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**Martin Ruszkowski, Vianey Garcia-Osorio, and B. Erik Ydstie
**

Chemical Engineering Dept., Carnegie Mellon University, 5000 Forbes Avenue, Pittsburgh, PA 15213 DOI 10.1002/aic.10543 Published online September 13, 2005 in Wiley InterScience (www.interscience.wiley.com).

Inventory control is based on the idea manipulating process ﬂows so that the inventories follow their set points. The operator mapping ﬂows to inventories in a coarse grained (macroscopic) system is passive and any input strictly passive (ISP) feedback controller can, therefore, be used to achieve input-output stability. Examples of ISP controllers include the PID controller, parameter adaptive feedforward control, optimal controllers and many nonlinear and gain scheduling controllers. Input-output stability and convergence of inventories, such as total mass and energy can be used to show that other internal state variables are bounded and belong to an invariant set. However, this does not necessarily imply convergence of all state variables to stationary valves because a stabilizability condition, known as strict state passivity, must be satisﬁed. The 2nd law of thermodynamics is used to develop sufﬁcient conditions for strict state passivity in the space of intensive variables. The theory relies on following two assumptions concerning nonequilibrium systems: (1) The hypothesis of local equilibrium, and (2) That a local entropy is deﬁned using semiclassical statistical mechanics. These assumptions allow us to deﬁne a local entropy function for the coarse grained system which is homogeneous degree one, concave, and has positive temperature. Subject to these conditions stability theory is developed for conjugate variables, such as temperature, pressure and chemical potential in inﬁnite dimensional reaction-diffusion-convection systems. In classical irreversible thermodynamics this type of analysis assumes linearity and symmetry of transport relations. The use of Gibbs tangent plane condition allows us to deﬁne a Lyapunov like storage function for passivity design, which gives stability criteria for nonlinear problems. The resulting sufﬁcient condition for stability can be expressed in terms of dimensionless groups, similar to the (second) Damkohler number. Simple simulation examples illustrate the application of the theory. © 2005 American Institute of Chemical Engineers

AIChE J, 51: 3147-3166, 2005

Keywords: process control, coarse graining, distributed parameter system, irreversible thermodynamics, feedback, passivity, invariant set, stability, entropy, reciprocity relations, nonlinear, convexity, minimum entropy production.

Introduction

In the context of control of distributed parameter systems in chemical engineering, four main categories of control problems

Correspondence concerning this article should be addressed to B. E. Ydstie at ydstie@andrew.cmu.edu.

© 2005 American Institute of Chemical Engineers

and their applications were reviewed by Christoﬁdes (2001).1 They included (1) control of spatial proﬁles with application to packed-bed reactors, CVD and etching, (2) control of size distributions with applications in aerosol production, crystallization and emulsion polymerization, (3) control of ﬂuid ﬂows with application in ﬂuid mixing, wave suppression and drag reduction, and (4) control of material microstructures with applications for thin ﬁlm growth and nanostructured coatings.

Vol. 51, No. 12 3147

AIChE Journal

December 2005

This work expands on the list since the objective is to control inventories by adjusting ﬂows. The inventory of a transportreaction process (TRP) is an integral measure that represents physical properties like total mass, energy or the holdup of a chemical constituent. The inventory is controlled by adjusting the ﬂows at the boundary or the reaction rate. Inventory control is closely related to mass and energy balance control (Buckley, 1964; Shinskey, 1967),2,3 and extensive variable control (Georgakis, 1986).4 The method was developed to its ﬁnal form by Farschman et al. (1998)5 who used Lyapunov theory to show that inventory control systems with PID feedback are indeed input-output stable. In this current article we show that the inventory control method can be applied to coarse-grained TRPs using strictly input passive feedback control. We also show that latent (intensive) variables like temperature, pressure and chemical potentials converge. A distinctive feature of the control problem at hand is that control may only be possible at one or only a few points at the boundary. Examples where this type of control may ﬁnd application include: plasma etching for microelectronics processing, moving and ﬁxed-bed reactors for chemical and metallurgical processes, bioreactors, membrane and hollow ﬁber reactors for nanoprocessing. Many methods have been proposed for control of TRPs (Ray, 1978; Christoﬁdes, 2001).6,1 In one approach the partial differential equations are spatially discretized to form large systems of ordinary differential equations using the method of lines. Controllers can then be synthesized using classical theory like pole placement, linear quadratic or model predictive control. However, neglecting the inﬁnite dimensional nature of the original system may lead to erroneous conclusions concerning the stability, controllability and observability properties of the system since the number of modes required to derive a ﬁnite dimensional ODE systems that yields a desired degree of approximation can in fact be very large (Aling et al., 1998; Balas, 1986; Christoﬁdes, 2000).7,8,9 Methods have been developed to reduce the dimensionality of the system before the controllers and observers are synthesized to reduce the complexity of the controller design. One very natural framework for deriving low-dimensional ODE systems that accurately reproduce their solution is based on the concept of inertial and approximate inertial manifolds (IM/ AIM). The IM appears as the dominant solution to a highdimensional input-output system under feedback when all but very few modes are heavily damped. In such systems the high-order dynamics dissipate and control only need to take effect in a low dimensional space. For example, the dynamics of a parabolic PDE system is restricted on an inertial manifold described by a set of ODEs (Temam, 1988; Brown et al., 1990; Smoller, 1996).10,11,12 Systematic methods for the derivation of the inertial form has been proposed by Deane et al., 1991; Christoﬁdes and Daoutides (1997), and Kazantzis and Good (2003).13,14,15 The Lyapunov method for control system design is based on the idea of deﬁning an energy related function which captures the dynamics of the state and choosing a controller to make the energy function decrease. A review of this approach applied to ﬁnite dimensional systems can be found in the books by Slotine and Li (1992) and Sontag (1998).16,17 The method has been applied to control for robust control of PDE systems (Christoﬁdes and Daoutidis, 1998, and Christoﬁdes, 1998).18,19 More

