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GENERALIZATION 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: (a) the definition of specific heat, latent heat of fusion and latent heat of vaporization. (b) the units of heat energy. (c) the determination of heat required to raise or lower the temperature of a substance. (d) the determination of the specific heat of a substance by experimental data. (e) the determination of the heat flow required to raise or lower the temperature of a flowing substance. 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]. The new length becomes : eq.(1-1)

BASIC THERMODYNAMICS

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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 eq.(1-3)

eq.(1-2)

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?

D a ta Lo to t1

60. m 5. d e g C 23. d e g C 1.21. 10 5 . d e g C 1

L = 0.013068 m

ste e l

(p .1 7 D B )

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. EXAMPLE 2 eq.(1-4)

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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

2. l 2. l

l steel . t f to

3

V bottle_at_20 . 1 + V bottle_at_20

3

...

l V bottle

steel alcohol to tf

V alcohol

2

V overflow = 5.17 10

45 . degC

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. eq.(1-5)

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.

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to

Data m water to t1 c

5. 10 3 . 998.2 . kg

(p.20 Databk)

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 Where: Qf [J] is the total heat for fusion. Lf [ ] is the latent heat of fusion per 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.

Solution . Q m benzenec. t o Q = 1398.8 kJ Data m benzene to t1 c Lf

7.5 . kg

eq.(1-6)

t1

. m benzeneL f

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

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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. Lv [ ] is the latent heat of vaporization per kg. m is the total mass of liquid. EXAMPLE 5 Calculate the amount of heat required to vaporize 2 kg of benzene at 15C. Solution . Q m benzenec. t boiling Q = 1010.7 kJ . m benzene L v Data m benzene to

2. kg

eq.(1-7)

to

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) 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 is no external losses). This can be expressed mathematically as Qgained = Qlost or m1c1(tf - ti1) = m2c2(ti2 - tf) eq.(1-9) eq.(1-8)

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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 Hot: mh ch t h_o Cold: mc t c_o cc

50. kg 10. degC 2.3564 .

t c_o

165 . kg 0.448 .

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 ?.

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sJ t0 ec a m @ 9 0 k / s e

n -5 N o n a n e @ 2 C , ? k g / s e c

n -n N o a n e @ 8 o 0 C

w ac tk e re @ 3 0 0 J / s

Solution:

q m. c. t f ti (h qm Q) h c. t f Q ti kg sec

Q kJ 900. sec kJ 300. sec c ti . 2.1855 kJ . degC kg tf

q m = 4.992

80. degC 25. degC

The mass flow rate of n-Nonane is 4.992 kg/sec. PROBLEMS 1. A brass bar 2 cm square in cross section measures 87.75 cm long at room temperature (21oC). It is placed in an oven at 95oC where its length is measured to be 87.88 cm. What is the coefficient of linear expansion of the material of the bar? The horizontal trusses in the roof of the Coliseum are constructed from individual (carbon) steel beams each 15 m long at 5C. 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? A stainless steel measuring tape is graduated to read correctly at 20oC. An instrumentation technologist uses the tape to make a measurement outdoors when the temperature is -18oC. If the tape indicates 315.4 cm (read at -18C), does the number show the true length ? If not, what is the true length of the object measured? What is the measurement error ?

2.

3.

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4.

The North-South section of the Syncrude 360 kPaa steam line is 120 m long (carbon steel). It was welded together when the average outdoor temperature was 10oC. How much would the line expand when the line was put into service? The temperature of the steam is 140oC. A 0.5 liter carbon steel spherical bottle is completely filled with ethyl alcohol at 20C. If the bottle is heated to 35C, how much ethyl alcohol will overflow ? Determine the heat required in each of the following cases. a. b. c. d. To raise the temperature of 17.5 kg of Carbon Tetrachloride from 10oC to 35oC. To raise the temperature of 1.00 Imp gallon of Methyl Alcohol at 15oC to its boiling point temperature. To heat 2 liters of water in an electric kettle from 20oC to its boiling point temperature in Edmonton. To heat 20,000 bbl per hour of heavy crude oil (specific heat 2.14 ) from 95oC to 260oC in a fired heater if the heater is 78% efficient. (Barrels are at 15oC).

5.

6.

7.

Determine the heat to be added/removed in each of the following cases. a. b. c. To freeze 10.5 kg of Benzene initially at 38oC. To vaporize 2.10 US gal of Ethyl Alcohol initially at 22oC. To thaw out 2 Imp gal of Ethylene Glycol at its freezing point, and raise its temperature to 15oC. (The gallons were measured out at 20oC.)

8.

A 45.4 kg (100 lb ) block of ice at an initial temperature of -40oC is to be vaporized at an atmospheric pressure of 101.3 kPaa. Calculate the amount of heat required in each of the following cases. a. To raise the temperature of the ice from -40oC to 0oC. The specific heat of ice is 2.102 . To melt the ice at 0oC. To raise the temperature of the water produced from 0oC to 100oC.

b. c.

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d. e.

To vaporize the water to steam at 100oC. What is the total heat required to convert the ice at -40oC into steam at atmospheric pressure ?

9.

8.00 kg of water is to be heated from 4oC to 62oC in an iron kettle which has a mass of 1.80 kg. a. b. c. d. How much heat energy is required to heat the water alone ? How much energy is required to heat the kettle alone ? How much energy is needed to heat both the water and the kettle ? If the heatup is to be completed in 8 minutes, how many watts of power must the heater put out ? A carbon steel container has a mass of 152 kg and is at a temperature of 60oC. 45.3 kg of ethyl alcohol at an initial temperature of 5oC is poured into the container. What will be the final temperature of the container and the alcohol ? To determine the specific heat of an unknown liquid, the following procedure was used. 3.00 kg of the liquid was poured into a copper container which has a mass of 0.870 kg. The equilibrium temperature of the container and the liquid was measured to be 21.3oC. A bar of copper, mass 2.55 kg, was heated to a temperature of 88.3oC, and then dropped into the liquid in the container. The resulting temperature was measured to be 31.6oC. What is the specific heat of the liquid ? What is the liquid ? To determine the specific heat of a metal, a procedure similar to that in 9(b) is used. 4.50 kg of water is placed in a copper container which has a mass of 0.580 kg. The equilibrium temperature is measured to be 23.8oC. A 3.75 kg bar of the metal is heated to a temperature of 67.2oC, then immersed in the water. The resulting temperature is 25.7oC. What is the specific heat of the metal? What is the metal ?

10.

a.

b.

c.

11. A heat exchanger uses high pressure steam to heat up benzene. The initial heat energy of the flowing steam is 700 . After going through the exchanger, the steam condenses to water

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which carries only 210 . The benzene has an initial temperature of 25C and flows at at rate of 6 , what is the final temperature of the exiting benzene ?.

benzene@25C, 6 kg/sec

benzene @ ?C

GENERALIZATION

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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 : (a) the concept of vapour pressure. (b) the absolute and gauge pressure. (c) how to find vapour pressure at a given temperature from tables. (d) the relationship between pressure at boiling points and vapour pressure of liquids 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. 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. 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.

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4. THE RELATIONSHIP BETWEEN THE PRESSURE AT BOILING POINT AND 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. 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.

