You are on page 1of 10

CTDCHA2 Chemical Thermodynamics 2A BET

FACULTY OF ENGINEERING AND THE BUILT ENVIRONMENT (FEBE)

DEPARTMENT OF CHEMICAL ENGINEERING

CTDCHA2: Chemical Thermodynamics 2A

TUTORIAL 2 MEMO

1. Is iced water a pure substance? Why?


Solution: Yes. Because it has the same chemical composition throughout

2. What is the difference between saturated liquid and compressed liquid?


Solution: A liquid that is about to vaporize is saturated liquid; otherwise it is compressed
liquid or subcooled

3. What is the difference between saturated vapour and superheated vapour?


Solution: A vapour that is about to condense is saturated vapour; otherwise it is
superheated vapour

4. Is there any difference between the intensive properties of saturated vapour at a given
temperature and the vapour of a saturated mixture at the same temperature?
Solution: No

5. Is there any difference between the intensive properties of saturated liquid at a given
temperature and the liquid of a saturated mixture at the same temperature?
Solution: No

6. If the pressure of a substance is increased during a boiling process, will the temperature
also increase or will it remain constant? Why?

Page 1 of 10
CTDCHA2 Chemical Thermodynamics 2A BET

Solution: The temperature will also increase because the boiling or saturation
temperature of a pure substance depends on pressure

7. What is the difference between the critical point and the triple point?
Solution: At critical point the saturated liquid and the saturated vapour states are
identical. At triple point the three phases of a pure substance coexist in equilibrium

8. Is it possible to have water vapour at -10°C?


Solution: Yes

9. A househusband is cooking beef stew for his family in a pan that is (a) uncovered, (b)
covered with a light lid, and (c) covered with a heavy lid. For which case will the cooking
time be the shortest? Why?
Solution: Case (c) when the pan is covered with a heavy lid. Because the heavier the
lid, the greater the pressure in the pan, and thus the greater the cooking temperature

10. In what kind of pot will a given volume of water boil at a higher temperature: a tall and
narrow one or a short and wide one? Explain
Solution: A given volume of water will boil at a higher temperature in a tall and narrow
pot since the pressure at the bottom (and thus the corresponding saturation pressure)
will be higher in that case

11. Most equations of state are developed to cover which range of states?
Solution: Most equations of state are developed to cover the gaseous phase, from low
to moderate densities. Many cover high-density regions as well, including the
compressed liquid region

12. Is an equation of state valid in the two-phase regions?


Solution: No. In a two-phase region, P depends only on T. There is a discontinuity at
each phase boundary. This means that V cannot influence the system but equations of
state are for PvTdata.

13. What is the benefit of the generalized charts? Which properties must be known besides
the charts themselves?
Solution: The generalized charts allow for the approximate calculations of enthalpy
changes (and P-v-T behaviour), for processes in cases where specific data or equation
of state are not known. They also allow for approximate phase boundary determinations.

Page 2 of 10
CTDCHA2 Chemical Thermodynamics 2A BET

It is necessary to know the critical pressure and temperature, as well as ideal-gas


specific heat.

14. A certain pressure cooker has a volume of 6 L and an operating pressure of 75kPa
gauge. Initially, it contains 1 kg of water. Heat is supplied to the pressure cooker after the
operating pressure is reached. Assuming an atmospheric pressure of 100kPa, determine
the temperature at which cooking takes place.
Solution: 𝑃𝑎𝑏𝑠 = 𝑃𝑔 + 𝑃𝑎𝑡𝑚 = 175𝑘𝑃𝑎
Since saturation conditions exist in the cooker at all times, the cooking temperature must
be the saturation temperature corresponding to this pressure. From steam tables, it is
𝑇 = 𝑇𝑠𝑎𝑡@175𝑘𝑃𝑎 = 116.04oC which is about 16°C higher than the ordinary cooking
temperature