3148 December 2005

recently El-Farra (2003)20 extended the method to cover systems with input constraints, whereas Kazanzis and Kravaris (1999)21 related the energy based method to predictive control. Sliding mode control (Palazoglu and Owens, 1987; Hanczyc and Palazoglu, 1995; Sira-Ramirez, 1989)22,23,24 has been applied to control TRPs. The main idea behind this technique is to let a discontinuous feedback controller deﬁne a so-called sliding surface on which the system has desirable behavior. A Lyapunov-like stability condition guarantees that the distance to the sliding surface decreases exponentially along all system trajectories. Application of sliding mode control, a form of high gain feedback (the feedback gain is inﬁnitely large), requires that the input-output pairing (or transformations thereof) are passive. Finally, Godasi et al. (2002)25 develop a symmetry group representation which they use to develop control methods for PDE systems. The inventory approach for stabilization of TRPs distinguishes itself from the methods mentioned previously in that we develop stabilizing controllers using macroscopic (integrated) properties for feedback. The method is related to the averaging methods used to study nonlinear systems and stochastic processes since the use of inventories leads to “smearing” of the detailed structure of the dynamics. However, in the inventory approach we obtain the reduced order model by averaging over space rather than time. This gives a coarse grained view of the system dynamics and in this way the method can be linked to the classical methods of irreversible thermodynamics and statistical mechanics. The resulting manifold is described by a small number of ODE’s (one for each control objective) derived from the macroscopic conservation equations. The ﬁnal control design is achieved using either Lyapunov or passivity design techniques. A description of this approach and its application to ﬁnite dimensional systems with and without input constraints is given by Farschman et al. (1998).5 Ydstie and Jiao (2004)26 applies inventory and ﬂow control to a ﬂoat glass production system and Ruszkowski et al. (2005)27 applied inventory and ﬂow control to real-time optimization of a silicon furnace. Passivity, a concept derived from electrical circuit theory, is encountered in many scientiﬁc disciplines (Desoer and Vidyasagar, 1975).28 The fundamental idea is based on dissipation of useful work by irreversible transformations and input-output pairings with phase shift no more than /2. Willems (1972a,b)29,30 developed a systems perspective for dissipativity and linked the concept to state space representations. Byrnes et al. (1991)31 showed that passivity and Lyapunov stability is equivalent for a class of feedback systems using geometric methods. Van der Schaft (1996)32 developed control methods linking passivity and L2 stability, while Slotine and Li (1992)16 and Ortega et al. (1998, 2001)33,34 stressed passivity based on physical arguments following from the law of conservation of energy. Krstic et al (1995)35 linked passivity and nonlinear adaptive control. Ydstie and Alonso (1997)36 advanced the idea of combining thermodynamics and passivity and showed that passivity could be motivated using a storage function related to the available work, and Gibbs tangent plane criteria for phase stability. Alonso and Ydstie, (2001)37, Ydstie (2002)38, and Coffey et al. (2000)39 highlighted the importance of concavity of the entropy function, and used the Poincare inequality to estimate the impact of the size on stability of the system. The main objectives of the current article are: (1) to give a

Vol. 51, No. 12 AIChE Journal

We can for example have Z (U.42 The implied function relating Z (U. We may.N) to S given by the two equations earlier is called a fundamental relation.41. Mi is mass or moles of chemical component i and X can correspond to the charge. temperature and chemical potential). Thus. T ( U/ S) 0(the temperature is positive). The fundamental equation provides the key for constructing the operator S since it contains all information needed to characterize how the variables y change in response to a given action u. N) numerically have recently been developed by Wang and Landau (2001) and Shell et al. We will follow an approximate approach to nonequilibrium theory called “coarse graining via the hypothesis of local equilibrium” (HLE).36 To make the discussions precise. heat and mass ﬂow. consider the example of semiclassical statistic mechanics. In this approach we grid the system into sub-regions and make the assumption that Boltzman’s principle holds for each sub-region. Classical Thermodynamics Let . All these properties are due to the deﬁnition of the logarithm and Assumption A1 is. We also want to note that the assumption of concavity is not needed for passivity design.V. and the use of classical thermodynamic variables in nonequilibrium settings gives excellent predictions in all but very extreme cases. (2) concave.M1. 51. V. V. p and q are the momenta and positions. Three actions (change of volume. .X)T where U is the internal energy. Equilibrium thermodynamics can be viewed as an input-output theory of systems. The developments below do not depend on a particular deﬁnition of S since we do not actually need to evaluate the entropy function numerically. is a scaling constant with units of energy and ( )is the Dirac delta function. and Dorfman. In the case of an ideal gas with constant heat capacity the result is very clear since we get an explicit formula for the entropy so that S2 S1 c Vln U2 U1 R ln V2 V1 U. however. The results of the article are based on the premise that Assumption A1 and HLE hold. A mapping P: is called a thermodynamic process (Figure 1). Q. The requirement that the entropy is twice differentiable is convenient but not necessary to obtain the main results of the paper. q 3N dp 3Ndq 3N where H the Hamiltonian. be called the space of extensive variables and let Z denote an arbitrary point. A coarse grained system with an input-output operator S and dynamics constrained by a Vol.1 – A1. called the entropy so that1: S (Z) (S 1. it is useful to represent the thermodynamic process by the input output operator S so that y Su Together these expressions give an entropy function which is (1) ﬁrst-order homogeneous. For control purposes. 1971). a convex subset of Rn 2 . 3. heat and mass) provide the inputs to the system. The entropy is now deﬁned using Boltzman’s principle so that S k Bln U.3.V. 12 3149 AIChE Journal December 2005 . S : R . Assumption A1 (The structure of equilibrium thermodynamics): There exists a C2 function. By deﬁning the corresponding input vector u and output vector y we can represent the thermodynamic processes as a control system as shown in the ﬁgure on the right. as well as microscopic system properties. N In more general cases it can be quite difﬁcult to evaluate S numerically.tutorial overview of passivity based control. For all points Z 1 .Mn. An important technical contribution of the article is that we exploit the homogeneity of the entropy function more fully than we have achieved in previous articles. This approach to thermodynamics is based on a limited number postulates expressed in mathematical form. 2. ( /T)) T . No.. For any positive constant we have S( Z) is positively homogeneous of degree one). The system response is observed by a change in the conjugate variables (pressure. We develop this result using a Lyapunov-like “energy” function. for example. which exploits macroscopic. and (2) to show that passivity based methods are effective in stabilizing inﬁnite dimensional transport reaction systems. Z 2 and any positive constant we have S Z1 1 Z2 S Z1 1 S Z2 (S is concave). degree of magnetization. (P/T). It is possible to make good approximations. This is demonstrated in the ﬁrst part of the article by Ydstie and Alonso (1997). momentum et cetera. therefore. The microcanonical partition function for a single component system of N structureless particles is deﬁned so that (Ruelle. satisﬁed (Kestin 1 We follow the approach espoused by Caratheodory and Callen. In nonequilibrium systems it may not be possible to deﬁne a unique entropy function since the concept of an equilibrium state loses its precise interpretation. is Planck’s constant (divided by 2 ).43 Methods to evaluate (U.. we are interested in modeling how intensive variables respond to a ﬁnite change in volume. . (2002). In the coarse grained approach we model systems distributed in time and space by cascading simple systems while making the assumption that each unit cell still obeys the assumptions A1. M) T and y ((1/T). and (3) has positive temperature. In general it sufﬁces that S is C1. area. It sufﬁces that there exists an entropy function which satisﬁes the axioms given earlier. It sufﬁces that the entropy is over-bounded by a concave function. N 3N N! U H p 3N. V is the volume. 1969)40 Figure 1. have u ( V. V.

