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Summer 2015
HW#2
Due Thurs., June 4
T 5 2 Qx,int
k 2 m x
s x R x ln
ln
3
px
h
h
x
T
(1)
where Rx is the mass specific gas constant for species x, mx is the mass of species
x, px is the partial pressure of species x, Qx,int is the partition function for the internal
energy modes of x (not including translational energy) and hx is its enthalpy per unit
mass.
b) Should the enthalpy term in equation (1) include the offset energy of the
molecule relative to the common energy zero level of the whole system of
molecules in the mixture or be referenced to the lowest energy level for that
molecule?
2. Equilibrium Constant
Consider the following stoichiometric reaction
CO2
CO
1
O2
2
Brot
(cm-1)*
vib1
(cm-1)*
vib2
(cm-1)*
vib3
(cm-1)*
go,el
g1,el
1,el
(cm-1)*
hf(0K)
(kJ/mol)**
CO2
44.01
0.389
1330
667.3
2349
---
----
-393.151
CO
28.01
1.945
2167.6
---
---
64,958
-113.805
The wavenumber (a kind of frequency unit) values given in the table can be converted to
characteristic temperatures (e.g., rot and vib) by multiplying by hc/k, where c is the speed of
light, h is Plancks constant, and k is Boltzmanns constant.
**
The formation enthalpy is the amount of energy required to form a mole of a species from its
elements. The formation enthalpies (at 0 K) given here are from the JANNAF tables, which
use O2 and C(s) as the elemental forms of oxygen and carbon (i.e., it assumes that O2 and C
have zero chemical energy). Also mol here means gmol (not kmol).
Note: carbon dioxides (O-C-O) bending mode (vib2) is doubly degenerate, i.e., that
two of the vibrational (bending) modes have the same characteristic frequency.
hmix RA2 4 * T 1 * D
an ideal dissociating gas in terms of: , (/T)p, and D; assuming D/T >> 1.
b) Sketch qualitatively how the normalized mixture specific heat should vary with
temperature (from a low T with no dissociation to a high T with complete
dissociation, but assuming D/T still much greater than one). The only
numbers you need on this sketch are the values of the normalized specific
heat in your low and high temperature limits.
4. Saha Equation
An arc heater is used to produce a partially ionized argon plasma at a static
pressure of 0.01 atm. Assuming that the gas is in equilibrium, all its constituents are
ideal gases, and that that you can neglect multiply ionized species, at what
temperature will 1.0% of the argon be ionized? What temperature would be
required to produce the same ionization level if the pressure was increased to 1.0
atm.
You may find the following properties (ionization energies and electronic energy
level data) for Ar and Ar+ useful.
ioniz (eV) *
go,el
g1,el
1,el (eV)*
g2,el
2,el (eV)*
Ar
15.76
12
11.6
---
---
27.63
0.178
13.5
Ar
*
An electron volt (eV) is typically associated with an energy value, i.e., the energy acquired
-19
by a particle with a charge of 1 e accelerated through 1 Volt (=1.60210 J) but it can
be converted to temperature units by dividing by Boltzmanns constant (i.e., /k). Thus
1 eV 11,600 K.