B49CE Exam Answers v1

Exam Answers
HERIOT-WATT UNIVERSITY
School of Engineering & Physical Sciences
_______________________
Chemical Engineering
_______________________
Course Title: Multiphase Thermodynamics

Course Code: B49CE
Date & Time
Location:
ANSWER 3 QUESTIONS FROM SECTION A

AND 1 QUESTION FROM SECTION B
Additional information and appendices
HERIOT-WATT UNIVERSITYB49CE August 2015 v1
Exam Answers
2
SECTION A
1.
a) Explain why equations of state are used to determine the equilibrium constant K
for a compound.
[5]
b) A compound has an accentric factor =0.251 with T c = 469.6K and Pc=33.74
bar. Use the generalised compressibility charts based on the Lee-Kesler
equation of state to calculate the equilibrium constant K for this compound at
102.5C and 10.12 bar where the (f/p)L = 0.49.
[16]
c) Use the de Priester chart to show how you can determine this compound.
[4]
The generalised compressibility charts based on the Lee-Kesler equation of state and a
de Priester chart are attached.
Contd
Exam Answers
2.
a) Define bubble point and dew point and show how they can be calculated.
[4]
b) An overhead vapour stream is leaving the top bubble cap plate in a fractionating
column with the composition listed in Table 2.1 and enters a condenser at 6 bar.
What is the temperature in the condenser if the gas leaving the condenser must
be a minimum of 90 mole% ethane?
[9]
c) What is the vapour fraction leaving the condenser?
[6]
d) If there is a pressure drop between the top plate of the column and the
condenser of 1 bar, discuss any considerations you might take into account
before refluxing the condenser liquid.
[6]
Table 2.1: Overhead vapour stream composition
Component
Mole fraction
Ethane
0.7
Propane
0.3
Contd
Exam Answers
4
3.
(a) Discuss how you can identify if a system forms an azeotrope and state the
expressions for the activity coefficients of a binary system at that point.
[4]
(b) A Dichloroethylene (DCE) - Methanol system has the vapour pressure data given in
Table 3.1 at 760 mmHg. It forms an azeotrope at 51.5C containing 0.65 liquid
mole fraction of DCE. Use the Van Laar and related equations to calculate the
corresponding vapour mole fractions for DCE and draw the x-y diagram for DCE.
[14 marks]
(c) If you attempt to distill a Dichloroethylene (DCE) Methanol 50:50 mixture what will
the maximum DCE concentration be that you can obtain? Explain the answer and
suggest thermodynamic solutions on how to break the azeotrope.
[7 marks]
Table 3.1: Vapour pressure data for Dichloroethylene (DCE)-Methanol at 760mmHg.

Temperature
DCE
Methanol
XDCE
C
mmHg
mmHg
64.8
0
55.9
721
547
0.2
52.6
642
477
0.4
51.5
617
455
0.65
52.0
628
465
0.8
52.6
642
477
0.9
58.9
1
Van Laar equations:ln
AAB
A
AAB
ln
AAB x A
ABA x B
x B ln
x A ln
ln
ABA
B
ABA x B
AAB x A
2
B
A
ABA
ln
x A ln
x B ln
2
A
B
Activity coefficient:
A
py A
p A, sat x A
Contd
Exam Answers
5
4.
Formaldehyde can be formed by gas-phase pyrolysis of methanol according to

CH4O(g) CH2O(g) + H2(g)
The Thermodynamic data for the compounds are given in Table 4.1
a) Use the equilibrium constant to show that the reaction will virtually not take place at
ambient conditions.
[5]
b) Assuming that the enthalpy of reaction stays constant, calculate the equilibrium
constants at 1 bar at 600C, 1000C and 1400C. Based on a compromise between
thermodynamics and energy costs which temperature would you pick?
[8]
c) What would the extent of reaction be at the temperature you picked in Q4 b) ?
[8]
d) Unconverted methanol containing hydrogen gas is recycled into the reactor. Use a
thermodynamic argument to show how the recycled hydrogen will affect the extent of
reaction.
[4]
Table 4.1: Thermochemical data
g0f,298
h0f,298
-1
[kJ mol ]
[kJ mol-1]
CH4O
-162
-200.7
CH2O
-110
-116.0
H2
0
0
Contd
Exam Answers
6
SECTION B
5. (a) Give the equation for the work of a reversible, isothermal compression of 1 mol
of gas in a piston/cylinder assembly if the molar volume of gas is represented by
RT
P
where b and R are positive constants.

