Feature Report

Applying Thermo? Then Guard Against Misconceptions

n process engineering and design, thermodynamics theory is applied to real and complex chemical-process applications. Software design simulators, such as HYSYS, PROII and Aspen Plus, serve as powerful tools that simplify process thermodynamic calculations. They eliminate the need for the engineer to solve complex differential equations, and they allow the application of variety of property packages to the modeling of unit operations. In a highly competitive setting where time and technical competency are critical, the proper and accurate use of these simulation tools can be of great value. However, an overreliance on simulation can lull the user into a disregard for the underlying engineering principles. Conversely, a lack of solid engineering knowledge can induce the user to reject some simulation results that are, in fact, fully valid. In either case, among the most serious consequences can be flaws in the relevant material and energy balances, which are fundamental to a valid design. Consequent errors in the front-end design can lead to major engineering-revision costs, if they are detected in the detailed engineering phase; and if they are not detected there, then the consequences for the project and plant can of course be far more grave. There are several misconceptions concerning thermodynamic calculations related to material and energy balances that tend to rise especially
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Abdelsalam Zeidan Bantrel Co. (Bechtel Group) and Inder Rattan Consultant

Simulation packages are highly valuable. But let neither a blind reliance on, nor an unfounded distrust of, their results lead you into errors, let alone into lapses of common sense
often. These are addressed below. As the reader will see, some of the misconceptions are due simply to a failure to apply common sense. In thermodynamics, a system of a set composition is defined by any two of three basic properties: pressure, P, volume, V and temperature, T. In place of any of these properties can be substituted internal energy, u, enthalpy, h, or entropy, s. In this article, properties defined per unit mass or unit mole (namely, intensive properties) are denoted by small letters, while extensive properties are denoted by capital letters. For example, enthalpy (an intensive property) is denoted as h, whereas heat flow (an extensive property) is denoted as H. See the Nomenclature box for definitions of other terms . ances over distillation towers, flash vessels and reactors. Another misconception is that enthalpy values cannot be negative. Engineers obtaining heat-flow curves from simulators for heat-exchangerdesign sometimes change the negative sign in front of a heat-flow value to positive, believing that they are correcting a value that was misreported. Others simply disregard negative values, thinking that they are unrealistic. It is not uncommon for an engineer to compare an enthalpy value from a given simulation against one from a different simulation or a published table and to be disturbed upon finding a seeming discrepancy. In most cases, however, the reason for the difference is very simple; it lies in the choice of reference enthalpy, href. Different simulator or published data sources may well employ different reference enthalpies. The enthalpy of a given component at a given set of process conditions is calculated by the simulator on the basis of isotherms and isobars, as shown in the following two equations:
h = h IG + h IG h IG = h ref + f (T )

Setting the stage

In applied engineering thermodynamics, the absolute values of enthalpy or heat flow are not generally important; instead, the value of interest is almost always the change, H or mh, where m is either the molar or the mass flowrate. For example, it is the change in heat flow or enthalpy that defines heat exchangers duties, as well as the enthalpy or heat bal-

ENTHALPY MISCONCEPTIONS

(1) (2)

Here, hIG is the enthalpy depar-

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NOMENCLATURE
Cp heat capacity, Btu/(lb)(F) Cp,avg average heat capacity, Btu/ (lb)(F) f(T) enthalpy function based on the integral of the ideal-gas heat-capacity function h enthalpy, Btu/lb href reference enthalpy, Btu/lb hIG ideal-gas enthalpy, Btu/lb hl,b enthalpy of liquid at bubble point, Btu/lb hs enthalpy of steam at dew point, Btu/lb hStream1 enthalpy of Stream 1 in latent heat calculations, Btu/h hStream2 enthalpy of Stream 2 in latent heat calculations, Btu/h hw enthalpy of water at dew point, Btu/lb hv,b enthalpy of a vapor bubble when a system is at bubble point, Btu/lb H heat flow, Btu/h H1 heat flow of a system after complete condensation or bubble point, Btu/h H2 heat flow of a system after complete vaporization or dew point, Btu/h Hlatent latent heat flow, Btu/h Hsensible sensible heat flow, Btu/h HStream1 heat flow of Stream 1, Btu/h HStream2 heat flow of Stream 2, Btu/h Hl,Stream2 heat flow of the liquid phase of Stream 2, Btu/h HStream3 heat flow of Stream 3, Btu/h m flowrate, lb/h or lb-mol/h P pressure, psia s entropy, Btu/(lb)(F) T temperature, F u internal energy, Btu/lb V volume, ft3 h change of enthalpy, Btu/lb hIG enthalpy departure from idealgas enthalpy, Btu/lb H change of heat of flow, Btu/lb vapor fraction Stream2 vapor fraction of Stream 2 in light-component latent heat calculations latent heat, Btu/lb avg average latent heat, Btu/lb