hence. Alonso and Ydstie (2001)37 showed that taking the Legendre transform of S(w) does not yield unique results due to the homogeneity of S. We see that the variables Z and w are dual. . Sandler. The space * {w: Z } is called the space of intensive variables. Proof: For any positive constant S Z1 1 Z2 S Z1 S 1 Z2 Using homogeneity gives dS S Z1 1 Z2 S Z1 1 S Z2 1 dU T P dV T 1 T dM 1. No. Entropy functions below the line are in violation of the second law. Using these deﬁnitions we can also generate the Legendre transform of S so that S* w w TZ S Z Z is now regarded as a function of w and S*. and. 1985. The following result shows that the classical deﬁnition of the second law and Assumption A1. Result R1 (Equivalence of concavity and the second law): The entropy S(Z) is concave if and only if for all Z 1 .. and (b) shows a projection. .1 – A1. as it might arise in a cubic equation of state like the Van der Waals equation. The actual entropy is deﬁned to be the smallest concave relaxation as indicated by the straight line segment. The slope of the tangent line. 51. Gibbs showed that dim( 0) is equal the number of phases present is a nonreactive. as indicated. For a simple system. We now introduce the set of conjugate variables S Z Euler’s theorem for homogeneous functions gives2 S Z w TZ (3) w (1) Using Eq. The intensive variables therefore deﬁne the slope of the entropy as shown in Figure 2..2 are in fact equivalent. . 1999)45 2 Euler’s theorem asserts that if f( x) f( x) then we must have f( x) ( f/ x) x. The reverse argument follows immediately.45 The Second Law: S Z3 S Z1 S Z2 This expression states that the entropy of combined systems at equilibrium is never smaller than the sum of the entropies of the subsystems. Z2 and let Z3 Z1 Z3. and the nullspace of M deﬁnes invariant sub-spaces 0 of (Figures 2 and 3). From Eq. . 1999)44. The second law of thermodynamics for a simple system can now be stated in the following. n T dMn (2) It follows that S is concave. . w1 deﬁnes the intensive variables at that point. we can make the assignment 1 P .. the intensive variables are the same. T T T 1 n w T . Z 2 Z S Z1 Z2 S Z1 S Z2 Figure 2.. In this case the EOS gives three points where the slope. simple system. Equation 4 is often written on the form 0 dw TZ (5) For a simple system this gives the Gibbs-Duhem equation (Sandler. 3. 12 AIChE Journal . (a) Shows a projection of an entropy function and a unique point of stability indicated at the point Z1. which for a simple system we write out term by term so that 3150 December 2005 The matrix M of second derivatives of S is symmetric and nonpositive. 1997).fundamental relation satisfying axioms A1. and the chain rule we can now write ( S/ Z) ( w/ Z) Z w T . Vol. It follows from Eq. and maybe more familiar manner (Callen. This simply means that we can scale “size of the system”without changing the intensive variables. 1 we now have the Gibbs equation dS w T dZ. 1 that MZ where 0 (4) called the vector of intensive variables. T M ij S Zi Zj 2 0 where the negative signs are introduced to follow the standard notation.3 is called a process system (Ydstie and Alonso. The symmetry gives rise to the Maxwell relations.36 Consider now two points Z1.

. Subregions with positive measure (regions in with phase or reaction equilibrium ) map to points with zero measure (in *). Assumption A1 is assumed to be valid for each subregion provided that the tessellation is sufﬁciently ﬁne. . 1974). It is easy to to see that this condition is equivalent to w1 w2. which is based on ﬁxing the canonical ensemble (T.That A1 (Z2) is non-negative is easy to verify geometrically as shown in Figure 2. Such a line maps a point w1 in * . 3) we have A1 Z2 T w 1Z 2 S Z2 Thus. indicating that pressure. and the concavity of the entropy as their point of departure. The vector p represents the rate of production. M 1t. 12 3151 . Controlling intensive variables neither guarantees stability or convergence in the space of the extensive variables. . We then get the following (very nice) decomposition for the thermodynamic process t v t v 0 0 pds A1 Z2 AIChE Journal S Z1 T w1 Z2 Z1 S Z2 0 (8) 3 Note that A does not deﬁne a metric on the space * since we do not necessarily have symmetry. 200147) dv dt 0 ˆ dw TZ d P ˆ V T d 1 ˆ U T d 1 T ˆ M 1. Figure 3. we see that A is closely related to S* only that we have ﬁxed w1. December 2005 Vol. Neither the Helmholtz function F U TS. temperature and chemical potential remain invariant. The line 1. Consider two arbitrary points Z1 and Z2. In this approach.N). From Eq. . . . . They used the microcanonical ensemble description. Z2 in we have The subscript t refers to “total” in order to distinguish the inventories from extensive variables. Both functions fail for similar reasons. d n T ˆ Mn (6) p which turns out to play a particularly important role in our developments. U t. 8 and the Euler identity (Eq. M nt (7) n and M ¥ i 1 M i denotes the total mass (moles). The mapping w PZ from the space of extensive to the space of intensive variables is not one to one. The state of the subregions. One way to overcome this problem is to use coarse graining. independent of scale. From the Gibbs tangent plane condition we have that two points Z1 and Z2 are in equilibrium if and only if A1 (Z2) 0. . M 1. 51. corresponds to uniform scaling of the extensive variables. This theory led to deﬁnition a Lyapunov function related to thermodynamic availability and exergy deﬁned so that for any pair of points Z1. ﬁxed reference point w 1 *3. M n T v is here the vector of coarse grained variables (inventories) corresponding to the total internal energy.V. . U . . as well as the overall system may then change continuously. The Helmholtz function fails because here is no way to guarantee that N and U are ﬁxed unless the system already is well controlled. volume and number of moles (mass) of each species so that vT V t.N) nor Gibbs function G H TS. No. measures distance from an arbitrary. In practice these problems show up as a problem of lower-boundedness of G and F in unconstrained systems (Coleman and Owen. The speciﬁc (or molar) properties are deﬁned so that ˆ Z Z/M ˆ ˆ ˆ ˆ V . indicating that the distance measured in one direction is not equal to the distance measured in the opposite direction.P. Transport and Reaction In order to introduce the theory of transport reaction systems we must deal with the following problem: Classical thermodynamics does not consider the spatial dependency of the system. The function A. . can be written on the form (Hangos and Cameron. provide convenient starting points for the development of process control theory. open system. . therefore. we tessellate physical space into N subregions. which is based on ﬁxing the micro-canonical ensemble (U. We may then have A1(Z2) A2(Z1).46 Ydstie and Alonso (1997)36 proposed to overcome the problem of lower-boundedness by deﬁning a Lyapunov function which measure distance to a ﬁxed reference point in a stationary. The ﬂows between the subregions will be governed by classical transport theory so that m fi i 1 where fi gives the net rate of transport. The macroscopic balances for each sub-region. The Gibbs function fails because we need to develop methods to stabilize pressure and temperature before we can use the stability theory. Coarse Graining.

