Chemical Engineering Thermodynamics II Tutorial022k17

Question 1.
For a particular binary liquid solution at constant T and P, the molar enthalpies of mixtures are
represented by the equation: h = x1(a1 + b1x1) + x2(a2 + b2x2) where ai and bi are constants. Since the
equation has the form of h= Σxihi , it might be that hi = xi(ai + bixi).

a) Show whether hi = xi(ai + bixi) is valid by using the Gibbs-Duhem equation.

b) Derive expressions for h1 and h2 based on the definition of a partial molar property.

Question 2.
The heat of mixing data for the n-octanol + n-decane liquid mixture at atmospheric pressure are
approximately fitted by
h = x1x2(A + B(x1 – x2)) J/mol

where A = -12,974 + 51.505 T and B = +8782.8 - 34.129 T with T in K and x1 being the n
octanol mole fraction.

a) Compute the difference between the partial molar and pure component enthalpies of
n-octanol and n-decane at x1 = 0.5 and T = 300 K.

b) Compute the difference between the partial molar and pure component heat
capacities of noctanol and n-decane at x1 = 0.5 and T = 300 K.

c) An x1 = 0.2 solution and an x1 = 0.9 solution are to flow continuously into an

isothermal mixer in a mole ratio of 2:1 at 300 K. Will heat have to be added or
removed to keep the temperature of the solution leaving the mixer at 300 K? What
will be the heat flow per mole of solution leaving the mixer?

d) Plot h vs. x1 at 300 K. Show the relationship between the plotted data and your
answers in part a) by placing your value for n-octanol at x1 = 1.0 and your value for
n-decane at x1 = 0.0.

e) Using the plot, estimate values for h1∞ and h2∞ .

Question 3.
For a ternary solution at T and P, the composition dependence of molar property m is given by:

m = x1m1 + x2m2 + x3m3 + x1x2x3C

where m1, m2, m3 are the values of m for pure species of 1, 2, and 3, respectively, and C is a
parameter independent of composition. Determine expressions for m1 , m2 , and m3 by the
application of the equation:
mi=[δ(nm)/δni]P,T,nj≠1
As a partial check of your results, verify that they satisfy the relationship: m= Σ ximii
Question 4.
The Redlich-Kwong equation can be written as: P=RT/(v-b) - a /[T0.5 v(v+ b)] and manipulated to
give: Z= 1+ b /(v- b) − a /[RT 1.5 (V +b)] where a = 0.42748R2 Tc2.5 /Pc and b =
0.08664RTc /Pc.

a) Show that lnφ= − ln(1− b/v)- [a ln (1+ b/v)]/(bRT1.5) + Z-1-ln Z. As a hint, consider the use
of either g/RT=∫oP (Z - 1) dP/P or dg/RT=∫oP (Z − 1) d ρ/ρ + Z − 1 - ln Z where ρ = 1/V .

b) Determine the fugacity of n-butane gas at 500 K and 50 bar using the equation derived in a).

c) Determine the fugacity of n-butane gas at 500 K and 50 bar using the values of h = -4.51
R

kJ/mol and S = -6.55 J/mol-K determined n-butane under these conditions.

R

d) Determine the fugacity of n-butane gas at 500 K and 50 bar using generalized correlations.

Question 5.
Experimental data taken from 0.0 to 50.0 bar give the fugacity of a pure gas to be f=P*exp(-CP)
where P is the pressure in bar and C a constant that depends on temperature. For the region
given by 0.0 oC to 100.0 oC, the value of C is given by: C = -0.065 + 30.0/T, where T is in
Kelvin.
(a) Find a viald EOS for this gas from 0.0oC to 100.0 oC.
(b) What is the molar volume at 80.0oC and 30.0 bar.

Question 6.
For a binary system at constant T and P the molar volume in cm3/mol is given by:
v=100ya+80yb+2.5yayb
(a) What is the pure species molar volume for species a, va?
(b) Derive an expression for the partial molar volume, va, in terms of yb and find the partial
molar volume at infinite dilution, va∞.
(c) Show and explain whether the volume change of mixing, ∆vmix is greater than, equal to or
less than 0.

Question 7.
Steam undergoes an isothermal change in state from 9000 kPa and 400 ºC to 300 kPa and 400
ºC. Determine using steam tables, the ratio of the fugacity in the final state to that in the initial
state.
(Hint: this question requires only a little bit of calculation, so think first about how to connect
fugacities or rather, fugacity ratios given the type of data in a steam table.)

Question 8.
Calculate the fugacity of water at 647.0 K and 114 atm using (a) the steam tables (b) the van der
Waals EOS and (c ) generalized correlations.

Question 9.
Develop expressions for fugacity and fugacity coefficient for a pure species based on the
Redlich-Kwong equation of state.
Question 10.
Experimental data taken from 0.0 to 50.0 bar give the fugacity of a pure gas to be f=P*exp(-CP)
where P is the pressure in bar and C a constant that depends on temperature. For the region
given by 0.0 oC to 100.0 oC, the value of C is given by: C = -0.065 + 30.0/T, where T is in
Kelvin.
a. Find a viald EOS for this gas from 0.0oC to 100.0 oC.
b. What is the molar volume at 80.0oC and 30.0 bar.

Question 11.
Derive expressions for hE, sE, vE and the activity coefficients for a binary mixture as described by
GE
 Bx1 x 2
the expression: RT

Question 12.
The activity coefficient for species 1 in a binary mixture is given by:
ln  i  ax 22  bx 23  cx 24
Where a,b & c are concentration-independent parameters. What is the expression for lnγ2 in
terms of these parameters?

Question 13.
Estimate the fugacity of water vapour at 600.0 oC & 18.0 bar and compare with values from
steam tables.

Question 14
Calculate the fugacity and fugacity coefficient of steam at

(a) 2.0 Mpa and 500.0 oC

(b) 50.0 Mpa and 500.0 oC

Question 15
Calculate the fugacity of water at 647.0 K and 114.0 atm using:
a. the steam tables
b. the van der Waals equation of state
c. Generalized correlations

Question 16
Consider a system containing pure hydrogen sulphide at 300.0 K and 20.0 bar. The following
equation of state characterizes the PvT behaviour of H2S well under these conditions:

 PTc  0.422Tc1.6 
Pv  1   0.083  
 Pc T  T 1 .6 
Using this equation of state, find the fugacity and fugacity coefficient.

Question 17
The excess enthalpy of a liquid mixture of species 1 & 2 at fixed T & P is represented by the
equation: hE=x1x2(40x1+20x2) where hE is in J mol-1. Derive expressions for :
E E
h1 , h2 as functions of x1

Question 18
a. Fnd expressions for gE, sE and hE as functons of T if C PE is a cons tan t independent of T

b. From the equations developed above calculate gE, sE and hE for an equimolar solution of
benzene(1) in n-hexane(2) at 323.15 K given the following excess property values for an
equimolar solution at 298.15 K:

CPE  2.86 J mol 1 K 1 h E  897.9 J mol 1 g E  384 .5 J mol 1