14

Thermal equation of state in molar units

Starting from the form of the thermal equation of state derived
for 1 kmol perfect gas:
pVM = RMT
and considering the expression of the molar volume:

it results:
V
p = RM T  pV = nM RM T thermal equation of state
nM
for nM [kmol[ perfect gas
OBS: The amount of perfect gas can be expressed by:
• mass [kg],
• number of kmol [kmol],
• volume in the normal state [m3N].
The units help to get the relation linking these quantities:
m V V N
nM = = = N =
M VM VM , N N A

2.2.2. Mixture of Perfect gases

In thermal machines and devices generally evolve gas mixtures
as working fluid, i.e. air, combustion gases.
By definition, a mixture of gases is considered a perfect gas.
Thus, the thermal eq. of state for the mixture is: pV = mRT
 15

2.2.2.1. Study assumption

A gas mixture of 3 gases is considered:
gas A: x at pA, VA, TA
gas B: o at pB, VB, TB
gas C: · at pC, VC, TC
1. Real assumption: each gas of the mixture (component)
occupies the entire available volume.
xo· x· ox·
· x o· xo· x
xxo · ox·o
· o x· · ox· o·
V
VA = VB = VC = V  pA ≠ pB ≠ pC

TA = TB = TC = T  pA + pB + pC = p Dalton Law

OBS: pA, pB, pC are absolute pressures!

Under these conditions: mA + mB + mC = m
and the mass fractions are defined as:
m m m
g A = A , gB = B , gC = C , with  gi = 1
m m m i

2. Ideal assumption: the gases are considered imaginarily

separated by semi-permeable walls, so that
each gas has the same p and T.

x x x · · · o o .. ..
pA = pB = pC = p 
x x x · oo . . .  VA
+ VB + VC = V
x x x · · ·· o o .. ..
x x x · o· o . . . . TA = TB = TC = T  Amagat Law
VA VB VC
The following ratios are defined as volume fractions:
 16

VA VB VC
rA = rB = rC = with  ri = 1
V V V i

OBS: volume fractions are also molar fractions:

- thermal eq. of state for component A: p VA = nM , A RM T
- thermal eq. of state for mixture: pV = nM RM T
VA nM , A nM , i
 = or ri = , with i = component
V nM nM

2.2.2.2. Characteristic properties of mixture

a) Specific constant of the mixture – R [J/kg K]
For gases A, B, C, the thermal equation of state is expressed in
the real assumption (1°) conditions:
pA V= mA RA T
pB V= mB RB T
pC V= mC RC T
(pA + pB + pC) V= (mA RA + mB RB + mC RC) T
For the Mixture: p V = m R T
Considering Dalton Law that acts, pA + pB + pC = p, it results:
m R = mA RA + mB RB + mC RC
m R + mB RB + mC RC
 R= A A = g A RA + g B RB + gC RC
m
or R =  Ri gi [J/kg K]
i

The constant of a mixture is weighted with mass fractions.

b) Density of the mixture –  [kg/m3]
The gas mixture is considered in assumption 2° (ideal) as the
component density can be defined under same p and T values for
all gases.
 17

m p
= = 
V RT
 mi  i Vi
where m =  mi  = i
= i
i V V
mi
i = 
Vi

  =  i ri [kg/m3]
i

The density of a mixture is weighted by volume fractions.

c) Average molar mass of the mixture – M [kg/kmol]
Start from the expression: mA + mB + mC = m in which the mass
of each component and mixture is replaced as follows:
nM M = nM, A MA + nM, B MB + nM, C MC

nM , A M A + nM , B M B + nM , C M C
M= = rA M A + rB M B + rC M C
n
or M =  M i ri [kg/kmol]
i

The average molar mass is weighted with volume fractions.

d) Partial pressure of a mixture component - pi [Pa]
The transition from imaginary to real assumption is considered
to be an isotherm process, expressed for component i:
V
p Vi = pi V  pi = p  i = p  ri or pi = p ri
V
e) Specific heat of the gas mixture
Considering the elementary heating (infinitely small) of a gas
mixture with dT, the heat transferred to the mixture is expressed
in two ways:
 18

