TOPIC 1.

Worked Examples Q&A 1

1.3.3 Example 1

Estimate the fugacity of gaseous propane at 2.4 MPa. and 344 K using the
following P − v − T data for propane at 160o F.

Molar Mass of propane is 44.097 kg/kmol

Pressure and specific volume data is as follows:

P v

(MN/m2) (m3/kg)
0 --
0.1724 0.36910
0.3447 0.18100
0.6895 0.08652
1.0342 0.05512
1.2066 0.04598
1.3790 0.03903
2.4000 0.01783

Answers:

Estimate of fugacity coefficient at 24bar and 344 K Φ = 0.7541

Estimate of fugacity at 24bar and 344 K f = 1810kPa

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 1. Worked Examples Q&A 2

Solution:

First calculate the ideal gas specific volume at each pressure using a constant
temperature of 344K:

RT 8.314 J / mol.K × 344 K

V = = = 0.0166m 3 / mol
P 172400 Pa
v = 0.0166m / mol ÷ 44.097 g / mol = 3.7644 ×10 −4 m 3 / g = 0.37644m 3 / kg
ig 3

Now calculate v R using the formula:

v R = v ig − v
v R = 0.37644 − 0.36910 = 7.34 × 10 −3 m 3 / kg

NOTE: In the summary table the v R value is multiplied by 1000 for tabular
simplicity.

Next find the average v R values:

(7.34 × 10 −3 m 3 / kg + 0.00m 3 / kg +) / 2 = 3.67 × 10 −3 m 3 / kg

and the pressure steps:

(0.1724 MN / m 2 − 0 MN / m 2 ) = 0.1724 MN / m 2 = 172.4kN / m 2

Multiply each average v R and pressure step and then sum all the steps:

v ave × ∆P = 3.67 × 10 −3 m 3 / kg × 172.4kN / m 2 = 0.6327 kJ / kg

R

See the summary table overleaf for full solutions.

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 1. Worked Examples Q&A 3

P v v ig vR v ave
R ∆P v ave × ∆P
R

× 10 3 × 10 3
(MN/m2) (m3/kg) (m3/kg) (kN/m2)
(m3/kg) 3
(m /kg) (kJ/kg)
0 -- -- 0.00 -- --
3.67 172.4 0.6327
0.1724 0.36910 0.37644 7.34
7.25 172.3 1.2492
0.3447 0.18100 0.18816 7.16
7.35 344.8 2.5343
0.6895 0.08652 0.09406 7.54
7.57 344.7 2.3094
1.0342 0.05512 0.06271 7.59
7.68 172.4 1.3240
1.2066 0.04598 0.05375 7.77
7.89 172.4 1.3602
1.3790 0.03903 0.04703 8.00
8.60 1034.2 8.8941
2.4000 0.01783 0.02702 9.19

∑v R
∆P 18.3039

Use the fugacity coefficient formula to find the coefficient and solve for the
fugacity:

P
1 1
LnΦ = − ∫
RT 0
v R dP = −
8314 J / kmol.K
× 18303.9 J / kg = −0.2822
× 344 K
44.097 kg / kmol
f
Ln = −0.2822
p
f
= 0.7541
p
f = 0.7541 × 2.4 MPa = 1810kPa

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 1. Worked Examples Q&A 4

1.3.6 Example 2

Estimate the fugacity of gaseous propane at 2.4 MPa. and 344 K. Estimate the
compressibility factor Z (at each Pr ) from the charts in Appendix A.
Complete this example by hand in this workbook using the following critical
and other properties for propane:

Molar Mass 44.097 kg/kmol

Critical Temperature TC 369.8 K
Critical Pressure PC 42.48 bar
Acentric Factor 0.152

Use the following incremental pressure steps:

(MN/m2)
0
0.1724
0.3447
0.6895
1.0342
1.2066
1.379
2.4

Answers:

Estimate of fugacity coefficient at 24 bar and 344 K Φ = 0.7412

Estimate of fugacity at 24 bar and 344 K f = 1779kPa

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 1. Worked Examples Q&A 5

Solution:

Calculate the reduced temperature at each incremental stage using the

formula:
T 344
Tr = = = 0.93
Tc 369.8
Note that this will remain constant as we are looking at the change in pressure.

Calculate the reduced pressure at each incremental stage using the formula:
P 0.1724
Pr = = = 0.0406
Pc 4.248

Use the reduced temperature and pressure values to find the associated
Z 0 and Z 1 values graphically. (Note that the values you find may differ from
those given in the summary table due to graphical reading error).

Now calculate each Z value using the formula:

Z = Z 0 + ωZ 1 = 0.980 + (0.152 × −0.01) = 0.9785

P Tr Pr Z0 Z1 Z
= Z + ωZ 1
0

(MN/m2)
0 0.93 0 1 0 1
0.1724 0.93 0.0406 0.980 -0.01 0.9785
0.3447 0.93 0.0811 0.960 -0.015 0.9577
0.6895 0.93 0.1623 0.920 -0.03 0.9154
1.0342 0.93 0.2435 0.890 -0.04 0.8839
1.2066 0.93 0.2840 0.880 -0.055 0.8716
1.379 0.93 0.3246 0.850 -0.08 0.8378
2.4 0.93 0.5650 0.700 -0.15 0.6772

Z −1
Now calculate the associated values:
P

Z −1 0.9785 − 1
= 2
= −1.247 × 10 − 4 m 2 / kN
P 172.4kN / m

NOTE: this value is multiplied by 10,000 for tabular clarity.

Z −1
Now multiply the values by the pressure difference:
P
 Z −1 −4
 ∆P = (−1.247 × 10 m / kN × 172.4kN / m ) = −0.0215
2 2

 P 

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 1. Worked Examples Q&A 6

 Z −1 
Sum all of the values to get the cumulative  ∆P term of -0.2995.
 P 

P Z −1 ∆P  Z −1 
 ∆P
(MN/m2)
P
(kN/m2)  P 
(kN/m2)-1
× 10 4
0 0 - -
0.1724 -1.247 172.4 -0.0215
0.3447 -1.227 172.3 -0.0211
0.6895 -1.227 344.8 -0.0423
1.0342 -1.123 344.7 -0.0387
1.2066 -1.064 172.4 -0.0183
1.3790 -1.176 172.4 -0.0203
2.4000 -1.345 1021.0 -0.1373

 Z −1
∑  P 
∆P
-0.2995

This then gives a solution to the fugacity coefficient equation:

P
ln Φ = ∫ (Z − 1)
dP
= −0.2995
0
P
Therefore:

Φ = exp(−0.2995) = 0.7412

f = Φ × P = 0.7412 × 2.4 MPa = 1.779 MPa = 17.79bar = 1779kPa

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 1. Worked Examples Q&A 7

1.3.8 Example 3

Estimate the fugacity of gaseous propane at 2.4 MPa. and 344 K using the
charts supplied in Appendix B. Complete this example using the following
critical and other properties for propane:

Molar Mass 44.097 kg/kmol

Critical Temperature TC 369.8 K
Critical Pressure PC 42.48 bar
Acentric Factor 0.152

Answers:

Tr = 0.93

Pr = 0.565

Φ 0 = 0.770

Φ 1 = 0.890

Φ = 0.7565

f = 1816kPa

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 1. Worked Examples Q&A 8

Solution:

Calculate the reduced temperature and pressure:

T 344 P 24
Tr = = = 0.93 and Pr = = = 0.565
Tc 369.8 Pc 42.48

Use the generalised fugacity coefficient charts to find Φ 0 and Φ 1 then use:

( )( ) = (0.77)(0.89)
Φ = Φ 0 Φ1
ϖ 0.152
= 0.7565

The fugacity is then found to be:

f = Φ × P = 0.7565 × 2400kPa = 1816kPa

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 1. Worked Examples Q&A 9

1.3.11 Example 4

Estimate the fugacity of liquid propane at 4.8 MPa. and 344 K using the same
gaseous P − v − T data for propane at 160oF (344 K) as provided in Example
1. The saturated vapour pressure of propane at 344 K is 2.56 MPa.

