02 Basic Thermodynamics

UNIT 1
THERMAL PROPERTIES OF LIQUIDS AND SOLIDS

Introduction
Materials are often subjected to temperature variations in various industrial applications. Their physical properties such as dimensions, densities, viscosity, etc. vary significantly with temperatures. Specific terms such as specific heats, latent heat of fusion, latent heat of vaporization, etc. are used in describing the physical change of the material with temperature. An understanding of how the physical nature of materials changes with temperature is essential.
General objectives
The student will learn about: 1. 2. 3. 4. 5. The definition of specific heat, latent heat of fusion and latent heat of vaporization. The units of heat energy. The determination of heat required to raise or lower the temperature of a substance. The determination of the specific heat of a substance by experimental data. The determination of the heat flow required to raise or lower the temperature of a flowing substance.
LESSON 1
Expansion of Solids and Liquids

The physical dimensions of solids and liquids change as they are subjected to any change of temperature. The thermal energy in the molecules of a solid or liquid increases as it is heated. The molecules become more energetic and move more vigorously. This process is reversed when cooling takes place. A. Linear and Volume expansion of solids For solids, the change in length of the material, l is: l = lo t where lo [m] is the original length of the solid [/Co or /K] is the coefficient of linear expansion of the solid t is the change in temperature from t1 to to [Co].
Integrated Training Program / Phase A Basic Thermodynamics Copyright 2004 International Human Resources Development Corporation Page 2 of 46
eq.(1-1)
The new length becomes: lt = lo (1 + t) Extending into 3 dimensions, the new volume of any solid material is Vt = Vo (1 + t)3 Where: Vo [m3] is the original volume of the solid. Example 1 The horizontal trusses in the roof of the Coliseum are constructed from individual carbon steel beams, each 20 m long. It takes 3 beams end to end to make one truss. If the temperature inside of the Coliseum varies from 5oC to 23oC, how much allowance must be made for the changes in length of each truss? eq.(1-3) eq.(1-2)
S o lu tio n L s t e .eL l o . t 1 to
D a ta Lo to t1
6 0. m 5. d 2 3. d
L = 0 . 0 1 3 0 6m8
eg C eg C (p .1 7 D B )
s t e e l 1 . 2 .11 0 5 . d e g 1 C
B. Volume expansion of liquids
Since liquid does not have its own definite shape, one can only consider the bulk expansion of the liquid. The new volume of any liquid material is Vt = Vo (1 + t) where [/Co or /K] is the coefficient of volume expansion of the liquid. eq.(1-4)
Integrated Training Program / Phase A Basic Thermodynamics Copyright 2004 International Human Resources Development Corporation
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Example 2 A 2 liter carbon steel spherical bottle is completely filled with ethyl alcohol at 20C. If the bottle is heated to 45C, how much ethyl alcohol will overflow?
Solution V alcohol alcohol . V alcohol_at_20 . t f
2
to
Data V bottle_at_20 V alcohol_at_20
2. l 2. l
V alcohol = 5.35 10 V bottle
l steel . t f to
3
V bottle_at_20 . 1 + V bottle_at_20
3
...
V bottle = 1.82 10 V overflow
l V bottle
steel alcohol to tf
1.21 . 10 5. degC 1 1.07 . 10 3. degC 1
V alcohol
2
V overflow = 5.17 10
(p.18 databook) 20 . degC

45 . degC
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LESSON 2
Heat Transfer Of Solids and Liquids

The temperature of an object rises as thermal energy is supplied to it. Similarly, its temperature will fall if thermal energy is taken away from it. The amount of thermal energy absorbed or lost can be calculated as follows: Q = mc t Where: Q [J] is the amount of heat absorbed or lost. m [kg] is the mass of the object in discussion. t [Co] is the absolute difference between the initial and final temperature. c [or ] is the specific heat of the object. The specific heat of solids and liquids are given in tables. Example 3 Determine the heat required to heat 5 liters of water in an electric kettle from 20oC to its boiling point temperature in Edmonton. Solution Q m water. c. t 1 Q = 1629.7 kJ Data m water to t1 c eq.(1-5)
to
5. 10 3 . 998.2 . kg
(p.20 Databk)
20 . degC 98 . degC 4.1863 .
kJ (23-3 SI databk) . kg degC
When a solid material is heated, the molecules become more energetic and vibrate so much that they become loosely bound to each other. The material changes from solid phase to liquid phase. The temperature at which this takes place is called the melting point of the solid. The amount of heat required to change 1 kg of solid at melting point to liquid is called the latent heat of fusion. In the process of melting, any heat absorbed by the material is used for melting and no heat is used to raise the temperature. The temperature thus remains at the melting point until all material is melted. The latent heat of fusion for a solid can be calculated by Qf = mLf eq.(1-6)
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Where:
Qf [J] is the total heat for fusion. Lf [ J ] is the latent heat of fusion per kg. kg m is the total mass of solid.
Example 4 Determine the heat which must be removed to freeze 7.5 kg of Benzene initially at 40oC.
S o lu tio n . c. t Q mbenze ne o Q = 1 3 9 8 . 8k J
t1
.L mbenze n fe
D a ta m b e n z e n e7 . 5. k g t o 4 0. d e g C t 1 5 . 5 3. 3d e g C kJ c 1 . 7 1 4. 7 . ( p .2 3 - 3 S I d a t a b k ) k gd e g C kJ L f 1 2 7 ..4 k g ( p .1 8 d a t a b k )
If the same liquid is further heated, its temperature rises again. More energy is absorbed by the molecules and consequently each molecule can be totally free from each other at this stage, the liquid turns into vapor. Any supplied energy is used for phase conversion and thus the temperature remains constant The temperature is called the boiling point. The amount of heat required to change 1 kg of liquid at boiling point to vapor is called the latent heat of vaporization. The latent heat of vaporization for a liquid is expressed as Qv = mLv Where: Qv [J] is the total heat for vaporization. J Lv [ kg ] is the latent heat of vaporization per kg. m is the total mass of liquid. eq.(1-7)
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Example 5 Calculate the amount of heat required to vaporize 2 kg of benzene at 15C. Solution . c. t Q m benzene boiling Q = 1010.7 kJ Data m benzene to
to
.L m benzene v
2. kg
15. degC
t boiling 80.07 . degC (p.23-2 SI databk) kJ c 1.7147 . . kg degC (p.23-3 SI databk) kJ Lv 393.78 . kg (p.23-4 SI databk)
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LESSON 3
Heat Transfer in Mixtures

When two non-chemically reacting material at different temperatures are mixed together in an isolated system, their thermal energies are exchanged until their temperatures achieve an equilibrium value. By the principle of conservation of energy, the amount of heat gained by one material is equal to the amount of heat lost by the other (provided there are no external losses). This can be expressed mathematically as Qgained = Qlost or m1c1(tf - ti1) = m2c2(ti2 - tf) where: m1 is the heat gaining mass. m2 is the heat losing mass. c1, c2 are the specific heats of the corresponding masses. t f is the final temperature of the mixture. t i1, is the initial temperature of the mass gaining heat t i2 is the initial temperature of the mass losing heat. Example 6 A carbon steel container has a mass of 165 kg and is at a temperature of 40oC. 50 kg of ethyl alcohol at an initial temperature of 10oC is poured into the container. What will be the final temperature of the container and the alcohol?
Solution m h. c h. t h_o t final m c. c c. t final m h. c h. t h_o m c. c c. t c_o t final m h. c h m c. c c t final = 21.6 degC Data t c_o Hot: mh ch t h_o Cold: mc t c_o cc
50. kg 10. degC 2.3564 . 165. kg 0.448 .
eq.(1-8)
eq.(1-9)
kJ (p.17 db) . kg degC 40. degC
kJ . kg degC (p.23-3 SI db)
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Example 7 A heat exchanger uses high pressure steam to heat up n-Nonane. The initial heat energy of the flowing steam is 900. After going through the exchanger, the steam condenses to water which carries only 300. If the n-Nonane has an initial temperature of 25C and reaches a final temperature of 80 oC, what is the flow rate of the n-Nonane?.
s t e a m @ 9 0 0 k J / s e c
n N o n a n e @ 2 5 C , ? k g / s e c
n N o n a n e @ 8 0o C
w a t e r @ 3 0 0 k J / s e c
Solution:
q m. c. t f ti (h qm Q) h c. t f Q ti kg sec
Data Steam: h water:

Q kJ 900. sec kJ 300. sec c ti . 2.1855 kJ . kg degC tf
q m = 4.992
n-Nonane: (p.23-2 SI db)

80. degC 25. degC
The mass flow rate of n-Nonane is 4.992 kg/sec.
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UNIT 2
VAPOUR PRESSURE
Introduction
The flow of fluids in pipes such as water pipes or instrumentation air supply lines are frequently subjected to a change in pressure and temperature. Such changes may cause liquids to vaporize or vapours to condense. Flashing and cavitation in valves are due to such phase changes in liquids. The change in phase of a fluid depends on its vapour pressure which is temperature dependent. It is necessary to understand the different pressure and temperature conditions which govern the phase changes of liquids.
General objectives
The student will gain a knowledge about : 1. 2. 3. 4. The concept of vapour pressure. The absolute and gauge pressure. How to find vapour pressure at a given temperature from tables. The relationship between pressure at boiling points and vapour pressure of liquids
LESSON 1
Occurrence
Whether a substance is in its liquid or vapour state, its molecules are always in motion. It is the collision of the molecules of the substance with the inner walls of a containing vessel that creates the pressure against these surfaces. If a closed vessel is completely evacuated, and then partly filled with a sample liquid, the molecules near the liquid surface leave the liquid and migrate up into the space above the liquid to form vapour. This will continue until the space above the liquid saturates with vapour molecules, at which time the reverse effect occurs. Some vapour molecules in the space return to the liquid. Eventually, an equilibrium condition is reached at which the number of molecules leaving the liquid per unit time exactly matches the number of molecules returning from the vapour to the liquid. Since molecular collision creates pressure, there will be a measurable pressure in the space. This pressure is the vapour pressure of the substance.
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LESSON 2
Units of Vapour Pressure

Vapour pressure is always reported in absolute pressure units (kPaa, psia, etc). Otherwise, a different table of vapour pressure values for liquids would be required for every different location.
LESSON 3
Variation Of Vapour Pressure with Temperature

The vapour pressure of a liquid increases considerably as the temperature of the liquid increases. It is because more liquid molecules become energetic and are ready to leave the liquid forming vapour. The vapour - temperature relationship is not linear. Thus, any vapour pressure reading for a liquid is meaningless unless the temperature of the liquid is also given.
LESSON 4
The Relationship between the pressure at boiling point at the vapour pressure of the LIQUID
If the temperature of the liquid is raised to the point where the vapour pressure of the liquid becomes equal to the surrounding pressure, the liquid boils. Consequently, a liquid can be caused to boil either by raising its temperature, or by lowering the ambient pressure. This explains, for example, why water will boil at a lower temperature at higher elevations where the atmospheric pressure is lower. Liquids having relatively high vapour pressures will evaporate faster if the container is left open. This is caused by the higher molecular mobility in liquids which have higher vapour pressures. For pure liquids, the relationships between temperature and vapour pressure are well known and are predictable. Hence, it is possible to build a thermometer which is activated by the vapour pressure of a liquid, and which is used, with a suitable correlation, to indicate temperature.
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LESSON 5
Variation of atmospheric pressure with elevation

