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**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

34

I

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-

CHEMICAL ENGINEERING WWW.CHE.COM JANUARY 2006

656 HYSYS -101. calculated by those various packages are identical (within the margin of simulation precision). °F u internal energy. The application of this definition is quite clear when the engineer LATENT HEAT MISCONCEPTIONS Unfortunately. Differing choices for the reference enthalpy not only account for seeming discrepancies in enthalpy values between sources. 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. Btu/lb λavg average latent heat.133 15.398 5. engineers commonly (and appropriately) use the simulator to flash the system at bubble point (vapor fraction = 0) or at a negligible vapor fraction. COMPARISON OF DIFFERENT SOURCES OF ENTHALPY AND LATENT HEAT ASME 21. When involved with simulations of pure component systems. In fact.909 -117.NOMENCLATURE Cp heat capacity. except for special cases such as azeotropes. Btu/lb V volume. For the engineer.00001. Because the vapor and liquid compositions of a pure-component system are in fact the same. the latent heats of vaporization) for the three simulation packages and ASME published data. which relates to saturated steam and water at 100 psig. latent-heat calculations for wide-boiling-range mixtures and for pure-component mixtures should be approached in different ways. as is to be expected. one simulation package’s reference enthalpy for a give compound may be its heat of formation at 25°C whereas another package’s reference enthalpy for that compound may be zero at 0°C. incoming and outgoing) that constitute a change in heat flow or enthalpy.868 Source hs of saturated steam at 100 psig. such as 0. Software tools display the enthalpy of the liquid at saturation point and the enthalpy of the first generated bubble. Btu/lb hs enthalpy of steam at dew point. it is based upon the integral of ideal-gas heat capacity function. Depending on the reference point and the actual operating conditions. Btu/h hStream2 enthalpy of Stream 2 in latent heat calculations. (The definition of “wide” in this context depends on the type of system and its components.b − hl. 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. Btu/h HStream1 heat flow of Stream 1.COM JANUARY 2006 . enthalpies obtained from simulations can be negative. hv. in Table 1. the changes of enthalpy. Btu/h hw enthalpy of water at dew point. Btu/h m flowrate. Btu/(lb)(°F) T temperature. Btu/lb ∆H change of heat of flow.566 15. zero or positive. The general equation for latent-heat calculation for a stream of liquid is normally expressed as follows. and m is the total mass flow. Btu/lb α vapor fraction αStream2 vapor fraction of Stream 2 in light-component latent heat calculations λ latent heat.860 ture from ideal-gas enthalpy hIG due to changes in pressure. Btu/h Hlatent latent heat flow. H2 is the heat flow at complete vaporization.566 15. h. Btu/lb PROII 21.832 Aspen Plus -102. Since enthalpy is an intensive property of the system. Btu/lb hw of saturated water at 100 psig. Btu/(lb)(°F) Cp. it is valid to determine the latent heat by subtracting the enthalpy of the liquid phase. Btu/h Hl.777 15. forgetting or not realizing that this equation is only applicable to onecomponent systems. where H1 is the heat flow at liquid saturation.b Pure-component systems (4) The latent heat. which accounts for deviation from ideal gas enthalpy based on changes in temperature.b enthalpy of a vapor bubble when a system is at bubble point. but confusion can arise when mixtures of wide boiling-point ranges are concerned. Btu/lb H heat flow.b. Btu/h HStream3 heat flow of Stream 3. Btu/lb hl.b enthalpy of liquid at bubble point. the composition of the liquid phase differs from that of the vapor phase at any vaporization point. For instance.avg average heat capacity. Btu/lb hStream1 enthalpy of Stream 1 in latent heat calculations. Btu/lb hIG ideal-gas enthalpy.273 -118.b. Btu/lb hv. Btu/lb hs – hw. As for f(T) in Equation (2). notice the differences in individual enthalpy values and the near equality among the enthalpy changes (that is. Btu/lb href reference enthalpy. psia s entropy. . Btu/h H2 heat flow of a system after complete vaporization or dew point. Btu/h HStream2 heat flow of Stream 2.222 5. Btu/lb ∆hIG enthalpy departure from idealgas enthalpy. such as the Peng-Robinson equation of state. from that of the vapor phase. hl.) In multicomponent systems. 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. at the bubble point: λ = hv. some engineers mistakenly apply Equation (4) to wideboiling-range multicomponent systems. lb/h or lb-mol/h P pressure. λ= H2 − H1 Hlatent = m m (3) TABLE 1. Btu/h H1 heat flow of a system after complete condensation or bubble point. Btu/h Hsensible sensible heat flow. Even though the individual enthalpy values thus differ between simulation packages. For example.Stream2 heat flow of the liquid phase of Stream 2. ft3 ∆h change of enthalpy. Btu/lb is handling one-component system.CHE. Following are two methods that each provide a valid way to employ a simulation package to calculate the latent 35 Wide boiling-point ranges CHEMICAL ENGINEERING WWW. Btu/ (lb)(°F) f(T) enthalpy function based on the integral of the ideal-gas heat-capacity function h enthalpy. but can also explain why such values can be negative. this departure is calculated by the simulator by means of the property package it employs.