Molar Mass of propane is 44.097 kg/kmol

The specific volume and pressure data for the liquid (past the point of
saturation) is given below:

P v
× 10 3
(MN/m2) (m3/kg)
2.551 2.446
2.758 2.446
3.447 2.404
4.800 2.338

Answers:

Fugacity coefficient (saturated vapour) at 25.6 bar and 344 K Φ = 0.7401

Fugacity (saturated vapour) at 25.6 bar and 344 K f = 1895kPa

Fugacity coefficient (subcooled liquid) at 48 bar and 344 K Φ = 0.0830

Fugacity (subcooled liquid) at 48 bar and 344 K f = 2059kPa

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 1. Worked Examples Q&A 10

Solution:

First extend the vapour phase data from example 1 up to the point of
liquefaction (2.56MPa as given in the question):
2.56 2.56
× ∫ α × dP = × 18.3039kJ / kg = 19.5242kJ / kg
2.4 2.4

Note: the value is taken directly from example 1 however in practice the
number would need to be calculated using the example 1 method and so the
associated specific volumes and pressures would be given.

Use the formula to solve for fugacity:

P
1 1
LnΦ = −
RT 0∫ v R dP = −
8314 J / kmol.K
× 19524.2 J / kg = −0.3010
× 344 K
44.097 kg / kmol
f
Ln = −0.3010
p
f
= 0.7401
p
f = 0.7401 × 2.56 MPa = 1895kPa

Next the liquid P-v-T data is required to calculate its associated area.
Therefore the average specific volume is calculated for each pressure step
(Note that there is no need to manipulate the specific volume in this instance
as a liquid volume is assumed to be negligibly effected by pressure).

Average specific volumes:

(2.446 × 10 −3 m 3 / kg + 2.404 × 10 −3 m 3 / kg ) / 2 = 2.425 × 10 −3 m 3 / kg

and the pressure steps:

(3.447 MN / m 2 − 2.758MN / m 2 ) = 0.689MN / m 2 = 689kN / m 2

Multiply each average specific volume and pressure step and then sum all the
steps:

v ave × ∆P = 2.425 × 10 −3 m 3 / kg × 689kN / m 2 = 1.671kJ / kg

The sum of all the steps gives a final area of 5.3851kJ / kg .

See the summary table overleaf:

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 1. Worked Examples Q&A 11

P v v ave ∆P v ave ∆P
× 10 3 × 10 3
(MN/m2) (m3/kg) 3 (kN/m2) (kJ/kg)
(m /kg)
2.551 2.446 - - -
2.446 207 0.5063
2.758 2.446 - - -
2.425 689 1.6708
3.447 2.404 - - -
2.371 1353 3.2080
4.800 2.338 - - -

∑ v∆P 5.3851

Next use the equation to solve for fugacity:

P
f 1 1
Ln
f sat
≈
RT ∫ vdP = 8314 J / kmol.K
× 5385.1J / kg =0.0830
P sat × 344 K
44.097 kg / kmol

f = 1.0865 × 1895kPa = 2059kPa

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 1. Worked Examples Q&A 12

1.3.12 Example 5

Repeat the previous example using the generalised fugacity coefficient charts.

Answers:

Φ 0 = 0.76
Φ 1 = 0.89
Φ satvap = 0.7467
f satvap = 1912kPa
f = 2080kPa

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 1. Worked Examples Q&A 13

Solution:

Calculate the fugacity coefficient of propane at the saturated vapour pressure

i.e. 2.56MPa.

First calculate the new reduced pressure, reduced temperature does not
change:

T 344 P 25.6
Tr = = = 0.93 and Pr = = = 0.60
Tc 369.8 Pc 42.48

Use the generalised fugacity coefficient charts to find Φ 0 and Φ 1 then use the
fugacity coefficient equation:

Φ = Φ 0 Φ1( )( ) = (0.76)(0.89)
ϖ 0.152
= 0.7467

The saturated fugacity is then found to be:

f = Φ × P = 0.7467 × 2560kPa = 1912kPa

Now use the liquid fugacity estimation correlation to estimate the liquid fugacity
coefficient:

ln
f
≈
( )
v Lsat P − P sat
=
2.446 × 10 −3 m 3 / kg × (4800000 Pa − 2560000 Pa )
= 0.084
sat
f RT 8314 J / kmol.K
× 344 K
44.097 kg / kmol
Solving this for the liquid fugacity:

f
≈ exp(0.084) = 1.0876
f sat
f = 1.0876 × 1912kPa = 2080kPa

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 1. Worked Examples Q&A 14

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 2 Worked Examples Q&A 1

2.4.6 Example 1

For a substance i in a multi-component system, which exists in two phases

(liquid and vapour), determine the equilibrium constant K i .

Given:

p r = 0.35 , Tr = 1.0 and Z c = 0.27

Use the generalised fugacity coefficient chart.

Answer:

K i ≈ 2.39

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 2 Worked Examples Q&A 2

Solution:

Using the generalised fugacity coefficient chart it is found that, with the given
reduced temperature and pressure, the fugacity coefficient value is:

f
= 0.9
p

As can be noted from the chart the component is in vapour form and so the
fugacity coefficient value is for the pure vapour. Extrapolation of the available
liquid data is required to find the “fictitious” pure liquid fugacity.

The data available for the pure liquid using the chart at PR = 0.35 is:

TR  f 
 p L
0.60 0.03
0.65 0.11
0.70 0.19
0.75 0.34
0.80 0.50
0.85 0.75

Using this data a graph is plotted to allow for extrapolation to a T r value of 1.0:

Using the graph the value is estimated to be ≈ 2.15 , hence:

K = f L ( pure ) / f V ( pure ) = 2.15 / 0.9 = 2.39

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 2 Worked Examples Q&A 3

2.5.3 Example 2

Find the bubble point temperature of the liquid mixture defined below:

Liquid
Component Antoine ‘A’ Antoine ‘B’ Antoine ‘C’
Mol Fraction
Ethane 0.15 15.6637 1511.42 -17.16
Propane 0.20 15.7260 1872.46 -25.16
i-butane 0.60 15.5381 2032.73 -33.15
n-butane 0.05 15.6782 2154.90 -34.42

At P = 770kPa or P = 5775.5mmHg .

Note the data for the Antoine constants have P and T units of mmHg and K.

Answer:

T ≈ 14 o C

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 2 Worked Examples Q&A 4

Solution:

As the pressure is set by the question at 770kPa the temperature of the liquid
must be iteratively guessed.