[10 marks]
(b) Calculate the change in density of 20 kg of species A that results from the
isothermal (T = 373 K) compression of 25 dm3 from a starting pressure of 1.5 atm
to a final pressure of 275 atm. The isothermal compressibility of A equals 16
10-4
atm-1. Assume that is independent of P.

[15 marks]
6. (a) Demonstrate how virial equations can be used to correct for non-ideal
behaviour.
[10 marks]
(b) Calculate Z and V for sulphur hexafluoride at 75 oC and 15 bar using the following
equation of state approaches:
(i)
A truncated virial equation terminated at the B term where

B = -194 cm3 mol-1
[7 marks]
(ii)
Applying the Pitzer correlation to estimate B where
Tc = 319 K, Pc = 37.6 bar, Vc = 198 cm3 mol-1, = 0.286

Pitzer correlation data:
B0
0.083
0.422
Tr1.6
B1
0.139
0.172
Tr4.2
Note: R = 83.13 cm3 bar mol-1 K-1

[8 marks]
Exam Answers
7
Generalised compressibility charts from Lee-Kesler equation of state
z = z(0) + * z(1)
Exam Answers
8
de Priester chart(a) low and (b) high temperature
Exam Answers
Exam Answers
10
Answers:
1.
a) The equilibrium constant Ki for a compound i can be evaluated using the rigorous
equation with no simplifications:
lnK i
L
i
1
RT
vi
v i dp
[3]
V
i
Where v and v are usually obtained from equations of state, such as the BenedictWebb-Rubin equation of state, Lee-Kessler or Soave-Redlich-Kwong.
[2]
b)
The student should state the relationship between the equilibrium constant and the
fugacity of the pure liquid and the vapour:
Ki
fiL
f iV
The student should then be able to relate fugacity of a phase with the compressibility
factor Z
f
ln *
p
[2]
Z 1
dp
p
[4]
Where Z = pv/RT ln
f
p*
1
RT
vdp
p*
1
RT
RTZ
dp (not required but might be used by
p
*
p
student to elucidate the problem).

The student should identify the Tr=(102.5+273.15)/469.6=0.8 and Pr=10.12/33.74=0.3
for the compound
[2]
The student should note that the system will be in liquid phase and the fugacity of the
vapour phase will need to be extractpolated.
Exam Answers
11
[2]
The student should then pick some Pr to calculate the fugacity of the liquid phase and
the vapour phase.
Exam Answers
12
Fugacity vapour
Pressure Pr
Z0
Z1
bar
0
(Z-1)/p
Average
(Z-1)/p
bar-1
bar-1
Area
ln
3.37
0.100
0.94
-0.04
0.251
0.930 -0.02076
6.75
0.200
0.85
-0.12
0.251
0.820 -0.02669
10.12
0.300
0.74
-0.28
0.251
0.670 -0.03263
f
p
-0.010379
3.37 -0.03502
-0.023726
3.37 -0.08005
f/p
-0.029661
3.37 -0.10008
fV
Sum
Z 1
dp
p
0.8064232
-0.21515
The student should then calculate the K = 0.49/0.806= 0.61

c) Student should draw line between 102.5C and 1012kPa.
8.16 bar
[4]
[2]
[2]
Exam Answers
13
The line will indicate that the compound with K=0.61 is n-pentane.
[2]
2:
a) In a vapour-liquid equilibrium of the system the BUBBLE POINT is the
temperature at which the first bubble of vapour appears in the liquid and DEW
POINT is the temperature at which the first drop of liquid forms when the vapour
mixture condenses.
[2]
In terms of equilibrium constants, the bubble point and dew point are defined as and
calculated by trial and error based on K.
Exam Answers
14
k
bubble point :
yi
K i xi
i 1
dew point :
xi
i 1
1.0
i 1
i 1
yi
Ki
1.0
[2]
b) Student should solve the problem by finding the liquid fraction in the condenser
that correspond to a vapour phase containing 90 mole% ethane with a
corresponding dew point.
[2]
Compound n
mole
y
Ethane
0.7
Propane
0.3
-30C
K
0.9
0.1
x=y/K
1.5
0.6
0.29 0.344828
0.944828
-40C
K
-33C
x=y/K
K
x=y/K
1.2
0.75
1.46 0.616438
0.195 0.512821
0.26 0.384615
1.262821
1.001054
Where the K values are obtained from the de Priester chart
Exam Answers
15
[6]
c) Student should state the relationship
xi
ni
Ki 1 L
and solve it with respect to
xi
i 1
[2]
For Ethane: 0.616=0.7/(L+1.45(1-L)) => L = 70.5%