δQ = m c dT
Q =  Qi =  mi ci dT , with ci [J/kg K] – mass spec. heat
i i

The equalization of the two relationships results in:

c =  ci gi [J/kg K]
i

Similarly, the molar specific heat CM and the specific heat

relative to the normal state CN are determined as follows:
Q = nM CM dT
Q =  Qi =  nM , i CM , i dT  CM =  CM , i ri [J/kmol K]
i i i
respectively
Q = VN CN dT
Q =  Qi = V N , i C N , i dT  CN =  CN , i ri [J/m3N K]
i i i

Relations between fractions

a) gi = f (ri)
This relation is expressed in assumption 2° (pi = p and Ti = T):
m m
gi = i = i
m  mi
i
But from the state eq. in assumption 2° results:
p Vi p p
mi = = Vi = Vi M i
Ri T (RM / M i )T RM T
(Vi M i ) / V = M i ri M i ri
Finally: gi = or g i =
 (Vi M i ) / V  M i ri  M i ri
i i i
b) ri = f (gi)
Similarly:
ri =
nM , i
= i
m / Mi
=
(mi / m)(1/ M i ) or ri =
gi / M i
nM  mi / M i  (mi / m )(1 / M i )  gi / M i
i i i
 19

2.3. Real gas

Perfect gases –interaction forces between molecules are
neglected
– the dimensions of the molecules are neglected
Real gases – the distance between molecules below 10-6 mm
determines the interaction forces to act, which are
initially attraction forces Fattraction, after which they
turn into rejection forces Frejection;
– the size of the molecules is not negligible.
The mathematical description of the state of a real gas is
particularly complex – there are over 150 state equations for real
gases.
A method to consider the behavior deviation of real gases
compared to the one of perfect gases is based on the
compressibility coefficient, defined as:
pv >
z= < 1  p v = z RT
RT
But:
If z < 1 →vrg < vpg – the real gas is more compressible than p.g.
z > 1 →vrg > vgp – real gas is less compressible than p.g.

Fig. 3.1. The diagram

pv/T = f(T) for steam
 20

Fig. 3.2. The diagram

pv = f(p) for CO2 with the
Boyle curve

The behavior deviation of r.g. from p.g. was highlighted by

Andrew, who experimentally established the allure of
isothermals for CO2 (tcr = 31°C)

Fig. 3.3. Andrew’s

isothermal in p – v
diagram

OBS: if the gases have tcr < tamb they can be compressed but
they remain in gas phase.
 21

2.3.1. Real gas state equations

a) Van der Waals equation
The expression of this equation is based on the state equation of
p.g. to which corrections of p and v are made:
 a
 p + 2 (v − b ) = RT , with b –volume of the molecule
 v 
a/v2 – cohesion pressure
OBS: This equation is a third-degree eq. in function of v:
p v3 – (p b + R T) v2 +a v – a b = 0
 3 solutions for a couple of values (p, T)
➢ T > Tcr: 1 real root and 2 complex conjugated roots
➢ Tcr: 3 identical roots, inflection point = critical point
➢ T < Tcr: the isotherm should also be isobar, as shown
by experiments  2 real roots. As the third
root cannot be imaginary, it results the
undulating form B-C-D-E-F.

Fig. 3.4. Van der Waals

isothermals in p -v diagram

The Van der Waals equation is historically the first eq. that
characterizes a substance behavior in several phases.
 22

On its account there were deducted:

 a 
b) Berthelot equation:  p + 2 (v − b ) = RT
 Tv 
c
−
c) Dieterici equation: p (v − b ) = R T e RT v

d) Wukalovich – Novikov equation:

 a  c 
 p + 2
(v − b ) = RT 
 1 − (3+ 2 m ) / 2 
 v   vT 