5 and in the vapor phase is nearly 1. its specifics will be made more clear by the subsequent example: Step 1: Designate a material stream.b = (0. specify its composition and pressure. denoted as Stream 2. Thus.241. at bubble point (–26. which are –1.4°F) and atmospheric pressure. Consider an equal-mass-fraction system of two components.5)(–947. the mass fraction of propane in the liquid phase is 0. Two examples are also given. is the difference between the enthalpies of the two streams. as predicted by HYSYS. specify its composition and pressure. .b. m is the total flowrate.Stream2 is the vapor-phase heat flow of Stream 2. to represent the mixture in fully liquid phase at its bubble point.5)(–1241.3 = –1058. and assign it the desired vapor fraction (such as 5%) Step 3: Realize that the heat added to 36 the mixture to vaporize the specified fraction consists of two components: the latent heat flow used to generate that specified vapor fraction per se. light component Propane and heavy component n-hexane. Since propane is nearly the only component vaporized at the bubble point. in accordance with the logic represented by Figures 1 and 2. hv. In this case. representing the dew point. Hv. 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. In wide-boiling-point-range mixtures. 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. denoted as Stream 1.�������� ����������� Feature Report heat of a mixture whose components vary significantly in their boiling points. having the same composition and pressure as Stream 1. 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 –44°F and pure n-Hexane at –26. and Hv. At such conditions. the liquid phase enthalpy is approximated as the mass average of the pure component enthalpies: hl.0. it is desired to calculate the latent heat of the light components in a wide--boiling-point-range mixture.6) = –1. The light components are the first components to vaporize. as in Figure 1 �������� ������������� ���������������� ������ �������� ������ ��������������������� ��������� (5) Light-components latent heat procedure: In many situations. and the sensible heat Hsensible added to the vapor and liquid phases. the latent heat is calculated by the following two equations.6 Btu/lb respectively. This simulation diagram applies Equations (6) and (7).094.CHE. and assign it a vapor fraction of either zero (the bubble point) or a very small value Step 2: Designate a second stream.7 and –947. Step 4: Thus.Stream2 − HStream3 Note that the sensible heat of the CHEMICAL ENGINEERING WWW. λavg equals (Duty1 – Duty2)/(mα2) ��������� ����� ��������� ������������ FIGURE 2. having the same temperature and pressure as Stream 1 but having the composition of the liquid phase of Stream 2. the procedure is as follows: Step 1: Designate a material stream.Stream1 is the vapor phase (first bubble) heat flow of Stream 1: λ avg = HStream2 − HStream1 − Hsensible mα 2 vapor phase may be ignored. where the (negligible) sensible heat added to the vapor phase is ignored. denoted as Stream 3. 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. Here. denoted as Stream 1.7 + 183. Example 1: light and heavy (6) (7) Hsensible = Hl. Step 3: Since the composition of Stream 1 is equal to that of Stream 2. λ avg = HStream2 − HStream1 m = hStream2 − hStream1 �������� �������������� ������ �������� �������������� ������ �������� ����������������� ��������������������������� �������� ������������ ������ �������� ������ FIGURE 1. as it is negligible compared to that of the liquid phase. Hl.COM JANUARY 2006 . To calculate the sensible heat.7 Btu/lb The latent heat of propane at atmospheric pressure is 183. having the same composition and pressure as Stream 1 but assign a vapor fraction of 1.b = –1241. the temperature of the mixture keeps rising as more liquid is vaporized.Stream2 is the heat flow of the liquid phase of Stream 2.7) + (0. denoted as Stream 2. the enthalpy of the vapor. with sensible heat added to the vapor phase being ignored. designate a material stream. where 2 is the vapor fraction for Stream 2. This simulation diagram illustrates Equations (6) and (7).3 Btu/lb. is equal to the partial enthalpy of propane in the liquid plus the latent heat of propane: hv. which is based on Equation (3). and assign a vapor fraction of 0 (representing bubble point) Step 2: Designate a second stream. the latent heat.4 Btu/lb. 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).4°F.