For Propane: 0.385 = 0.3/(L+0.26(1-L)) => L=70.3%
Student should do at least one calculation
[2]
Exam Answers
16
V+L=1 => Vapour fraction is 100-70 = 30%
d) Student should identify that there might be a temperature difference.
[1]
[2]
Solve top plate at 7 bar with vapour composition from Table 2.1
Compound
-30C
K
y
Ethane
Propane
0.7
0.3
-28C
x=y/K
K
x=y/K
1.32 0.681818
1.4 0.642857
0.25
0.4
0.275 0.363636
1.081818
1.006494
[3]
Temperature difference between the top plate and the reflux from the condenser
will then be -28C - 32C = -4C and there might be a need for increasing the
temperature of the reflux.
[3]
3.
a) A system forms an azeotrope if at a point xA = yA
The activity coefficients can then be calculated as:
p
p
and
A
B
p A, sat
p B , sat
[2]
[2]
b) For calcultions A=DCE B=Methanol. Stundents might do this or use
different subscript.
At azeotropic point:
= P/Psat,A = 760mmHg/617mmHg = 1.231 => ln( A) = 0.2079
B = P/Psat,B = 760mmHg/455mmHg = 1.670 => ln( B) = 0.5131
A
[2]
The student can then use the van Laar equation to find the the constants AAB
and ABA at the azeotrope where xA=0.65 and xA+xB=1 => xB=0.35
AAB
ABA
ln
ln
x B ln
x A ln
x ln
1 A
xB ln
= 0.2079(1+(0.35*0.5131)/(0.65*0.2079))2 = 1.0373
B
A
2
A
= 0.5131(1+(0.65*0.2079)/(0.35*0.5131))2 = 0.7825
Exam Answers
17
[4]
Student should then identify that xA and yA over the entire V-L system can be
calculated since activation coefficients and constants are known using the
following equations:
ln
AAB
A
AAB x A
ABA xB
py A
.
p A,sat x A
[2]
Students should then do some of the following calculations:

Temp[C] x A
64.8
55.9
52.6
51.5
52
52.6
58.9
yA
0
0.2
0.4
0.65
0.8
0.9
1
0
0.43
0.57
0.65
0.71
0.78
1
2.250965
1.676717
1.231062
1.07851
1.020576
[4]
And draw the graph