15. A cylinder fitted with a piston contains liquid methanol at 20°C, 100kPa and volume 10L.
The piston is moved, compressing the methanol to 20MPa at constant temperature.
Calculate the work required for this process. The isothermal compressibility (𝜅) of liquid
methanol at 20°C is 1.22×10-9 m2/N.
𝑉
Solution: Using equation: ln 𝑉2 = 𝛽(𝑇2 − 𝑇1 ) − 𝜅(𝑃2 − 𝑃1 )
1

T is constant 𝛽(𝑇2 − 𝑇1 ) = 0 and


𝑉 𝑉
ln 𝑉2 = −𝜅(𝑃2 − 𝑃1 )orln 0.01
2
= −1.22𝑥10−9 (20𝑥106 − 100𝑥103 )
1

𝑉2 = 10𝑒 −0.02428 = 9.46𝐿


Plotting a graph gives:

1
𝑊 = 2 (100 + 20000)(10 − 9.46) =5.4kJ

Page 3 of 10
CTDCHA2 Chemical Thermodynamics 2A BET

16. Complete this table for H2O:


T, oC P, kPa v, cm3 g-1 Phase description
50 12.352 4160 Saturated mixture
120.21 200 885.8 Saturated vapour
250 400 595.2 Superheated vapour
110 600 1.051 Compressed liquid

17. Complete this table for H2O:


T, oC P, kPa U, kJ kg-1 Phase description
143.61 400 1450 Saturated mixture
220 2319.6 2601.3 Saturated vapour
190 2500 805.15 Compressed liquid
466.21 4000 3040 Superheated vapour

18. What is the physical significance of the compressibility factor Z?


Solution: It represents the deviation from ideal gas behaviour. The further away it is
from 1, the more the gas deviates from ideal gas behaviour

19. What is the principle of corresponding states?


Solution: All gases have the same compressibility factor Z at the same reduced
temperature and pressure

20. How are the reduced pressure and reduced temperature defined?
Solution: Reduced pressure is the pressure normalized with respect to the critical
pressure; and reduced temperature is the temperature normalized with respect to the
critical temperature

21. Determine the specific volume of superheated water vapour at 10 MPa and 400°C, using
(a) the ideal-gas equation, (b) the generalized compressibility chart, and (c) the steam
tables. Also determine the error involved in the first two cases. Use R = 0.4615
kPa.m3/kg·K, Tc= 647.1K, Pc=22.06 MPa

Page 4 of 10
CTDCHA2 Chemical Thermodynamics 2A BET

Solution:
𝑅𝑇 0.4615𝑥673
(a) 𝑣 = 𝑃
= 10000
= 0.03106𝑚3 /𝑘𝑔 (17.6% error, calculated against v from Steam

tables as actual value)


𝑃 𝑇
(b) 𝑃𝑟 = 𝑃 = 0.453and 𝑇𝑟 = 𝑇 = 1.04. From compressibility chart above Z=0.84
𝑐 𝑐

𝑣 = 𝑍𝑣𝑖𝑑𝑒𝑎𝑙 = 0.84𝑥0.03106 = 0.02609𝑚3 /𝑘𝑔 (1.2% error, calculated against v from


Steam tables as actual value)
(c) From superheated Steam tables (Table A-6), for T=400oC and P=10MPa,
v=0.02644m3/kg

22. Determine the specific volume of superheated water vapour at 3.5 MPa and 450°C
based on (a) the ideal-gas equation, (b) the generalized compressibility chart, and (c) the
steam tables. Determine the error involved in the first two cases. Use R = 0.4615
kPa·m3/kg·K, Tc= 647.1 K, Pc= 22.06 MPa
Solution:
𝑅𝑇 0.4615𝑥723.15
(a) 𝑣 = 𝑃
= 3500
= 0.09533𝑚3 /𝑘𝑔 (3.7% error, calculated against v from Steam

tables as actual value)


𝑃 𝑇
(b) 𝑃𝑟 = 𝑃 = 0.159and 𝑇𝑟 = 𝑇 = 1.12. From compressibility chart above Z=0.961
𝑐 𝑐

𝑣 = 𝑍𝑣𝑖𝑑𝑒𝑎𝑙 = 0.961𝑥0.09533 = 0.09161𝑚3 /𝑘𝑔 (0.4% error, calculated against v from


Steam tables as actual value)

Page 5 of 10
CTDCHA2 Chemical Thermodynamics 2A BET

(c) From superheated Steam tables (Table A-6), for T=450oC and P=3.5 MPa,
v=0.09196m3/kg

23. What is the percentage of error involved in treating carbon dioxide at 7 MPa and 380 K
as an ideal gas? Use Tc= 304.2 K and Pc= 7.39 MPa.