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

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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

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EXAMPLE 1 The room temperature is 22 oC and the relative humidity is found to be 45%. The barometric pressure is 95 kPa. a. Refer to the steam tables to find the saturated vapour pressure of water at 22 o (SI databook p 24-38) . IP 22 C LRV i 20 C SPAN i SPAN o y IP URV i LRV i LRV o LRV o 25 C LRV o 2.339kPaa URV o 3.169 kPaa

URV i URV o

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 to saturated vapour pressure,that is, water_vapour_pressure Humidity ( in_% ) saturated_vapour_pressure p H2O 0.45. y kPaa

p H2O = 1.202

c. At what temperature would the water vapour start to condense if the room air was cooled down. This temperature is called the dew point temperature 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 y IP 0.8721 kPaa URV i URV o URV i LRV i LRV o LRV o 1.2276kPaa LRV o 5C URV o 10C

y = 9.639C 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 SI databook 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 9.593 kPaa 50 C URV i 12.349kPaa

45 C URV i URV o

LRV o

y = 45.96 C f. What is the highest air pressure allowable in the air line at 22 oC 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

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). a) b) Acetone 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 . p at 93.5 kPa vapour pressure of acetone at 40 deg C pv 68. kPa (databook p.29) p suction. 60. kPa

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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PROBLEMS 1. Determine the gauge pressure or temperature, as required, in the following cases. The atmospheric pressure is reported to be 93.65 kPaa. a) Butane in a cigarette lighter is in the liquid phase. If the temperature is 22oC, what is the pressure inside the lighter? b) c) d) e) Propane is normally stored in liquid form. What will be the pressure of the propane vapour at 20oC? If a propane cylinder has a maximum pressure rating of 2000 kPag, what is the maximum temperature which it can tolerate? What pressure will be necessary to liquefy carbon dioxide at a temperature of 15oC? At what temperature would Freon 11 boil under normal atmospheric pressure at the location?

2.

The boiling point (temperature) of liquids depends on the prevailing pressure. For water, this temperature/pressure relationship is plotted with the graphs of vapour pressure vs. temperature for various liquids. It is also shown in the tables for steam, and for the physical properties of water. Use both data sources to determine the answers to the following questions. a) b) At what temperature will water boil if the barometer reads 689 mm of mercury with a temperature of 20oC? At what temperature would water boil at the top of Mt. Robson, 12972 feet above sea level? The air pressure at the top of Mt. Robson is 62.7 kPaa (as given by the chart for geopotential altitude versus pressure scale from Environmental Canada).

c) If water were used in barometers instead of mercury, what would be the error in the barometer reading due to vapour pressure at a temperature of 23oC? d) What will be the error due to vapour pressure when the barometer contains mercury? (The vapour pressure of mercury at 23oC is 0.0015 mm mercury) 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

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flow elements. This effect is called flashing. If the vapour formed condenses again 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 Edmonton. a) b) Acetone at 60oC enters a valve. If the inlet pressure is 20 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 -74.5 kPag. What is the maximum temperature which the alcohol can have before the pump begins to draw vapour as well as liquid ?

4.

A barometer is made by inverting a column of liquid in a glass tube as shown. If the liquid was acetone at 25C and the local atmospheric pressure was 97 kPaa, find (a) the error in pressure introduced by the vapour pressure of acetone (b) the height of the column of acetone.

5.

The room temperature is 33C and the relative humidity is found to be 75%. The barometric pressure is 100 kPaa. Find (a) the saturated vapour pressure of water at 33C (b) the partial pressure of the water vapour in the room (c) the temperature at which water vapour would start to condense if the room air was cooled down (d) the partial pressure of the water vapour in the high pressure air line from the compressor if an air compressor is used to compress the room air into instrument air at 1000 kPaa (e) the dew point temperature of the instrument air (f) the highest air pressure allowable in the air line at 33C so that condensation could not occur.

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GENERALIZATION 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: (a) explain the basic theory of gases and its relationship to the ideal gas law and general gas law. (b) determine volume, pressure, temperature or number of moles for gases under various conditions. (c) determine the density of gases with the general gas law. (d) state the conditions for STP, API or "contract" conditions. (e) explain the importance of calculating the volume or volume flow at STP or API conditions. (f) calculate the reduced pressure and reduced temperature and then determine the gas compressibility factors by graph. 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. 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) gases are made up of minute particles called molecules whose dimensions are very small as compared with the average distances between them.

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(b) 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. (c) all molecular collisions are perfectly elastic, resulting in no decrease in the total kinetic energy. (d) the average kinetic energy of the molecules of a gas is proportional to the absolute temperature. (e) 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) that there are no intermolecular forces between molecules.

(g) 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). 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)

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(a)

(b)

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?

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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2

. 0 .6 9 m . 1 3 5 4 6 .3 kg m3

3

. 4 .4 4 8

g V1 T1

p g au g e= 1 .0 3 4 1 0 k Pa p ab s p g au g e p atm o s

3

(p .1 9 d atab o o k ) m 9 .8 1 1 6 . 9 sec2 . 0 .6 5 m

3

2 0. d eg C

. 273 K

p ab s = 1 .1 2 6 1 0 k Pa p ab s. V 1 R. T 1 p ab s. M R. T 1 . V 1

T 1 = 293 K R M . 8 .3 1 4 4 kJ k m o .lK

a.

n = 0 .3 k m o l b. c. d. m ass V std = 1 3 .3 8 5 kg m3

2 8 .9 6 2 .5

p std T std

kg (p .2 3 -2 SI k m o l d atab o o k ) 1 0 1 .3 2 .5k Pa

1 5. d eg C

. 273 K

m ass = 8 .7 k g

T std = 2 8 8 K

4. REAL GASES

BASIC THERMODYNAMICS

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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). pR = where: p is the absolute gas pressure pC is the gas critical pressure TR Z

3

= = f(TR , pR )

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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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. 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? Data Solution Data . T T 273 K 18. degC a. T R T R = 1.65 Tc T = 255 K p pR p atmos 98. kPa p R = 2.99 pc 3 4 p 15. 10 . kPa p atmos Z 0.84 (from SI data book p.23-12) 4 p = 1.51 10 kPa 5p. V b. n n = 0.37 kmol 3 3 Z. R. T V 45. 10 . m 9 p. M kg Tc (p.23-2 SIdb) 154.5 . K c. = 269.66 . R. T Z 9 m3 7 pc (p.23-2 SIdb) 504 . kPa 3 d. mass n. M mass = 12.13 kg kg M (p.23-2 SIdb) 31.99 . 5 kmol . 9 e. Z std 288 K p 0.9992 T std 101.32. kPa std 5 Z std. n. R. T std V std V std = 8.96 m3 p std 2 FINDING Z FACTOR BY REDLICH-KWONG METHOD Another way of finding the Z factor is to use the Redlich-Kwong method4. 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 A = 0.42748*, B = 0.086647 * eq. (3-5) a. b. c. d. e.

EXAMPLE 3

4

Flow measurement Engineering Handbook, R.W. Miller, 2nd Edition, 1983. p. 2-18

BASIC THERMODYNAMICS

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(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 ? Data T Tc p pc Z 0.9 T R = 1.65 p R = 2.99 4 T . 273 K 18. degC

Solution a. T R pR Guess

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

mass = 11.87 kg

. T std p std 288 K 101.32. kPa 5 Z std. n. R. T std V std = 8.76 m3 p std

BASIC THERMODYNAMICS

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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 Redlich-Kwong method give quite close values. 5. AVOGADRO'S HYPOTHESIS Equal volumes of different ideal gases at the same pressure and temperature contain the same number of molecules.