1
0.9
yA
0.8
0.7
0.6
yA 0.5
0.4
0.3
0.2
0.1
0
0
0.2
0.4
0.6
0.8
XA
[2]
c) Student should be able to identify that the azeoptropic point will define the
maximum concentration of DCE that can be obtained.
[2]
Exam Answers
18
If they have carried out b) they can illustrate this by starting at xA=0.5 and
highlight that the XA=0.65 will be the end point
[2]
Thremodynamically this can be broken by: (i) changing the pressure to move
the azeotropic point, (ii) add a third component that shifts the volatility of the
DCE or methanol (azeotropic distillation), (iii) perfom extractive distillation
using a third liquid that separate layers where DCE is preferentially disolved,
or (iv) physical removal of methanol using solid precipitation, membrane, filter
etc.
[3]
4.
a) The student should state the relationship between the standard Gibbs
free energy of formation and the equilibrium constant at ambient, i.e.
standard, conditions:
g0
RTlnK
[2]
They should then calculate the g0rxn,298:
g0rxn,298 = g0f,CH2O + g0f,H2 - g0f,CH4O
= -110.0 + 0 (-162.0) = 52.0 kJmol-1
[1]
Then use this to calculate K
K = exp(-g0rxn,298 /RT) =
exp(-52,000J mol-1/(8.314J mol-1 K-1 * 298.15K)) = 7.64* 10-10
[1]
Student should reflect the K is so low that the reaction will in practice not take
place.
[1]
b)
Student should use Van't Hoff Equation to calculate change in K:
ln
K
K1
h0 1
R T
1
T1
[2]
The student should then calculate the h0rxn,298:
Exam Answers
19
h0rxn,298 = h0f,CH2O + h0f,H2 - h0f,CH4O
= -116.0 + 0 (-200.7) = 84.7 kJmol-1
[1]
The student should then calculate K for the different temperatures
Temp [K]
K
873
4.59
1273
179.72
1673
1217.80
[3]
Students should state that if K > 1 then it favours products and if K < 1 then it
favors the reactant. At 600C K = 4.6 and the reactants are already highly
favoured. Hence, there is probably no need to further increase K by
increasing the temperature since this could affect the economics of the plant..
[2]
c)
For the extent of reaction the student should identify the need to look at the
reaction co-ordinate and make the following relationships:
Compound
CH4O
H2
CH2O
moles
1-
1+
Mole fraction
(1 )/(1 + )
/(1+ )
/(1+ )
1
[3]
The student should then work out the ratio of mole fractions to calculate Ky
y Cc
, where A= CH4O, B= H2, C= CH2O, and a,b,c are the
y Aa y Bb
corresponding stoichiometric numbers
Ky
Ky = ((/(1+ )) 1 (/(1+ )) 1 ) / ((1 )/(1 + ))1 = 2/(1 )
The student then should state that K

ideal gas.
K K Ky p
vi
[2]
K since p=1 bar and
Student should then attempt to find by trial and error based on the
temperature they picked in Q4 b)
[1]
Exam Answers
20
Temp [K]
K
Ky
873
4.59
0.84
4.59
1273
179.72
0.99
179.72
1673
1217.80
1.00
1217.80
So at 600C there will be a 84% conversion
[2]
d) Recycling H2 back will result in e.g.

CH4O(g) + n H2(g) CH2O(g) + (1+n)H2(g)
e.g. if n = 1
Compound
CH4O
H2
CH2O
moles
1-
+1
2+
Mole fraction
(1 )/(2 + )
+1/(2+ )
/(2+ )
1
Ky = (2 + )/((2+ )*(1- ))
Filling in with =0.84 from Q4c) gives Ky= 3.4 which means that will
increase (=0.88).
[3]
Exam Answers
21
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22
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23
Exam Answers
24
Exam Answers
25
END OF PAPER
1
Answers:
1.
a)
Students should identify this as fugacity
[2]
Students should relate fugacity to the chemical potential (d/dP) T,n =V id -V how this can
be used as an indicator of equilibrium.
[3]
b)
Overall calculations in Table 1.1 and the following steps required to gain points:
Step 1: calculate volume difference at each pressure: a= V ideal -V spesific

