Académique Documents
Professionnel Documents
Culture Documents
(P14.1) An equimolar mixture of H2 and CO can be obtained by the reaction of steam with coal.
Compute the equilibrium compositions at 550 C based on an equimolar feed of H2, CO, and
H2O. The reaction is H2O + CO = H2 + CO2. Gf data at 550 C are given.
Compound In Out
H2O 0.333 0.333
CO 0.333 0.333
H2 0.333 0.333+
CO2 0
Total 1 1
( )(0.333 + ) * P 2
Ka = = 3.369
(0.333 ) *(0.333 )* P 2
= 0.176; Ans. y1 = 0.157, y2 = 0.157, y3 = 0.509, y4 = 0.176
(P14.2) One method for the production of hydrogen cyanide is by the gas-phase nitrogenation of
acetylene according to the reaction below. For a stoichiometric feed at 300C, calculate the
product composition at 1 and 200 bar given GT= 30.08 kJ/mole.
N2 + C2H2 = 2HCN
Solution: Two mole basis. Assume ideal gas.
# of moles (N2) = # of moles (C2H2) = 1.0
Compound In Out
N2 1 1
C2H2 1 1
HCN 0 2
Total 2 2
Ka = exp(-30080/(8.314*(300+273.15)) = 0.0018
(2* ) 2 * P 2
Ka = = 0.0018 , = 0.0208
(1 )2 * P 2
(Ans. y1 = 0.4896, y2 = 0.4896, y3 = 0.0416)
P = 2 bar
2 0.001 0.0012 0.0014 0.0016 0.0018
2
13 + * P
0
2 *P
Ka = -1
=
1 (13 + ) * (1 ) -2
13 + P -3
-4
Ka = 0.01933
ln Ka
-5
Noting that lnKa = -Gtot/RT, we can -6
identify the temperature by fitting a -7 y = -13996x + 14.34
trendline to the given data. -8
ln 0.01933 = -3.95, -9
substitute in the equation of straight line, -10
x = -(-14.34 3.95 )/13996. 1/T
x = 0.001306 = 1/T,
T = 765.22 K = 492OC
Compound In Out 2 *P
Ka = = 0.1118
C4H8 1 1- (2 + )* (1 )
C4H6 0
Similarly , T = 846.65K = 573.6 O C
H2 0
H2O 1 1 We need higher T.
Total 2 2+
H2 0 0 = 2 Ka[ z (1 + z ) + 2 ]
Total 1+z 1+z
(1-Ka) +Ka (1+z) - Ka z = 0 = {-Ka(1+z) + [Ka2(1+z)2+4z(1-Ka)Ka]1/2 }/[2(1-Ka)]
2
(P14.9) Calculate the equilibrium percent conversion of ethylene oxide to ethylene glycol at
298K and 1 bar if the initial molar ratio of ethylene oxide to water is 3.
In Out(zi)
EtO 3 3-
Water 1 (1-)
Glycol 0
Tot 4-
Kw = Psat/P = 0.0425; KEtO = 1.76; KGly = 8.6E-4; yi = zi Ki /[ Ki +L/F*(1- Ki)]
yGly P 7824
Ka = 2
= exp = 23.52 and yi = 1 are constraints, and L/F are
yEtO * yW * P 298.15*8.314
unknown. Guess, = 0.99, L/F = 1/3 (all glycol in liquid, all EtO in vapor).
(P14.10) Acetic acid vapor dimerizes according to 2A1 = A2. Assume that no higher-order
associations occur. Supposing that a value for Ka is available, and that the monomers and
dimers behave as an ideal gas, derive an expression for yA1 in terms of P and Ka. Then develop
an expression for PV/n0RT in terms of yA1, where n0 is the superficial number of moles
neglecting dimerization. Hint: write n0/nT in terms of yA1 where nT = n1+n2.
Solution:
n0 n1 + 2n2
= = y A1 + 2(1 y A1 ) = 2 y A1
nT nT
y A2 1 + 1 + 4 PKa
2
= Ka 1 y A1 = y A21PKa y A1 =
y A1 P 2 PKa
PV PV n 1
Ideal gas =1 = T =
nT RT n0 RT n0 2 y A1
Note: as Ka , PV/n0RT because the monomer is converted to dimer. Note also that
PV/n0RT is what we normally refer to as the compressibility factor, Z. This is an interesting
result with regard to equations of state and phase equilibria. Since Ka is simply a function of
temperature [ie. exp(-G/RT)], it says that we can compute Z given a pressure and temperature.
This is analogous to the pressure explicit virial equation (Section 6.4), but the form of the
pressure dependence is more complex. Exploring this perspective, generalizing to density-
dependent equations, and adapting to multimer-forming species and mixtures is the subject of
Chapter 15. Most of the physical insight contained in Chapter 15 is contained in this simple
practice problem.