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 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 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) (m3 STP) eq. (3-8) eq. (3-7) Mass = nM eq. (3-6)

The value of ZAPI at 15C is given in the SI data book p.23-3. (e) Process of iteration

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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

pc= 4599 kPa Tc= 190.56 K Z 1.00 0.797099 0.809113 0.807879 0.808003 0.807991 0.807992

= Z14.8301255106 Pa

P=Z14830.12 kPa 14830.12 kPaa 11821.08 11999.26 11980.96 11982.78 11982.61 11982.62 kPaa

pR =

p 4599

TR =

286.15 190.56

BASIC THERMODYNAMICS

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PROBLEMS 1. A balloon is filled with air. At a pressure of 100 kPaa and a temperature of 18 oC, its volume is 0.522 m3. Calculate its new volume under the following different conditions. a. b. c. d. e. f. 2. It is placed in a vacuum chamber and the pressure is reduced to 32 kPaa (the temperature remains at 18 oC). It is placed in a pressurized chamber and the pressure is increased to 550kPaa at the same temperature. It is heated in an oven to a temperature of 95 oC, at a pressure of 100,000 kPaa. It is cooled in a refrigerator to -70 oC, at 100 kPaa. It is cooled to -40 oC, and its pressure is increased to 150 kPaa. It is heated to 50 oC, and its pressure is decreased to 75kPaa.

A room is 4.0 m wide by 7.6 m long by 2.8 m high. A barometer located in the room reads 701.3 mm mercury and the temperature is 23 oC. a. b. c. d. How many kilomoles of air are there in the room? What is the mass of the air in the room? What is the density of the air in the room? Calculate the density of air using the ratio or the formula. What would the volume of the air be if it were at a temperature of 15 oC and 101.325 kPaa? This is the number of API meters (m3 API).

3.

A storage tank attached to an air compressor has a volume of 0.455 m3 . It contains air at a pressure of 105 psig. The temperature is 20 oC. The barometer reading at the location is 707.2 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?

4.

6.28 sm3 (standard cubic meters at API conditions) of nitrogen are compressed into a tank at 54 oC. The volume of the tank is 0.0625 m3. a. b. c. How many kilomoles of nitrogen are in the tank? What will be the absolute pressure of the nitrogen in the tank? What will a pressure gauge on the tank read if the Edmonton weather office reports an atmospheric pressure of 92.91 kPaa?

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d. 5.

For nitrogen, calculate the reduced temperature and reduced pressure in each of the following cases. Then determine the gas law deviation factor (compressibility factor) Z, from the Gas Compressibility charts and the Redlich-Kwong method. a. b. c. d. e. A pressure of 100 kPaa, and a temperature of 20 oC. 100 kPaa and 300 oC. 5.00 MPaa and 20 oC. 45.0 MPaa and 0 oC. 6.0 MPaa and 130 oC.

6.

Calculate the reduced temperature and the reduced pressure for the following gases at the specified p and T, then determine the gas law deviation factor (compressibility factor) Z. a. b. c. d. e. Air at a pressure of 7.5 MPaa, and a temperature of 55 oC. Hydrogen at 15.0 MPaa and 200 oC. Propane at 5.0 MPaa and 200 oC. Methane at 10.0 MPaa and 50 oC. Carbon Monoxide at 30.0 MPaa and 10 oC.

7.

A 32 litre cylinder of oxygen stored at a temperature of 25 oC has a gauge pressure of 21.7 MPag. The barometric pressure is 91.63 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 m3 API of oxygen are in the cylinder ?

8.

A tank contains 25 kg of nitrogen at a temperature of 10 oC and a pressure of 5800 kPag. The barometer is steady at the average Edmonton value. a. b. c. d. e. What is the value of Z at the tank pressure and temperature? What is the gas law deviation factor Z at API pressure and temperature. How many kilomoles of gas are in the tank? Calculate the volume of the tank. What is the density of the gas in the tank? How many API m3 of nitrogen are in the tank?

BASIC THERMODYNAMICS

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9.

A 35 litre gas cylinder contains 4.25 kg of methane at 25 oC. What will be the gauge pressure of the gas if the cylinder is stored in J32 which has an atmospheric pressure of 92 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.) Propane gas flows in a pipeline at a rate of 55 . The line pressure and temperature are measured to be 1025 kPag and 115oC respectively. The atmospheric pressure is 95 kPaa. a. b. c. d. e. What is the gas law deviation factor of the propane at pipeline conditions? What will be the density of the propane in the pipeline? What is the flow rate in ? What is the mass flow rate of the propane? What is the flow rate of the propane in API ?

10.

11.

The compressed air main in a refinery consists of 100 m of 6 inch Schedule 40 steel pipe. 22 of dry air are compressed into the line at 825 kPag and 20 oC. The air leaves the line at the far end at 700 kPag and 15 oC. The atmospheric pressure is 92.7 kPa. a. b. c. What is the flow rate of the air in kmol/s? What will be the density of the air at the inlet and the outlet of the main? What property of the (air) stream remains constant all along the main?

GENERALIZATION

BASIC THERMODYNAMICS

Page 31 of 75

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: (a) explain the energy equation for heat transfer in terms of the two specific heat constants (cV and cP) (b) derive the relationship for cP knowing cV, R and M. 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 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.

J J

eq.(4-1)

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 eq.(4-2)

BASIC THERMODYNAMICS

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cP is the amount of heat necessary to raise the temperature of 1 kg of gas at constant pressure by 1 Co or 1 Ko. It is measured in units of kg C o or 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 p V where V is the change in volume due to the temperature change.

J J

Fig. 4.1 The total heat supplied, H is (assuming no heat losses) H = Q + external work at constant pressure cPm t = cVm t + p V cP - cV =

p V m T

cP - cV =

eq.(4-3)

J

(p.23-3 SI databook)

BASIC THERMODYNAMICS

Page 33 of 75

cv = 5193.1

J J o - = 3115 kg C kg C o

Note that in the SI databook, only cp is given. The ratio, is defined as the isentropic constant, k or . 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 ( kg C o ) for chlorine. From this data, calculate the value of the specific heat at constant volume cV, and the cP ( = k) ratio of the specific heats cV Solution Cv Cp R M Data M Cp

70.9054 .

BASIC THERMODYNAMICS

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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. How much heat is required to raise the temperature of the air to 30o C, assuming that the tank is open to the atmosphere? b. How much heat is required to raise the temperature of the air to 30oC, assuming that the tank is completely sealed? Solution Data kg For ideal gas, Z 1 M 28.9625 . (p.23-2 SIdb) Finding specific heat at constant volume:

m air p atmos . V. M Z. R . T p atmos V T m air = 77.76 kg Cv Cp R M T = 293 K Cp t2 t 1) t1 1004 . J kg. K kmol 93.44 . kPa

J C v = 716.93 kg. K

(p.23-2 SIdb)

a.

m air. C p. ( t 2

Q = 780.73 kJ

b.

m air. C v. ( t 2

t 1)

H = 557.5 kJ

BASIC THERMODYNAMICS

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PROBLEMS 1. For the following gases, look up the value of the molecular mass (weight), and the specific heat at constant pressure cP ( kg C o ). From this data, calculate the value of the c specific heat at constant volume cV, and the ratio of the specific heats P (= k) cV a. Air b. c. d. 2. Methane Ethane Propane

J

A storage room is 4 m wide by 7 m long by 3.2 m high. Its temperature is 18 oC. The barometer is steady at the average Edmonton value. a. b. Determine the specific heat of air at constant pressure, and at constant volume. How much heat is required to raise the temperature of the air to 28 oC, assuming that the room is open to the atmosphere? c. How much heat is required to raise the temperature of the air to 28 oC, assuming that the room is completely sealed (keeping the volume constant)?

