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Chapter 5

Single-Phase Systems
Dr. Nahid Sanzida
nahidsanzida@che.buet.ac.bd

Density of Liquids and Solids
The density of a liquid or solid solution can be determined
by the following two equations:
5.1.1

5.1.2
where, xi is the mass fraction of component i.
ρ is the density of the solution,
ρi is the density of pure component i.
Equation 5.1.1 assumes that the total volume is the sum of the
individual volumes; Volume additivity is relatively accurate for solutions
of liquids with similar molecular structures.
The accuracy of equation 5.1.2 over equation 5.1.1 depends on
the system considered.

Example 5.1-1 Determination of a Solution Density
Determine the density in g/cm3 of a 50 wt% aqueous
solution of H2S04 at 20°C, both by
(1) looking up a tabulated value and
(2) assuming volume additivity of the solution components.

Answer: Strategy: To calculate the density of H2S04 and water
mixture, we will need the values of the densities of the pure
components of the liquid mixture.

834) = 1.3951)/l.998 + 0.3951] X 100% = 1.1.1-2 is better in this instance than that of Equation 5.29 .1-1 Determination of a Solution Density We then estimate from Equation 5.998 + 0. we could estimate the density from Equation 5.500/1.3951] X 100% = -7.834) cm3/g= 0.500 X 0.42 g/cm3 This leads to an estimation error of [(1.7736 cm3/g p= 1.29 g/cm3 This leads to an estimation error of [(1.Example 5.1-1: l/p = (0. .500/0.3%. Alternatively.5%.1-2: P = (0.1-1. Clearly.500 X 1.3951)/1.42-1. the accuracy of Equation 5.

Correlation: This is a mathematical fit of experimental data (usually using statistical methods). These three thermodynamic variables are easily measured and make up what is known as a PVT relationship. .Properties of Pure Ideal Components Incompressible: This term is used to specify the assumption of constant density of a material. Volume. and Temperature that exist inside a material (typically gas). These are used either in place of or in conjunction with physics based models. Incompressibility is closely followed by liquids and solids under many situations of interest. Equations of State (EOS): These are correlation or physically based equations that relate Pressure.

1 . The Ideal Gas Equation of State An equation of state relates the molar quantity and volume of a gas to temperature and pressure. The simplest and most widely used of these relationships is the ideal gas equation of state which usually appears in the form PV = nRT or PV  n RT 5.2.

The Ideal Gas Equation of State A gas whose PVT behavior is well represented by Equation 5. the gas particles can be treated as “point” particles).2-1 is said to behave as an ideal gas or a perfect gas. The ideal gas EOS is based on the primary assumptions that • There are no intermolecular forces between the gas particles. • The volumes of molecules are negligible (i.e. .

In an ideal gas mixture. thus its partial pressure is given by PAV= nART . This means that the pressure exerted by each component A is independent of the others. Ideal Gas Mixtures Imagine we have a gas mixture inside a container. We can then define: Partial Pressure (PA): This is the pressure. that the moles of gas A in the gas mixture would exert if the moles of gas A was all that was present in the container (at the same temperature T). vA. PA. that the moles of pure gas A would occupy at the total pressure P and temperature T of the mixture. the various gas molecules do not interact. Pure Component Volume (vA): This is the volume.

the partial pressures of the components of an ideal gas mixture add up to the total pressure (Dalton’s law). the partial pressure of a component in an ideal gas mixture is the mole fraction of that component times the total pressure. yA + yB +… = 1.2-7 That is. . pA + pB +… = (yA + yB +…)P = P 5. Ideal Gas Mixtures Dividing the second equation by PV = nRT yields p A nA   y A (the mole fraction of A in the P n gas mixture) or pA = yAP 5.2-8 Or. Since.

Dividing the PV= nRT vA nA   yA V n or vA = yAV 5. Ideal Gas Mixtures A similar series of calculations can be performed for pure components volumes: PvA = nA RT.2-9 vA + vB +… = V (Amagat’s Law) .

the molecules of which they are made must take up space also.  if molecules took up no space. In fact. Therefore there must be attractive forces between molecules. Since solids and liquids take up space. Non-ideal Gases  An ideal gas is a theoretical idea – in which there are no attractive forces between the molecules. and in which the molecules take up no space. then we could compress substances until they had no volume at all. Both of these assumptions are incorrect. since their molecules are basically touching each other. solids and liquids are almost incompressible. no substances would ever condense from the gas state to become liquids and solids.  if there were no attractive forces between molecules. . every substance does condense when it is cooled and compressed enough. In fact.

Tc. Pc. . Non-ideal Gases Critical Temperature (Tc) and Critical Pressure (Pc): The highest temperature at which a species can coexist in two phases (liquid and vapor) is the critical temperature of that species. and the corresponding pressure is the critical pressure.15°C and Pc = 218. Critical Point (Critical State) of a Fluid: A substance at Tc and Pc is said to be at its critical state. for water. Tc = 374. Supercritical Fluids: Substances at temperatures above Tc and pressures above Pc are referred to as supercritical fluids. Table B.l confirms that.3 atm.