Since the density of air decreases with height, the air pressure at higher altitudes is correspondingly lowered. The variation of atmospheric pressure with altitudes can be calculated by considering various factors such as wind speed, temperature, altitude and humidity. However, it can be approximated (within 20% error) by the expression: Ps = Pe (1 + 0.000127E) Where: Ps is the pressure at sea level (101.325 kPa). Pe is the pressure at elevation E. E is the elevation above sea level in meters.
LESSON 6
Humidity
The humidity of atmospheric pressure is a typical example of the presence of vapour pressure. Any volume of atmospheric air at a specific temperature contains a certain amount of water vapour. When the temperature of the air drops to a particular temperature, the water vapour in the air will condense back to tiny droplets of water. The air is said to be saturated with water. The air temperature at which this occurs is called the dew point. The vapour pressure of the water at saturation is called the saturation vapour pressure. The humidity of air at any temperature is measured in terms of this saturation vapour pressure. The percent humidity of air is defined as vapour pressure at a specific temperature %humidity = saturated vapour pressure at dew pointx 100%
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Example 1
o C and the relative humidity is found to be 45% The room temperature is 22 . The barometric pressure is 95 kPa. o 22 a. Refer to the steam tables to find the saturated vapour pressure of water at (SI databook p 24 -38) . IP 22 C LRV i 20 C SPA N i SPAN o IP y URV i LRV i LRV o . SPAN o LRV o 25 C LRV o kPaa 2.339 URV o 3.169 kPaa
URV i URV o LRV i SPAN i
y = 2.671 kPaa b. Find the partial pressure of the water vapour in the room. Since humidity is defined as the ratio of water vapour pressure aturated to s vapour pressure,that is, water_vapour_pressure Hum idity( in_% ) saturated_vapour_pressure p H2O .y 0.45
p H2O = 1.202 kPaa c. At w hat temperature would the water vapour start to condense if the room air was cooled down. This temperature is called the dew point tem perature or just the dew point . From the SI databook p 24 -38, the vapour pressure of the room is found to lie between those at 5C and 10C. IP p H2O LRV i SPAN i SPAN o IP y 0.8721 kPaa URV i URV o LRV i SPAN i URV i LRV i LRV o . SPAN o LRV o 1.2276kPaa LRV o 5 C URV o 10C
y = 9.639 C That is, if the air is cooled to 9.639C, the water vapour in the air will turn to liquid water. In other words, the air is saturated with water vapour at 9.639C
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d. The room contains an air compressor which produces instrument air at 800 kPaa. What is the partial pressure of the water vapour in the high pressure air line from the compressor? By direct proportions, at 95 kPaa, the vapour pressure is 1.202 kPaa; therefore, at 800 kPaa the vapour pressure is given as 800. 1.202 kPaa 95 p H2O = 10.122 kPaa e. Find the dew point temperature of the instrument air. p H2O From the SIdatabook p 24-38, it is found that the temperature of the calculated pressure obtained in (d) is between 45C and 50C. IP p H2O LRV i 9.593kPaa 50 C URV i 12.349kPaa
LRV o SPAN i SPAN o y IP
45C URV i URV o LRV i SPAN i
URV o LRV i LRV o . SPAN o
LRV o
y = 45.96 C f. What is the highest air pressure allowable in the air line at 22oC so that condensation could not occur? As the air is compressed, the water vapour pressure will rise along with the air pressure. The maximum water vapour pressure which can be attained at 22C without condensation is 2.671 kPaa. It is given that at 95 kPaa air pressure, the water vapour pressure is 1.202 kPaa. By direct proportions, the highest air pressure is p highest 2.671 95. 1.202 kPaa kPaa
p highest = 211.10 2
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Example 2 A barometer can be made by inverting a glass tube completely filled with a liquid. The liquid column will fall to a certain height at which the atmospheric pressure can sustain. The empty space above the liquid surface is ideally in vacuum. However, due to temperature changes, some of the liquid always vaporizes and fills the vacuum space. A vapour pressure is exerted on the column of liquid so that the height of the column does not represent the actual atmospheric pressure. Corrections to the reading of the column has to be made in order to account for this. If the liquid used in the column is mercury, find (a) the error in pressure (b) the height of the mercury column if the atmospheric pressure is 100 kPaa. Solution Data (a) The error is caused by the vapour pressure of mercury. At p 100. kPaa 25C the vapour pressure of mercury is 252 mPaa which is the atm error introduced to the atmospheric pressure. p vapour_Hg 252. mPaa (b) The height of the mercury column only represents an atmospheric pressure of p apparent p atm p vapour_Hg p apparent= 100 kPaa Since p= gh, the height of the mercury column is h p apparent Hg. g g Hg . 13534 kg m3
(databook p.19) . 9.81 m sec2
h = 0.753 m
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Example 3 The fact that liquids at their prevailing temperature will boil and create vapour if their pressure is reduced to a low enough value can lead to problems in pumps, valves, and flow elements. This effect is called flashing. If the vapour formed recondenses downstream, the effect is called cavitation. Both vaporization and cavitation can cause damage to plant equipment and piping. For the following questions, use the average barometric pressure at the Northern Alberta Institute of Technology (NAIT). abAcetone at 40oC enters a valve. If the inlet pressure is 30 psig, what will be the maximum allowable pressure drop across the valve if flashing is to be avoided ? The pressure at the suction of a methyl alcohol pump is -60 kPag. What is the maximum temperature which the alcohol can have before the pump begins to draw vapour as well as liquid ?
Data NAIT average pressure . kPa p at 93.5 vapour pressure of acetone at 40 deg C pv 68. kPa (databook p.29) p suction. 60. kPa
Solution 3. a. p inlet 6.89 . kPa 30. psi. 5 psi p at
p inlet = 300.3 kPa absolute 5 the permissible pressure drop is p inlet p v = 232.3 kPa 5 3b. p pump p at 60. kPa
p pump = 33.5 kPa absolute the temperature that results in that methyl alcohol vapour pressure is about T 39. degC (from databook p.29)
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UNIT 3
GAS LAWS
Introduction
Gases behave quite differently from liquids due to their compressible nature. Their physical behaviors were investigated. Theories and laws were deduced to predict how gases change with temperature and pressure. Such laws provide guidance in determining the proper control of gases used or produced in industrial plants. An understanding of how gases behave at various temperatures and pressures is crucial in the process of plant operation or production.
General objectives
The student will learn how to: 1. 2. 3. 4. 5. 6. Explain the basic theory of gases and its relationship to the ideal gas law and general gas law. Determine volume, pressure, temperature or number of moles for gases under various conditions. Determine the density of gases with the general gas law. State the conditions for STP, API or "contract" conditions. Explain the importance of calculating the volume or volume flow at STP or API conditions. Calculate the reduced pressure and reduced temperature and then determine the gas compressibility factors by graph.
LESSON 1
Definition of a Mole
A mole of substance is the amount of substance that contains 6.022*1023 elementary units of the substance. An elementary unit can be an atom or a molecule. The mass of one mole of substances is expressed in units of g/mole or kg/kmol. For example, one mole of Carbon-12 (C12) contains 6.022*1023 carbon atoms and has a mass of 12 grams ; one mole of Hydrogen (H2) contains 6.022*1023 molecules and has a mass of 2 grams.
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LESSON 2
Basic Theory Of Gases

The basic kinetic-molecular theory of gases is the basis for microscopic analysis of gas behavior. The basic theory assumes: (a) (b) (c) (d) (e) Gases are made up of minute particles called molecules whose dimensions are very small as compared with the average distances between them. The molecules of gases are in constant rapid motion colliding with each other and with the walls of their containers in a perfectly random fashion. All molecular collisions are perfectly elastic, resulting in no decrease in the total kinetic energy. The average kinetic energy of the molecules of a gas is proportional to the absolute temperature. Equal volumes of all gases at the same pressure and temperature contain the same number of molecules: i.e., 22.414 m3 of gas at 101.325 kPaa and at 273.15o K contain 6.022 x 1026 molecules (1 kilomole) of gas and have a mass (kg) equal to its molecular mass. (f) (g) That there are no intermolecular forces between molecules. That the volume occupied by the molecules is negligible compared to the volume of the container.
Statistical mechanics could be used to illustrate that the gas molecules in a container of volume (V) will set up an absolute pressure (p) that is proportional to the number of molecules (n kilomoles) in the container and their average kinetic energy or absolute temperature (T).
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LESSON 3
Ideal Gases
The gas equation which relates p, V, T of an ideal gas is: pV=nRT where: V p T R n = volume of gas in m3 = absolute pressure of gas in Pascals = absolute temperature of gas in K = universal gas constant = 8314.510 = number of kilomoles of gas eq. (3-1)
Variations of this equation are: (a) Boyle's Law1 p1 V1 = p2 V2 (b) Charles' Law2 = = constant (constant p,n) eq. (3-3) = constant (constant T,n) eq. (3-2)
Boyle's Law - the product of the pressure and volume of a given mass of gas is constant if the temperature and the number of moles do not change. 2 Charles' Law - the volume of a gas at constant pressure is proportional to its absolute temperature if the pressure and the number of moles do not change.
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Example 1 A storage tank attached to an air compressor has a volume of 0.65 m3. It contains air at a pressure of 150 psig. The temperature is 20 oC. The barometer reading at the location is 690 mm of mercury. a. b. c. d. How many kilomoles of air are there in the tank? What is the density of the air in the tank? What is the mass of the air in the tank? How many API cubic meters of air are in the tank?
D a ta h Hg
2
S o lu tio n p re s s u re p H g. g . h c o n v e rsn io a tm o s p a t m o s= 9 1 . 7 0 9 k P a
1. i n . l b . 4 . 4 4 .8N . p gauge 150 l b 2 .5 4 . 1 0 2. m i n2
.m 0 .6 9
1 3 5 4 6 .. 3
kg
m3
g V1 T1
p gauge = 1 . 0 3 41 0 k P a p ab s p g au g e p a tm o s
3
(p .1 9 d a t a b o o k ) . 9m 9 .8 1 1 6 s e c2 . m3 0 .6 5
2 0. d e g C
.K 273
p a b s = 1 . 1 2 61 0 k P a .V p abs 1 . R T1 .M p ab s R. T 1 . V 1 n. R. T
T 1 = 293 K R M
8 . 3 1 4. 4
a.
kJ k m o. lK
n = 0 .3 k m o l b. c. d. = 1 3 .3 8 5 kg m3
.5 2 8 .9 6 2
p std T std
kg (p .2 3 -2 S I k m o ld a ta b o o k ) .5 1 0 1 .3 2 kPa
1 5. d e g C
.K 273
m a ss V std
m a s s= 8 . 7 k g std V s t d = 7 . 0 9 9 m3
T std = 2 8 8 K
p std
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LESSON 4
Real Gases
The ideal gas equation assumes no interactive forces between molecules. Such forces, called Van der Waals forces do exist and become more significant as the average kinetic energy of the molecules becomes less (lower temperature) and/or the molecules are forced closer together (higher pressures). This can be illustrated by the fact that all gases can be liquefied at a unique temperature and pressure. Liquefaction occurs only when the cohesive forces which tend to bind the molecules together counteract their kinetic energy to a sufficient extent to keep the molecules confined to a relatively small volume. These interactive forces between gas molecules cause the gas equation to deviate from the ideal one. The pVT behavior of real gases can be analyzed by using the general equation: pV = ZnRT eq. (3-4)
In this equation, Z, the compressibility factor shows deviation from ideality. Z = 1.0 for an ideal gas and a departure from ideality will be measured by the deviation of Z from unity. Real gases at low pressure and high temperature have a Z value close to 1. More specifically Z will be close to 1.0 whenever the temperature of the gas is much greater than its critical temperature and its pressure is much lower than its critical pressure. The extent of the deviations from ideality depends on the gas absolute temperature and pressure and on the gas critical temperature and critical pressure. The gas critical temperature3 (TC) is the highest temperature at which a gas can still be liquefied and the gas critical pressure (pC) is the pressure necessary to liquefy the gas at TC. One of the most convenient ways to find Z for any gas is to use available gas compressibility (Z) graphs. To use these graphs we find the reduced pressure (pR) and the reduced temperature (TR) and then use these to find Z from the available graphs (SI Engineering Data Book p. 23-12 to 23-13).
The critical temperature and pressure of a substance have to do with the change of state of the substance between its gas and liquid phases. The critical temperature Tc is the more fundamental one. If the temperature of a gas is greater than Tc, then no amount of applied pressure will be able to cause it to change to its liquid state. The critical pressure pc is the pressure corresponding to Tc on the T-p equilibrium curve (i.e., the vapor pressure curve). This point is called the "Critical Point" (NB: the critical temperature establishes the critical point). There is also a critical density c corresponding to the critical point. Critical temperature, pressure, and density are definable only for pure substances, not for mixtures.
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pR
p pc
where: p is the absolute gas pressure pC is the gas critical pressure
TR
T TC
where: T is the absolute gas temperature TC is the gas critical temperature
= f(TR , pR )
Example 2 A 45 litre cylinder of oxygen stored at a temperature of 18 oC has a gauge pressure of 15MPag. The barometric pressure is 98 kPaa. a) b) c) d) e) What is the gas law deviation factor Z at the cylinder pressure and temperature? How many kilomoles of oxygen are in the cylinder? What is the density of the oxygen in the cylinder? What is the mass of the oxygen in the cylinder? How many API m3 of oxygen are in the cylinder?
Solution a. T R pR Z b. n c. d. mass e. Z std V std T Tc p pc T R = 1.65
Data .K T 273
18. degC
p R = 2.99 4 (from SI data book p.23-12) 0.84 . 5p V n = 0.37 kmol Z. R. T 9 p. M kg = 269.66 . . ZR T m3 7 n. M mass = 12.13 kg 5 .K T 288 0.9992 std p std 101.32. kPa 5 Z std. n. R. T std V std = 8.96 m3 p std 2
T = 255 K p atmos 98. kPa p