3.

An air cylinder with a movable piston is used to perform work at constant pressure. The pressure in the cylinder is 50 MPaa at 15 C. The initial volume of the cylinder is 0.5 L. It is heated from 15C to 100C. The volume of the air expands in order to keep the pressure constant. Consider the air to be an ideal gas. (a) How much work does the piston do? (b) If the diameter of the piston is 10 cm, how much does the piston move from its original position? Repeat Question #3 with air being a real gas. (a) Find the compressibility factor of air at 100oC (b) How much work does the piston do? (c) If the diameter of the piston is 10 cm, how much does the piston move from its original position?

4.

BASIC THERMODYNAMICS

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GENERALIZATION In many situations, the gas products are mixtures of gases. Such mixtures possess different properties than the pure ones. The density behaviour 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: (a) explain and use Dalton's law of partial pressure. (b) explain the significance of mass, volume and mole fraction and convert from one to the other. (c) calculate the compressibility factor for a gas mixture. (d) solve for two unknowns in a gas problem by iteration. (e) determine the quantities and pressures of pure gases required to make a calibration gas at a particular pressure and composition. 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)

BASIC THERMODYNAMICS

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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)

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 %

BASIC THERMODYNAMICS

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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.

B1

V1 = V t

eq.(5-4)

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 = Zt V1

Z1 Vt

Zt Z1

B1

eq.(5-5)

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

BASIC THERMODYNAMICS

Page 39 of 75

players

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. 2. PHYSICAL PROPERTIES OF A GAS MIXTURE (1) MOLAR 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)

BASIC THERMODYNAMICS

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Furthermore, the mass fraction of individual gas component can be stated as: W B1 =

x B1 M 1 M mix

eq.(5-7)

(2) 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 + ... and the specific heat at constant volume can be obtained from the equation : cvmix = cpmix R M mix

eq.(5-8)

eq.(5-9)

3. 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,

BASIC THERMODYNAMICS

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eq.(5-12) eq.(5-13)

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 : (1) first 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. (2) use the calculated pc, Tc values to determine the pseudo reduced pressure (pr) and the pseudo reduced temperature (Tr). 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. (3) From 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 RedlichKwong method to actually calculate the Z factor. 5. GAS LAW CALCULATIONS The general gas equation applies to all gas law calculations. pV = ZnRT eq.(5-16) eq.(5-14) eq.(5-15)

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.

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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 Carbon Monoxide 40% 50% 10%.

Record the data in a table and calculate the weighted average of the molar mass: gas N2 CO2 CO Mix Mass % 40 50 10 100 M 28.0134 44.01 28.01 36.0196

where: 36.0196 kg/kmol = 0.40*28.0134 + 0.5*44.01 + 0.10*28.01 Using x B1 = gas N2 CO2 CO Mix

WB1 M mix M 1

calculate the composition based on moles Rel mol 51.43 40.92 12.86 105.20

100 105 .20

Mass % 40 50 10 100

Note that the sum of the mol % is not 100. Therefore we must normalise the values by multiplying each by the normalisation factor relative Mass % M mol 40 28.0134 51.43 50 44.01 40.92 10 28.01 12.86 100 36.0196 105.20

Relative mol*

10 0 1 5 .2 0 0

M 1 M mix

Answer

x B1

gas to N2 CO2 CO

BASIC THERMODYNAMICS

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Mix

100.0

34.25

100.0

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% M 70 16.04 20 30.07 10 44.1 100 Tc 190.6 305.4 369.8 Pc 4599 4880 4240

gas CH4 C2H6 C3H8 Mix molar% M 70 16.04 20 30.07 10 44.1 100 21.65 Tc 190.6 305.4 369.8 231.5 Pc 4599 4880 4240 4619.3

gas CH4 C2H6 C3H8 Mix molar% M 70 16.04 20 30.07 10 44.1 100 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

gas CH4 C2H6 C3H8 Mix molar% M 70 16.04 20 30.07 10 44.1 100 21.65 Tc 190.6 305.4 369.8 231.5

B1

Z1 = Z x B1 mix

Z 0.9201 0.2395 0.1942 0.8336 rel vol 77.26 5.75 2.33 85.34

gas CH4 C2H6 C3H8 Mix molar% M 70 16.04 20 30.07 10 44.1 100 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 rel vol 77.26 5.75 2.33 85.34 vol% 90.54 6.73 2.73 100.00

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Done! 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 CH4 C2H6 C3H8 Mix vol% 90.54 6.73 2.73 100.00 M 16.04 30.07 44.1 Tc 190.6 305.4 369.8 Pc 4599 4880 4240

gas CH4 C2H6 C3H8 Mix vol% 90.54 6.73 2.73 100.00 M 16.04 30.07 44.1 17.75 Tc 190.6 305.4 369.8 203.2 Pc 4599 4880 4240 4608.1

gas CH4 C2H6 C3H8 Mix vol% 90.54 6.73 2.73 100.00 M 16.04 30.07 44.1 17.75 Tc 190.6 305.4 369.8 203.2 Pc 4599 4880 4240 4608.1 Z 0.9201 0.2395 0.1942 0.8980

gas CH4 C2H6 C3H8 Mix vol% 90.54 6.73 2.73 100.00 M 16.04 30.07 44.1 17.75 Tc 190.6 305.4 369.8 203.2 Pc 4599 4880 4240 4608.1

Zmix B1 Z1

Z 0.9201 0.2395 0.1942 0.8980 Rel mol 88.36 25.24 12.62 126.22

gas CH4 C2H6 C3H8 Mix vol% 90.54 6.73 2.73 100.00 M 16.04 30.07 44.1 17.75 Tc 190.6 305.4 369.8 203.2 Pc 4599 4880 4240 4608.1 Z 0.9201 0.2395 0.1942 0.8980 Rel mol 88.36 25.24 12.62 126.22 mol % 70.00 20.00 10.00 100.00

Done!