is handling one-component system, but confusion can arise when mixtures of wide boiling-point ranges are concerned. In fact, latent-heat calculations for wide-boiling-range mixtures and for pure-component mixtures should be approached in different ways. The general equation for latent-heat calculation for a stream of liquid is normally expressed as follows, where H1 is the heat flow at liquid saturation, H2 is the heat flow at complete vaporization, and m is the total mass flow.
=
H2 H1 Hlatent = m m

(3)

TABLE 1. COMPARISON OF DIFFERENT SOURCES

OF ENTHALPY AND LATENT HEAT

ASME 21,222 5,566 15,656 HYSYS -101,909 -117,777 15,868

Source hs of saturated steam at 100 psig, Btu/lb hw of saturated water at 100 psig, Btu/lb hs hw, Btu/lb

PROII 21,398 5,566 15,832

Aspen Plus -102,273 -118,133 15,860

ture from ideal-gas enthalpy hIG due to changes in pressure; this departure is calculated by the simulator by means of the property package it employs, such as the Peng-Robinson equation of state. As for f(T) in Equation (2), it is based upon the integral of ideal-gas heat capacity function, which accounts for deviation from ideal gas enthalpy based on changes in temperature. Differing choices for the reference enthalpy not only account for seeming discrepancies in enthalpy values between sources, but can also explain why such values can be negative. For example, one simulation packages reference enthalpy for a give compound may be its heat of formation at 25C whereas another packages reference enthalpy for that compound may be zero at 0C. Depending on the reference point and the actual operating conditions, enthalpies obtained from simulations can be negative, zero or positive. For the engineer, the moral of the story is that he or she should take care to use the same software tool or refer-

ence table for calculations of both of the values (for instance, incoming and outgoing) that constitute a change in heat flow or enthalpy. Even though the individual enthalpy values thus differ between simulation packages, the changes of enthalpy, h, calculated by those various packages are identical (within the margin of simulation precision), as is to be expected. For instance, in Table 1, which relates to saturated steam and water at 100 psig, notice the differences in individual enthalpy values and the near equality among the enthalpy changes (that is, the latent heats of vaporization) for the three simulation packages and ASME published data.

When involved with simulations of pure component systems, engineers commonly (and appropriately) use the simulator to flash the system at bubble point (vapor fraction = 0) or at a negligible vapor fraction, such as 0.00001. Software tools display the enthalpy of the liquid at saturation point and the enthalpy of the first generated bubble. Since enthalpy is an intensive property of the system, the difference between the vapor and liquid enthalpies has no physical meaning unless the liquid and vapor compositions upon which each enthalpy is based are the same. Because the vapor and liquid compositions of a pure-component system are in fact the same, it is valid to determine the latent heat by subtracting the enthalpy of the liquid phase, hl,b, from that of the vapor phase, hv,b, at the bubble point:
= hv,b hl,b

Pure-component systems

(4)

The latent heat, , of a pure component at a given pressure is the amount of heat required to vaporize one unit mass of the component in liquid form at that pressure. The application of this definition is quite clear when the engineer

LATENT HEAT MISCONCEPTIONS

Unfortunately, some engineers mistakenly apply Equation (4) to wideboiling-range multicomponent systems, forgetting or not realizing that this equation is only applicable to onecomponent systems. (The definition of wide in this context depends on the type of system and its components.) In multicomponent systems, the composition of the liquid phase differs from that of the vapor phase at any vaporization point, except for special cases such as azeotropes. Following are two methods that each provide a valid way to employ a simulation package to calculate the latent
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Wide boiling-point ranges