𝑃 𝑇
Solution: 𝑃𝑟 = 𝑃 = 0.947and 𝑇𝑟 = 𝑇 = 1.25. From compressibility chart Z=0.84
𝑐 𝑐

𝑣 − 𝑣𝑖𝑑𝑒𝑎𝑙 1 1
𝐸𝑟𝑟𝑜𝑟 = =1− =1− = −0.19 = 19%
𝑣 𝑍 0.84

24. What is the physical significance of the two constants that appear in the van der Waals
equation of state? On what basis are they determined?
Solution: The constant a represents the increase in pressure as a result of
intermolecular forces; the constant b represents the volume occupied by the molecules.
They are determined from the requirement that the critical isotherm has an inflection
point at the critical point.

25. A 1-m3 tank contains 2.841 kg of steam at 0.6 MPa. Determine the temperature of the
steam, using (a) the ideal gas equation, (b) the van der Waals equation, and (c) the
steam tables. Use R = 0.4615 kPa·m3/kg·K, Tc= 647.1 K, Pc= 22.06 MPa.
Solution:
𝑉 1
(a) 𝑣 = 𝑚 = 2.841 = 0.3520𝑚3 /𝑘𝑔
𝑃𝑣 600𝑥0.352
𝑇= = = 457.6𝐾
𝑅 0.4615
27𝑅2 𝑇𝑐2 𝑅𝑇
(b) 𝑎 = 64𝑃𝑐
= 1.705𝑚6 𝑘𝑃𝑎/𝑘𝑔2 and 𝑏 = 8𝑃𝑐 = 0.00169𝑚3 /𝑘𝑔
𝑐

1 𝑎
𝑇= (𝑃 + 2 )(𝑣 − 𝑏) = 465.9𝐾
𝑅 𝑣
(c) From superheated Steam tables (Table A-6), for P=0.6 MPa and v=0.3520m3/kg,
T=200oC=473.15K

26. Five kilograms of liquid carbon tetrachloride undergo a mechanically reversible, isobaric
change of state at 1 bar during which the temperature changes from 273.15 K (0°C) to
293.15 K (20°C). Determine Vt, W, Q, Ht and Ut. The properties for liquid carbon
tetrachloride at 1 bar and 273.15 K (0°C) may be assumed independent of temperature:
=1.2xl0-3 K-1, Cp=0.84kJ kg-1 K-1 and =1590 kg m-3.

Page 6 of 10
CTDCHA2 Chemical Thermodynamics 2A BET

Solution:
1 1
𝑉1 = = 𝑚3 𝑘𝑔−1
𝜌 1590
With  independent of T and with P constant
𝑑𝑉
𝑉
= 𝛽𝑑𝑇𝑉2 = 𝑉1 𝑒 [𝛽(𝑇2 −𝑇1 )] and ∆𝑉 = 𝑉2 − 𝑉1

∆𝑉𝑡𝑜𝑡𝑎𝑙 = 𝑚∆𝑉 = 7.638𝑥10−5 𝑚3


𝑊 = 𝑃∆𝑉𝑡𝑜𝑡𝑎𝑙 = −7.638 J
𝑄 = 𝑚𝐶𝑝 ∆𝑇 = 84 𝑘J
∆𝐻 = 𝑄 = 84𝑘 J
∆𝑈 = 𝑄 + 𝑊 = 83.99 kJ

27. One mole of an ideal gas with Cp=(7/2)R and Cv= (512) R expands from P1=8 bar and
T1=600K to P2=1bar by each of the following paths:
(a) Constant volume; (b) Constant temperature; (c) Adiabatically
Assuming mechanical reversibility, calculate W, Q, U and H for each process. Sketch
each path on a single PV diagram.
Solution:
𝑃1 𝑃2 𝑃2
(a) For constant V: W=0 and
𝑇1
=
𝑇2
𝑇2 = 𝑇1
𝑃1
and ∆𝑇 = 𝑇2 − 𝑇1 = −525𝐾