Astarita. 1981. 2005). This is the essence of HLE (Kreuzer. Q the heat We note that m ˙ ˙ ﬂow FDi the rate of diffusion. t (13) z f conv fdiff u x 2 (16) This means that the local state z(x.46. t dx where the sign chosen so that it is positive for ﬂow into the system and negative for ﬂow out. is the viscosity as used in the Navier-Stokes equations and i is the local rate of chemical reaction. so that if Vt (HLE)): For every 0.49. We normally divide the ﬂux density into orthogonal components (in the sense of GibbsDuhem) so that f f conv fdiff where fconv uz (15) v i 1 Zi By letting N 3 inventory i so that we can then deﬁne the density of the vi t Vt x. t f 0. t ˆ Z x. 14 and 15 ˆ U ˆ V ˆ . In course grained systems we 3152 December 2005 ˙ denotes the center of mass ﬂow. n 2 u is the center of mass velocity. and (x. transport and reaction engineering. t and p t 0 x. . and dVt is the measure of Vt (Kestin and Dorfman. The conservation law corresponding to volume (the second entry) does not add information and is only introduced for convenience4. 12 AIChE Journal . No. This term is reversible and 4 The corresponding conservation law is given by ( ( u/ x) which is true but uninteresting. 1971). .50 The main importance of HLE is that we can make the substitution z x. The division into diffusive and convective terms can be motivated on physical grounds and corresponds to a separation into Eulerian and Lagrangian components. 9) by a system of partialdifferential equations on the form z t f x (14) Figure 4. The term P( u/ x) is the generation of internal energy due to compression. and we assume furthermore that functions of x and t deﬁned on the domain [0. pressure and chemical potentials. . We let x represent the spatial dimension. According to the deﬁnitions above we can approximate the coarse grained system locally (Eq. Following the notation of Sandler (1999).t). 51.can furthermore calculate the gradients of intensive variables which are needed to estimate the rate of energy and mass ﬂow between the subregions. L] [0. These variables are connected to the macroscopic balances via the relationships L t As illustrated in Figure 4 we see that in order to predict the evolution of a process from its initial condition we need to evaluate a line integral (the action) involving three classical branches of chemical engineering: thermodynamics. and the balances given earlier. ) exist and are continuous. M1 ˆ M2 ˆ U ˆ V m ˆ . zi is the local state. t zi x. let dx represent dVt. In the coarse-grained system we have N f L. there exists ˆ then z(x. t) . transport and reaction engineering into distinct subﬁelds of process systems engineering. t) Z(x. .t) represents the density of production. t dVt i 1.t) represents the ﬂux density. ˙ M1 ˆ M2 ˙ Q 0 ˙ . and the speciﬁc propˆ erties Z are equivalent on small enough scales. FD1 ˙ FD2 P u x 2 u x 1 2 where is the molar or mass density. 1990. where f(x. HLE is very well tested and holds even at very small scales and quite sharp gradients.45 we can make the following assignments in Eqs.43 In order to maintain clarity of presentation we consider processes distributed in one spatial dimension only. Assumption A2: (The hypothesis of Local Equilibrium 0. Ottinger. ˆ V / x) ( m V / x) ˙ˆ Vol. We can then use statistical/quantum mechanics to develop fundamental equations that link the energy and mass conservation laws with thermodynamic quantities like temperature. Hypothesis of local equilibrium leads directly to the separation of thermodynamics. Consider now a process system with ﬁrst-order reaction to illustrate application of HLE.

For this development is convenient to deﬁne the “natural set of driving forces” X w x (18) A t ˜ Tw f ˜ x L ˜ TX f ˜ wT ˜ ˜ W t 0 A x. t i0 T. pressures. 18 and 19 to give w1 w2 k0 w1 w2 2 for some constant k0. and the second term represents the conversion potential energy to internal energy through diffusion. 14. exists among concentrations. This theory can be extended using the idea of contraction analysis as introduced by Lohmiller and Slotine (1998)51. 13 ˆ and set z( x. It follows that expression Eq. 51. If instead we consider a bioreactor with substrate inhibition model. The chemical potential of a mixture can be expressed so that i w ˜ ˜ X w1 X1 w2 X2 (19) x. 8) as an energy function.t) equal to zero if the system is at equilibrium. 17 is (Lipschitz) continuous in the intensive variables w. t cA x. We can analyze stability by studying the trajectories of the deviation system derived from Eq. More generally. 2. temperatures and chemical potentials. Corollary C1 (Dissipation equality for process systems): dW dt L We see that according to HLE we have X(x. Lemma L1 (Evolution equation for A): Suppose that assumptions A1 and A2 are satisﬁed. 12 3153 AIChE Journal December 2005 . Reaction rates expressed in terms of concentrations can. 14) using the potential A (deﬁned by Eq. We now investigate the stability properties of the conservation laws (Eq. 14 deﬁned so that z ˜ t ˜ f x where ai is the activity coefﬁcient. and the deviation variables (Eq. 1. We can now write A t w1 w2 T 1 1 c z 2 2 z Ks cS 2 c S/K i t where m is the maximum growth rate. For example. therefore. 19) we get A t wT ˜ ˜ f x ˜ ˜T ( w / x) f ˜ w T ( ˜/ ˜ f w2 k0 w1 w2 ˜ ˜ We now use the identity ( (f T w )/ x) x) and Eqs. t) Z ( x. t m S Proof: Since A1 and A2 are satisﬁed we can use Eq. The term ˜TX represents deviations due to convection f ˜ diffusion and heat conduction. A continuous relationship. cs is the concentration of substrate in the reactor. then we have x. t (17) ˜ using the function A as a Lyapunov like storage function. We furthermore notice that the righthand side consists of three distinct terms. We then have A t ˜ Tw f ˜ x ˜diffX fT ˜ wT ˜ ˜ The HLE allows us to express concentrations as continuous functions of the intensive variables except across phase boundaries. The term ˜T w L is due to deviations in boundary condif ˜ 0 tions. No.cancels in the 1D entropy balance as shown in Appendix5. P k BT ln ai zi where subscript 2 refers to the time invariant reference system. Proof: Follows from Lemma L2 by integration. for continuous functions (w) we can write w1 It follows that w1 w2 T By using the conservation laws Eq. The term 2 ( u/ x) 2 0 represents the irreversible generation of heat due to viscous dissipation. therefore. We see from Corollary C1 that the storage function W decreases if the righthand side is negative. t dx 0 (21) This gives the following key result. It is also convenient to deﬁne the deviation variables ˜ f ˜ f1 1 ˜ Tw f ˜ L 0 0 ˜T X f ˜ wT ˜ dx ˜ f2 2 5 In the general case the right hand side of the energy balance consists of additional n terms P: u ¥ i 1 f diff i Fi where the ﬁrst term represents the conversion of kinetic energy to internal energy through compression and viscous dissipation. Vol. t k 0exp E/RT x. the ﬁrst-order reaction A 3 B with Arrhenius rate expression can be written so that x. and Km and Ki are the growth constants and continuity still holds. be related to the chemical potentials and more generally to the afﬁnities as shown in the Appendix. t).