[2]
Step 2: Calculate a between the different pressures. Students should identify that at
P -> 0 a will go to 0 since this is close to ideal condition. Hence, for 3.79 bar a=(0.370)/2 = 0.18.
[4]
Step 3: Calculate P for each step, e.g. at 11.37bar P=11.37-7.58=3.79
[2]
Step 4: Calcualte the individual pressure range areas, e.g. at 7.58bar Area=
0.48[L/mol]*3.79bar.
[2]
Step 5: Sum up the areas and relate it to the equation:
Ln()= -(1/RT)adP, where the sum of areas = adP
[2]
Step 6: Calculate Ln()=ln (f/p)=-(1/(0.08314[Lbar/molK]*383K))*5.58Lbar/mol=-0.18
=0.84
[2]
Table 1.1
P [bar]
Specific vol [L/mol] Ideal vol [L/mol] a
3.79
8.03
8.39
7.58
3.79
4.20
11.37
2.37
2.80
15.16
1.57
2.10
a
0.37
0.41
0.43
0.53
p
0.18
0.39
0.42
0.48
3.79
3.79
3.79
3.79
Sum
Area
0.70
1.47
1.59
1.82 ln (f/P)
5.58 f/P
HERIOT-W ATT UNIVERSITYB48BCOctober 2014 v1
-0.18
0.84
c)
Student should use the relationship K=fL/fV where fV = *P =0.84*15.2bar= 12.8
bar was found in Q1 b)
[2]
From de Priester chart K=1.1 should be found (see chart below)
[2]
fL =K* fV = K* *P= 1.1*0.84*15.2bar = 14.0 bar
[2]
Q2
a)
Student should state that at low temperatures the mixture is probably one phase,
i.e. liquid. As the temperature is increased vapour will be formed and the system
will be two phase. With further increase in temperature only vapour will be present
and it is again a one phase system.
3
[3]
Students is then expected to gain the K values from the de Priester chart and carry
out calculations similar to Table 2.1.
Boiling point: When it goes from liquid phase only to a V-L system this is known as
the bubble point and is defined as (Ki*xi)=1.0. The students should calculate two
(Ki*xi) values using two different temperaures, normally one below 1 (e.g. 50C)
4
and one above 1 (e.g. 100C). The temperature where (Ki*xi)=1.0 can then be
found by extrapolation and verified by calculation.
[4]
Dew point: When it goes from a V-L system to vapour phase only this is known as
the dew point and is defined as (yi/Ki) =1.0. The students should calculate two
(yi/Ki) values using two different temperaures, normally one below 1 (e.g. 100C)
and one above 1 (e.g. 50C). The temperature where (Ki*xi)=1.0 can then be
found by extrapolation and verified by calculation.
[4]
Table 2.1
Bubble point
n-Butane
n-Pentane
Temp [C]
x i [mol fraction] Ki
0.5
0.5
(Ki*xi)
Temp [C]
50
Ki
Ki*x i
0.97
0.485
0.280
0.56
0.765
50
100
Ki
Ki*x i
2.5
1.250
1.05
0.525
1.775
100
70
Ki*x i
1.47
0.735
0.54
0.270
1.005
80
Dew point
n-Butane
n-Pentane
yi [mol fraction] Ki
0.5
0.5
(yi/Ki)
yi/Ki
Ki
0.97
0.515
0.56
0.893
1.408
yi/Ki
Ki
2.5
0.200
1.05
0.476
0.676
yi/Ki
1.78
0.281
0.7
0.714
0.995
b)
The student should identify that the liquid from the fractionating column will go back
into a V-L regime.
[2]
Since the pressure, temperature and total mixture composition is know, the
following expression can be used: xi=ni/(L+K*(1-L)), where xi is the liquid mole
fraction, ni is total mole fraction of mixture, K is eq. const. and L is liquid fraction. At
exuilibrium (xi)=1.0. The K values have been obtained in Q2 a)
[2]
Student should then use trial and error to obtain L =0.65 and N-Pentane = 0.84
[5]
5
T=80C
P=500kPa
L
Compound ni
Propane
n-Butane
n-Pentane
0.5
0.9
0.65
K
x=n/(L+K*(1-L)) x=n/(L+K*(1-L))
x=n/(L+K*(1-L))
0.1
4.5
0.036
0.074
0.045
0.15
1.78
0.108
0.139
0.118
0.75
0.7
0.882
0.773
0.837
(xi)
1.027
0.986
1.000
c)
Student should identify that system is no longer a two phase system, most likely
because the temperature in the reboiler has decreased.
[3]
Possible solutions are (i) increase the steam-rate to the reboiler or decrease
pressure if compressor available within the return system.
[2]
Q3
a) Student should identify this as an azeotropic point where the liquid mole fraction
equals the vapour mole fraction, i.e. x=y for ethanol, hence there is no deviation
from Raults law to distill upon.
[3]
b) The student should identify the at the azeotropic point the activity coefficients can
be expressed as:
A = P/P sat,E
and B = P/P sat,B
where A=Ethanol and B=Benzene

Using Antoine equation:
A
Ethanol
Benzene
B
12.3
9.28
C
3800
2790
-41.7
-52.4
ln(Psat) [bar]
-0.3899
-0.3823
Psat [mmHg]
514.6
518.5
[2]
Hence, A = P/P sat,A =760/514.6 = 1.4769 => ln( A ) = 0.3899
and B = P/P sat,B = 760/518.5 = 1.4657=> ln( B ) = 0.3823
[2]
Student should identify that at the azeotropic point x A = 0.45 and x B = 0.55
[1]
Therefore, they can now use the van Laar equations to find the constants for the
system:
AAB
x ln B
= ln A 1 + B
x A ln A
ABA
x ln A
= ln B 1 + A
x B ln B
Where A AB = 1.885 and A BA = 1.287