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Feature Report
heat of a mixture whose components vary significantly in their boiling points. Two examples are also given. Total latent heat procedure: The total latent heat of a mixture with wide-boiling-point range can be defined as the heat required to vaporize the entire system divided by the mass contained in the system at a given pressure. This heat-requirement value is readily provided as a stream property by the simulator when the composition and pressure are defined or could be calculated using the following procedure, which is based on Equation (3); its specifics will be made more clear by the subsequent example: Step 1: Designate a material stream, denoted as Stream 1, to represent the mixture in fully liquid phase at its bubble point; specify its composition and pressure, and assign a vapor fraction of 0 (representing bubble point) Step 2: Designate a second stream, denoted as Stream 2, having the same composition and pressure as Stream 1 but assign a vapor fraction of 1, representing the dew point. Step 3: Since the composition of Stream 1 is equal to that of Stream 2, the latent heat, , is the difference between the enthalpies of the two streams.
avg =
HStream2 HStream1 m = hStream2 hStream1

FIGURE 1. This simulation diagram applies Equations (6) and (7), where the (negligible) sensible heat added to the vapor phase is ignored. Here, avg equals (Duty1 Duty2)/(m2)

FIGURE 2. This simulation diagram illustrates Equations (6) and (7), with sensible heat added to the vapor phase being ignored, as in Figure 1

(5)

Light-components latent heat procedure: In many situations, it is desired to calculate the latent heat of the light components in a wide--boiling-point-range mixture. The light components are the first components to vaporize, so the latent heat is determined by vaporizing the small percentage of the liquid that yields the desired vapor fraction (such as 5% vaporization on a mass basis). In this case, the procedure is as follows: Step 1: Designate a material stream, denoted as Stream 1; specify its composition and pressure, and assign it a vapor fraction of either zero (the bubble point) or a very small value Step 2: Designate a second stream, denoted as Stream 2, having the same composition and pressure as Stream 1, and assign it the desired vapor fraction (such as 5%) Step 3: Realize that the heat added to
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the mixture to vaporize the specified fraction consists of two components: the latent heat flow used to generate that specified vapor fraction per se, and the sensible heat Hsensible added to the vapor and liquid phases. In wide-boiling-point-range mixtures, the temperature of the mixture keeps rising as more liquid is vaporized. Sensible heat can be viewed as the heat required for the temperature of the system to progress towards the boiling point of the mixture at given vaporization point. To calculate the sensible heat, designate a material stream, denoted as Stream 3, having the same temperature and pressure as Stream 1 but having the composition of the liquid phase of Stream 2. Step 4: Thus, in accordance with the logic represented by Figures 1 and 2, the latent heat is calculated by the following two equations, where 2 is the vapor fraction for Stream 2, m is the total flowrate, Hv,Stream2 is the vapor-phase heat flow of Stream 2, Hl,Stream2 is the heat flow of the liquid phase of Stream 2, and Hv,Stream1 is the vapor phase (first bubble) heat flow of Stream 1:
avg =
HStream2 HStream1 Hsensible m 2

vapor phase may be ignored, as it is negligible compared to that of the liquid phase. Consider an equal-mass-fraction system of two components, light component Propane and heavy component n-hexane, at bubble point (26.4F) and atmospheric pressure. At such conditions, the mass fraction of propane in the liquid phase is 0.5 and in the vapor phase is nearly 1.0. The partial enthalpies of the two components in the liquid phase (for Stream 1 in the total-latent-heats calculation procedure outlined above) are approximated as the enthalpy of pure propane at its bubble point of 44F and pure n-Hexane at 26.4F, which are 1,241.7 and 947.6 Btu/lb respectively, as predicted by HYSYS. Thus, the liquid phase enthalpy is approximated as the mass average of the pure component enthalpies: hl,b = (0.5)(1241.7) + (0.5)(947.6) = 1,094.7 Btu/lb The latent heat of propane at atmospheric pressure is 183.3 Btu/lb. Since propane is nearly the only component vaporized at the bubble point, the enthalpy of the vapor, hv,b, is equal to the partial enthalpy of propane in the liquid plus the latent heat of propane: hv,b = 1241.7 + 183.3 = 1058.4 Btu/lb.