∆𝑈 = 𝑄 = 𝐶𝑣 ∆𝑇 = −10.91𝑘𝐽/𝑚𝑜𝑙 and ∆𝐻 = 𝐶𝑝 ∆𝑇 = −15.28𝑘𝐽/𝑚𝑜𝑙


𝑃
(b) For constant T:U=H=0 and 𝑄 = 𝑊 = 𝑅𝑇1 ln 𝑃2 = −10.37𝑘𝐽/𝑚𝑜𝑙
1

𝛾−1⁄
𝑃2 𝛾
(c) For Q=0 and 𝑇2 = 𝑇1 ( ) = 331.227𝐾
𝑃1

∆𝑈 = 𝑊 = 𝐶𝑣 ∆𝑇 = −5.586𝑘𝐽/𝑚𝑜𝑙 and∆𝐻 = 𝐶𝑝 ∆𝑇 = −7.821𝑘𝐽/𝑚𝑜𝑙

28. An ideal gas, initially at 303.15 K(30°C) and 100kPa, undergoes the following cyclic
processes in a closed system:
(a) In mechanically reversible processes, it is first compressed adiabatically to 500kPa,
then cooled at a constant pressure of 500kPa to 303.15 K (30°C), and finally expanded
isothermally to its original state.
(b) The cycle traverses exactly the same changes of state, but each step is irreversible
with an efficiency of 80% compared with the corresponding mechanically reversible
process.
Calculate Q, W, U, and H for each step of the process and for the cycle. Take
Cp=(7/2)R and Cv=(5/2)R

Page 7 of 10
CTDCHA2 Chemical Thermodynamics 2A BET

Solution:
(a) Adiabatic compression from point 1 to point 2:
𝛾−1⁄
𝑃 𝛾
Q12=0; 𝑇2 = 𝑇1 ( 2 ) = 331.227𝐾∆𝑈12 = 𝑊12 = 𝐶𝑣,12 ∆𝑇 = 3.679𝑘𝐽/𝑚𝑜𝑙
𝑃1

∆𝐻12 = 𝐶𝑝 ∆𝑇 = 5.15𝑘𝐽/𝑚𝑜𝑙
Cooling at P2 from point 2 to point 3:
T3=T1; 𝑄23 = ∆𝐻23 = 𝐶𝑝 ∆𝑇 = −5.15𝑘𝐽/𝑚𝑜𝑙 ∆𝑈23 = 𝐶𝑣 ∆𝑇 = −3.679𝑘𝐽/𝑚𝑜𝑙
𝑊 = 𝑃∆𝑉 = 1.471𝑘𝐽/𝑚𝑜𝑙
Isothermal expansion from point 3 to point 1:
𝑃
U31=H31=0; P3=P2; 𝑊31 = −𝑄 = 𝑅𝑇3 ln 𝑃1 = −4.056𝑘𝐽/𝑚𝑜𝑙
3

For the cycle: ∆𝑈 = ∆𝐻 = 0


𝑄 = 𝑄12 + 𝑄23 + 𝑄31 = −1.094𝑘𝐽/𝑚𝑜𝑙
𝑊 = 𝑊12 + 𝑊23 + 𝑊31 = 1.094𝑘𝐽/𝑚𝑜𝑙

(b) If each step that is 80% efficient accomplishes the same change of state, all property
values are unchanged and H and U values are the same as in part (a). However,
Q
𝑊12
Step 12: 𝑊12 = 0.8
= 4.598𝑘𝐽/𝑚𝑜𝑙