To estimate the first iteration find the individual boiling points of each
component assuming Pi sat = P and using the Antoine equation to solve for T:

Bi
Ti sat = − Ci
Ai − ln Pi sat

Solving for ethane:

1511.42
Ti sat = + 17.16 = 233.0 K = −40.0 o C
15.6637 − ln(5775.5)

Solving for propane:

1872.46
Ti sat = + 25.16 = 290.2 K = 17.2 o C
15.7260 − ln(5775.5)

Solving for i-butane:

2032.73
Ti sat = + 33.15 = 328.7 K = 55.7 o C
15.5381 − ln (5775.5)

Solving for i-pentane:

2154.90
Ti sat = + 34.42 = 341.5 K = 68.5 o C
15.6782 − ln(5775.5)

Now use the approximation T( 0 ) = ∑ xi Ti sat to estimate the first iteration

i
temperature:

T( 0 ) = (−40.0 × 0.15) + (17.2 × 0.20) + (55.7 × 0.60) + (68.5 × 0.05) = 34.3o C ≈ 34 o C

Use the De-Priester chart to find the values of K at 34oC and 770kPa.

Once all values are obtained, multiply each K value by the individual
component molar fraction. If the value is correct the sum of all molar fractions
will equate to 1.

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 2 Worked Examples Q&A 5

Liquid Vapour Mol

Component Mol Fraction o
K at 34 C Fraction
xi y i = Kxi
Ethane 0.15 4.90 0.74
Propane 0.20 1.60 0.32
i-Butane 0.60 0.70 0.42
n-Butane 0.05 0.50 0.03
Total: 1.51

The value found shows that the estimate is someway off of the correct answer.
Because increasing the temperature would increase the K values it is evident
that a reasonable temperature reduction is required for the next step. As a
preliminary estimate take 10oC:

Liquid Vapour Mol

Component Mol Fraction o
K at 10 C Fraction
xi y i = Kxi
Ethane 0.15 3.10 0.47
Propane 0.20 0.90 0.18
i-Butane 0.60 0.38 0.23
n-Butane 0.05 0.18 0.01
Total: 0.89

This time the value is below the required vapour mol fraction and so the
temperature must again be increased. To reduce the error of estimation it is
sensible to interpolate the two values calculated to estimate the next iteration
temperature:
 y − y10 
T? = T10 + (T34 − T10 ) ×  1 
 y 34 − y10 

 1.00 − 0.89 
T? = 10 + (34 − 10) ×   = 14 C
o

 1.51 − 0.89 

Liquid Vapour Mol

Component Mol Fraction K at 14oC Fraction
xi y i = Kxi
Ethane 0.15 3.50 0.53
Propane 0.20 1.00 0.20
i-Butane 0.60 0.40 0.24
n-Butane 0.05 0.30 0.02
Total: 0.99

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 2 Worked Examples Q&A 6

This solution gives an answer of a vapour molar fraction very close to 1.0. This
could be further iterated but a value within 0.01 is a good tolerance given
reading errors. Therefore the mixture bubble point is roughly 14oC at 770kPa.

2.5.4 Example 3

Find the dew point temperature for the same mixture in Example 2 at the same
pressure.

Liquid
Component Antoine ‘A’ Antoine ‘B’ Antoine ‘C’
Mol Fraction
Ethane 0.15 15.6637 1511.42 -17.16
Propane 0.20 15.7260 1872.46 -25.16
i-butane 0.60 15.5381 2032.73 -33.15
n-butane 0.05 15.6782 2154.90 -34.42

At P = 770kPa or P = 5775.5mmHg .

Note the data for the Antoine constants have P and T units of mmHg and K.

Answer:

≈ 40 o C

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 2 Worked Examples Q&A 7

Solution:

Follow the same procedure as the previous bubble point calculation to find the
initial iterative temperature estimate with the Antoine equation rearrangement.
Hence the initial estimate is ≈ 34 o C

Use the De-Priester chart to find the values of K at 34oC and 770kPa.

Once all values are obtained, divide each individual component molar fraction
by the associated K value. If the temperature value is correct the sum of all
molar fractions will equate to 1.

Vapour Liquid Mol

Mol Fraction o Fraction
Component K at 34 C
yi
yi xi =
K
Ethane 0.15 4.90 0.03
Propane 0.20 1.60 0.13
i-Butane 0.60 0.70 0.86
n-Butane 0.05 0.50 0.10
Total: 1.12

It is shown that the estimate is reasonable but out with the tolerable limit and
so the temperature must be increased for the next iteration. Adding 10oC is a
sensible estimation.

Vapour Liquid Mol

Mol Fraction Fraction
Component K at 44oC
yi
yi xi =
K
Ethane 0.15 5.20 0.03
Propane 0.20 1.90 0.11
i-Butane 0.60 0.88 0.68
n-Butane 0.05 0.60 0.08
Total: 0.90

So the estimate of 44oC was a reasonable over estimation which has overshot
the actual value. For the final iteration an interpolation of the two known values
is used:
 x − x34 
T? = T34 + (T44 − T34 ) ×  1 
 x 44 − x34 

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 2 Worked Examples Q&A 8

 1.00 − 1.12 
T? = 34 + (44 − 34) ×   = 39.5 ≈ 40 C
o

 0.90 − 1.12 

Vapour Liquid Mol

Mol Fraction Fraction
Component K at 40oC
yi
yi xi =
K
Ethane 0.15 5.00 0.03
Propane 0.20 1.70 0.12
i-Butane 0.60 0.79 0.76
n-Butane 0.05 0.58 0.09
Total: 1.00

This gives a dewpoint temperature for the mixture of 40oC at 770kPa.

The final sum term is exactly 1.00 however there is still potential for error in
this due to reading the graph, as such it is sensible to term the answer as a
dewpoint of roughly 40oC at 770kPa.

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 2 Worked Examples Q&A 9

2.5.6 Example 4

Find the fraction of vapour and liquid in the following mixture at 80oF and 150
psia.

Component ni
CH 4 0.05
C2H8 0.10
C3H8 0.30
i-C 4 H 10 0.55

Note that ni is the mixture molar composition (i.e. is both liquid and vapour)

Conversions:

[ C ] = ([ F ] − 32)× 95
o o

1 psi = 6894.8 Pa = 6.9kPa

Answers:

xi yi
Component
Liquid Vapour
CH 4 0.01 0.20
C2H8 0.07 0.22
C3H8 0.30 0.33
i-C 4 H 10 0.62 0.27

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 2 Worked Examples Q&A 10

Solution:

First convert the temperature and pressure supplied into units that are
compatible with the De-Priester charts.

[ C ] = ([ F ] − 32)× 95 = (80 − 32) × 95 = 26.7

o o o
C

kPa
150 psi × 6.9 = 1035kPa
psi

For ease of reading on the De-Priester chart a temperature of 27oC and a

pressure of 1050kPa is used. With this information the K-values can be found:

Component ni K-Value
CH 4 0.05 16.25
C2H8 0.10 3.30
C3H8 0.30 1.00
i-C 4 H 10 0.55 0.42

With the K-values found the liquid fraction “L” can be iteratively solved using:

ni
xi =
L + K i (1 − L)

Estimating L = 0.5 is always a good first guess and so this is the first iteration.