51. 1992)52. From Corollary C1 we then have dW dt L ˜ ˜ XT X ˜ Tw f ˜ L 0 0 0 ˜ ˜ X TX dx Using the Poincare inequality (Straughan. heat conduction and chemical reaction using linear relations so that f LX and Kw L ˜ TX f ˜ 0 w T ˜ dx ˜ ˜ Tw f ˜ L 0 0 w Tw ˜ ˜ where L and K are symmetric with nonnegative and all positive eigenvalues. we can now conclude that there exists a ˜ constant 0 so that w T w ˜ ˜ A(Z ). 12 AIChE Journal . 0w w W(t) is radially bounded and positive deﬁnite on *. The term w T ˜ represents deviations due to chemical ˜ reaction and power of compression.59 We also note that if the conditions above are satisﬁed then we use the theory to establish the existence of an inertial manifold. The conditions are satisﬁed if we use the Arrhenius or substrate inhibition rate described above and Fourier-Fick theory for heat conduction and diffusion. coupled systems like the van der Vusse system and exothermic reactions may give kL negative. This theory is explored more fully in the context of process networks by Jillson and Ydstie (2005). The entropy production due to diffusion and heat-conduction can now be written as XTLX which deﬁnes the Riemannian metric. and stability follows by choosing the boundary conditions so that ˜T w L f ˜ 0 0. so that W(t) ˜T˜ 0. Instead we derive a broader class of stability conditions which can be tried for nonlinear problems. Assumption A3 (Sufﬁcient conditions for dissipativity): There exists constants kL and 0 0 so that 1 wT ˜ ˜ k Lw Tw ˜ ˜ and 2 ˜T X f ˜ 0 where 0 is smallest eigenvalue of L. The remainder of the article does not rely on linearity and symmetry. Vol. ˜ 1990)54 for the intensive variables w . LIT is based on modeling diffusion ﬂow. Autocatalytic. Hence dW t dt 2 where L is the length. S2 are not topologically equivalent to those obtained from the Gibbs tangent-plane method across phase boundaries due to discontinuities in S. Struwe. linear laws and stability is given in the Appendix. A further discussion of the framework of classical equilibrium thermodynamics. Proof: The Poincare inequality for homogeneous boundary conditions gives L 2 L ˜ Tw f ˜ L 0 0 0 L 2 W t 0 ˜ ˜ X TX dx 0 L2 0 w Tw dx ˜ ˜ It follows that W(t) is a (control) Lyapunov function (Sontag. We now introduce the following assumption. respectively.. Result R3 (Stability of Process Systems): Suppose that there exists positive 0 so that 3154 December 2005 and the result follows from Result R3 using 2 0 0 L 2 kL By rearranging the inequality in Result 4 we see that the process system with homogeneous boundary conditions is stable if 2 kL 0 L 2 This expression shows that the process system is always stable if kL is positive.53 we can write dW dt 2 L We see that condition (1) of Assumption A3 is satisﬁed if ˆ (w) is Lipschitz continuous in w. The dissipation condition of Result 3 holds true if 0 and kL deﬁned in Assumption A3 satisfy the inequality 2 ˜ Tw f ˜ L 0 0 L 2 0 w Tw dx ˜ ˜ 0 L2 kL 0 From Result R2.3. Proof: Follows from Corollary C1 by integration and using the fact that according the Result R2 and HLE we a positive constant 0. often referred to as the Rayleigh-Onsager dissipation function. His approach gives local results and it cannot be applied to phase equilibria since the stability conditions obtained from the second-order variation. 1992. Using linearity we can write ˜diffX fT ˜ ˜ ˜ XT LX ˜ ˜ XT X and wT ˜ ˜ wT Kw ˜ ˜ 0 0 Then we have (dW(t)/dt) 0 W(t) for some positive constant 0. Corollary C2 (Sufﬁcient condition for dissipativity): Suppose that Assumption A3 is satisﬁed. It follows that W is a Lyapunov function for the intensive variables in the ﬁnite dimensional case. Prigogine developed a similar stability result using the second variation of entropy as a Lypunov function. No. We will now review very brieﬂy the substance of linear irreversible thermodynamics (LIT).

t W t W 0 0 uyds Figure 5. The inequality shows that the electrical energy stored in circuit at time t is less or equal to what initially stored plus the integrated power supply. 2001). The classical example of a passive system is an electrical circuit made op of resistors. Let G(s) have the controllable state space realization {C. Convergence results then show that all trajectories converge to stationary behavior determined by the reference system.37 In order to develop spatiotemporal patterns in reaction diffusion equations we. Note the Bode stability criterion does not apply due to the presence of the unstable pole. Trajectories of passive process systems with different initial conditions. Systems that display this kind of behavior are said to be passive.A. The plot shows that the phase shift of G(s) is never more than 90°. The Bode plot of G(s) shown in Figure 6 reveals one aspect of the input output behavior of the system however. so that dW dt . Independently of the complexity of the circuit we can now write AIChE Journal December 2005 Figure 6. It then follows that G(s) is passive if and only if there exists a positive deﬁnite matrix P and vector d so that A TP PA PB C ddT 0 In such cases it is possible to achieve stability in distributed reaction diffusion systems by counterbalancing reaction by diffusion and heat conduction if L is not too large (Alonso and Ydstie. The function V XT Px turns out to be a Lyapunov function for the unforced system. capacitors. We note that there is a close connection between passivity and Lyapunov stability theory which can be expressed through the Kalman-Yakubovich-Popov type stability theory. No. G(s) is real for real s. 22 generated by MATLAB. Bode diagram of the transfer function shown in Eq. and the same boundary conditions converge to a single trajectory in the mean square sense. A linear transfer function G(s) is passive if 1.5 s G s s 4 (22) is impossible to stabilize because there is an unstable pole-zero cancellation. Vol. Deﬁnition D1: Consider system S in Figure 1 with input u and output y. One way is to view System 2 as a stationary reference for System 1. 51. Another way is to view deviations as spontaneous/stochastic ﬂuctuations that die out after period of time. There are many ways to interpret deviation variables as illustrated in Figure 5. In this case the input u in Figure 1 represents the applied voltage and the output y represents the current. 12 3155 . For example. Suppose that there exists a nonnegative C1 function W(t). The system S is u Ty 2 2 Passivity of Input Output Systems It is quite easy to develop “counter examples” to control. 2. In passivity theory. and inductors connected in parallel with resistors. need to satisfy certain limiting size constraints as might be expected. we ignore the gain and we use instead the phase margin for stability. More generally and assuming that W(t) is differentiable we have the following deﬁnitions for nonlinear systems. where W represents the stored electrical energy and product uy represents the power supply. In the small gain theory we ignore phase and rely on gain margin for stability.B} with A having all its eigenvalues in the closed left half plane. the linear transfer function s 3 s 0. therefore.5 10 s 0. Passivity provides a counterpart to small gain stability theory. Re[G(s)] for all Re(s) 0. The difference has been dissipated as heat in the resistors.