𝑄12 = ∆𝑈12 − 𝑊12 = −0.92𝑘𝐽/𝑚𝑜𝑙


𝑊23
Step 23: 𝑊23 = 0.8
= 1.839𝑘𝐽/𝑚𝑜𝑙

𝑄23 = ∆𝑈23 − 𝑊23 = −5.518𝑘𝐽/𝑚𝑜𝑙


Step 31: 𝑊31 = 𝑊31 𝑥0.8 = −3.245𝑘𝐽/𝑚𝑜𝑙
𝑄31 = −𝑊31 = 3.245𝑘𝐽/𝑚𝑜𝑙
For the cycle: ∆𝑈 = ∆𝐻 = 0
𝑄 = 𝑄12 + 𝑄23 + 𝑄31 = −3.192𝑘𝐽/𝑚𝑜𝑙
𝑊 = 𝑊12 + 𝑊23 + 𝑊31 = 3.192𝑘𝐽/𝑚𝑜𝑙

29. For methyl chloride at 373.15K (100°C) the second and third virial coefficients are:
B= -242.5 cm3 mol-1 C= 25 200 cm6 mol-2
Calculate the work of mechanically reversible, isothermal compression of 1 mol of methyl
chloride from 1 bar to 55 bar at 373.15 K (100°C). Base calculations on the following
forms of the virial equation:
𝐵 𝐶
(a) 𝑍 = 1 + 𝑉 + 𝑉 2

(b) 𝑍 = 1 + 𝐵′ 𝑃 + 𝐶 ′ 𝑃2

Page 8 of 10
CTDCHA2 Chemical Thermodynamics 2A BET

𝐵 𝐶−𝐵2
Where 𝐵′ = 𝑅𝑇 and 𝐶 ′ = (𝑅𝑇)2

Why don't both equations give exactly the same result?


𝐵 𝐶−𝐵2
Solution: 𝐵′ = 𝑅𝑇 = −7.817𝑥10−3 𝑏𝑎𝑟 −1 and 𝐶 ′ = (𝑅𝑇)2 = −3.492𝑥10−5 𝑏𝑎𝑟 −2
𝑃1 𝑉1 𝐵 𝐶
𝑍1 = =1+ + solving for V1=30780cm3/mol
𝑅𝑇1 𝑉1 𝑉12
𝑃2 𝑉2 𝐵 𝐶
𝑍2 = 𝑅𝑇2
= 1 + 𝑉 + 𝑉 2solving for V2=241.33cm3/mol
2 2

Eliminating P from work formula using virial equation gives:


𝑉2
𝐵 𝐶 1 𝐵 𝐶 241.33
𝑊 = −𝑅𝑇 ∫ (1 + + 2 ) 𝑑𝑉 = −𝑅𝑇 [ln 𝑉 − − 2 ] = 12.62𝑘𝐽/𝑚𝑜𝑙
𝑉1 𝑉 𝑉 𝑉 𝑉 2𝑉 30780

(b) Eliminating dV from work equation by the virial equation in P:


−1
𝑑𝑉 = 𝑅𝑇 〈 2 + 𝐶 ′ 〉 𝑑𝑃
𝑃
𝑃2 𝑃2 55
−1 1 2
𝑊 = −𝑅𝑇 ∫ 𝑃 〈 2 + 𝐶 ′ 〉 𝑑𝑃 = −𝑅𝑇 ∫ (− + 𝐶 ′ 𝑃) = −𝑅𝑇 [ + 𝐶 ′ 𝑃]
𝑃1 𝑃 𝑃1 𝑃 𝑃 1

𝑊 = 12.596𝑘𝐽/𝑚𝑜𝑙

30. Calculate Z and V for sulphur hexafluoride at 348.15 K (75°C) and 15 bar by the
following equations:
𝑃𝑉 𝐵 𝐶
(a) The truncated virial equation 𝑍 = =1+ + with the following experimental
𝑅𝑇 𝑉 𝑉2

values of virial coefficients:


B= -194 cm3 mol-1 C= 15 300 cm6 mol-2
𝑃𝑉 𝐵𝑃
(b) The truncated virial equation 𝑍 = =1+ , with a value of B from the generalized
𝑅𝑇 𝑅𝑇
𝐵𝑃𝑐
Pitzer correlation 𝑅𝑇𝑐
= 𝐵0 + 𝜔𝐵1 .