K- L = 0.5 L = 0.6 L = 0.8

Component ni y i = K i xi
Value xi xi xi
CH 4 0.05 16.1 0.01 0.01 0.01 0.20
C2H8 0.10 3.20 0.05 0.05 0.07 0.22
C3H8 0.30 1.00 0.30 0.30 0.30 0.33
i-C 4 H 10 0.55 0.43 0.77 0.71 0.62 0.27
Total: 1.12 1.07 1.00 0.99

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 2 Worked Examples Q&A 11

A liquid fraction of 0.8 gives a liquid compositional fraction which equates to

1.00. Therefore this is the composition of the liquid in the mixture. The vapour
composition can then be found using the liquid composition and the K value
relationship.

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 2 Worked Examples Q&A 12

Generalised Fugacity Coefficient Chart

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 3A Worked Examples Q&A 1

3.4.6 Topic 3A: Example 1

Use Raoult's Law and the vapour pressure given below to produce a
T − x1 − y1 diagram for the ethanol/water system at 2000 mmHg.

Vapour Pressure Data.

Temperature Ethanol Water

o
( C) Vapour Pressure (mmHg)
104.8 2000.00 899.70
110.0 2372.95 1074.41
115.0 2786.81 1267.84
120.0 3257.91 1488.98
125.0 3792.01 1740.72
129.6 4344.22 2000.00

Assume that Ethanol is component (1) and Water is component (2).

Answer:

Temperature (oC) x1 y1
104.8 1.0000 1.0000
110.0 0.7128 0.8457
115.0 0.4820 0.6716
120.0 0.2889 0.4706
125.0 0.1264 0.2396
129.6 0.0000 0.0000

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 3A Worked Examples Q&A 2

Solution:

Firstly calculate the liquid and vapour compositions of ethanol at the varying
temperatures using the equations:

P − P2sat x1 P1sat
x1 = sat and y1 =
P1 − P2sat P

Hence:

2000 − 1074.41
x1 = = 0.7128
2372.95 − 1074.41

and

y1 =
(0.7128) × 2372.95 = 0.8457
2000

See the summary table below for the full solutions:

Temperature (oC) x1 y1
104.8 1.0000 1.0000
110.0 0.7128 0.8457
115.0 0.4820 0.6716
120.0 0.2889 0.4706
125.0 0.1264 0.2396
129.6 0.0000 0.0000

Using the information calculated for the table above, construct a T-x 1 -y 1
diagram with T on the y-axis and both x 1 and y 1 on the x-axis.

Note that at 104.8oC and 129.6oC the vapour pressures of ethanol and water
respectively equal the system pressure. This indicates the boiling point of each
component and so sets the boundaries of the T-x 1 -y 1 diagram.

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 3A Worked Examples Q&A 3

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 3A Worked Examples Q&A 4

3.4.8 Example 2

Use Raoult's Law to produce an x1 − y1 plot for the propane (1)/n-butane (2)
system at a pressure of 400 mmHg.

Vapour pressures can be evaluated using the Antoine equation

B
lnP sat = A −
T +C

Where P sat = vapour pressure (mmHg)

T = temperature (K)

A B C
Propane (1) 15.7260 1872.46 -25.16
n-butane (2) 15.6782 2154.90 -34.42

Answers:

x1 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
y1 0.000 0.402 0.603 0.722 0.802 0.859 0.901 0.934 0.960 0.982 1.000

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 3A Worked Examples Q&A 5

Solution:

In this example the vapour pressure data is not given and so must be
evaluated using the Antoine equation.

Firstly rearrange the equation to solve for T:

B
lnP sat = A −
T +C

B
T= −C
A − ln P sat

Solve the equation for propane and n-butane to find their respective boiling
points. For propane:

1872.46
T= + 25.16 = 217.5 K = −55.5 o C
15.726 − ln(400)

For n-butane:

2154.90
T= + 34.42 = 256.9 K = −16.1o C
15.6782 − ln(400)

This sets the boundaries of the x 1 -y 1 plot.

Now set a range of temperatures between the boundaries and solve the
Antoine equation for pressure at each temperature, once the P sat values are
P1sat
found the relative volatility can be found using β = :
P2sat

Temperature (K) 217.5 227.4 237.3 247.2 256.9

P sat Propane (mmHg) 399.8 643.8 991.8 1470.0 2092.3
P sat n-Butane
49.8 91.1 157.1 257.5 400.4
(mmHg)
β 6.02 7.07 6.31 5.71 5.23
Average β 6.07

With the average relative volatility known the y 1 values can be calculated by
setting the x 1 values and using the equation:

βx1
y1 = , hence:
1 + (β − 1)x1

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 3A Worked Examples Q&A 6

x1 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
y1 0.000 0.402 0.603 0.722 0.802 0.859 0.901 0.934 0.960 0.982 1.000

Use the data found in the calculation to plot the x 1 -y 1 diagram shown below:

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 3A Worked Examples Q&A 7

3.5.6 Example 3
Water and ethanol form an azeotrope at 78.15oC and 1 bara with a water mole
fraction of 0.106.

Using the van Laar method and the following vapour pressure data determine
the composition of the vapour stream in equilibrium with a liquid containing a
water mole fraction of 0.5.

Vapour Pressure
Temperature
o (mmHg)
C
Water (1) Ethanol (2)
78.15 330 751
78.4 334 760
80 355 805
90 526 1153
100 760 1648

Answers:

0.3079 water, 0.6921 ethanol

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 3A Worked Examples Q&A 8

Solution:

At the azeotrope:

γ 1 = p / p1sat = 760 / 330 = 2.303

γ 2 = p / p 2 sat = 760 / 751 = 1.012

Hence:

ln γ 1 = ln(2.303) = 0.834
ln γ 2 = ln(1.012) = 0.012

Now the BIP’s for the Van Laar equation can be calculated:

 0.894(0.012 ) 
2 2
 x ln γ 2 
A12′ = ln γ 1 1 + 2  = 0.8341 +  = 1.049
 x1 ln γ 1   0.106(0.834 ) 

 0.106(0.834 ) 
2 2
 x ln γ 1 
′ = ln γ 2 1 + 1
A21  = 0.0121 +  = 1.025
 x 2 ln γ 2   0 .894(0. 012 ) 

Note that as the mixture is two component x 1 =1-x 2 and vice versa.

To find the vapour composition at 0.5 mol fraction water liquid composition the
β value is required so that following equation can be used:

βx1
y1 =
1 + (β − 1)x1

To find β in this instance requires:

 p  γ 
β =  1sat   1 
 p 2 sat  ave  γ 2  at 0.5

 p1sat 
To find   the supplied vapour pressure data is used:
 p2 sat  ave

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 3A Worked Examples Q&A 9

Temperature
Vapour Pressure  p1sat 
o
C
(mmHg)  p 
Water (1) Ethanol (2)  2 sat  ave
78.15 330 751 0.4394
78.4 334 760 0.4395
80 355 805 0.4410
90 526 1153 0.4562
100 760 1648 0.4612
Average: 0.4475

Next the ln γ 1 and ln γ 2 values at 0.5 x 1 fraction are calculated along with the
β value:

A12 1.049
ln γ 1 = = = 0.2562
 1.049(0.5) 
2 2
 A12 x1 
1 +  1 + 1.025(0.5) 
 A21 x 2   

A21 1.025
ln γ 2 = = = 0.2622
 1.025(0.5) 
2 2
 A21 x 2 
1 +  1 + 1.049(0.5) 
 A12 x1   

γ 1 = 1.2920
γ 2 = 1.2998

 p  γ   1.2920 
β =  1sat   1  = (0.4475)  = 0.4448
p γ
 2 sat  ave  2  at 0.5  1 . 2998 

Next the water vapour fraction is calculated:

βx1 0.4448(0.5)
y1 = = = 0.3079
1 + (β − 1)x1 1 + (0.4448 − 1)0.5

Finally the ethanol vapour content is found:

y 2 = 1 − y1 = 1 − 0.3079 = 0.6921

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 3A Worked Examples Q&A 10

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 3B Worked Examples Q&A 1

4.4.5 Example 3B.1

Construct a T-x-y diagram for the partially miscible system ether-water at 1

atm total pressure using the following data for saturated (i.e. three phase)
vapour-liquid equilibrium at various pressures.