LATENT HEAT CALCULATIONS COMPARISON �������������� OF EQUIMOLAR TWO-COMPONENT SYSTEMS AT 100 PSIA USING DIFFERENT SIMULATION TOOLS HYSYS Aspen Plus Propane. use of Equations (6) and (7) provides reasonable values. This point is illustrated by Figures 3 and 4. 3 and 4). has a higher mass latent heat than n-hexane.0 �������������� ��������� ���� ������ ���� ���� ���� ���� ���� ���� ���� ���� ���������������� FIGURE 4. PROII gives reasonable values even when one is using Equation (4).1 1. or –911. (In HYSYS and Aspen Plus. In general. This outcome arises because the reference enthalpy in PROII is set to zero at standard conditions for all components. (4).b – hl. light components have lower boiling points but higher massbased latent heats.b. Btu/h λ from Eq. however. two calculations methods Note from Table 2 that for purecomponent System 1.05.b does not equal (–1094. It can be seen that at a given pressure (such as 100 psia). which has a normal boiling point of 156°F. Logically.908 System 3 Propane. Btu/h Propane.TABLE 2. the latent heat required to vaporize 5% (mass basis) of any of Systems 2. In Table (3). the calculated latent heat using Equations (6) and (7) gets closer to match the propane latent heat shown in System 1. -188.05. The calculations were generated using the HYSYS Peng-Robinson property package. 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. heavy CHEMICAL ENGINEERING WWW. It is a common misconception that light components’ latent heats (on mass basis) are lower than those of heavy components. Btu/h l from Eq. In Systems 2. which would significantly minimize the errors in calculations using Equation (4).4 149. (6) and (7).2 154.993 System 4 Propane. that is. 3 and 4.9 146.1 154.000 System 2 Propane.5 PROII ��� ��� ��� ��� � Components λ from Eq. careful analysis of such semilogarithmic plots of vapor pressure against bubble point.COM JANUARY 2006 . Surprisingly at first. α = 0. on the other hand. C30 paraf. whereas using Equation (4) provides totally incorrect results. n-Hexane 40.6 153. which differs greatly from one component to another.1 154. p-Xylene -603. α � 0. the light component is propane.7) = 36. Propane pressure-enthalpy curve ��� ������������ ��������� TABLE 3. the enthalpy of a component at standard conditions is taken as the enthalpy of formation for that compound. they require more heat to vaporize per unit of mass. it is not recommended to blindly use Equation (4) in PROII. application of Equation (4) to calculate the latent heat of propane gives = hv. implying that cooling is required to achieve vaporization! Note also that as the propane mass fraction in the vapor phase increases. propane.CHE.4 Btu/lb To further emphasize the point. p-Xylene -605. and Equations (6) and (7) together — for a one-component system (System 1) and for three two-component systems (Systems 2.b = –1058. Table (2) shows a comparison of the latent heat calculated in two ways — namely. (6) & (7). For multicomponent Systems 2. and try to utilize other sources. the results are compared using different simulation tools. which is totally incorrect.) Nevertheless. be- cause the enthalpies of the components may differ greatly in other systems.4 149. in System 1. 3 and 4.8 0. Some of these lastnamed values are negative. hv. which has a normal boiling point of –44°F. So even though the light components in a mixture of hydrocarbons vaporize first.7 + 183.2 0. 154. that alkane is the sole component. the latent heat calculation using either Equation (4) or Equations (6) and (7) yield the same value. n-Hexane pressure-enthalpy curve It is important to emphasize the enthalpy of the vapor. resulting in very close enthalpies among the components at other conditions.2 Propane.4 – (–1094. using Equations (4) alone. Example 2. (4). is not equal to the enthalpy of the liquid (propane plus hexane) plus the latent heat of vaporized components. α = 0.3).1 Btu/lb. As a result of this misconception about relative latent heats. p-Xylene -603. for hydrocarbon streams. p-Xylene 156. engineers sometimes consider relevant simulation results inaccurate.4 1. hv. LATENT-HEAT CALCULATION COMPARISON FOR ONE-COMPONENT SYSTEM AND DIFFERENT EQUIMOLAR TWO-COMPONENT SYSTEMS AT 100 PSIA System 1 Components λ from Eq. (In fact.000 �������������� ��� ��� ��� ��� ��� ��� ��� � ������������ ��������� ����������� ����������� ������ ������ ������ ������ ������ ������ ������ ���� ���� ���������������� FIGURE 3.3 Btu/lb. Btu/h Propane mass fraction in vapor Propane 154. showing HYSYS-generated pressure-enthalpy envelopes for propane and hexane. 38) 37 Light vs. molecular weight and latent heat shows that light components identified by lower molecular weight have higher mass-based latent heat. such as Cox charts published by the American Petroleum Institute. by contrast.) (Continues on p.

