CHARACTERISTIC EQUATION OF STATE
At extremely high temperatures above the critical values and extremely low pressure, vapours
tend to obey hyperbolic law (combined gas law):
pv
= constant = R
T
pv = RT
This equation is called characteristic equation of state of a perfect gas, and the constant R is
called the specific gas constant. The unit of R is kJ/kg.K. For a defined mass and volume:
pV = mRT
But molar mass is defined as:
m
m
̃ =
n
In which n is the number of moles in a mass of the working fluid. Rearranging:
m = nm
̃
Substituting into characteristics equation:
pV = nm
̃ RT
Or;
pV
m
̃R =
nT
pV
The term is called molar gas constant and is the same for all gases (8314.5 J/kmol K):
nT
pV
̃=
R =m ̃R
nT
̃T
pV = nR
̃
R
R=
m
̃
It means that the specific gas constant for any gas can be calculated from its molar mass.
Example 1
A vessel, 0.2 m3, contains nitrogen at 1.013 bar and 15OC. If 0.2 kg of nitrogen is now pumped
into the vessel, calculate the new pressure when the vessel returns to its initial temperature.
The molar mass of nitrogen is 28 kg/kmol, and it may be assumed to be a perfect gas.
Solution
The specific gas constant of nitrogen:
̃ 8314.5
R
R= = = 296.95 J⁄kg 𝐾
m
̃ 28
For the initial conditions:
p1 V1 = m1 RT1
Then the initial mass:
p1 V1 1.013 × 105 × 0.2
m1 = = = 0.2369 kg
RT1 296.95 × (273 + 15)
Final mass:
𝑚2 = 0.2 + 0.2369 kg = 0.4369 kg
Also;
p2 V2 = m2 RT2
m2 RT2 0.4369 × 296.95 × 288
p2 = = = 186821.9352 𝑃𝑎
V2 0.2
The final pressure is the gas returns to its initial temperature is 1.868 bar.
SPECIFIC HEAT CAPACITY
Def: the quantity of heat required to raise temperature of a unit mass of matter by one Kelvin.
For reversible nonflow process:
dQ
c=
mdT
Where:
dQ is heat input,
m is the mass of the substance,
dT is temperature increase,
For gases, increase in temperature with addition of heat depends on the pressure and volume.
Therefore, specific heat capacity is defined for constant pressure (cp) and volume (cv). Where;
𝜕𝑢
𝑐𝑣 = ( )
𝜕𝑇 𝑣
𝜕ℎ
𝑐𝑝 = ( )
𝜕𝑇 𝑝
Then quantity of heat can be calculated for reversible non-flow processes at constant volume
or volume:
𝑑𝑄 = 𝑚𝑐𝑣 𝑑𝑇
𝑑𝑄 = 𝑚𝑐𝑝 𝑑𝑇
The specific heat capacity varies with temperature but is assumed constant for perfect gases.
Net heat added can then be arrived at by integration.
For constant volume:
dQ = mcv dT
T2
T
Q = mcv ∫ dT = mcv |T|T21 = mcv (T2 − T1 )
T1
For constant pressure:
𝑑𝑄 = 𝑚𝑐𝑝 𝑑𝑇
T2
T
Q = mcp ∫ dT = mcp |T|T21 = mcp (T2 − T1 )
T1
Joule’s Law
The internal energy of a perfect gas is a function of its absolute temperature only:
𝑢 = 𝑓(𝑇)
Derivation
Consider a unit mass of a perfect gas heated at a constant volume. From non-flow energy
equation:
dQ + dW = du
Since the volume remains constant:
dW = −mpdv = 0
Then:
dQ = du
Also:
dQ = mcv dT
For a unit mass, m=1:
dQ = cv dT
Substituting back:
du = dQ
du = cv dT
Integrating:
2
u = ∫ cv dT
1
u = cv T
For a specific value of mass m:
U = mcv T
And gain in internal energy through a thermodynamic:
U2 − U1 = mcv (T2 − T1 )
Relationship between CP and CV
Form non-flow energy equation, increase in internal energy for a perfect gas heated from T 1
to T2 at constant pressure is defined as:
U2 − U1 = Q + W
But:
U2 − U1 = mcv (T2 − T1 )
And:
Q = mcp (T2 − T1 )
Also, work done for a constant pressure is given by the product of the pressure and change
in volume:
W = −p(V2 − V1 ) = −pV2 + pV1
Recall characteristic equation of state:
pV = mRT
For constant pressure:
pV1 = mRT1
pV2 = mRT2
Substituting back:
W = −pV2 + pV1 = −mRT2 + mRT1
W = −mR(T2 − T1 )
Substituting for change in internal energy (U2 – U1), work (W), and heat (Q) in the energy
equation:
U2 − U1 = Q + W
mcv (T2 − T1 ) = mcp (T2 − T1 ) − mR(T2 − T1 )
cv = cp − R
R = cp − cv
Specific Enthalpy
From the definition of enthalpy:
h = u + pv
Recall:
pv = RT
u = cv T
Substituting:
h = cv T + RT = (cv + R)T
Also:
R = cp − cv
cv = cp − R
So, the enthalpy is:
h = (cp − R + R)T = cp T
For a specified mass, m:
H = mcp T
Ratio of Specific Heat Capacities
Ratio of the specific heat capacity at constant pressure and that at constant volume:
cp
γ=
cv
Since:
R = cp − cv
And the specific gas constant R is a positive number, it can be concluded that:
𝑐𝑝 > 𝑐𝑣
And that:
cp
γ= >1
cv
And has been estimated to be around 1.6 for monoatomic gases, 1.4 for diatomic, 1.3 for
triatomic gases, and 1.11 for long-chain hydrocarbons.
Also:
R = cp − cv
Dividing through by cv:
R cp cv
= − =𝛾−1
cv cv cv
𝐑
𝐜𝐯 =
𝛄−𝟏
Also:
cp
γ=
cv
Then
cp = γcv
𝛄𝐑
𝐜𝐩 =
𝛄−𝟏