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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. What will be the molar mass, the pseudo critical pressure, and the pseudo critical temperature of the mixture? b. What will be the compressibility factor (gas law deviation factor) of the mixture at its storage P and T? c. What is the volume of the cylinder? d. How many API cubic meters of the gas mixture are contained in the cylinder? e. 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 % mol 70 18 2 10 100 M Tc Pc 16.043 190.56 4599 30.07 305.41 4880 34.082 373.37 8963 28.0134 126.21 3398 20.12568 208.4542 4616.76

Calculate Z of the mixture gas CH4 C2H6 H2S N2 Mix % Vmol 70 18 2 10 100 M Tc Pc Z 16.043 190.56 4599 30.07 305.41 4880 34.082 373.37 8963 28.0134 126.21 3398 20.12568 208.4542 4616.76 0.7864

d. Calculate Zstd using Redlich-Kwong Zstd = 0.9972

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2.00 kg J 0.9972 8314.51 288 K m kmol K Z* R T 20.126 kg kmol M Vstd = = = 2.343 m 3 3 p 101.325 10 Pa

e. =

m 2.00 kg kg = = 104.3 3 -2 3 V 1.917 10 m m

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. What will be the molar mass, the pseudo critical pressure, and the pseudo critical temperature of the mixture? b. What will be the compressibility factor (gas law deviation factor) of the mixture at its storage P and T? c. What is the volume of the cylinder? d. How many API cubic meters of the gas mixture are contained in the cylinder? e. 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% 70.00 18.00 2.00 10.00 100.00 M Tc Pc 16.04 190.56 4599 30.07 305.41 4880 34.082 373.37 8963 28.0134 126.21 3398 20.1236 208.454 4616.76

gas CH4 C2H6 H2S N2 Mix vol% 70.00 18.00 2.00 10.00 100.00 M Tc Pc Z 16.04 190.56 4599 0.8525 30.07 305.41 4880 0.3460 34.082 373.37 8963 0.1838 28.0134 126.21 3398 0.9888 20.1236 208.454 4616.76 0.7881

gas CH4 C2H6 H2S vol% 70.00 18.00 2.00 M 16.04 30.07 34.082 Tc 190.56 305.41 373.37 Pc 4599 4880 8963 Z 0.8525 0.3460 0.1838

Zt Z1

B1

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N2 Mix

10.00 28.0134 126.21 3398 0.9888 7.97 100.00 20.1236 208.454 4616.76 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% 70.00 18.00 2.00 10.00 100.00 M Tc Pc Z 16.04 190.56 4599 0.8525 30.07 305.41 4880 0.3460 34.082 373.37 8963 0.1838 28.0134 126.21 3398 0.9888 20.1236 208.454 4616.76 0.7881 rel mol 64.71 41.00 8.57 7.97 122.26 mol % 52.93 33.54 7.01 6.52 100.00

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% 70.00 18.00 2.00 10.00 100.00 M Tc Pc Z 16.04 190.56 4599 0.8525 30.07 305.41 4880 0.3460 34.082 373.37 8963 0.1838 28.0134 126.21 3398 0.9888 20.1236 208.454 4616.76 0.7881 rel mo 64.71 41.00 8.57 7.97 122.26 mol % 52.93 33.54 7.01 6.52 100.00 M Tc Pc Z 16.04 190.56 4599 30.07 305.41 4880 34.08 373.37 8963 28.01 126.21 3398 21.0021 212.009 4318.57 0.7641

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 Vstd = = = 2.245 m 3 p 101.325 103 Pa

e. =

EXAMPLE 9

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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.

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assume Z = 1.0 Examining the cal gas bottle we see there are 20 L @ 350 kPa The partial pressure of oxygen is p O2

0.8 . 350 . kPa 0.2. 350 . kPa

20. L . 10. L

The initial volume of each gas was 10 L, thus the initial pressures become a. p O2 p O2

p O2 = 560 kPa b. p N2

20. L 10. L

.p

N2

p N2 = 140 kPa c. M N2 T n O2

28.0134 .

kg kmol

M O2

31.9988 .

kg kmol

(p.23-2 SIdb)

293 . K

p O2. 10. L R. T

n O2 = 0.002 kmol

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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

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PROBLEMS 1. Determine the molar mass, the pseudo critical pressure, and the pseudo critical temperature, for the following gas mixtures. The compositions are mole percent. a. b. c. d. e. 2. Nitrogen 79%, Oxygen 21%. Fluorine 18%, Chlorine 82%. (Fluorine : Tc =-129C, pc=5573 kPa) Helium 70%, Oxygen 12%, Nitrogen 18%. Methane 83%, Ethane 16%, Propane 1%. Nitrogen 85%, Carbon Dioxide 5%, Oxygen 5%, Carbon Monoxide 5%.

Calculate the mole percent of each of the components in the following gas mixtures. The compositions have been provided on a mass percent basis. a. b. c. Nitrogen 60%, Carbon Dioxide 30%, Carbon Monoxide 10%. Helium 50%, Oxygen 30%, Carbon Dioxide 20%. Methane 78%, Ethane 18%, Propane 4%.

3.

A gas mixture consists of 58% Methane, 7% Ethane, 2% Hydrogen Sulfide, and 33% Nitrogen, by volume. 2 kg mass of this mixture is stored in a cylinder at a temperature of 25 oC and a pressure of 15000 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?

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4.

A gas mixture consists of 62% Methane, 8% Ethane, and 30% Propane, by mole. Two point five (2.5) kg of this mixture is to be stored in a cylinder, which has a volume of 28 L. The temperature is 30oC. a. b. What will be the molar mass, the pseudo critical pressure, and the pseudo critical temperature of the mixture? What absolute pressure must be applied in order to store the 2.5 kg of the mixture in the cylinder?

5.

A calibration gas sample consisting of 60% Oxygen and 40% Nitrogen by volume is to be prepared. Two 10 liter 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 250 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.

6.

Natural Gas as it comes from the well has a typical composition of 82% Methane, 14% Ethane, 2% Propane, and 2% Hydrogen Sulfide, by mole fraction. It is piped to a gas treatment plant at a pressure and temperature of 3.35 MPag and 45 oC, at the rate of 150 actual . The atmospheric pressure is 99.75 kPaa. a. b. c. What is the flow rate of the gas in ? If the component gases are separated at the treatment plant, what will be the mass flow rate of each component? As the Methane is produced, it is piped off to be sold as fuel gas. What will be the flow rate of the Methane in API ? d. What will be the draw off rate of the Methane in actual if its pressure and temperature are 253 kPag and 18oC?

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7.

Natural gas has a typical composition of methane 72%, ethane 19%, and propane 9% by mole. Determine the following quantities. a b c The specific heat at constant pressure (cP). and at constant volume (cV). The heat required to raise the temperature of 150 kmol of the natural gas from 0oC to 50oC at constant volume. The heat which must be removed from the 150 kmol of the gas in order to cool it back down to 0oC at constant pressure.

Chapter 6 STEAM

GENERALIZATION High pressure and temperature steam is widely used in many industrial production plants such as power plants, chemical plants, pulp mills or heavy crude oil processing plants.

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Various types of steam may be used throughout a plant according to the required temperature and pressure. Proper understanding and operation of steam generation and maintenance are essential. GENERAL OBJECTIVES The student will learn how to: (a) explain the concept of generating steam (b) define specific volume and enthalpy at saturated and unsaturated conditions (c) define saturated, superheated and wet steam (d) define the quality factor (x) for wet steam (e) explain the pressure versus specific volume curve for water (f) perform calculations for heat transfer in boilers, heat exchangers and turbines using the steam table in the SI Engineering data book. THE BASIC CONCEPT Steam is used to move thermal energy from a boiler through pipes to a device which will extract the energy such as a heat exchanger or steam turbine. It is similar to wires carrying electrical energy from a generator to heaters or motors. The analogy can be carried further. In electricity the rate of energy flow is given by Power = V I where V is the potential difference in volts and I is the current in amps. One volt is defined as 1 joule per coulomb (J/C) and one amp is a flow rate of 1 coulomb per second (C/s). (Recall that the coulomb is a unit of electric charge which equals combined charge of 6.25*1018 electrons.) In steam generation the analogous formula is given by Power = H qm where H is the change of thermal energy measured in kilojoules per kilogram (kJ/kg) and is called the change of ENTHALPY. The term qm is the rate of steam flow in kilograms per second (kg/s). 2. CONCEPT OF STEAM GENERATION When water boils, steam is generated. Fig.1 shows the amount of heat content, called specific enthalpy, absorbed by 1 kg of water at 101.325 kPaa and from 0C to 300C.