[3]
c) Student should identify that in Q3 b) the activity coefficients ( A and B ) are only
valid for the azeotropic point while the A AB and A BA constants to be over the entire mole
fraction range from 0 to 1.
[1]
Therefore, they can now use the van Laar equations to find the activity coefficients for
the two mixtures (x A =0.2 / x B =0.8 and x A =0.8 / x B =0.2) asked for.
AAB
ABA
ln B =
ln A =
2
2
ABA x B
AAB x A
1 +
1 +
AAB x A
ABA x B
[1]
Using the equation: For (x A =0.2 / x B =0.8)
-> ln( A )= 1.0097 and ln( B )= 0.0924

-> A = 2.745 and B = 1.026
For (x A =0.8 / x B =0.2) -> ln( A )= 0.0401 and ln( B )= 0.9388

-> A = 1.041 and B = 2.557
[3]
This can then be related to the relative volatility: = p A,sat /p B,sat * A / B where the
p A,sat /p B,sat = 514.6/518.5 = 0.9925 ratio is derived from the azeotropic point
Using the equation: For (x A =0.2 / x B =0.8)
For (x A =0.8 / x B =0.2)
-> = 0.9925 *2.745/1.026 = 2.655

-> = 0.9925 *1.041 /2.557= 0.404
[2]
They can now find the vapour molar fraction from

x A
yA =
1 x A + x A
For (x A =0.2) -> y A = 2.655*0.2/(1-0.2+2.655*0.2) = 0.383
For (x A =0.8) -> y A = 0.404*0.8/(1-0.8+0.404*0.8) = 0.618
[2]
c)
[5]
4.
a)
The student should state that the Reaction co ordinate or extent of reaction can be
used to determine the number of moles of each reaction component after the reaction
has gone some way according to the following equation
=
n
i
vi
i =1
i =1
n
Where ni = mole change of compound i, = Reaction Co ordinate, and v i is the

stoichiometric number of i within the reaction.
[4]
Student should then calculate the material balance
IN OUT Mole fraction OUT
CO
1 1
(1 )/2
H2O
1 1
(1 )/2
CO 2
0
/2
H2
0
/2
TOTAL 2
2
1
[5]
b)
Student should state that the composition component, Ky, of the equilibrium constant
can be expressed as:
Ky = products/reactants = ([CO 2 ]*[H 2 O]) /([CO]*[H 2 O])
[2]
Based on the mole fraction out from the material balance in Question 4 a) this will give
Ky = (( /2)*( /2)) / (((1 )/2)* ((1 )/2)) = (2/4) / ((1-2+ 2)/4) = 2/(1-2+ 2)
[4]
c)
Student should state that the full expression for K = KKKy.Pv where K and K can
be assumed to be 1 if the system is approximated as ideal, P= pressure and v is the
stoichiometric numbers from the reaction equation.
Therefore, K = Ky.Pv = Ky*100(2-2) = Ky
[2]
Student should then identify that the g can be calculated:
g(600 K) = products - reactants = (-394.1 + 0) (-164.8 + -214.2) = -15.1 kJmol-1
g(1300 K) = products - reactants = (-396.4 + 0) (-227.1 + -175.9) = 6.6 kJmol-1
[2]
Student should then identify the relationship g = -RT lnK
The K values can then be calculated:
ln K 600 = -g/RT = -15.1 kJmol-1/((8.314 Jmol-1K)x 600K) = -3.027 -> K 600 = 0.0485
ln K 1300 = -g/RT = 6.6 kJmol-1/((8.314 Jmol-1K)x 1300K) = 0.611 -> K 1300 = 1.84
[4]
d)
Student should identify that K 1300 > K 600 so 1300K would have higher converstion into
H2.
[1]
Student should identify that the extent of reaction can be calculated using trial and
error.
e.g. =0.5 -> K = Ky = 2/(1-2+ 2) = 0.52/(1-2*0.5+ 0.52) = 0.25/0.25 = 1
e.g. =0.6 -> K = Ky = 2/(1-2+ 2) = 0.62/(1-2*0.6+ 0.62) = 0.36/(-0.2 +0.36) = 2.25
Hence, converstion into H 2 is about 57%.
Alternatively, the student can solve Ky = 2/(1-2+ 2) = 1.84 -> = 0.576
[3]
10
11
12
13
14
END OF PAPER