The interconnected feedback system with input d and C output e has L2 gain g 1/ C. Result R3 shows that process systems are strictly passive if Assumptions A1-A3 are satisﬁed. 0 f ˜ t. Byrnes et al. No. x Tw t. We can then write dW t dt L Figure 7. The input and the output in the average have the same sign. This can be observed by deﬁning a proportional control u Ky. if u is positive then y should be positive “most of the time”. strictly state passive if represents the state and The notation 2 denotes the L2 norm for a function deﬁned on a domain so that for square integrable vectors we have 2 2 T d In this article is deﬁned by the semiclosed set [0. Conversely. Substituting this control law into expression Eq. In the nonlinear case this translates into a sector condition which plays a crucial role in nonlinear stability theory. This result can be strengthened to one of asymptotic stability of the signals have uniformly bounded ﬁrst derivative. 4. In other words. This gives convergence of y and w since W(t) cannot ˜ decrease indeﬁnitely6. Lemma L2 (Stability of feedback systems): Consider a passive system S and an input strictly passive controller C connected in feedback as shown in Figure 7. ﬁnite dimensional systems using passivity. u and 0. passive if 0. 0 ˜ w t. deﬁning W WS WC and setting u d u we ˆ get dW dt e Td eT e C We now integrate over the interval [0. 2. 3. The central result of passivity aimed at stability analysis of interconnected systems is the passivity theorem. ) [0. Strict state passivity (in the space of intensive variables) follows when we make the assignment w ˜ . and a strictly passive controller C. Feedback interconnection between a passive system S. W is convex. It was shown that a ﬁnite dimensional system is stabilizable if it is feedback equivalent to a passive system. if u is negative then y should be negative “most of the time”.T] to give 6 Note that convergence is in the L2 sense. 51. It turns out that it it quite easy to establish that this is the case if the smallest eigenvalue of L is bounded away from zero. The following result is most useful for out purposes. These results suggest a close relation between passivity and the methods of irreversible thermodynamics. L ˜ u y Thus. 12 AIChE Journal . L]. Proof: The proof is instructive so we give it here for completeness. 23 convinces us that the storage function decreases according to 3156 December 2005 Vol. First we note that we have dW S dt and dW C dt ˆ eT u eT e uT e Thus. In this case. and it is also a Lyapunov function. K 0 C where u is deﬁned in Figure 7. We note that passivity has a very nice intuitive interpretation which is evident from inequality (Eq. 23). x dx ˜ ˜ (23) where we made the assignments ˜ t. and subsets thereof. L f w t. and if L is sufﬁciently small. strictly output passive if 0. (1991)31 developed these ideas further and established conditions for stabilizability of nonlinear. T T L W t W 0 0 Ky 2dt 0 0 0 w Tw dt ˜ ˜ u Ty 0 0 w t. strictly input passive if y and 0. Willems (1972b)30 proved that if W has a strong local minimum then there is an intimate connection between dissipativity and Lyapunov stability. The respective storage functions WS and WC have dissipation rates S 0 and 0.1. and it is in fact decreasing if either of the vectors y or w is not identically equal to zero for some ﬁnite period of ˜ time. the input vector consists of ﬂow deviations at the boundary and the measurement consists of intensive variable deviations at the boundary. By adding the two storage ˆ functions. One aspect concerning passive systems is that they are easy to control. meaning that the error signals are square integrable. the stored energy never increases under negative output feedback.

We furthermore note that (Eq. We can then use Lemma L2 to show that the gain from the ˜ p to set point errors is given by the inverse of ˜ error d the L2 gain of the operator C. It follows from Lemma L2 and Result R4 that inventory control is input/output stable when we use feedback-feedforward control in the form u ˆ m. What we see here is that we distinguish between two types of inputs and outputs to the process system.T W t W 0 0 e Td C eT e dt Since W is nonnegative we can re-arrange this so that T C 0 T eT edt W0 0 eT ddt Using the Schwartz-inequality we get T C 0 T T eT edt W0 0 dT ddt 0 eT edt Hence T C 0 0 Figure 8.28. state variables z. z. shows that the gain from the disturbance input d to the error e is ﬁnite and bounded by the constant 1/ C. Inventory controller acts on transformed measurements and generates a set of synthetic control outputs which need to be transformed to real process inputs through control variable synthesizers (CVs). d p m. Result R4: Let v* denote a time-varying reference. and disturbances d. (1998)5 used the macroscopic balance dv dt m. No. d ˆ dv* dt Ce (26) to derive control structures for chemical processes. Furthermore. These ﬂows connect with other process systems Vol. d p m. We have indicated that the ﬂux and production variables depend on vectors of manipulated variables m. 24) is a “positive system” since the state consists of elements that are nonnegative. z. Lemma L2.4 eT edt W0 T T dT ddt 0 eT edt is passive. z. The structure of the control system is shown in Figure 8. and p denotes the estimate of the net production. 51. 12 3157 . which maps ˆ errors into synthetic controls. By differentiating V we get ˙ V e Te ˙ eT v ˙ v* ˙ e Tu The result then is established by letting T 3 . should be strictly input passive. We now have the following result. Other results concerning the interconnection of passive systems can be found in the books by Desoer and Vidyasagar (1975) and Khalil (1996). d (24) Passivity follows.55 Inventory and Flow Control Farschman et al. let ˜ ˆ and p ˜ p p . This structure is similar to the extensive variable controller proposed by Georgakis (1986). One type of inputs and outputs concern the physical ﬂows. The input output pair is called synthetic since it does not necessarily correspond to what is directly measured and manipulated in the real process. Deﬁnition D2 (Inventory Control): A control strategy which ensures that an inventory asymptotically tracks a desired set point is called inventory control. The synthetic input and output pair u AIChE Journal p dv* dt e v v* December 2005 ˆ In this expression ˆ denotes the estimate of the net ﬂow. Proof: Let V 1 v 2 v* T By ignoring the effect of initial conditions we can write T T v v* (25) e Tedt/ 0 0 d Tddt 1 C That the vectors u and e are related in a passive manner is now easily veriﬁed. The passivity theorem. All states of the system are stabilized (in the sense of Lyapunov) if the total energy and total mass is bounded. z. The operator C(e).