Non-ideal Gases Reduced Pressure (Pr): This is the actual pressure of a fluid divided by its critical pressure. when compared at the same reduced temperature Tr and reduced pressure Pr . Pr = P/Pc Reduced Temperature (Tr): This is the actual temperature of a fluid divided by its critical temperature. Tr = T/Tc Law of Corresponding States: This is an empirically based principle that states that all fluids deviate from ideality in a similar fashion.

Non-ideal Gases Pitzer Accentric Factor (ω): This factor is a parameter used in non-ideal equations of state that takes into account the geometry and polarity of a molecule. .

V.  Methods for nonideal gases must be used to account for the effect of these interactions on the relationship between P. all real gases are nonideal.  At higher pressures and/or lower temperatures the impact of intermolecular interactions on gas behavior increases. EQUATIONS OF STATE FOR NONIDEAL GASES  Because in reality molecules of a gas do interact.  The ideal gas EOS may be a very good approximation at low pressures and high temperatures.  Below. Van der Waals Equation of State 3. the following three methods will be introduced: 1. and T (and related properties such as density) of a gas. Virial Equation of State 2. Soave-Redlich-Kwong (SRK) Equation of State .

third. Most often.1). and fourth virial coefficients. C. EQUATIONS OF STATE FOR NONIDEAL GASES Virial Equation of State The Virial Equation of State is an infinite power series in the inverse of the specific molar volume: where B. can be estimated from the following corresponding states correlations: Our text lists values for the Pitzer accentric factor in table 5. and D are functions of temperature and are known as the second.3-1 and for the critical pressure and temperature in Appendix B (table B. the virial EOS is truncated after the second term to simplify to: B. . respectively.

.8° C.150.Example 5. Taking the second estimate to be correct. Solution: From the ideal gas equation of state.3-1: Two gram-moles of nitrogen is placed in a three-liter tank at . Estimate the tank pressure using the ideal gas equation of state and then using the Virial equation of state truncated after the second term. calculate the percentage error that results from the use of the ideal gas equation at the system conditions.

Example 5.3-1: .

Example 5.3-1: .

and it remains useful for discussing deviations from ideal behavior. . the second term on the right accounts for attractive forces between molecules and b is a correction accounting for the volume occupied by the molecules themselves. In the van der Waals derivation. Cubic Equations of State Van der Waals Equation of State It is the earliest of these expressions.

Cubic Equations of State Soave-Redlich-Kwong (SRK) Equation of State The parameters of the SRK EOS are calculated from the following: .

58: A 5. Solution: .0m3 tank is charged with 75. Use the SRK equation of state to estimate the pressure in the tank. then calculate the percentage error that would result from the use of the ideal gas equation of state for the calculation.Exercise 5.0 kg of propane gas at 25°C.

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2. Pitzer acentric factor (Table 5. TEST YOURSELF 1. What physical properties of a species do you have to look up in order to use the SRK equation of state? Where can you find values of these properties in this text? Ans: Critical temperature and pressure (Table B.l).3-1) . Why is the SRK equation of state called a cubic equation of state? Ans: The equation to determine V for given values of T and P is a cubic equation.

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Solution . (c) the average molecular weight of the gas. 20% methane.25: An ideal gas mixture contains 35% helium.Exercise 5. (b) the mass fraction of methane. and (d) the density of the gas in kg/m3 .00 atm absolute and 90° C. Calculate (a) the partial pressure of each component. and 45% nitrogen by volume at 2.

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which evaporates most or all of the liquid. The resulting mist is contacted with hot air. all of which evaporates. The milk fed to the atomizer contains 70% water by mass.Exercise 5. . The outlet gas contains 12 mole% water and leaves the chamber at 83° C and 1 atm (absolute) at a rate of 311 m3/min. leaving the dried solids to fall to a conveyor belt at the bottom of the chamber. Powdered milk is produced in a spray dryer 6 m in diameter by 6 m high. Air enters at 167° C and -40 cm H2O.17: Spray drying is a process in which a liquid containing dissolved or suspended solids is injected into a chamber through a spray nozzle or centrifugal disk atomizer.

c) What problem would you guess would occur if the velocity is too high? .a) Calculate the production rate of dried milk and the volumetric flow rate of the inlet air. b) Estimate the upward velocity of air (m/s) at the bottom of the dryer.

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where it is burned with 8% excess air. Calculate the required flow rate of air in SCMH (standard cubic meters per hour).30: fuel gas containing 86% methane. .5. 8% ethane. and 6% propane by volume flows to a furnace at a rate of 1450 m3/h at 15° C and 150 kPa (gauge).

. 8% ethane. Calculate the required flow rate of air in SCMH (standard cubic meters per hour). where it is burned with 8% excess air. and 6% propane by volume flows to a furnace at a rate of 1450 m3/h at 15° C and 150 kPa (gauge).30: fuel gas containing 86% methane.5.