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Course Title: Multiphase Thermodynamics

ANSWER 3 QUESTIONS FROM SECTION A

Additional information and appendices

HERIOT-WATT UNIVERSITYB49CE August 2015 v1

HERIOT-WATT UNIVERSITYB49CE August 2015 v1

HERIOT-WATT UNIVERSITYB49CE August 2015 v1

Table 3.1: Vapour pressure data for Dichloroethylene (DCE)-Methanol at 760mmHg.

HERIOT-WATT UNIVERSITYB49CE August 2015 v1

Formaldehyde can be formed by gas-phase pyrolysis of methanol according to

HERIOT-WATT UNIVERSITYB49CE August 2015 v1

where b and R are positive constants.

atm-1. Assume that is independent of P.

A truncated virial equation terminated at the B term where

Applying the Pitzer correlation to estimate B where

Tc = 319 K, Pc = 37.6 bar, Vc = 198 cm3 mol-1, = 0.286

Note: R = 83.13 cm3 bar mol-1 K-1

HERIOT-WATT UNIVERSITYB49CE August 2015 v1

HERIOT-WATT UNIVERSITYB49CE August 2015 v1

HERIOT-WATT UNIVERSITYB49CE August 2015 v1

student to elucidate the problem).

HERIOT-WATT UNIVERSITYB49CE August 2015 v1

HERIOT-WATT UNIVERSITYB49CE August 2015 v1

The student should then calculate the K = 0.49/0.806= 0.61

HERIOT-WATT UNIVERSITYB49CE August 2015 v1

Where the K values are obtained from the de Priester chart

HERIOT-WATT UNIVERSITYB49CE August 2015 v1

and solve it with respect to

For Ethane: 0.616=0.7/(L+1.45(1-L)) => L = 70.5%

HERIOT-WATT UNIVERSITYB49CE August 2015 v1

HERIOT-WATT UNIVERSITYB49CE August 2015 v1

Students should then do some of the following calculations:

And draw the graph

HERIOT-WATT UNIVERSITYB49CE August 2015 v1

The student should then calculate the h0rxn,298:

HERIOT-WATT UNIVERSITYB49CE August 2015 v1

Ky = ((/(1+ )) 1 (/(1+ )) 1 ) / ((1 )/(1 + ))1 = 2/(1 )

The student then should state that K

K since p=1 bar and

HERIOT-WATT UNIVERSITYB49CE August 2015 v1

So at 600C there will be a 84% conversion

d) Recycling H2 back will result in e.g.

HERIOT-WATT UNIVERSITYB49CE August 2015 v1

HERIOT-WATT UNIVERSITYB49CE August 2015 v1

HERIOT-WATT UNIVERSITYB49CE August 2015 v1

HERIOT-WATT UNIVERSITYB49CE August 2015 v1

HERIOT-WATT UNIVERSITYB49CE August 2015 v1

HERIOT-WATT UNIVERSITYB49CE August 2015 v1

Step 1: calculate volume difference at each pressure: a= V ideal -V spesific

HERIOT-W ATT UNIVERSITYB48BCOctober 2014 v1

and B = P/P sat,B

where A=Ethanol and B=Benzene

Where A AB = 1.885 and A BA = 1.287

-> ln( A )= 1.0097 and ln( B )= 0.0924

For (x A =0.8 / x B =0.2) -> ln( A )= 0.0401 and ln( B )= 0.9388

-> = 0.9925 *2.745/1.026 = 2.655

They can now find the vapour molar fraction from

Where ni = mole change of compound i, = Reaction Co ordinate, and v i is the

HERIOT-W ATT UNIVERSITYB48BCOctober 2014 v1

HERIOT-W ATT UNIVERSITYB48BCOctober 2014 v1

HERIOT-W ATT UNIVERSITYB48BCOctober 2014 v1

HERIOT-W ATT UNIVERSITYB48BCOctober 2014 v1

HERIOT-W ATT UNIVERSITYB48BCOctober 2014 v1