and 50 degc, you still lose about 350 kj/kg heat
in a simple gas cycle. That gives you a low efficiency. Therefore, the concept of the combined gas cycle has evolved.

Credit: Google