Saturated Saturated Vapour Vapour

Total
Temperature Water Phase Ether Phase Pressure Pressure
Pressure
(oC) Composition Composition Water Ether
(atm)
Mole fraction ether (atm) (atm)
34.15 1.005 0.0122 0.9451 0.053 0.983
40.00 1.250 0.0116 0.9416 0.073 1.212
50.00 1.744 0.0103 0.9348 0.121 1.679
60.00 2.381 0.0093 0.9271 0.196 2.271
70.00 3.195 0.0075 0.9212 0.306 3.018
80.00 4.229 0.0069 0.9158 0.467 3.935
90.00 5.514 0.0058 0.9107 0.691 5.040
100.00 7.040 --- --- 1.000 6.390

Assume that Raoult’s Law is valid for ether in the ether-rich phase and for
water in the water-rich phase.

Note that an azeotrope forms at ≈ 34oC between water and ether.

Answers:

Temperature
x 1A y 1A x 2A y 2A
(oC)
34.15 0.9879 0.0524 0.0121 0.9476
40.00 0.9909 0.0723 0.0091 0.9277
50.00 0.9944 0.1203 0.0056 0.8797
60.00 0.9966 0.1953 0.0034 0.8047
70.00 0.9982 0.3054 0.0018 0.6946
80.00 0.9990 0.4665 0.0010 0.5335
90.00 0.9996 0.6907 0.0004 0.3093
100.00 1.0000 1.0000 0.0000 0.0000

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 3B Worked Examples Q&A 2

Solution:

For the liquid ‘A’, the water-rich phase – a solution of ether (2) and water (1):

p1sat x1 A
Raoult’s Law is valid for 1: y1 A =
p

h21 x 2 A h21 (1 − x1 A )
Henry’s Law is then valid for 2: y 2 A = 1 − y1 A = =
p p

Thus:

p1sat x1 A h (1 − x1 A )
= 1 − 21
p p

Rearranging this gives:

p − h21
x1 A = and;
p1sat − h21

p − p1sat x1 A
h21 =
1 − x1 A

Use the h21 equation to find h21 at each temperature (note that x1 A = 1 − x 2 A ):

p − p1sat x1 A 1.005 − (0.053 × 0.9878)

h21 = = = 78.09
1 − x1 A 1 − 0.9878

Temperature Pressure
x 2A x 1A p 1sat h 21
(oC) (atm)
34.15 1.005 0.0122 0.9878 0.053 78.09
40.00 1.250 0.0116 0.9884 0.073 101.54
50.00 1.744 0.0103 0.9897 0.121 157.69
60.00 2.381 0.0093 0.9907 0.196 235.14
70.00 3.195 0.0075 0.9925 0.306 385.51
80.00 4.229 0.0069 0.9931 0.467 545.68
90.00 5.515 0.0058 0.9942 0.691 832.24
100.00 7.040 --- --- 1.000 ---

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 3B Worked Examples Q&A 3

p − h21
Now use x1 A = to find the values at 1atm at each temperature:
p1sat − h21

x 1A y 1A x 2A y 2A
Temperature p 1sat
h 21 p − h21 p1sat x1 A
(oC) (atm) 1 − x1 A 1 − y1 A
p1sat − h21 p
34.15 0.053 78.09 0.9879 0.0524 0.0121 0.9476
40.00 0.073 101.54 0.9909 0.0723 0.0091 0.9277
50.00 0.121 157.69 0.9944 0.1203 0.0056 0.8797
60.00 0.196 235.14 0.9966 0.1953 0.0034 0.8047
70.00 0.306 385.51 0.9982 0.3054 0.0018 0.6946
80.00 0.467 545.68 0.9990 0.4665 0.0010 0.5335
90.00 0.691 832.24 0.9996 0.6907 0.0004 0.3093
100.00 1.000 --- 1.0000 1.0000 0.0000 0.0000

Note: the x 1A value at 100oC is estimated based on the boiling point of water
and the evident trend of the data i.e. it is not calculated. y 1A however, is
calculated using the x 1A estimate. As such both values equate to 1.0 and ‘tie-
up’ the graph.

The same procedure can be followed for the other liquid phase of a solution of
water in ether however because the boiling point of ether is 34.15oC and the
azeotrope has an estimated boiling point of 34.0oC there is no need to carry
out the calculations. This would add the other “loop” to the graph on the left.

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 3B Worked Examples Q&A 4

4.5.2 Example 3B.2

Using the vapour pressure data given below, construct a T − y diagram for the
toluene/water system at 760 mm Hg pressure.

Vapour Pressure Data:

B
ln P sat = A −
T +C

Where,
P sat is the vapour pressure (mm Hg)
T is the temperature (K)

The Antoine constants for each component are listed below:

A B C
Water: 18.3036 3,816.44 -46.13
Toluene: 16.0137 3,096.52 -53.67

Answers:

Temperature
y ww y wt
(K)
383.8 1.445 -0.001
378 1.186 0.154
373.2 1.002 0.267
370 0.893 0.335
360 0.613 0.517
358 0.567 0.548

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 3B Worked Examples Q&A 5

Solution:

First find the boiling point of both water and toluene at the system pressure
using the Antoine equation rearranged to solve for temperature:

B
T= −C
A - ln P sat

For water:

3816.44
T= + 46.13 = 373.2 K = 100.2 o C
18.3036 - ln (760 )

For toluene:

3096.52
T= + 53.67 = 383.8 K = 110.8 o C
16.0137 - ln (760 )

For the water phase it is assumed that x ww = 1.0 and so y ww = p wsat / p

For the toluene phase it is assumed that x wt = 0.0 and so y wt = 1 − ( ptsat / p )

Solve this from the upper temperature limit continuing until the combined
saturation pressures falls to roughly 760mmHg:

Temperature
p wsat p tsat y ww y wt
(K)
383.8 1098.09 760.52 1.445 -0.001
378 910.26 643.08 1.186 0.154
373.2 761.30 557.15 1.002 0.267
370 678.40 505.13 0.893 0.335
360 466.05 366.96 0.613 0.517
358 431.09 343.38 0.567 0.548

Draw the diagram with temperature on the y-axis and vapour composition on
the x-axis (remember to only plot between 0 and 1 on the x-axis).

Summary diagram is shown overleaf:

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 3B Worked Examples Q&A 6

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

Topic 4 Worked Examples Q&A 1

4.2.2 Topic 4: Worked Example 4.1

Assume 10 moles of H 2 reacting with 5 moles of N 2 to produce NH 3 . Find the

molar fraction of each component of the reaction exiting the system in terms of
extent of reaction.