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Starting at 0C, the water temperature rises to 100C at 101.325 kPaa atmospheric pressure. The amount of heat can be calculated by the heat gain equation, Q = mc t. The first rising section of the straight line represents the amount of heat absorbed during the process of reaching the boiling condition. When the water reaches its boiling point, any further supply of heat does not raise the temperature of the water but will only change the phase of the water from liquid to vapour, namely, steam. This process continues until all liquid water is vaporized into steam. The amount of heat, Qv, supplied during this time of phase transition can be calculated with the expression mLv. Lv is the latent heat of vaporization as discussed in previous sections. The horizontal section of the curve in Fig.6.1 represents the phase transition during which heat is gained but temperature remains unchanged. After the water is completely vaporized, any additional heat will cause the steam to increase in temperature and volume at constant pressure. The steam behaves like a gas. The amount of heat can be calculated with the expression Q = mcp t, where cp is the specific heat of steam at constant pressure. The second rising section of the straight line in Fig. 1 represents this process.

Fig. 6.1 EXAMPLE 1 Find the total amount of heat required to convert 1 kg of water at 0C to 1 kg of steam at 101.325 kPaa.

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to

m. L v

Data m 1. kg c water Lv to tf

4.1863 . 2256.64 . 0. degC 100 . degC

kJ kg

EXAMPLE 2 If the steam from Example 1 is heated further to a temperature of 150C at atmospheric pressure (101.325 kPaa) ,find the additional amount of heat needed and the total heat required to convert 1 kg of water at 0C to steam at 150C and 101.325 kPaa. Solution Q m. c p. t f Q = 93.085 kJ Q for steam at 150C : Q 150 2675 . kJ Q Q 150 = 2.768 103 kJ (from the superheated steam table on p.24-40, Q is 2776.4 kJ @100 kPaa and 150C) However, the calculation of the enthalpy using the discussed equation is not exact since the specific heat of water and steam is a function of temperature. The exact amount of enthalpy absorbed by 1 kg of steam can be looked up from steam tables. It is always important to state the temperature and pressure of steam. 3. TYPES OF STEAM AND STEAM TABLES In section 24-38 to 24-42 of the SI databook, the thermodynamic quantities of 1 kg of steam are provided. The values are categorized under two main types of steam, namely, saturated steam and superheated steam. The following section explains the various types of steam. Data m 1. kg cp to tf kJ kg. degC 100 . degC 150 . degC

1.8617 .

to

(p.23-3 SIdb)

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A. Saturated steam and saturated steam tables Saturated steam is referred to the type of steam, which does not contain any trace of water drops (mist) and is at the boiling temperature under the specified pressure (at saturation condition). It is completely in the vapour phase. This type of steam is also called dry saturated steam. Saturated steam condenses readily into water (in mist form) when its temperature and pressure drop below its saturation condition. Certain terminologies are adopted in the saturated steam tables. A section of the header of the saturated steam pressure table (p.24-39 SI data book ) is shown and explained as follows :

Press. kPa P Temp C T Specific volume Sat. Sat. Liquid Vapour vf vg Internal Energy Sat. Sat. Liquid Evap Vapour uf ufg ug Enthalpy Sat. Sat. Liquid Evap. Vapour hf hfg hg Entropy Sat.... Liquid ... sf...

1. saturation temperature, t sat- the boiling temperature of water or the temperature of the saturated steam. 2. saturation pressure, psat - the pressure of the saturated steam at the saturation temperature 3. hf - the specific enthalpy (heat energy in its saturation temperature

k J ) required to bring 1 kg of water from 0C to k g

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saturation temperature and pressure. This is equivalent to the latent heat of vaporization. 5. hg - the total specific enthalpy (

k J ) required to convert 1 kg of water at 0C to vapour at its k g

saturation temperature and pressure. This is the sum of hf and hfg. hg = hf + hfg

[]

eq.(6 -1)

The specific enthalpies hf, hfg, hg are shown graphically in Fig.6.1. 6. vf - the specific volume of 1 kg of water at the saturation temperature in 7. vg - the specific volume of 1 kg of steam in density of steam. vg = vf + vfg where: vfg is the volume of steam during the phase change. It is the difference of specific volumes between the steam and the saturated liquid. The quantities u and s are the specific internal energy and specific entropy respectively. Values of enthalpies and specific volumes are tabulated according to temperature (saturated steam : temperature table) or pressure (saturated steam : pressure table). EXAMPLE 3 Dry saturated steam at 2500 kPa absolute is produced from feedwater at 0oC. Using the steam tables, determine: a. b. c. d. e. The saturation temperature. The specific volume and density of the water at saturation temperature. The specific volume and the density of the steam at saturation temperature. The heat required to raise 1 kg of water to the saturation temperature. The heat required to raise 1 kg of water at the saturation temperature to dry steam at the saturation temperature.

m3 kg m3 kg

[]

eq.(6 -2)

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f.

The total heat required to raise 1 kg of water at 0oC to dry saturated steam at the saturation temperature. Data p = 2500 kPa t water = 0 degC

Solution From SI data book, p.24-39 pressure table, at 2500 kPa a. tsat = 223.99 degC b. vf = 0.001197 = = = 835.42 c. vg = 0.07998 = = 12.5 d. hf = 962.11 e. hfg = 1841 f. hg = hf + hfg hg = 2803.11 EXAMPLE 4

m3 kg

Determine the heat flow rate in that must be supplied and the volume in for saturated steam at 165oC flowing at a rate of 15 with feedwater at a temperature of 15oC.

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Solution heat added per kg h h feedwater kJ h = 2.7 103 kg heat added per second P h. q m P = 4.05 104 P = 4.05 10

4

Data qm t steam

15.

hg

kg sec

165 . degC 15. degC

t feedwater

kJ sec kW

2763.5 . 0.2727 .

kJ kg m3 kg

B. Superheated steam and superheated steam tables When (dry) saturated steam is heated at a specified pressure, its temperature and volume continue to increase and the steam becomes superheated. The difference between the temperature of the superheated steam and the saturated temperature is called the degree of superheat. degree of superheat = t steam - tsat C eq.(6 -3)

The superheated steam contains more enthalpy than the saturated steam and stays as a gas. Any change in pressure or temperature will not cause the steam to condense unless the pressure and temperature reach the saturation condition. The values of enthalpy and specific volume for superheated steam are tabulated in the superheated steam tables in the SI data book p.24-40 to p.24-42. The header in each superheated steam table gives the pressure of the superheated steam and its saturation temperature. In the header as shown, the saturation temperature is 45.81C at a pressure of 10 kPa. P = 10 kPa (45.81C) T Sat. v 14.674 u 2437.9 h 2584.7 s 8.1502