3 15. 10 . kPa 4
p atmos
p = 1.51 10 kPa
3 3 45. 10 . m Tc 154.5 . K 9 pc 504 . kPa 3 kg M 31.99 . kmol 9
(p.23-2 SIdb) (p.23-2 SIdb) (p.23-2 SIdb)
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Finding Z Factor by Redlich-Kwong Method
Another way of finding the Z factor is to use the Redlich-Kwong method. In this method, the Z factor is solved from the equation: Z3- Z2 - (B2 + B -A)Z - AB = 0 where Z is the compressibility factor Pr A = 0.42748* T 2.5 , B = 0.086647 * r eq. (3-5)
Pr Tr
Example 3 (same as example 2 except that Redlich Kwong's method was used for finding the Z factor) A 45 litre cylinder of oxygen stored at a temperature of -18 oC has a gauge pressure of 15MPag. The barometric pressure is 98 kPaa. a. b. c. d. e. What is the gas law deviation factor Z at the cylinder pressure and temperature? How many kilomoles of oxygen are in the cylinder? What is the density of the oxygen in the cylinder? What is the mass of the oxygen in the cylinder? How many API m3 of oxygen are in the cylinder?
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Solution a. T R pR Guess Z T Tc p pc 0.9 T R = 1.65 p R = 2.99 4
Data T .K 273 18. degC
T = 255 K p atmos 98. kPa p

3 15. 10 . kPa 4
p atmos
For part a, using Redlich-Kwong method, pR A 0.4274. A = 0.36 T R2.5 8 6 pR B B = 0.15 0.08664. TR 7 7 Using the calculator to solve Z from the equation, we get: Z3 Z2 B2 B A .Z A. B 0
p = 1.51 10 kPa
3 3 V 45. 10 . m (p.23-2 SIdb) Tc 154.5 . K 9 . pc (p.23-2 SIdb) 504 kPa 3 kg M 31.998. kmol (p.23-2 SIdb) 8
Z = .86 b. n c. d. e.
p. V Z. R. T p. M Z. R. T n.M 1.0
n = 0.37 kmol 1 = 263.8 kg m3
mass Z std V std
mass = 11.87 kg
.K T std p std 288 101.32. kPa 5 Z std. n. R. T std 3 V std = 8.76 m p std
This method is used explicitly for non-hydrocarbon products. However, when the Z value is high enough, namely, greater than 0.8, both the graph method or the RedlichKwong method give quite close values.
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LESSON 5
Avogadro's Hypothesis
Equal volumes of different ideal gases at the same pressure and temperature contain the same number of molecules.
LESSON 6
Gas law calculations

(a) Mass of gas
The mass of gas in a container cannot change without a leak; therefore, it is independent of p, V, T, and Z. It is the product of n (in kilomoles) and the molecular mass ( M ) of the gas. i.e.: (b) Density of gas. density = = (c) Volume of gas at STP conditions eq. (3-7) Mass = nM eq. (3-6)
The normal standard temperature and standard pressure are 0 0C (273.15 K) and 101.325 kPaa respectively. The volume of 1 kmol of gas at these conditions, using the real gas law, can be worked out to be : VSTP = 22.414 ZSTP (d) Volume of gas at API conditions (m3 STP) eq. (3-8)
The API (American Petroleum Institute) conditions refer to a base pressure of 101.325 kPaa and a base temperature of 15 oC (288.15 K). In this course, API conditions will always be used as the standard reference. If you ever encounter the word standard in this manual, it will mean API conditions. The simplified real gas law is : VAPI = 23.645 ZAPI (m3 API) eq. (3-9)
The value of ZAPI at 15C is given in the SI data book p.23-3.
Page 26 of 46
(e)
Process of iteration
In certain real gas law problems, the gas equation might involve two unknowns. An example of this is to find the pressure of a sealed tank of gas. In such a case, the pressure, p, cannot be solved explicitly since the Z factor is pressure dependent. Iteration has to be used. The iteration process involves an initial guess of one parameter (namely, Z) and find the other parameter (namely, p). Once the new value of p is found, a more accurate value of Z can be found. As soon as a more accurate value of Z is found, p can be recalculated again. This process is repeated until the values of p repeats itself or become very close.
Example 4 A 20 litre gas cylinder contains 2 kg of methane at 13 oC. What will be the gauge pressure of the gas if the cylinder is stored in J32 which has an atmospheric pressure of 92.03 kPaa? (Note: this problem requires a trial and error approach. Start with Z = 1 and adjust Z with each trial until the calculated value of Z matches the estimated value.) p=Z m R T 2.00 8314.51 (273.15 + 13) = Z M V 16.043 20 10 3 = Z14.8301255106 Pa
pc= 4599 kPa Tc= 190.56 K p 4599 286.15 190.56 1.5016 1.5016 1.5016 1.5016 1.5016 1.5016 TR =
Z 1.00 0.797099 0.809113 0.807879 0.808003 0.807991 0.807992
P=Z14830.12 kPa 14830.12 kPaa 11821.08 11999.26 11980.96 11982.78 11982.61 11982.62 kPaa
pR = 3.2246 2.5703 2.6091 2.6051 2.6055 2.6055
Znew 0.797099 0.809113 0.807879 0.808003 0.807991 0.807992
pg = 11982.62 kPaa + 92.03 kPa = 12 074.65 kPag
Page 27 of 46
UNIT 4
THERMAL PROPERTIES OF GASES