Answers:

H 2 = 10 − 3ε
15 − 2ε

N2 = 5 − ε
15 − 2ε

NH 3 = 2ε
15 − 2ε

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

Topic 4 Worked Examples Q&A 2

Solution:

The balanced equation is found to be:

N 2 + 3H 2 → 2 NH 3

It can then be shown that:

dn H 2 dn N 2 dn NH 3
= = = dε
υH 2 υN2 υ NH 3

Or

dn H 2 dn N 2 dn NH 3
= = = dε
−3 −1 +2

For H 2 dn H 2 = −3dε , therefore:

nH 2 ε

∫ dnH 2 = −3∫ dε
10 0

nH 2 − 10 = −3(ε − 0)
nH 2 = 10 − 3ε

Similarly for N 2, dn N 2 = −1dε :

nN 2 ε

∫ dn
5
N2 = −1∫ dε
0

nN 2 − 5 = −1(ε − 0)
nN 2 = 5 − ε

And for NH 3, dn NH 3 = 2dε

nNH 3 ε

∫ dn
0
NH 3 = 2 ∫ dε
0

nNH 3 − 0 = 2(ε − 0)
nNH 3 = 2ε

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

Topic 4 Worked Examples Q&A 3

Simply expressed in tabular form:

Component Moles in Moles out Mole fraction out

H2 10 10 − 3ε 10 − 3ε
15 − 2ε
N2 5 5−ε 5−ε
15 − 2ε
NH 3 0 2ε 2ε
15 − 2ε
Total 15 15 − 2ε 1

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

Topic 4 Worked Examples Q&A 4

4.3.5 Example 4.2

Develop expressions for the equilibrium constant and the standard free
energy change as a function of temperature for the reaction:

CO 2 (g) + H 2 (g) → CO(g) + H 2 O(g)

Dimensionless CO H2O CO 2 H2
a 3.376 3.470 5.457 3.249
b × 10 3 0.557 1.450 1.045 0.422
c × 10 6 --- --- --- ---
d × 10 −5 -0.031 0.121 -1.157 0.083
using:

(a) The experimentally determined values of the equilibrium constant.

T (oC) K
686 0.534
1309 2.930

(b) The first of the above values and the standard enthalpy change for
the reaction.

Δhr0 = +9838cal/mol = +41190kJ/kmol at 298 K

(c) The standard enthalpy change for the reaction and the standard
free energies of formation.

∆g 0f at 298K
Species
(cal/mol)
CO 2 -94,260
CO -32,808
H2O -54,635

Answers:
− 6102.839 58200
(a) Ln( K ) = − 1.86 Ln(T ) + 2.7 × 10 − 4 T + + 18.184
T T2
− 5875.201 58200
(b) Ln( K ) = − 1.86 Ln(T ) + 2.7 × 10 − 4 T + + 17.948
T T2
− 6102.839 58200
(c) Ln( K ) = − 1.86 Ln(T ) + 2.7 × 10 − 4 T + + 18.056
T T2

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

Topic 4 Worked Examples Q&A 5

(a) Solution
In this instance the C i coefficient is 0 and so on the A i , B i and D i coefficients
are used (these were found in Smith and Van Ness for reference).

Dimensionless CO H2O CO 2 H2 ∆
a 3.376 3.47 5.457 3.249 -1.860 ∆A
b × 10 3
0.557 1.45 1.045 0.422 0.540 ∆B
d × 10 −5 -0.031 0.121 -1.157 0.083 1.164 DD

Using the equation:

−I DBT DD
Ln( K ) = + DALn(T ) + + +J
RT 2 2T 2

Form two simultaneous equations with the known T and K values:

−I 0.54 × 10 −3 × 959 1.164 × 10 5

Ln(0.534) = − 1.86 Ln(959) + + +J
8.314 × 959 2 2 × (959) 2
− 0.627 = −1.254 × 10 − 4 I − 12.770 + 0.259 + 0.063 + J

J = 1.254 × 10 −4 I + 11.821 (1)

−I 0.54 × 10 −3 × 1582 1.164 × 10 5

Ln(2.930) = − 1.86 Ln(1582) + + +J
8.314 × 1582 2 2 × (1582) 2
1.075 = −7.603 × 10 −5 I − 13.701 + 0.427 + 0.023 + J

J = 7.603 × 10 −5 I + 14.326 (2)

Taking equation (2) away from equation (1) gives:

J − J = 7.603 × 10 −5 I − 1.254 × 10 −4 I + 14.326 − 11.821

0 = −4.937 × 10 −5 I + 2.505
I = 50739

Solving either equation with the now known I value gives:

J = 7.603 × 10 −5 × 50739 + 14.326

J = 18.184

Therefore, the expression for the equilibrium constant can be given as:

− 6102.839 58200
Ln( K ) = − 1.86 Ln(T ) + 2.7 ×10 − 4 T + + 18.184
T T2

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

Topic 4 Worked Examples Q&A 6

(b) Solution

 T 2 ∆∆ 
∆h = I + R ∆AT + ∆B
0
+ 
2 −T 
T


Subbing in the values:

 −3  298
2
 1.164 × 10 5 
41190 = I + 8.314− 1.86 × 298 + 0.54 × 10    + 
  2  − 298 
41190 = I + 8.314[− 554.280 + 23.977 − 390.604]
41190 = I − 7656.421
I = 48846.421

−I DBT DD
Solve Ln( K ) = + DALn(T ) + + + J for “ J ”:
RT 2 2T 2

− 48846.421 0.54 × 10 −3 × 959 1.164 × 10 5

Ln(0.534) = + (−1.86 × Ln(959)) + + +J
8.314 × 959 2(959 )
2
2
− 0.627 = −6.126 − 12.771 + 0.259 + 0.063 + J
J = 17.948

Therefore, the expression for the equilibrium constant can be given as:

− 5875.201 58200
Ln( K ) = − 1.86 Ln(T ) + 2.7 × 10 − 4 T + + 17.948
T T2

(c) Solution

∆g r0 = −94620 − (−32808) − (−54635) = −6817cal / mol = 28541kJ / kmol

As with the findings of part (b), it is found that I = 48846.421 :

∆BRT 2 R∆∆
∆g 0 = I − ∆ARTLn(T ) − − − JRT solved at 298K
2 2T
28541 = 48846.421 + 26253.824 − 199.345 − 1623.741 − 2477.572 J
J = 18.056

Therefore, the expression for the equilibrium constant can be given as:

− 6102.839 58200
Ln( K ) = − 1.86 Ln(T ) + 2.7 × 10 − 4 T + + 18.056
T T2

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

Topic 4 Worked Examples Q&A 7

4.4.7 Example 4.3

C 2 H 4 + 2 H 2 → 2CH 4

Conditions:

1,500K
10bar
There are 3 moles of ethane to 1 mole of hydrogen in the feed stream

From the plot of Ln(K) vs. 1/T for the following two reactions:

C + 2 H 2 → CH 4 A Ln(K) = -6.0 (eqn.A)

2C + 2 H 2 → C 2 H 4 B Ln(K) = -12.5 (eqn.B)

Find the conversions of C 2 H 4 to CH 4 and H 2 to CH 4 through K p value and

reaction extent manipulation.