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v - specific volume of superheated steam in u - specific internal energy of superheated steam in h - specific enthalpy of superheated steam in s - specific entropy of superheated steam in kg K EXAMPLE 5 If the temperature and pressure of an unknown steam are 450C and 5000 kPaa, find the following quantities : (a) the saturation temperature (b) the specific volume (c) the enthalpy of the superheated steam at the given pressure and temperature (d) the enthalpy of the steam at saturated condition From p.24-41 SI Databook, the table for 5000 kPaa gives the following values : (i) t sat = 263.99C (ii) v = 0.0633 (iii) h = 3316.2 (iv) hg = 2794.3 (p.24-39 SI databook)

kJ

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EXAMPLE 6 Determine the amount of power that could be obtained from 25 kg/min. of superheated steam at 1300oC and 7 MPa (abs) pressure if it is cooled at constant pressure to saturated conditions. Also, determine the degrees of superheat. Solution (SI Data Book p 24-41 hsuperheat = 5393.7 kJ/kg hsat = 2772.7 kJ/kg qm = 25 kg/min qm = 0.40 kg/s

h = hsuperheat- h sat h = 2621.6 kJ/kg Power = h * qm = 1092.3 kJ/s = 1092.3 kW degree of superheat = tsuperheat = 1300 oC - 285.88 oC = 1014.1 Co C. Wet Steam

Wet steam is formed when the temperature or the pressure of the (dry) saturated steam drops below the saturation condition. Part of the saturated steam condenses into fine water drops or mist. Hence, the steam becomes wet .This can be clearly explained with the PV diagram for water in the following section. The heat content or enthalpy of such steam consists of the enthalpy of the saturation liquid and a fractional part of the heat of vaporization, hfg. h wet = hf + xhfg where (1) hf and hg are enthalpies of the saturated liquid and saturated vapour respectively. (2) hfg equals (hg - hf) (3) x is called the steam quality of the wet steam. It represents the fraction of wet steam which is in the vapour phase. A value of 0.6 or 60% indicates that the wet steam contains 60% vapour and 40% saturated liquid. A steam quality of 0 % indicates that the steam is all in liquid form (point A in Fig. 1) and a quality of 100% indicates that the steam is all in vapour form (point B in Fig.6.1). eq. (6 -4)

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Referring to Fig.6.1, the enthalpy and temperature of wet steam is along the flat portion of the curve. The line indicates that the temperature of the wet steam remains at the saturated value (at boiling temperature) and the enthalpy varies within the section of the curve according to the value of the fraction (steam quality). The specific volume of wet steam is given by:

v wet = vf + xvfg

where

eq. (6 -5)

(1) vf and vg are the specific volumes of the saturated liquid and saturated vapour respectively. (2) vfg equals (vg - vf) . EXAMPLE 7 Determine the saturation temperature, the enthalpy and specific volume of a wet steam at 300 kPaa if the steam quality is at 80 %. Solution (1) t sat = 133.55C (2) h wet = hf + xhfg = 561.47 + 0.8 x 2163.8 = 2292.5 (3) v wet = vf + xvfg = 0.001073 + 0.8 x (0.6058 - 0.001073) = 0.48485 DATA From p.24-39 SI databook t sat = 133.55C hf = 561.47 hfg = 2163.8 vf = 0.001073 , vg = 0.6058 x = 0.8 (given)

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EXAMPLE 8 Saturated steam at 3500 kPa absolute is produced from feedwater at 40oC. If the steam has a steam quality of 0.7, how much heat is required to produce 1 kg of such steam ? Solution heat required to produce steam with steam quality x = 0. 9 .h h x fg h f h f_feedwater h = 2109.77 kJ kg Data steam properties at 3500 kPa abs (SI data book p.24-39) hf h fg

1049.75 . 1753.7 .

kJ kg kJ kg

x 0.7 enthalpy of feedwater at 40 degC kJ h f_feedwater 167.57 . kg (p.24-38 SI db) 4. P-V DIAGRAM FOR WATER In the discussion of ideal gases, we learned about the Boyle's law which states that the pressure of an ideal gas is inversely proportional to its volume at constant temperature and mass. This relationship is plotted as a hyperbolic curve, called isotherm, in a PV diagram as shown. However, no gases are ideal gases. Consequently, the isotherms do not behave exactly as hyperbolae. When a real gas is compressed at constant temperature, its pressure increases. This will continue until the gas starts to liquefy (point b or f). At this stage, a sudden drop in volume without any significant change in pressure occurs. The isotherm displays a zero slope (level) curve (section b-a or f-d) in this region. When the phase transition is completed, the gas totally becomes a liquid under the specified pressure and temperature (point a or d). Any further increase in pressure can only reduce the volume of the liquid by a small amount as liquid is relatively incompressible. The isotherm displays a steep negative slope line (section d-e). At higher temperatures, the gas liquefies at a higher pressure and a smaller volume as compared to the lower temperature situation ( point b for lower temperature versus point f for higher temperature). It also converts to a liquid more readily at higher temperature as shown by a shorter isotherm section (section b-a versus f-d) as temperature increases. When the temperature reaches a critical value (point c), the critical temperature, the gas can not liquefy at all. At this state, the gas fully obeys the Boyle's law. In other words, the gas does not liquefy at all no matter how high a pressure one applies to the gas. The region within which

BASIC THERMODYNAMICS

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liquefaction occurs is bounded by the dotted bell shaped curve. It is within this region where a mixture of vapour and liquid exist at the specified pressure, volume and temperature. Steam is a real gas and its PV diagram looks like the one shown. In particular, the bell shaped region displays the saturation zone in which water (liquid) and steam(vapour) can both exist.

p res s u re

c g a s

d f liq u id a

v a p o u r s o l i d v a p ob u r

v a p o u r so lid

v o lu

me

V

te m

pe

u ra t

re

. Fig.6.2 PVT diagram for water The state (its pressure, volume and temperature) of a wet steam lies within the bell shaped zone. If the temperature of a saturated steam which has a state at f (right at the edge of the bell contour) drops, its state will fall from one isothem into another one at a lower temperature. It can be seen from the bell shaped envelope that the state of the saturated steam is changed into a state located in the wet steam zone. The saturated steam condenses readily with a decrease in temperature and pressure. Alternatively, a saturated steam can turn into a wet steam by reducing the volume of the steam while keeping the temperature and pressure at the same saturation conditions. This corresponds to moving the state of the steam along one of the isotherm.