Introduction
When thermal energy is supplied to a gas, the energy is absorbed by the gas molecules of which the kinetic energy increases correspondingly. Consequently, the temperature of the gas increases as a result of an increase in internal energy. The energy per kilogram of the gas can be increased under constant volume or constant pressure. The ratio of these two types of energies is defined as the isentropic constant, which is used in orifice flow metering and sizing.
General objective
The student will be able to: 1. 2. Explain the energy equation for heat transfer in terms of the two specific heat constants (cV and cP) Derive the relationship for cP knowing cV, R and M.
LESSON 1
Specific Heat At Constant Volume (Cv)

The quantity of heat necessary to change the temperature of m kg of gas enclosed in a fixed volume from T1 to T2 is: Q = cV m ( T2 - T1 ) where cV is the amount of heat necessary to raise the temperature of 1 kg of constant J J volume gas by 1 Co or 1 Ko. It is measured in units of kg C o or kg K o . Note that the notation Co and Ko refer to a temperature range, not the actual temperatures. Actual temperatures are measured in oC (degrees celcius) or K (kelvins) Since the volume does not change, no external work is done by this system. All the heat added/removed is gained /lost to the internal energy in the gas. eq.(4-1)
Page 28 of 46
LESSON 2
Specific Heat At Constant Pressure (cP)

The heat necessary to change the temperature of m (kg) of gas contained under a constant pressure (P) from T1 to T2 is : H = cP m (T2 - T1) where cP is the amount of heat necessary to raise the temperature of 1 kg of gas at J J constant pressure by 1 Co or 1 Ko. It is measured in units of o or kg C kg K o .. In order to keep the gas pressure constant, the volume of the container must change to accommodate for gas expansion due to a rise in gas temperature. As a result, external work is done by the additional heat. The external work done is pV where V is the change in volume due to the temperature change. eq.(4-2)
Fig. 4.1 The total heat supplied, H is (assuming no heat losses) H = Q + external work at constant pressure cPmt = cVmt + pV cP - cV = p V m T
Page 29 of 46
Using the gas law to replace
p V by , the equation becomes m T eq.(4-3)
cP - cV = Example 1: For monatomic helium M = 4.0026 , cp = 5193.1 J J o - = 3115 kg C kg C o
J (p.23-3 SI databook) kg C o
cv = 5193.1
Note that in the SI databook, only cp is given. The ratio, is defined as the isentropic constant, k . This constant will be used in the orifice flow metering section.
Example 2 Look up the value of the molar mass, and the specific heat at constant pressure cP ( J ) for chlorine. From this data, calculate the value of the specific heat at constant kg C o cP (= k) volume cV, and the ratio of the specific heats cV
Solution Cv Cp R M Data M Cp
70.9054 .
J C v = 358.74 kg. K Cp k k = 1.33 Cv
kg (SI databook,p.23-2) kmol J 476. . kg K
Page 30 of 46
Example 3 The temperature of a 70 m3 steel tank contains air at 20 oC. The barometer is steady at the average Edmonton value. a. b. How much heat is required to raise the temperature of the air to 30o C, assuming that the tank is open to the atmosphere? How much heat is required to raise the temperature of the air to 30oC, assuming that the tank is completely sealed?
Solution For ideal gas,
Data
Z 1 M 28.9625 . kg (p.23-2 SIdb) kmol 93.44 . kPa
Finding specific heat at constant volume:

m air p atmos . V. M Z. R . T
p atmos V T
70. m3 20. degC 273 . K
m air = 77.76 kg Cv Cp R M T = 293 K Cp t2 t 1) t1 1004 . J kg. K
J C v = 716.93 kg. K
(p.23-2 SIdb)
30. degC 20. degC
a.
m air. C p. ( t 2
Q = 780.73 kJ
b.
m air. C v. ( t 2
t 1)
H = 557.5 kJ
Page 31 of 46
UNIT 5
MIXTURES OF GASES
Introduction
In many situations, the gas products are mixtures of gases. Such mixtures possess different properties than the pure ones. The density behavior of a mixture of gases is similar to that of a pure gas. The pressure and temperature characteristics of a mixture can be measured in the same way as those of a pure gas. However, specific gravity, compressibility and specific heat must be calculated by certain mixture laws.
General objectives
The student will be able to: 1. 2. 3. 4. 5. Explain and use Dalton's law of partial pressure. Explain the significance of mass, volume and mole fraction and convert from one to the other. Calculate the compressibility factor for a gas mixture. Solve for two unknowns in a gas problem by iteration. Determine the quantities and pressures of pure gases required to make a calibration gas at a particular pressure and composition.
LESSON 1
Mole Fraction, Volume Fraction And Mass Fraction