Answers:

ε = 0.388
C 2 H 4 = 12.9%
H 2 = 77.6%

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

Topic 4 Worked Examples Q&A 8

Solution:

To find the required equation, equation (A) must be multiplied by 2 and

equation (B) taken away from this:

∆g = 2 × ∆g A − ∆g B

Ln( K ) = 2 Ln( K A ) − Ln( K B )

Ln( K ) = 2 × (−6) − (−12.5) = 0.5

K = exp(0.5) = 1.649

Producing the extent of reaction balance table:

Component Moles in Moles out Mole fraction out

C2H4 3 3−ε 3−ε
4−ε
H2 1 1 − 2ε 1 − 2ε
4−ε
CH 4 0 2ε 2ε
4−ε
Total 4 4−ε 1

Assuming that K φ and K γ are 1

KP = K y p∑
vi

 2ε 
2

 
 4−ε 
1.65 = × 10 −1
 3 − ε  1 − 2ε 
2

  
 4 − ε  4 − ε 

4ε 2 (4 − ε )
16.5 =
(3 − ε )(1 − 2ε ) 2

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

Topic 4 Worked Examples Q&A 9

This must then be solved iteratively:

ε Left hand side of equation

0.3 3.08
0.4 22.15
0.38 13.86
0.39 17.39
0.387 16.23
0.388 16.60

Therefore it is shown that the value of ε lies between 0.387 and 0.388, closer
to 0.388. For the further use in this question 0.388 will be used.

Product stream table:

Component Moles out Mole fraction out

C2H4 3−ε 2.612 0.723
H2 1 − 2ε 0.224 0.062
CH 4 2ε 0.776 0.215
Total 4−ε 3.612 1

Conversion of C 2 H 4 to CH 4 :

Moles of C 2 H 4 reacted 3 − 2.612

= = 0.129 or 12.9%
Moles of C 2 H 4 entering 3

Conversion of H 2 to CH 4 :

Moles of H 2 reacted 1 − 0.224

= = 0.776or 77.6%
Moles of H 2 entering 1

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

Topic 4 Worked Examples Q&A 10

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 5: Worked Examples Q&A 1

Example Worked Solutions

Example 1:
Constant
1  dV  Mass
κ =−   Density =
V  dP  T Volume

A change of 0.08% equates to:

dV
= −0.08 × 10 − 2
V

Rearranging the “ κ ” equation gives:

dV 1
dP = −
V κ
1
dP = −0.08 × 10 − 2 × = 362atm
− 2.21 × 10 −6 atm −1

Example 2:

1  dV 
β=  
V  dT  P

Plot the graph of temperature and volume:

The slope of the line gives the value of β to be 9 × 10 −3 K −1

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 5: Worked Examples Q&A 2

Example 3:

W = − PdV
1 dV
κ =− ( )T
V dP
=> dV = −V × κ × dP

Placing this back into the original work equation:

W = − P (−V × κ × dP ) = P × V × κ × dP

Taking the integral of the right-hand side of the equation (removing V as it is

independent of P):

200 200
W = V ∫ k × P × dP = V ∫ (4 × 10 −6 − (1.5 × 10 −10 P)) × P × dP
1 1
200
W = V ∫ 4 × 10 −6 P − 1.5 × 10 −10 P 2 × dP
1
200
 4×10− 6 2 1.5×10−10 3 
W =V  P − P 
 2 3  1

 4 × 10 × 200
−6
1.5 × 10 × 200   4 × 10 −6 × 12 1.5 × 10 −10 × 13 
2 −10 3
W = 5 ×  −  −  − 
 2 3   2 3 
−6
W = 5m × (0.0796atm − 2 × 10 atm) = 0.40m atm = 40kJ
3 3

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 5: Worked Examples Q&A 3

Example 4:

B
Pv = RT (1 + )
v
BRT
Pv = RT +
v
BRT
Pv − RT − =0
v
Pv 2 − RTv − BRT = 0

Universal gas constant manipulation:

R = 8.314 J / mol.K = 8.314kg.m 2 / s 2 .mol.K = 8.314 Pa.m 3 / mol.K

R = 8.314 × 10 −5 bar.m 3 / mol.K = [Link] 3 / mol.K

Solving the equation:

10 × v 2 − (83.14 × 363 × v) − (−194 × 83.14 × 363) = 0

10v 2 − 30179.82 + 5854885.08 = 0

− b ± b 2 − 4ac
Solving this using :
2a

30179.82 ± 26012.04
=
20

+ = 2810cm 3 /mol
− = 208cm 3 /mol

Solve for Z in ideal gas equation:

Pv 10 × 2810
Z= = = 0.93
RT 83.14 × 363

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 5: Worked Examples Q&A 4

Example 5:

R is taken to be [Link] 3 / mol.K , v is found from:

Pv 2 − RTv − BRT = 0
15v 2 − (83.14 × 348 × v) − (−194 × 83.14 × 348) = 0
15v 2 − 28932.72v + 5612947.68 = 0

− b ± b 2 − 4ac
Solving using :
2a

28932.72 ± − 28932.72 2 − 4 × 15 × 5612947.68 28932.72 ± 22367.96

=
2 × 15 30

+ = 1710cm 3 mol −1
− = 219cm 3 mol −1

Solve for Z:

Pv 15 × 1710
Z= = = 0.89
RT 83.14 × 348

Now solve with the inclusion of the C term:

Pv BP C − B 2
= 1 + B' P + C ' P 2 = 1 + +
RT RT ( RT ) 2
RT (C − B 2 )
v= +B+ P
P RT
83.14 × 348 (15300 − (−194 2 ))
v= − 194 + 15 = 1928.8 − 194 − 11.6 = 1723cm 3
15 83.14 × 348

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 5: Worked Examples Q&A 5

Example 6:

Ideal gas:

Pv = RT
RT 83.14 × 273
v= = = 227cm 3 mol −1
P 100

Using Virial expansion:

Pv 2 − RTv − BRT = 0
100v 2 − (83.14 × 273 × v) − (−21.7 × 83.14 × 273) = 0
100v 2 − 22697.22V + 492529.67 = 0

− b ± b 2 − 4ac
Solving using :
2a

22697.22 ± − 22697.22 2 − 4 × 100 × 492529.67 22697.22 ± 17836.81

=
2 × 100 200

+ = 203cm 3 mol −1
− = 24.3cm 3 mol −1

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 5: Worked Examples Q&A 6

Example 7:

V2

Wrev ( piston) = −n ∫ PdV = −Wsteam

V1

0.01kg 0.01kg
n= = = 0.56mol
18kg / kmol × 0.001kmol / mol 0.018kg / mol

1dm 3 = 1 × 10 −3 m 3

2 × 10 −3
v1 = = 0.0036m 3 mol −1
0.56
20 × 10 −3
v2 = = 0.036m 3 mol −1
0.56

Using the Virial expansion:

Pv B C
Z= = 1+ +
RT v v
v2
1 B C
Wsteam = nRT ∫ ( + 2 + 3 )dv
v1
v v v
 v 1 1 1 1 
= nRT ln 2 + B (− + ) + C (− 2
+ 2 
)
 v1 v 2 v1 2v 2 2v 1 
[ −6 −12
= 0.025 2.303 − 142.2 × 10 (450) − 7140 × 10 (123750) ]
= 0.056m 3 .bar = 5.6kJ

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 5: Worked Examples Q&A 7

Example 8:

 dV   dV 
dV =   dT +   dP Isothermal hence this is equal to 0.
 dT  P  dP  T

1  dV 
κ =−  
V  dP  T
dV
= −κdP
V
V 
ln 2  = −κ ( P2 − P1 )
 V1 
V 
ln 2  = −4 × 10 − 4 (500 − 1)
 10 
V 
ln 2  = −0.1996
 10 
V2
= 0.819
10
V2 = 8.19m 3

18% decrease in volume.