Example 1: light and heavy

(6) (7)

Hsensible = Hl,Stream2 HStream3

Note that the sensible heat of the

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TABLE 2. LATENT-HEAT CALCULATION COMPARISON FOR ONE-COMPONENT SYSTEM AND DIFFERENT EQUIMOLAR TWO-COMPONENT SYSTEMS AT 100 PSIA System 1 Components from Eq. (4), Btu/h from Eq. (6) & (7), = 0.05, Btu/h Propane mass fraction in vapor Propane 154.1 154.1 1.000 System 2 Propane, n-Hexane 40.9 146.8 0.908 System 3 Propane, p-Xylene -603.4 149.2 0.993 System 4 Propane, C30 paraf. -188.2 154.4 1.000

FIGURE 3. Propane pressure-enthalpy curve

TABLE 3. LATENT HEAT CALCULATIONS COMPARISON

OF EQUIMOLAR TWO-COMPONENT SYSTEMS AT 100 PSIA USING DIFFERENT SIMULATION TOOLS

HYSYS Aspen Plus Propane, p-Xylene -605.6 153.5 PROII

Components from Eq. (4), 0, Btu/h l from Eq. (6) and (7), = 0.05, Btu/h

Propane, p-Xylene -603.4 149.2

Propane, p-Xylene 156.1 154.0

FIGURE 4. n-Hexane pressure-enthalpy curve

It is important to emphasize the enthalpy of the vapor, hv,b, is not equal to the enthalpy of the liquid (propane plus hexane) plus the latent heat of vaporized components; that is, hv,b does not equal (1094.7 + 183.3), or 911.4 Btu/lb To further emphasize the point, application of Equation (4) to calculate the latent heat of propane gives = hv,b hl,b = 1058.4 (1094.7) = 36.3 Btu/lb, which is totally incorrect.

Table (2) shows a comparison of the latent heat calculated in two ways namely, using Equations (4) alone, and Equations (6) and (7) together for a one-component system (System 1) and for three two-component systems (Systems 2, 3 and 4). The calculations were generated using the HYSYS Peng-Robinson property package. In Systems 2, 3 and 4, the light component is propane; in System 1, that alkane is the sole component. Logically, the latent heat required to vaporize 5% (mass basis) of any of Systems 2, 3 and 4 should be equivalent or close to the latent heat of propane (System 1) because the vapor generated consists mainly consist of that component.

Example 2; two calculations methods

Note from Table 2 that for purecomponent System 1, the latent heat calculation using either Equation (4) or Equations (6) and (7) yield the same value, 154.1 Btu/lb. For multicomponent Systems 2, 3 and 4, on the other hand, use of Equations (6) and (7) provides reasonable values, whereas using Equation (4) provides totally incorrect results. Some of these lastnamed values are negative, implying that cooling is required to achieve vaporization! Note also that as the propane mass fraction in the vapor phase increases, the calculated latent heat using Equations (6) and (7) gets closer to match the propane latent heat shown in System 1. In Table (3), the results are compared using different simulation tools. Surprisingly at first, PROII gives reasonable values even when one is using Equation (4). This outcome arises because the reference enthalpy in PROII is set to zero at standard conditions for all components, resulting in very close enthalpies among the components at other conditions, which would significantly minimize the errors in calculations using Equation (4). (In HYSYS and Aspen Plus, by contrast, the enthalpy of a component at standard conditions is taken as the enthalpy of formation for that compound, which differs greatly from one component to another.) Nevertheless, it is not recommended to blindly use Equation (4) in PROII, be-

cause the enthalpies of the components may differ greatly in other systems. It is a common misconception that light components latent heats (on mass basis) are lower than those of heavy components. In general, for hydrocarbon streams, light components have lower boiling points but higher massbased latent heats. So even though the light components in a mixture of hydrocarbons vaporize first, they require more heat to vaporize per unit of mass. This point is illustrated by Figures 3 and 4, showing HYSYS-generated pressure-enthalpy envelopes for propane and hexane. It can be seen that at a given pressure (such as 100 psia), propane, which has a normal boiling point of 44F, has a higher mass latent heat than n-hexane, which has a normal boiling point of 156F. As a result of this misconception about relative latent heats, engineers sometimes consider relevant simulation results inaccurate, and try to utilize other sources, such as Cox charts published by the American Petroleum Institute. (In fact, however, careful analysis of such semilogarithmic plots of vapor pressure against bubble point, molecular weight and latent heat shows that light components identified by lower molecular weight have higher mass-based latent heat.) (Continues on p. 38)
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Light vs. heavy

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FIGURE 5. Latent heat and volumetric relief load of crude oil, generated using data from HYSYS sample file R-1.hsc.