(1998)5 demonstrated that we get a unique solution to the inventory control problem and stability provided the equation ˆ m. Farschman et al. t T has a unique inverse with respect to the manipulated variable m. it is often possible to write m. Result R5: The PID control ˆ m. t e AIChE Journal 3158 December 2005 . d. For example. 28 ˙ eu Kc e2 It follows from Deﬁnition D1 that the PID controller is input strictly passive with dissipation rate C Kc. d.58 Inventory control is most useful for when the term p is absent since the modeling requirements are minimal. t p m.is strictly input passive for any choice of Kc 0 and 0.27 There are many examples of control that at are strictly input passive.56. The method is not limited to PID control. then the closed-loop response is given by the ﬁrst-order equation e t exp Kc t e 0 Thus.t) is a vector which depends on observable quantities. The beginnings of a theory for how such systems are connected. z. and combining Eq.z. Farschman et al. 12 edt 0 de D dt dv* dt Ce g m. and can be used to deﬁne large and very complex networks of process systems as indicated in Figure 9.57 Jillson and Ydstie (2005)51 recently developed a process systems analog of Tellegen’s theorem which allows for the very efﬁcient analysis of complex thermodynamic networks. A further discussion is provided by Ruszkowski at al (2005). This is case for conserved properties like total mass. t m. We now deﬁne u Kc e 1 I s D e ˙ Hence. No. d p m. (1999). by multiplying through with e Figure 9. and the stability can be analyzed is described by Gilles (1998). z. the closed loop time-constant is given by CL 1/Kc. t T ˆ dˆ dt Vol. 51. Farschman et al. z. Proof: First deﬁne the variables s e ˙ Kc 2 Kc D 2 e s 2 T 2 I. energy and components that do not undergo chemical transformation. d. z. eu Hence eu Kc e2 1 I es D ee ˙ K ce 2 Kc I es Kc D ee ˙ (27) and boundary conditions. d. The dissipation rate is given by C Kc. Result R6: The parameter adaptive controller u m. D V where dot denotes time derivative. 2005). d. In such systems a very natural decomposition ensues which allows one to develop distributed process control and optimization methods using strong stability and optimality results that have been developed for the analysis of electrical circuits (Peusner.5. Setting Kc very large gives fast response whereas setting Kc small gives slow response. and Hangos et al. d ˆ 0 We now differentiate the storage function to give ˙ V By using the fact that e we get ˙ V Kc T ss ˙ K c Dee ˙ (28) s. d ˆ dv* dt Kc e 1 I t (29) where (m. This condition fails close to maximum conversion point for component B in reaction scheme A 3 B 3 C. (1998).60. Ydstie. If I and D are equal to zero.d. (1998)5 refers to this property as controllability. Each node corresponds to a passive system and inventory controllers may be used to control the node in a decentralized fashion by acting on inputs u using measurements y. 1986. The nodes themselves may consist of more devices connected together as indicated. d p z. 27 and Eq. z. Process systems can be connected together to form large networks. and is a vector of unknown parameters. z.

.32 ˆ t T ˆ t v* ˙ Invariant Sets and Stabilizability In this section. d. t Kc v v* v v* is strictly state passive on the set * if there exist. By continuity and concavity we conclude that similar invariant sets are deﬁned for the intensive variables. .. z. . Strict input passivity is easy to establish. We then get lim M t30 We. A recent exposition of passivity theory. t AIChE Journal p m. t p m. . We are now interested in seeing what happens to the remainder of the variables. 12 . and its connections with nonlinear and H robust control is given by van der Schaft (1996). 51. Finally. We have seen that application of ISP inventory control to a process system guarantees according to the passivity theorem that the inventories converge to their setpoints. t Ci e . It follows that there exist invariant sets Z so that limt3 Z Z. i 1. and the deﬁnition of u. Proof: We ﬁrst note that from Eq. We can use nonlinear feedback. 30 we get ˙ V eu e T Mi i 1 and E U K P ˆ t T m. z. with exception of U which can be deﬁned relative to an arbitrary reference point). t) T ˆ (t) v* ˙ C(e). It is well known that the invariant sets corresponding to the remaining variables may be quite complex. December 2005 Proof: First deﬁne the storage function 3159 Vol. Sliding mode inventory control is described by Wang and Ydstie (2004).is strictly input passive for any choice of adaptive gain g 0 provided the feedback controller C is strictly input passive.2. We are in particular interested in seeing what happens if we control the total mass and energy of the system to constant setpoints E* and M*. 14). we can write u T where Ci I 1.61 As noted by Shinskey (1967)3 it is often advantageous to use a nonlinear feedback gain so that the controller takes the form dv* dt All these variables are bounded from below (by zero. . . We now have the following results Lemma L3: The process system with input and output pair deﬁned so that L u ˜ 0 f y ˜ L f 0 ˜ dx M M* dv* dt m. and so that L 0 0 This gives the high gain for large errors and small gain for small errors. we can implement any kind of gain scheduling (hybrid) controller dv* dt ˜ TX f ˜ 0 w T ˜ dx ˜ ˜ Tw f ˜ L 0 0 w Tw ˜ ˜ m. No. t e ˆ t ev * ˙ From the control expression we have (m. have by multiplying through with e eu e T ˆ t e T ˆ t ev * ˙ This we re-arrange to give T ˆ t e eu e T ˆ t ev * ˙ (30) We now deﬁne the storage function 1 2g ˆ t T V ˆ t By differentiating V we get ˙ V g 1 M* 0 and lim E t30 U* 0 ˆ t T ˙t ˆ The total mass and energy are deﬁned so that n By using the adaptive update law for ˆ (t) we have M ˙ V Using Eq. In our context this means that we can apply Assumptions A1 and A2 to the system of conservation laws (Eq. d. z.3. . A process system was deﬁned by Ydstie and Alonso (1997)36 to be system of conservation laws with a concave extension which satisﬁes the laws of thermodynamics. z. z. therefore. It follows that we may write ˙ V eu eC e The input strict passivity property follows from Deﬁnition 1 since C is input strictly passive. 29. especially for the case of chemical reactions..denotes a sequence of dynamic operak tors so that i 1 Ci is passive for all k. N. The sets are especially simple for the total mass and energy since they are determined by the setpoints. z. we are interested in establishing the existence of invariant sets when we apply inventory control to process systems.