Under identical conditions of temperature (> 0 oC) and pressure (< 10 atmospheres), equal volumes of any gas mixture contain equal number of molecules. That is, one kilomole of any gas mixture contains 6.022 x 1026 molecules and has a mass in kilograms which is equal to its molar mass, M. The composition of a gas mixture can be expressed by either specifying the mole fraction, volume fraction or the mass fraction of each gas component. a. Mole fraction
Mole fraction is the most fundamental. It is defined as the ratio of the number of moles of a gas component, n1, in a gas mixture to the number of total moles, nt, of the gas mixture. x B1 = eq.(5-1)
Page 32 of 46
Example 1 At a dance there is a group of 20 football players and another group of 15 cheerleaders. Find the molar fraction of each. nfootballplayers = 20 ncheerleaders = 15 ntotal = 35
xfootballplayers = 20/35 = 0.571 = 57.1% xcheerleaders = 15/35 = 0.429 = 42.9 % In other words 57.1% of the persons at the dance are football players b. Mass fraction
Mass fraction is defined as the ratio of the mass of a gas component, m1, in a gas mixture to the total mass, mt, of the gas mixture.
WB1 =
m1 mt
eq.(5-2)
In real gas situations, the mass fraction and the mole fraction differ by the ratio of their molar masses. It can be shown that x B1 = M t m1 M t = WB1 M1 m t M1 eq.(5-3)
Page 33 of 46
Example 2 At a dance there are 20 football players and 15 cheerleaders. Each player weighs 85 kg and each cheerleader weighs 55 kg. Find the mass fraction of each group. mplayers =20 * 85 kg/player = 1700 kg Mcheerleaders = 15 * 55 kg/cheerleader = 825 kg Mt = 1700 kg + 825 kg = 2525 kg Wplayers = 1700 kg / 2525 kg = 0.673 = 67.3 % Wcheerleaders = 825 kg / 2525 kg = 0.327 = 32.7 % In other words although the football players make up 57.1% of the number of persons they make 67.3% of the total mass. c. Volume fraction
Volume fraction is defined as the ratio of the volume of a gas component, V1, in a gas mixture to the total volume, Vt, of the gas mixture.
eq.(5-4)
B1
V1 = Vt
The volume V1 is the volume of component 1 at the total pressure of the mixture. In ideal gas situations, the volume fraction, B1, and the mole fraction, x B1, are identical since all Z's are 1. However, in real gas situations, the volume fraction and the mole fraction differ by the ratio of their compressibility factors. It can be shown, using the real gas law, that x B1 = Z t V1 Z1 Vt = Zt Z1 eq.(5-5)
B1
Page 34 of 46
Example 3 At a dance there are 20 football players and 15 cheerleaders. Each player weighs 85 kg and each cheerleader weighs 55 kg. The density of a muscular young man is 999 kg/m3, and the density of a cheerleader is 995 kg/m3. Find the volume fraction of each group. = m/V V = m/ Vplayers = (20 * 85kg/player)/999 kg/m3= 1.7017 m3 Vcheerleaders = (15 * 55 kg/cheerleader)/995 kg/m3= 0.8291 m3 Vt = 1.7017 m3 + 0.8291 m3 = 2.5308 m3
players
= 1.7017 m3 / 2.5308 m3 = 0.6724 = 67.24 % = 0.8291 m3 / 2.5308 m3 = 0.3276 = 32.76 %
cheerleaders
Note that in the case of a gas mixture the volume fraction and the mass fraction will generally be very different from one another.
Page 35 of 46
LESSON 2
Physical Properties of A Gas Mixture

aMOLAR MASS
The molar mass of a pure gas is a physical property associated with the gas. However, the molar mass of a gas mixture does not exist, but it can be computed based on the molar masses of individual gas components. The computed value provides us a convenient way of finding other physical properties such as the critical pressure or volume for the gas mixture. Suppose a gas mixture is made up of several pure gases which have molar masses, M1, M2, M3, etc. The corresponding portion of each individual gas is measured by the number of moles, namely, n1, n2, n3, etc. The total number of moles of mixed gas, nt = n1 + n2 + n3 +... The total mass of gas mixture, mt = n1 M1 + n2M2 + n3M3 + ... Let the molar mass of the mixture be Mmix, then, the total mass of the gas mixture mt = ntMmix Comparing the expressions for the total mass of the mixture, we have ntMmix = n1M1 + n2M2 + n3M3 + ... Dividing the expression by nt, Mmix = M1 + M2 + M3 + ... or Mmix = x B1 M1 + x B2M2 + x B3 M3 + ... eq.(5-6) Furthermore, the mass fraction of individual gas component can be stated as: W B1 = x B1 M 1 M mix eq.(5-7)
Page 36 of 46
b-
Specific Heat at Constant Pressure
The specific heat of a gas mixture at constant pressure can be approximated as the sum of the products of the mole fraction and specific heat of each individual component. (p.2-103, Miller) cpmix = x B1 cp1 + x B2 c p2 + x B3 c p3 + ... eq.(5-8)
and the specific heat at constant volume can be obtained from the equation : cvmix = cpmix R M mix eq.(5-9)
LESSON3
Dalton's Law of Partial Pressures

The pressure exerted independently by any single gas component in a mixture of gases is called its partial pressure. Dalton's law of partial pressures states that "Each gas in a gaseous mixture exerts a partial pressure equal to the pressure which it would exert if it were the only gas present in the same volume. The total pressure of the mixture is the sum of the partial pressures of all the component gases." This law may be used to calculate the total pressure (ptotal) or the total volume (Vtotal) of a gas mixture. ptotal = p1 + p2 + p3 +. . . eq.(5-10)
where p1, p2, p3 are partial pressures which individual gases would exert if contained alone in the same volume and at the same temperature as the mixture. Vtotal = V1 + V2 + V3 + . . . eq.(5-11)
where V1, V2, V3, are volumes which individual gases would occupy if present alone at the given temperature and at the total pressure of the mixture. The partial pressure and partial volume of a gas component can be found by using the mole fractions. Namely, p1 = x B 1 pmix V1 = x B 1 Vmix eq.(5-12) eq.(5-13)
Page 37 of 46
LESSON 4
Pseudo-Critical Properties of Gas Mixtures

In section 23 of the SI data book (p.23-10 to 23-30), a discussion of the Z factor is presented. The computation of the compressibility factor, Z of a gas mixture is summarized as : 1first determine the pseudo-critical pressure (pC) and the pseudo-critical temperature (TC) of the gas mixture pC = x B 1 pC1 + x B 2 pC2 + x B 3 pC3 + . . . TC = x B 1 TC1 + x B 2 TC2 + x B 3 TC3 + . . . where pC1, pC2, pC3 are critical pressures of each component. TC1, TC2, TC3 are critical temperatures of each component. 2use the calculated pc, Tc values to determine the pseudo reduced pressure (pr) and the pseudo reduced temperature (Tr). eq.(5-14) eq.(5-15)
Pseudo-reduced pressure, pr = where p is the absolute pressure of the mixture. Pseudo-reduced temperature, Tr = where T is the absolute temperature of the mixture. 3From the compressibility graphs given in Sec. 23 (p.23-12) of the SI Engineering Data Book, look up the value of Z(pr, Tr) for hydrocarbons. For pure gases, use the Redlich-Kwong method to actually calculate the Z factor.
Page 38 of 46
LESSON 5
Gas Law Calculations