If the engineer desires. including heat balances that involve significant change in pressure. L4V 1W1. especially for distillation. Ont. This approach leads to excessively oversized relief valves. for moderate changes in temperature at atmospheric pressure and assuming an average Cp. design and project experience with major multinational operating firms. the approach of taking the difference of enthalpies of the vapor and liquid phases at a specific vaporization point is incorrect. Stone & Webster and Bantrel. (9) The first term of the right side of Equation (9) represents CpdT. these may however give a higher volumetric relief load when compensated by the molecular weight. Equation (8) is valid for ideal conditions. Unilever and Syncrude. But when a significant change of pressure is observed in the system. He has published several papers in international journals and is a registered professional engineer in Ontario. Mississauga. Mississauga. Thus. Currently. This approach gives a far more accurate indication of the required relief valve size. the second term in the right hand side of this equation is 38 CHEMICAL ENGINEERING WWW. generated using data from HYSYS sample file R-1. 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. (Bechtel Group) in Toronto. Latent heat and volumetric relief load of crude oil.hsc. email: inderrattan@sympatico. see Sizing Safety-relief Valves for Any Conditions. Equation (8) may become outright inaccurate. Edited by Nicholas P. there is much diversity among the methods used to calculate the latent heat of multicomponent hydrocarbon systems. 0. however. To ensure calculating relief loads that are neither excessive nor underestimated. the latent heat should be determined for incremental vaporization points of the system. Suite 900.* As shown above. Equation (9) reduces to Equation (8). Ontario. ca His 34 year career has included in-depth operating. and could be extended to non-ideal conditions with less accuracy. Phone: 905362-6712. However. At ideal conditions. Very commonly. such as in relief load calculations. Bantrel is a major Canadian EPC company (5925 Airport Road.. Fax: 905-607-7724. generated using data from HYSYS sample file gstrt-ss. He is a registered professional engineer in Ontario and holds a bachelor’s degree from the University of Toronto and a master of science degree from the University of Western Ontario. as well as with engineering-procurement-construction companies. pp. AspenTech and Bantrel. among them Exxon (now part of ExxonMobil) .CHE. at ideal conditions. 42–50. stripping or absorption towers. Inder Rattan is an independent consultant (5199 Forest Hill Drive. Latent heat and volumetric relief load of propylene glycol reactor contents. He holds baccalaureate and master’s degree from the Indian Institute of Technology . which generates lower vapor relief loads on a mass basis.2389 of 12-C3 diol and 0. This diversity can result in significantly different relief loads calculated for a given system. The reason is that Equation (8) is solely a simplification of Equation (9) the fundamental thermodynamic relationship that defines the relationship between enthalpy. among them Stearns-Roger. email: zeidana@bantrel. pressure and temperature: dh = ∂h dT + ∂h dP ∂T P ∂P T Authors Abdelsalam Zeidan is a process engineer with Bantrel Co. Phone: 905607-7719. Abdelsalam is a process engineer at Bantrel’s Toronto office. 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. such as Hyprotech. September 2005. �������������������������� FIGURE 6. A common fault in this vein consists of using Equation (8) indiscriminately at all scenarios. CE.avg ∆T CpT misconceptions (8) usually assumed zero since the change of enthalpy per unit of pressure is very small. engineers apply the above equation to a given enthalpy at a certain temperature in order to calculate new enthalpy at a different temperature. it is advised to use Equation (9). in the field of simulation of chemical and biochemical processes. Molar composition is 0.COM JANUARY 2006 ����������������������������� ����������� ����������� ����������������������������� �� ����� ��� ��� ��� ��� ��� ��� ��� ��� ��� � � . the calculations are sometimes made using the numerically high latent heat of very light components. Still the process engineer needs to be aware that this generalization may not always hold.hsc. *For a detailed review of other methods.avg is the average heat capacity at a constant pressure. at non-ideal conditions and for significant changes in pressure. Chopey where Cp.����� ����� ����� ����� ����� ����� ��� ��� ��� ��� � ������������������� �� �� �� �� �� � � ����� ������������������� ��� ��� ��� ��� � � ��� ��� ��� ����������� ����������� � ��� ��� ��� ��� � ��� �������������������������� FIGURE 5.0116 of 12-C3 oxide. as can be see in Figures 5 and 6. And as emphasized earlier. L5M 5A5.com) His career has included developing thermodynamics engines and modeling refinery and chemical processes for multinational simulation and engineering companies. New Delhi. Or. Equation (8) can then be used as a rough tool to ■ check the simulation results. by means of simulation tools such as the ones mentioned in this article. The volumetric relief load (or relief valve size) should then be calculated using the properties of the vapor generated at each of the increments. Fax 905-362-6767.0151 of methanol Latent heat is a key variable in some approaches to the calculations of pressure-relief-valve loads.7344 water. 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. 0.

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