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 5: Worked Examples Q&A 8

Example 9:

Rearrange the molar volume equation for pressure:

RT
P=
v−b

Isothermal work given by:

v2

W = − ∫ Pdv
v1
v2
1
W = − RT ∫ dv
v1
v − b
W = − RT [Ln(v − b)]v12
v

v −b
W = − RT ( Ln 2 )
 v1 − b 
 2 − (−42.6) 
W = −83.14 × 390 × Ln 
 10 − (−42.6) 

[Link] 3
W = 5349.5 = 535 J / mol
mol

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 5: Worked Examples Q&A 9

Example 10:

BP
Z = 1+
RT
BP  Pr 
Z = 1+ C  
RTC  Tr 
P 
Z = 1 + ( B 0 + ωB 1 ) r 
 Tr 

Calculate the reduced pressure and temperature:

T 70 + 273
Tr = = = 1.04
TC 330
P 6
Pr = = = 0.14
PC 42

Calculate B 0 and B 1 :

0.422 0.422
B 0 = 0.083 − 1.6
= 0.083 − = −0.313
Tr 1.041.6
0.172 0.172
B 1 = 0.139 − 4.2
= 0.139 − = −0.007
Tr 1.04 4.2
Solve for Z:

 0.14 
Z = 1 + (−0.313 + 0.273 × −0.007)  = 0.958 ≈ 0.96
 1.04 

Solve for v :

ZRT 0.96 × 83.14 × 343

v= = = 4563cm 3 / mol
P 6

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 5: Worked Examples Q&A 10

Example 11:

(a):
Pv 2 − RTv − BRT = 0
15v 2 − 83.14 × 323 × v − (−156.7 × 83.14 × 323) = 0
15v 2 − 26854.22v + 4208056.27 = 0

− b ± b 2 − 4ac 26854.22 ± 21648.69

Solving using = :
2a 30

+ = 1617cm 3 / mol
− = 174cm 3 / mol

Pv 15 × 1617
Z= = = 0.903
RT 83.14 × 323

(b):

T 323
Tr = = = 1.06
TC 305
P 15
Pr = = = 0.31
PC 48.7

Solve for B0 and B1:

0.422 0.422
B 0 = 0.083 − 1.6
= 0.083 − = −0.301
Tr 1.061.6
0.172 0.172
B 1 = 0.139 − 4.2 = 0.139 − = 0.004
Tr 1.06 4.2

Solve for Z:
P 
Z = 1 + ( B 0 + ωB1 ) r 
 Tr 
 0.31 
Z = 1 + (−0.301 + 0.1× 0.004)  = 0.912 ≈ 0.91
 1.06 

Solve for v :

ZRT 0.91 × 83.14 × 323

v= = = 1629cm 3 / mol
P 15

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 5: Worked Examples Q&A 11

Example 12:

RT a
P= − 1
v − b T 2 v (v + b )

2.5
0.428 R 2TC 0.087 RTC
a= and b =
PC PC

0.428(83.14) 2 (319) 2.5

a= = 1.4 × 10 8 cm 3 .bar.K 0.5 .mol − 2
38

0.087 × 83.14 × 319 3

b= = 60.72 cm
38 mol

RT a
P= − 1
v − b T 2 v (v + b )
83.14 × 363 1.4 × 10 8
10 = −
v − 60.72 1
363 2 v(v + 60.72)
30179.82 7348094.34
10 = −
v − 60.72 v 2 + 60.72v

Solving this gives:

v = 2827cm 3 mol −1

There are in fact three roots but the root quoted is the only real root.
This is most easily solved iteratively using a computer program but can be
done by hand .

Solving for Z:

Pv 10 × 2827
Z= = = 0.94
RT 83.14 × 363

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 5: Worked Examples Q&A 12

Example 13:

Find the aT and b parameters using:

2
R 2TC
aT = 0.42748 a (T )
PC
RT
b = 0.08664 C
PC

1
In this instance α (T ) = 0.5
so:
Tr
1
α (T ) = = 0.937
(363319)0.5

aT is then:

83.14 2 × 319 2
aT = 0.42748 × 0.937 = 7,414,352bar cm 6 mol − 2
38

b is then:

83.14 × 319
b = 0.08664 = 60.5cm 3 mol -1
38

Convert these to dimensionless values A and B:

aT P [Link] 6 mol −2 × 10bar

A= = = 0.0814
R 2T 2 ( 2
)
[Link] 3 .mol −1 .K −1 × (363K )
2

bP 60.5cm 3 .mol −1 × 10bar

B= = = 0.0200
RT [Link] 3 .mol −1 .K −1 × 363K

Placing these values into the equation:

Z 3 + (−1) Z 2 + ( A − B − B 2 ) Z + (− AB) = 0

Z 3 + (−1) Z 2 + (0.0814 − 0.02 − 0.02 2 ) Z + (−0.0814 × 0.02) = 0

Z 3 − Z 2 + 0.061Z − 0.0016 = 0

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 5: Worked Examples Q&A 13

Typical a computer tool would be used to solve the cubic equation however,
because the last worked example used the same information use the answer
of Z = 0.94 and see if this works:

0.94 3 − 0.94 2 + 0.061 × 0.94 − 0.0016 = 0.003

This is close enough to zero to say that 0.94 is a solution.

(using an online quadratic solver – such as that at [Link]/[Link]-

the complete solutions are found to be: 0.937, 0.032+0.027i and 0.032-0.027i).

Final step is to calculate v for this system:

ZRT 0.937 × 83.14 × 363

v= = = 2828cm 3 / mol
P 10

Now complete the procedure with the longer α (T ) function:

[ (
α (T ) = 1 + (0.48 + 1.57ω − 0.17ω 2 ) 1 − Tr 0.5 )]
2

2
  0.5

(
α (T ) = 1 + 0.48 + 1.57 × 0.21 − 0.17 × 0.212 ) 1 −  363   = 0.896
  319  
  

aT is then:

83.14 2 × 319 2
aT = 0.42748 × 0.896 = 7,089,925bar cm 6 mol − 2
38

b is then:

83.14 × 319
b = 0.08664 = 60.5cm 3 mol -1
38

Convert these to dimensionless values A and B:

aT P [Link] 6 mol −2 × 10bar

A= = = 0.0778
R 2T 2 ( 2
)
[Link] 3 .mol −1 .K −1 × (363K )
2

bP 60.5cm 3 .mol −1 × 10bar

B= = = 0.0200
RT [Link] 3 .mol −1 .K −1 × 363K

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1

TOPIC 5: Worked Examples Q&A 14

Placing these values into the equation:

Z 3 + (−1) Z 2 + ( A − B − B 2 ) Z + (− AB) = 0

Z 3 + (−1) Z 2 + (0.0778 − 0.02 − 0.02 2 ) Z + (−0.0778 × 0.02) = 0

Z 3 − Z 2 + 0.0574 Z − 0.0016 = 0

Using an online cubic solver the roots are found to be:

0.941
0.030 + 0.029i
0.030 – 0.029i

Final step is to calculate v for this system:

ZRT 0.941 × 83.14 × 363

v= = = 2840cm 3 / mol
P 10

©HERIOT-W ATT UNIVERSITY B49CE August 2015 v1