FIGURE 6. Latent heat and volumetric relief load of propylene glycol reactor contents, generated using data from HYSYS sample file gstrt-ss.hsc. Molar composition is 0.7344 water, 0.0116 of 12-C3 oxide, 0.2389 of 12-C3 diol and 0.0151 of methanol

Latent heat is a key variable in some approaches to the calculations of pressure-relief-valve loads, especially for distillation, stripping or absorption towers.* As shown above, however, there is much diversity among the methods used to calculate the latent heat of multicomponent hydrocarbon systems. This diversity can result in significantly different relief loads calculated for a given system. And as emphasized earlier, the approach of taking the difference of enthalpies of the vapor and liquid phases at a specific vaporization point is incorrect. An alternate approach sometimes taken consists of using the numerically lower latent heat of heavy components while using the vapor properties of the light components. This approach leads to excessively oversized relief valves. Or, the calculations are sometimes made using the numerically high latent heat of very light components, which generates lower vapor relief loads on a mass basis; these may however give a higher volumetric relief load when compensated by the molecular weight. Still the process engineer needs to be aware that this generalization may not always hold. To ensure calculating relief loads that are neither excessive nor underestimated, the latent heat should be determined for incremental vaporization points of the system. The volumetric relief load (or relief valve size) should then be calculated using the properties of the vapor generated at each of the increments. This approach gives a far more accurate indication of the required relief valve size.
*For a detailed review of other methods, see Sizing Safety-relief Valves for Any Conditions, CE, September 2005, pp. 4250.

Latent heat and relief load

Plotting both the latent heat and the volumetric relief load against vapor fraction on the same graph (using two scales for the vertical axis) provides a revealing picture of the maximum relief point that should be considered, as can be see in Figures 5 and 6. The heating duty across heat exchangers and the enthalpy at relief conditions could be calculated using the basic and well-known equation
h = C p,avg T

CpT misconceptions

(8)

usually assumed zero since the change of enthalpy per unit of pressure is very small. Thus, at ideal conditions, for moderate changes in temperature at atmospheric pressure and assuming an average Cp, Equation (9) reduces to Equation (8). However, at non-ideal conditions and for significant changes in pressure, it is advised to use Equation (9), by means of simulation tools such as the ones mentioned in this article. If the engineer desires, Equation (8) can then be used as a rough tool to check the simulation results. Edited by Nicholas P. Chopey

where Cp,avg is the average heat capacity at a constant pressure. Very commonly, engineers apply the above equation to a given enthalpy at a certain temperature in order to calculate new enthalpy at a different temperature. A common fault in this vein consists of using Equation (8) indiscriminately at all scenarios, including heat balances that involve significant change in pressure, such as in relief load calculations. Equation (8) is valid for ideal conditions, and could be extended to non-ideal conditions with less accuracy. But when a significant change of pressure is observed in the system, Equation (8) may become outright inaccurate. The reason is that Equation (8) is solely a simplification of Equation (9) the fundamental thermodynamic relationship that defines the relationship between enthalpy, pressure and temperature:
dh = h dT + h dP T P P T

Authors
Abdelsalam Zeidan is a process engineer with Bantrel Co. (Bechtel Group) in Toronto. Bantrel is a major Canadian EPC company (5925 Airport Road, Suite 900, Mississauga, Ont., L4V 1W1. Phone: 905362-6712; Fax 905-362-6767; email: zeidana@bantrel.com) His career has included developing thermodynamics engines and modeling refinery and chemical processes for multinational simulation and engineering companies, such as Hyprotech, AspenTech and Bantrel. Currently, Abdelsalam is a process engineer at Bantrels Toronto office. He is a registered professional engineer in Ontario and holds a bachelors degree from the University of Toronto and a master of science degree from the University of Western Ontario, in the field of simulation of chemical and biochemical processes. Inder Rattan is an independent consultant (5199 Forest Hill Drive, Mississauga, Ontario, L5M 5A5. Phone: 905607-7719; Fax: 905-607-7724; email: inderrattan@sympatico. ca His 34 year career has included in-depth operating, design and project experience with major multinational operating firms, among them Exxon (now part of ExxonMobil) , Unilever and Syncrude, as well as with engineering-procurement-construction companies, among them Stearns-Roger, Stone & Webster and Bantrel. He has published several papers in international journals and is a registered professional engineer in Ontario. He holds baccalaureate and masters degree from the Indian Institute of Technology , New Delhi.

(9)

The first term of the right side of Equation (9) represents CpdT. At ideal conditions, the second term in the right hand side of this equation is

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