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5. INDUSTRIAL APPLICATIONS OF STEAM In many industrial plants, steam is an indispensable medium for transporting energy. Steam is generated by boilers and is used for propelling turbines or for heating products in heat exchangers. This section will briefly explain the features of a boiler, a turbine and a heat exchanger. a. Boiler A boiler is a vessel in which water is boiled to form steam. It is part of a steam generating unit which consists of steam generator system, fuel burning system, ash removal system and air draft system. Figure 6.3 to 6.5 illustrate the various parts of a typical steam generating system. b. Heat exchanger A heat exchanger is that part of a heat exchanging system where heat is transferred from the hot product to the cold product. The tubes shown in Fig.6.3 , 6.4 and 6.5 can be considered as typical heat exchangers. Heat is transferred from the fire into water flowing inside the tubes.

s t e a m - w m i x t u r e

a t e r

s t e a m

H e a t e d r i s e r

u n h e a t e d w a t e r

a t e r

Fig. 6.3 water circulates from unheated side to heated side and forms steam bubbles

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ste a m o u tle t

R is e rs

d o w n c o m e rs

boiler drum

stoker

gas flow

Fan

air

c. Steam turbines Turbines are energy converters which transform heat energy into mechanical energy. Steam turbine is a type of turbine which converts internal energy from pressurized steam into rotational energy. Superheated steam is guided through a series of blades mounted on a

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rotating shaft as shown in Fig. 6.6 and Fig. 6.7. The blades gain kinetic energy as the steam hits the blade surfaces. After the steam passes through the blades, its pressure and temperature drops leading to a loss in its internal energy. The loss in the steam internal energy is balanced by a gain of rotational energy of the blades. Fig. 6.8 illustrates the turbine blades in two separate stages in a steam turbine.

steam

reheater steam

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When calculating heat exchanges involving boilers , turbines and heat exchangers, one has to keep in mind that there are two major processes involved. One is the loss of heat by steam in the case of turbines and heat exchangers. Super heated steam loses heat by losing pressure and/or temperature. Saturated steam loses heat by partial condensation, namely, from dry saturated steam to wet steam. The net heat loss can be calculated by finding the differences between the specific enthalpies at the initial and the final state. The other process is the heat gaining process. In turbines, the heat loss by the steam is converted into mechanical energy. Incorporated with the efficiency of the turbine, one can find out the power output by equating the heat loss by steam to the mechanical energy gained. In heat exchangers, the heat is gained by a product circulated in the exchanger. The heat gained by the product is obtained from the heat loss by steam. Using the Q=mc t formula, one can find out the change in temperature of the product. In the case of boilers, steam gains heat. The net gain of heat can be found from the differences between the specific enthalpies of the generated steam and the feedwater . From the calculated heat gain, one can find out the amount of power supplied to the boiler by using the conservation of energy principle.

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Fig. 6.8 The above picture shows the two stages of steam flow in a steam turbine. In impulse stage above, nozzles direct steam into buckets mounted on rim of rotating disk. In the reaction stage, stationary blades direct steam jets into passages between moving blades; pressure drops across both fixed and moving blades. In impulse stage, it drops only across nozzle. (excerpted from Power special report, June 1962)

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PROBLEMS 1. Determine the steam temperature, density, and heat content for saturated steam at the following pressures, in Edmonton. a. b. c. d. 2. 350 kPaa 1907 kPag 150 psia 600 psig

Dry saturated steam at 1000 kPa absolute is produced from feedwater at 0oC. Using the steam tables, determine : a. b. c. d. e. f. The saturation temperature. The specific volume of the water at the saturation temperature. The specific volume of the steam at the saturation temperature. The heat required to raise 1 kg of water to the saturation temperature. The heat required to raise 1 kg of water at the saturation temperature to dry steam at the saturation temperature. The total heat required to raise 1 kg of water at 0oC to dry saturated steam at the saturation temperature.

3.

Determine the heat flow rate in that must be supplied and the volume in for the following cases. a. Saturated steam at 120oC flowing at a rate of 5 with feedwater at a temperature of 15oC. Saturated steam at 300oC flowing at a rate of 6200 with feed water at a temperature of 60oC. Saturated steam at 500oF flowing at a rate of 80 with feed water at a temperature of 120oF.

b.

c.

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4.

Determine the quality of the wet steam in the following cases: a. b. c. Saturated steam at 295oC which contains 2200 of heat. Saturated steam at 350oC which loses 500 to line losses. Dry saturated steam at a pressure of 4000 kPaa and flowing at 40 supplying 28000 kJ/min. of energy to a heat exchanger. The pressure of the wet steam leaving the exchanger is 300 kPaa. and its temperature is 133.55C.

5.

10 kg of steam with steam quality 0.8 is produced from water at 0oC. If the pressure of the steam is 93.5 kPaa, how much heat is required ? Wet steam at 2000 kPa absolute is produced from feedwater at 60oC. If the steam has a steam quality of 0.9, how much heat is required to produce 1 kg of such steam ? 1000 of steam at 1500 kPaa is produced from feedwater at 40oC. If the steam quality is 0.95, what will be : a. b. the volume of 1 kg of the wet steam in m3 the heat flow required to produce the steam in kJ/s

6.

7.

8.

What is the enthalpy of 1 kg of steam, produced from water at 0oC, at a pressure of 2000 kPa and a temperature of 300oC ? Determine the amount of thermal power that could be obtained from superheated steam if it is cooled at constant pressure to saturated conditions. Also, determine the degrees of superheat. a. b. c. 10 kg/min. of superheated steam at 600oC and 2 MPa (abs) pressure. 1100 kg/hr of superheated steam at 550oC and 10 MPa (abs) pressure. 25 lb/min. of superheated steam at 600oC and 10 MPa pressure.

9.

10.

A boiler produces 2700 of steam at 8000 kPaa and 450oC from boiler feedwater (BFW) at 18oC. The steam is used to drive a turbine which extracts 719 kW (30% of the heat

BASIC THERMODYNAMICS

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added by the boiler) from the steam. The pressure of the exhaust steam from the turbine is 1500 kPaa. a. Is the steam produced by the boiler wet, saturated, or superheated? What numbers verify this? How much power in conditions? c. d. e. 11. What is the power output of the generator if it is 68% efficient? Is the steam exhausted by the turbine wet, saturated, or superheated. What numbers confirm this ? What is the quality of the steam exhausted by the turbine?

kJ is required to generate 2700 of steam under these s

b.

A natural gas fired boiler generates 50000 of steam at a temperature of 400oC from BFW at 195oC. A pressure gauge on the boiler steam discharge line reads 6.00 MPag. The atmospheric pressure is 93.65 kPaa. a b c d What is the quality of the steam produced by the boiler? What numbers confirm this? How much thermal power, in , must the boiler fire supply in order to produce this amount of steam under these conditions? How much thermal power must the fuel gas provide if the boiler is 60% efficient in transferring heat to water? If the heat of combustion of the fuel gas is 50 in standard API , what flow rate in standard for the gas is required?

12.

A heat exchanger requires 10 of saturated steam to heat 200 of Methyl Alcohol initially at a temperature of 15oC. The steam supply pressure gauge reads 106.9 kPag. A local barometer reads 700.7 mm of mercury at 21oC. a. b c d If the BFW temperature is 95oC, how much heat is required from the boiler to generate this steam in 1 second ? What is the volume flow rate of the steam from the boiler to the exchanger? What is the heat content of the steam leaving the exchanger if its quality is 60 percent? The pressure of steam remains unchanged. What is the heat absorbed by the exchanger in 1 second ?

BASIC THERMODYNAMICS

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e 13.

If the exchanger has an efficiency of 80 percent, what will be the output temperature of the methyl alcohol?

A process in an industrial plant requires that 20,000 liters of water be heated each hour from 20oC to 80oC. The heating is done by a steam coil immersed in the water. The coil is supplied with dry saturated steam at 1200 kPaa, and the condensate leaving the coil is at temperature of 90oC. How many kg of steam are required per hour ? Superheated steam at 8.00 MPaa and 205 degrees of superheat is used to drive a small turbine/generator system. The steam exits the turbine unsaturated at 3.00 MPaa. The flow rate of steam is 25.0 kg/min. If the turbine/generator is 60.0% efficient and the generator output power is 450 kW, what is the quality of the steam leaving the turbine/generator ?

14.

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