Chemical Engineering Thermodynamics-II

Lecture-5 Gibbs theorem

(Properties change of Ideal gas mixtures)

Prof.Hitesh N. Panchal
Department of Chemical Engineering
FOT, D. D. University
Nadiad-387001
 Ideal gas-Assumptions
 This is derived directly from the kinetic theory of gases and
valid for a gas consisting of molecules that are
 Infinitesimally small (volume of gas molecules is negligible
compared to the volume of space in which they move0
 Gas molecules move in a straight line between frequent
collisions with the walls of the container and themselves.
 All collisions are elastic, i.e. no energy is lost.
 Exert no intermolecular forces(negligible forces acting between
molecules)
 As P0, all gases approach ideal gas behaviour

http://www.dynamicscience.com.au/tester/solutions1/chemistry/gas/kinetictheory.htm
The Ideal gas mixture

Consider an isolated system

consists of four separate
subsystems containing He, Ne,
Ar and Xe, each at a pressure of
1 bar. The barriers separating
these subsystems can be
removed, leading to mixing
The Ideal gas mixture
Gibbs’s Theorem
Enthalpy change of mixing(Ideal gases)
 Internal Energy
 Internal (molecular) energy can be divided into two:
 Molecular kinetic energy:
 Because of translational, rotational and vibrational motion of
molecules
 It manifests itself by velocities of molecules and is directly related to
measureable variable, temperature, via Maxwell-Boltzmann statistics
 Molecular potential energy:
 Results from position of one molecule relative to others in the system
 This also referred to as “intermolecular potential energy”
 Since this intermolecular potential energy depends on position, it can
be directly related to measurable variable, pressure
Internal Energy depends only on T(Ideal gases)

 There are no intermolecular forces in the case of ideal gases

 Thus the position of molecules relative to others does not
matter
 Internal energy of ideal gas is independent of pressure and
depends only on temperature
 In the absence of intermolecular forces, that internal energy
is independent of pressure and function of only temperature,
that is, the molecular kinetic energy of molecules:
𝒖𝒊𝒅𝒆𝒂𝒍 𝒈𝒂𝒔 = 𝒇(𝑻)
Entropy change of mixing(Ideal gases)
Entropy change of mixing(Ideal gases)
 Examples

 2 moles of an ideal gas X and 2 moles of an ideal gas Y,

initially at the same temperature & pressure are mixed under
isothermal-isobaric condition. The entropy change on mixing
is ___________ J/K.
 A vessel is divided into two compartments. One contains
100 moles nitrogen at 298K and 1 bar and the other contains
100 moles of oxygen at the same conditions. The barrier
separating them is removed and the gases are allowed to
reach equilibrium under adiabatic conditions. What is the
change in entropy of the contents of the vessel?
 Answers

 2 moles of an ideal gas X and 2 moles of an ideal gas Y,

initially at the same temperature & pressure are mixed under
isothermal-isobaric condition. The entropy change on mixing
is ___________ J/K. [Ans.22.9765 J/K]
 A vessel is divided into two compartments. One contains
100 moles nitrogen at 298K and 1 bar and the other contains
100 moles of oxygen at the same conditions. The barrier
separating them is removed and the gases are allowed to
reach equilibrium under adiabatic conditions. What is the
change in entropy of the contents of the vessel?
[Ans.1152.57 J/K]
Gibbs energy change of mixing(Ideal gases)
 Example

 Consider the system which is divided into four

compartments with the help of removable partition. Assume
that the separate compartments contain 1 mol of He, 3 mol
of Ne, 2 mol of Ar, and 2.5 mol of Xe at 298.15 K. The
pressure in each compartment is 1 bar. Now, the partition is
withdrawn and the gases are allowed to mix. Assume ideal
gases. (i) Calculate enthalpy & entropy change of mixing
(ii)Gibbs free energy change of mixing (iii) What is the
driving force for the mixing of gases.
Solution
 Examples

 A stream of N2 flowing at 22.148kg/s and is mixed with a

stream of O2 flowing at 6.688 kg/s adiabatically in a steady
state flow process. Assume that all the streams are at
300K.Find the rate of entropy change, if the gases can be
assumed to be ideal.
 It can be shown that the minimum work for separation
necessary to separate an ideal gas mixture equals .
calculate the minimum work necessary to separate 1 mole of
air containing 80%N2 and rest O2 at 300K.
Chemical Potential of species in Ideal gas mixtures
Chemical Potential of species in Ideal gas mixtures
Ideal solution
 Ideal gas versus Ideal solution

 For liquids, one cannot extrapolate (ideal gas law) to state that there are
no intermolecular interactions
 Because presence of intermolecular forces makes condensed phase
(liquid/solid) to exist
 On macroscopic level, a solution is ideal when all mixing rules are same
as for an ideal gas, i.e., Δ𝑣𝑚𝑖𝑥 𝑖𝑑𝑒𝑎𝑙 = 0 & Δℎ𝑚𝑖𝑥 𝑖𝑑𝑒𝑎𝑙 = 0
 Although concept of an ideal solution developed in analogy to an ideal
gas, there are a few following interesting differences
 A pure gas can be non-ideal gas but a pure liquid cannot be non-ideal
solution because
 all intermolecular forces in a pure liquid are same
 Increase in pressure leads to deviation from ideal gas behavior
whereas deviation from ideal solution are caused due to changes in
composition because
 non-ideal behavior results primarily from chemical differences of species in a
mixture even at low pressures
Ideal solution
Ideal solution
Ideal solution examples
Thank you