For sulphur hexafluoride, Tc = 318.7 K, PC = 37.6 bar, Vc = 198 cm3mol-l, and  = 0.286
Solution:
𝑇 𝑃
(a) 𝑇𝑟 = 𝑇 = 1.092 and 𝑃𝑟 = 𝑃 = 0.399
𝑐 𝑐

𝑅𝑇
Guess initial V0: 𝑉0 = = 1930𝑐𝑚 𝑚𝑜𝑙 −1
3
𝑃
𝑃𝑉𝑖 𝐵 𝐶
=1+ + 2
𝑅𝑇 𝑉𝑖 𝑉𝑖
𝑃𝑉
After iterations: V=1722cm3/mol and 𝑍= = 0.893
𝑅𝑇

0.422 0.172
(b) 𝐵0 = 0.083 − 𝑇𝑟1.6
= −0.283 and 𝐵1 = 0.139 − 𝑇𝑟4.2
= 0.02

Page 9 of 10
CTDCHA2 Chemical Thermodynamics 2A BET

𝑃 𝑍𝑅𝑇
𝑍 = 1 + (𝐵0 + 𝜔𝐵1 ) 𝑇𝑟 = 0.899 and 𝑉= 𝑃
= 1734𝑐𝑚3 𝑚𝑜𝑙 −1
𝑟

31. Determine Z and V for steam at 523.15K (250°C) and 1800kPa by the following:
𝑃𝑉 𝐵 𝐶
(a) The truncated virial equation 𝑍 = 𝑅𝑇 = 1 + 𝑉 + 𝑉 2 with the following experimental

values of virial coefficients:


B= -152.5 cm3 mol-1 C = -5 800 cm6 mol-2
𝑃𝑉 𝐵𝑃
(b) The truncated virial equation 𝑍 = 𝑅𝑇 = 1 + 𝑅𝑇 , with a value of B from the generalized
𝐵𝑃𝑐
Pitzer correlation 𝑅𝑇𝑐
= 𝐵0 + 𝜔𝐵1 .

(c) The steam tables (Appendix F).


For steam, Tc = 647.1 K, PC = 220.55 bar and  = 0.345
Solution:
𝑇 𝑃
(a) 𝑇𝑟 = 𝑇 = 0.808 and 𝑃𝑟 = 𝑃 = 0.082
𝑐 𝑐

𝑅𝑇
Guess initial V0: 𝑉0 = 𝑃
= 2416.4𝑐𝑚3 𝑚𝑜𝑙 −1
𝑃𝑉𝑖 𝐵 𝐶
=1+ + 2
𝑅𝑇 𝑉𝑖 𝑉𝑖
𝑃𝑉
After iterations: V=2250cm3/mol and 𝑍= = 0.931
𝑅𝑇

0.422 0.172
(b) 𝐵0 = 0.083 − 𝑇𝑟1.6
= −0.51 and 𝐵1 = 0.139 − 𝑇𝑟4.2
= −0.281
𝑃𝑟 𝑍𝑅𝑇
𝑍 = 1 + (𝐵0 + 𝜔𝐵1 ) = 0.939 and 𝑉= = 2268𝑐𝑚3 𝑚𝑜𝑙 −1
𝑇𝑟 𝑃

(c) Table F2:

124.99𝑐𝑚3 18𝑔
MH2O=18.015 g/mol 𝑉= 𝑥 = 2252𝑐𝑚3 𝑚𝑜𝑙 −1
𝑔 𝑚𝑜𝑙

𝑃𝑉
𝑍 = 𝑅𝑇 = 0.932

Page 10 of 10

You might also like