The general gas equation applies to all gas law calculations. pV = ZnRT eq.(5-16)
Since some gas mixtures are not "ideal" at standard conditions, check Z and use it in your calculations if it deviates from 1.000 by more than 0.001. Example 4 Calculate the mole percent of each of the components in the following gas mixtures. The compositions have been provided on a mass percent basis as follows: Nitrogen Carbon Dioxide 40% 50%
Carbon Monoxide 10%. Record the data in a table and calculate the weighted average of the molar mass: gas N2 CO2 CO Mix Mass % M 40 28.0134 50 44.01 10 28.01 100 36.0196
where: 36.0196 kg/kmol = 0.40*28.0134 + 0.5*44.01 + 0.10*28.01 Using x B1 = WB1 M mix calculate the composition based on moles M 1 gas Mass % M Rel mol N2 40 28.0134 51.43 CO2 50 44.01 40.92 CO 10 28.01 12.86 Mix 100 36.0196 105.20
Note that the sum of the mol % is not 100. Therefore we must normalise the values by 100 multiplying each by the normalisation factor 105.20
Page 39 of 46
gas N2 CO2 CO Mix
Mass % 40 50 10 100
M 28.0134 44.01 28.01 36.0196
relative mol Relative mol* 105.20 51.43 48.87 40.92 38.91 12.86 12.23 105.20 100.0
100
Answer
You can check your answer by using W B1 = x B1 mass composition gas N2 CO2 CO Mix mol % 48.87 38.91 12.23 100.0 M 28.0134 44.01 28.01 34.25 Mass % 40.0 50.0 10.0 100.0
M 1 to convert back to the original M mix
Example 5 A gas mixture consists of 70% methane, 20 % ethane and 10 % propane by mol fraction. Find the proportions by volume fraction. Write the data in tabular form: gas CH4 C2H6 C3H8 Mix molar% 70 20 10 100 M 16.04 30.07 44.1 Tc 190.6 305.4 369.8 Pc 4599 4880 4240
Page 40 of 46
Calculate the weighted averages gas CH4 C2H6 C3H8 Mix molar% 70 20 10 100 M 16.04 30.07 44.1 21.65 Tc 190.6 305.4 369.8 231.5 Pc 4599 4880 4240 4619.3
Calculate the Zs using Redlich-Kwong gas CH4 C2H6 C3H8 Mix molar% 70 20 10 100 M 16.04 30.07 44.1 21.65 Tc 190.6 305.4 369.8 231.5 Pc 4599 4880 4240 4619.3 Z 0.9201 0.2395 0.1942 0.8336
Calculate the Vol % using gas molar% M CH4 70 16.04 C2H6 20 30.07 C3H8 10 44.1 Mix 100 21.65
B1
Z1 x B1 Z mix
Z rel vol 0.9201 77.26 0.2395 5.75 0.1942 2.33 0.8336 85.34
Tc Pc 190.6 4599 305.4 4880 369.8 4240 231.5 4619.3
Sum not 100 Normalise by multiplying by 100/85.34 gas molar% M CH4 70 16.04 C2H6 20 30.07 C3H8 10 44.1 Mix 100 21.65 Done! Tc Pc 190.6 4599 305.4 4880 369.8 4240 231.5 4619.3 Z rel vol vol% 0.9201 77.26 90.54 0.2395 5.75 6.73 0.1942 2.33 2.73 0.8336 85.34 100.00
Page 41 of 46
Example 6 A gas mixture consists of 90.54 % methane, 6.73 % ethane and 2.73 % propane by volume fraction. Find the proportions by mol fraction. Write the data in tabular form gas vol% M Tc CH4 90.54 16.04 190.6 C2H6 6.73 30.07 305.4 C3H8 2.73 44.1 369.8 Mix 100.00
Pc 4599 4880 4240
Calculate the weighted averages gas vol% M Tc Pc CH4 90.54 16.04 190.6 4599 C2H6 6.73 30.07 305.4 4880 C3H8 2.73 44.1 369.8 4240 Mix 100.00 17.75 203.2 4608.1 Calculate the Zs using Redlich-Kwong gas vol% M Tc Pc CH4 90.54 16.04 190.6 4599 C2H6 6.73 30.07 305.4 4880 C3H8 2.73 44.1 369.8 4240 Mix 100.00 17.75 203.2 4608.1 Calculate the mol % using x B1= Z 0.9201 0.2395 0.1942 0.8980
Z mix B1 Z1
Z Rel mol 0.9201 88.36 0.2395 25.24 0.1942 12.62 0.8980 126.22 Sum is not 100
gas vol% M Tc Pc CH4 90.54 16.04 190.6 4599 C2H6 6.73 30.07 305.4 4880 C3H8 2.73 44.1 369.8 4240 Mix 100.00 17.75 203.2 4608.1
Normalise by multiplying by 100/126.22 gas vol% M Tc Pc CH4 90.54 16.04 190.6 4599 C2H6 6.73 30.07 305.4 4880 C3H8 2.73 44.1 369.8 4240 Mix 100.00 17.75 203.2 4608.1
Z Rel mol mol % 0.9201 88.36 70.00 0.2395 25.24 20.00 0.1942 12.62 10.00 0.8980 126.22 100.00
Page 42 of 46
Example 7 A gas mixture consists of 70% Methane, 18% Ethane, 2% Hydrogen Sulfide, and 10% Nitrogen, by mole fraction. 2 kg mass of this mixture is stored in a cylinder at a temperature of 25oC and a pressure of 10000 kPag. The barometer is steady at the average Edmonton value. a. b. c. d. e. What will be the molar mass, the pseudo critical pressure, and the pseudo critical temperature of the mixture? What will be the compressibility factor (gas law deviation factor) of the mixture at its storage P and T? What is the volume of the cylinder? How many API cubic meters of the gas mixture are contained in the cylinder? What is the density of the gas in the cylinder at the conditions stated in the question?
Solution a & b. Write the data in tabular form and calculate the weighted averages gas CH4 C2H6 H2S N2 Mix Calculate Z of the mixture gas CH4 C2H6 H2S N2 Mix c. % Vmol M Tc 70 16.043 190.56 18 30.07 305.41 2 34.082 373.37 10 28.0134 126.21 100 20.12568 208.4542 Pc 4599 4880 8963 3398 4616.76 Z % mol 70 18 2 10 100 M Tc 16.043 190.56 30.07 305.41 34.082 373.37 28.0134 126.21 20.12568 208.4542 Pc 4599 4880 8963 3398 4616.76
0.7864
2.00 kg J 0.7864 8314.51 298 K m kmol K Z* R T 20.126 kg kmol M V= = = 1.918 10-2 m 3 7 p 1.009 10 Pa
Page 43 of 46
d.
Calculate Zstd using Redlich-Kwong Zstd = 0.9972 2.00 kg J 0.9972 8314.51 288 K m kmol K Z* R T 20.126 kg kmol M = = = 2.343 m 3 3 p 101.325 10 Pa = m 2.00 kg kg = = 104.3 3 -2 3 V 1.917 10 m m
Vstd
e.
Example 8 A gas mixture consists of 70% Methane, 18% Ethane, 2% Hydrogen Sulfide, and 10% Nitrogen, by volume fraction. 2 kg mass of this mixture is stored in a cylinder at a temperature of 25oC and a pressure of 10000 kPag. The barometer is steady at the average Edmonton value. a. b. c. d. e. What will be the molar mass, the pseudo critical pressure, and the pseudo critical temperature of the mixture? What will be the compressibility factor (gas law deviation factor) of the mixture at its storage P and T? What is the volume of the cylinder? How many API cubic meters of the gas mixture are contained in the cylinder? What is the density of the gas in the cylinder at the conditions stated in the question?
Solution a . Write the data in tabular form and calculate the weighted averages
gas CH4 C2H6 H2S N2 Mix vol% M Tc Pc 70.00 16.04 190.56 4599 18.00 30.07 305.41 4880 2.00 34.082 373.37 8963 10.00 28.0134 126.21 3398 100.00 20.1236 208.454 4616.76
Calculate Z of the mixture and of each of the components

gas CH4 C2H6 H2S N2 Mix vol% M Tc Pc 70.00 16.04 190.56 4599 18.00 30.07 305.41 4880 2.00 34.082 373.37 8963 10.00 28.0134 126.21 3398 100.00 20.1236 208.454 4616.76 Z 0.8525 0.3460 0.1838 0.9888 0.7881
Page 44 of 46
Calculate the mole fractions using xB1=

