Energy Analysis Involving

Ideal Gases
Gas Laws:
 Boyle’s Law PV = c
 Charles’ Law V/T=c
 Gay Lussac’s Law P/T=c
 Combined Gas Law PV / T = c

Ideal Gas Equation: (Equation of State)

PV = nRT
 Processes
Reversible Process:
 Direction can be reversed at any point by an
infinitesimal change in external conditions without loss
or dissipation of energy.

Irreversible Process:
 At all times, the pressure of the gas and the opposing
pressure differ an infinitesimal amount
 Finite changes are made
 System is not at equilibrium throughout the process.
 At the same point in an irreversible cycle, the system will be
in the same state but the surroundings are permanently
changed after each cycle.
Constant Volume Process
(Isochoric)
a) dW = 0 W = 0
b) dU = dQ U = Q (1st Law)
c) Specific Heat or Heat Capacity
dQ = nCVdT Q = nCVT
dQ = mCVdT Q = mCVT
If CV =  + T + T2 dQ = ∫ m ( + T + T2) dT
d) At any process:
U = nCV  T (general equation)
U = mCV T
e)
P P1 P2
=c =
T T1 T2
Constant Pressure Process
(Isobaric)
a) dW =  PdV =  P (V2  V1)
b) dU = dQ + dW
U = Q  P (V2  V1)
c) dQ = nCPdT
d) dH = nCPdT (general equation)
Relationship Between CP and CV
from Definition of Enthalpy
dH = dU + d (PV)
From Ideal Gas Equation: PV = nRT
dH = dU + d (nRT)
nCPdT = nCVdT + nRdT
CP= CV + R
Let  = CP / CV  = 1 + R / CV CV = R / (  1)
Since CP =  CV Cp = =  R / (  1)

For an ideal gas, U depends on Ts.

Since nCVdT must be true for all process with the same T,
CV = CP  R.
Thus, CP > CV at all times.
Cp  Cv  R
Cp Cv R
 
Cv Cv Cv
R Cp
  1 Since Cp  Cv from  
Cv Cv
Cv  Cv  R and Cp  Cv  R
(  1)Cv  R Cp
Cp  R
R 
Cv 
 1 Cp  Cp  R
Cp(  1)  R
R
Cp 
 1
Problem:
An ideal gas (CP = (5/2)R) has a volume of 18 L at
a pressure of 4 atm and a temperature of 312C. It
undergoes a change of state to a final pressure of
2 atm. Calculate Q, W, U, and H (all in kJ) if the
change is isochoric.
Constant Temperature Process
(Isothermal)
a)Since T = 0 dU = 0 dH = 0
dW  0 dQ  0
b) 1st Law: U = Q  W  W = dQ
c) PV = c P1V1 = P2V2

For isothermal and against a constant P (Irreversible)

Qirrev = Wirrev = ∫ Popp dV
For isothermal and reversible process
Qrev =  Wrev = ∫ PdV
 
V2
Q irrev  W irrev   p g dV
V1

nRT
Popp  Pg   
V2
dV
V1 V
nRT V2
 W rev   dV   nRT ln
V V1
V2
Q rev  nrT ln
V1
P1 P1
W rev   nRT ln  -P1 V1 ln
P2 P2
Problem:
An ideal gas initially at 184C, 3 atm with a volume
of 25 L and undergoes expansion to a final
pressure of 1.4 atm. Determine the work done by
the gas if the expansion is
(a) isothermal and against a constant
opposing pressure of 1.4 atm.
(b) isothermal and reversible.
 Adiabatic Process
- No heat is transferred between
system and surroundings.
a) dQ = 0 Special Eqns. for an Adiabatic
b) dU =  W & Reversible Process
W =  nCVdT •T&V TV1 = c
dU =  nCVdT •P&V PV = c
c) Wrev = Pgas dV •T&P T P1 = c
Popp = irrev.
Derive the special equations from
nRT
dU  dW nCV dT  PdV nCV dT   dV
V
Problem:
One g-mol of an ideal monatomic gas [CV = (3/2)R]
has an initial pressure of 6 atm and a temperature
of 200C. It expands to a final pressure of 2 atm.
Calculate the work done by the gas on expansion if
the expansion is:
(a) adiabatic and reversible
(b) adiabatic and against a constant
opposing pressure of 1 atm.
Problem 3.9/(p.112-7th ed):
An ideal gas initially at 600K and 10 bar undergoes
a 4-step mechanically reversible cycle in a closed
system. In step 12, pressure decreases isothermally
to 3 bar; in step 23, pressure decreases at constant
volume to 2 bar; in step 34, volume decreases at
constant pressure; and in step 41, the gas returns
adiabatically to its initial state.
(a) Sketch the cycle on a PV diagram.
(b) Determine (where unknown) both T and P
for states 1,2, 3, and 4.
(c) Calculate Q,. W, U and H for each
step of the cycle.
Problem 3.10/(p.112-7th ed):
An ideal gas, CP = (5/2) R and CV = (3/2) R, is changed
from P = 1 bar and V1 = 12 m3 to P2 = 12 bar and V2 = 1 m3
by the following mechanically reversible processes:
(a) Isothermal compression;
(b) Adiabatic compression followed by
cooling at constant pressure;
(c) Adiabatic compression followed by
cooling at constant volume;
(d) Heating at constant volume followed by
cooling at constant pressure; and
(e) Cooling at constant pressure followed by
heating at constant volume.
Calculate Q, W, U, H. Sketch the path of all processes
on a single PV diagram.