gas CH4 C2H6 H2S N2 Mix vol% M Tc Pc 70.00 16.04 190.56 4599 18.00 30.07 305.41 4880 2.00 34.082 373.37 8963 10.00 28.0134 126.21 3398 100.00 20.1236 208.454 4616.76
Zt Z1
x B1
Z Rel mol 0.8525 64.71 0.3460 41.00 0.1838 8.57 0.9888 7.97 0.7881 122.26
Note that the sum is not 100 Because the sum is greater than 100 so we must normalize the mol % by multiplying by 100/121.74
gas C CH4 C2H6 N2 Mix vol% M Tc Pc 70.00 16.04 190.56 4599 18.00 30.07 305.41 4880 2.00 34.082 373.37 8963 10.00 28.0134 126.21 3398 100.00 20.1236 208.454 4616.76 Z rel mol mol % 0.8525 64.71 52.93 0.3460 41.00 33.54 0.1838 8.57 7.01 0.9888 7.97 6.52 0.7881 122.26 100.00
b. Find the weighted averages of M and Tc and Pc and finally find the Z of the mixture
gas CH4 C2H6 H2S N2 Mix vol% M Tc Pc 70.00 16.04 190.56 4599 18.00 30.07 305.41 4880 2.00 34.082 373.37 8963 10.00 28.0134 126.21 3398 100.00 20.1236 208.454 4616.76 Z rel mo mol % M 0.8525 64.71 52.93 16.04 0.3460 41.00 33.54 30.07 0.1838 8.57 7.01 34.08 0.9888 7.97 6.52 28.01 0.7881 122.26 100.00 21.0021 Tc Pc Z 190.56 4599 305.41 4880 373.37 8963 126.21 3398 212.009 4318.57 0.7641
2.00 kg J 0.7641 8314.51 298 K m kg kmol K Z* R T 21 . 0021 c. V = kmol M = = 17.87 10 3 m 3 p 1.009 107 Pa
d. Calculate Zstd using Redlich-Kwong Zstd = 0.9968 2.00 kg J 0.9968 8314.51 288 K m kmol K Z* R T 21.0021 kg kmol M = = = 2.245 m 3 p 101.325 10 3 Pa
Vstd
e. =
m 2.00 kg kg = = 111.9 3 3 3 V 17.87 10 m m
Page 45 of 46
Example 9 A calibration gas sample consisting of 80% Oxygen and 20% Nitrogen by volume is to be prepared. Two 10 litre bottles are evacuated, then charged from high pressure component storage cylinders. One of the bottles is filled with Oxygen, the other with Nitrogen. Then the two bottles are connected together to provide 2 bottles of the required mix. There is to be enough gas mixture in each bottle so that the bottle has a "full" pressure of 350 kPaa at 20oC. a. b. c. d. The initial pressure in the 10 liter bottle of Oxygen. The initial pressure in the other 10 liter bottle containing Nitrogen. The total mass of the gases in the two sample bottles. The number of API cubic meters of calibration gas produced.
a s s u m eZ = 1 . 0 E x a m i n in gth ec a lg a sb o ttlew es e eth e r ea r e2 0L @ 3 5 0k P a T h ep a r tia lp r e s s u r eo fo x y g e ni s T h ep a r tia lp r e s s u r eo fn it r o g e nis pO 2 pN 2

0 .8 . 3 5 0 .k P a 0 .2 . 3 5 0 .k P a
pO 8 0 2 =2
k P a
pN 0 k P a 2 =7
T h ei n it ia lv o lu m eo fe a c hg a sw a s1 0L ,th u st h ein itia lp r e s s u r e sb e c o m e a . pO 2

2 0 . L. 1 0. L
pO 2
pO 6 0 2 =5 b . pN 2
k P a .p N 2
2 0. L 1 0. L
pN 4 0 2 =1 c . MN 2 T nO 2
k P a g . k k m o l MO 2
3 1 .9 9 8 8
2 8 .0 1 3 4 2 9 3 .K
g . k k m o l
( p . 2 3 2S I d b )
. 0. L pO 2 1 .T R k m o l
nO .0 0 2 2 =0
Page 46 of 46
m O2
n O2. M O2
m O2 = 0.074 kg p N2. 10. L n N2 R. T n N2 = 5.747 10 4 kmol m N2 n N2. M N2 m N2 = 0.016 kg m total m O2 m N2 m total = 0.09 kg T std 288 . K p std 101.325 . kPa V std n O2 n N2 . R. T std p std
d.
V std = 67.906 L
Page 47 of 46

02 Basic Thermodynamics

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UNIT 1

THERMAL PROPERTIES OF LIQUIDS AND SOLIDS

Expansion of Solids and Liquids

Data V bottle_at_20 V alcohol_at_20

V alcohol = 5.35 10 V bottle

V bottle = 1.82 10 V overflow

1.21 . 10 5. degC 1 1.07 . 10 3. degC 1

(p.18 databook) 20 . degC

Heat Transfer Of Solids and Liquids

20 . degC 98 . degC 4.1863 .

kJ (23-3 SI databk) . kg degC

Heat Transfer in Mixtures

kJ (p.17 db) . kg degC 40. degC

kJ . kg degC (p.23-3 SI db)

Data Steam: h water:

n-Nonane: (p.23-2 SI db)

The mass flow rate of n-Nonane is 4.992 kg/sec.

Units of Vapour Pressure

Variation Of Vapour Pressure with Temperature

Variation of atmospheric pressure with elevation

URV i URV o LRV i SPAN i

LRV o SPAN i SPAN o y IP

45C URV i URV o LRV i SPAN i

URV o LRV i LRV o . SPAN o

(databook p.19) . 9.81 m sec2

Solution 3. a. p inlet 6.89 . kPa 30. psi. 5 psi p at

Basic Theory Of Gases

where: p is the absolute gas pressure pC is the gas critical pressure

where: T is the absolute gas temperature TC is the gas critical temperature

Solution a. T R pR Z b. n c. d. mass e. Z std V std T Tc p pc T R = 1.65

T = 255 K p atmos 98. kPa p

(p.23-2 SIdb) (p.23-2 SIdb) (p.23-2 SIdb)

Finding Z Factor by Redlich-Kwong Method

Solution a. T R pR Guess Z T Tc p pc 0.9 T R = 1.65 p R = 2.99 4

Data T .K 273 18. degC

T = 255 K p atmos 98. kPa p

n = 0.37 kmol 1 = 263.8 kg m3

mass Z std V std

Gas law calculations

The value of ZAPI at 15C is given in the SI data book p.23-3.

Z 1.00 0.797099 0.809113 0.807879 0.808003 0.807991 0.807992

pR = 3.2246 2.5703 2.6091 2.6051 2.6055 2.6055

Znew 0.797099 0.809113 0.807879 0.808003 0.807991 0.807992

pg = 11982.62 kPaa + 92.03 kPa = 12 074.65 kPag

THERMAL PROPERTIES OF GASES

Specific Heat At Constant Volume (Cv)

Specific Heat At Constant Pressure (cP)

Using the gas law to replace

p V by , the equation becomes m T eq.(4-3)

cP - cV = Example 1: For monatomic helium M = 4.0026 , cp = 5193.1 J J o - = 3115 kg C kg C o

J C v = 358.74 kg. K Cp k k = 1.33 Cv

kg (SI databook,p.23-2) kmol J 476. . kg K

Solution For ideal gas,

Finding specific heat at constant volume:

70. m3 20. degC 273 . K

m air = 77.76 kg Cv Cp R M T = 293 K Cp t2 t 1) t1 1004 . J kg. K

30. degC 20. degC

Mole Fraction, Volume Fraction And Mass Fraction

= 1.7017 m3 / 2.5308 m3 = 0.6724 = 67.24 % = 0.8291 m3 / 2.5308 m3 = 0.3276 = 32.76 %

Physical Properties of A Gas Mixture

Specific Heat at Constant Pressure

Dalton's Law of Partial Pressures

Pseudo-Critical Properties of Gas Mixtures

Gas Law Calculations