(2004)27 apply the inventory control method to more complex examples. 21 and V by Eq. the results in this section establish that chemical process systems are strictly passive and. t 0 and for all w* denotes the solution to the steady-state problem. . In the limit this allows us to use the classical contraction type analysis which is used in variational calculus to establish tight bounds for stability using ﬁrst-order conditions. The total mass and energy is controlled using ISP inventory control. . 31. Proof: Follows directly from Lemma 3. We get L ˜ 0 f ˜ L f 0 ˜ dx Kc M M* dv* . No. 51. 12 AIChE Journal . We get. Application to 1D TRPs ˜ TX f ˜ w T ˜ dx ˜ dv* dt In this section we illustrate the application of inventory control to a TRP described by the equation v v* T ˜ Tw f ˜ L 0 0 p c t with t [0. To summarize. Lemma L3 gives sufﬁcient conditions for strict state passivity on the set * for a process system with nonlinear reaction and transport rates. dt Kc 0 (32) Vol. we get lim T1 t3 T* 0 lim P1 t3 P* 0 lim t3 i1 * i 0 In this case the invariant set is very simple and corresponds to a point in the space of intensive variables. we now consider developing stable control structures with passive input and output pairs as shown in Eq. using Corollary C1 and Result R4 dY dt L number and all intensive variables converge to stationary points under inventory control. hence. t c0 t c L. L ˜T X w T ˜ dx ˜ f ˜ 0 ˜T˜ 0. If set points and boundary conditions are constant and the solutions to the steady-state equations fi x i 1. 25. Full developments are given by Ruszkowski (2003). . ) and x v c x 2 D c x2 The result follows. 22) with input and output deﬁned so that L w Tw dt ˜ ˜ 0 0 c0 and 0 eT edt c1 If in addition wi and y are uniformly continuous then it follows that limt3 w ˜ 0 and limt3 y 0. A proportional feedback controller is the simplest type of controller which is strictly input passive.27 We see that the system is stable since k is positive.51 Result R7: Suppose that we have following properties satisﬁed ˜ ˜T w L 1. . hence. n u ˜ 0 f e ˜ L f 0 ˜ dx M* (31) M is strictly passive if D 2 L2 x 0. Hulburt boundary conditions c 0. stabilizable if the reaction rates are Lipshitz continuous L 0 and the dimension of the system (L) is not too large. In light of the motivation behind passivity theory for control design. In this example there is only one state variable. This approach for stability analysis of nonlinear systems can give tight bounds for nonlinear stability as long as the trajectories are noncritical. t 0 x and undergoing a ﬁrst-order reaction of the form A 3 B with reaction rate kc where k is constant and c is the local concentration of chemical specie A. The stability condition can be expressed in terms of a Dahmkohler type 3160 December 2005 Proof: Follows by application of Lemma L1 and Corollary C2.Y W V where W is deﬁned by Eq. Result R8: The transport-reaction system (Eq. Then there exist constants c0 and c1 so that we have t L (0. Ydstie and Jiao (2004)26 and Ruszkowski et al. 0 f 0 w w for some 0 2. The main objective of the section is to look at a range of feedback control structures that can be used to control the inventory. The theory can be extended to study stability more complex and time-varying invariant sets due to the introduction of the storage function R. L). L i are continuous then we can conclude that lim w x * t3 k 0 w x.

The PI and PID controllers also represents a strictly passive systems so the interconnection will be stable. this may set some limitations on selection of the manipulated variables as we discuss a companion article (Ruszkowski et al. a feedforward (FF) signal from offset in the reaction rate and a constant. This can always be achieved by choosing L small. One disadvantage of the proportional control approach is the necessity for a priori knowledge of steady-state offsets. 1. Example 1. The control law (Eq. but nonetheless a new concentration proﬁle is achieved due to a change in space-time velocity. 32) to be solvable. The term L ˜ dx can be omitted from the control law if 0 it is bounded.27 The second point ensures that all states (controlled and uncontrolled) reach a stable stationary point. 32) takes the form vc 0 v*c* 0 vc L L b* v*c* 0 v*c* L 0 *dx The control consists of proportional feedback (P-FB) term. and the transport velocity (v) is chosen as the manipulated variable. One way of overcoming this inconvenience is to drop the steady state terms and use integral action. inlet composition or the total reaction rate. The response will be nonlinear instead of linear. A step change is induced to the inventory set point. The geometry of the system must be chosen so that the system is strictly dissipative. The inlet boundary condition is unchanged. L We can choose to manipulate the transport velocity (v) or the inlet concentration (c(0)). This control law is well deﬁned as long as c(0) is not equal to c(L). 32) must be well deﬁned and invertible with respect to the manipulated variable so that the control action can be implemented. In our particular case the inlet ﬂux f (0) admits the decomposition ˜ 0 f vc 0 v*c* 0 Figure 11. In this example. for the control law (Eq.The control law is quite general in the sense that we are free to choose manipulated variables including ﬂow rate.. If there is no reaction present then the controllability is lost and it is not possible to control the concentration of A using this or any other method. 2004). but asymptotic stability is maintained. The term 1/(c(0) c(L)) is positive and can be ignored. The simulation is now repeated without any a prior knowledge of the steady state related terms. Servo control simulation results under proportional feedback and nonlinear feedforward control for Example 1. No. The transport velocity converges to a stationary value as the inventory (M) converges to its set point. 2. The requirements are as follows: 1. We can now use high-gain feedback like sliding Vol. 12 3161 AIChE Journal December 2005 . as shown in Figure 11. The righthand side of control law (Eq. The ﬁrst point ensures that a control action can actually be calculated. The response of the inventory will be given the ﬁrst-order relationship M t M* e Kct M 0 v*c* L * dx 0 Kc M M* Solving for velocity (v) we obtain ratio control 1 c 0 c L L v Kc (M M*) 0 ˜ dx b* Thus. which is the case if the reaction is present. The graph on the right shows the manipulated input (Velocity u v). 2. 1/Kc gives the time constant of the closed-loop system. We now consider approximations that can be made while maintaining passivity. The response is comparable to previous results as shown in Figure 12. we perform a servo control study. The graph on the left shows the controlled output (Inventory y MA). In this case. Figure 10 shows the system’s response to an inventory set point change. Regardless of the choice. In the following examples we do not include the term dv*/dt in the control laws. the new proportional and integral action feedback-feedforward (PI-FB/ FF) control law becomes 1 c 0 c L 1 I t where the constant b* is deﬁned so that v Kc (M M*) (M 0 M*)dt L ˜ dx 0 Figure 10. speciﬁc criteria must be satisﬁed. 51. Initial (dashed) and ﬁnal (solid) concentration proﬁles for Example 1.

Note that the concentration proﬁle adjusts so that molar holdup of component A is kept constant. The class of systems we consider is quite broad and encompasses a wide range of classical processes in chemical. a proportional feedback/ feed-forward controller was tested. In the examples we achieved the desired inventory levels employing two different control approaches. Example 3: We perform a regulatory control study were the transport velocity acts as a step disturbance. We provided a review of the notion of passivity and related this to the second law of thermodynamics. mode control. Disturbance rejection simulation results under proportional feedback and nonlinear feedforward control for Example 3. Initial (dashed) and ﬁnal (solid) concentration proﬁles for Example 3. c 0 c L Kc (M M*) 0 ˜ dx b* where b* is constant as deﬁned earlier. The proﬁle is “tilted” counterclockwise with respect to allow a velocity change while maintaining the holdup of component A constant. and no knowledge of the process model. it is possible and advantageous to choose the manipulated variable that facilitates greatest controllability and stability. as long as the Boltzman principle holds and coarse graining can be applied. Passivity ensures that we converge to a sliding surface characterized by zero error (Wang and Ydstie. The inlet concentration converges to a stationary value as the mass inventory M exponentially converges to its set point. The graph on the right shows the manipulated input (Inlet concentration u c(0)). No. as well as control of small-scale systems. The graph on the bottom right shows the outlet concentration c(L). 2004).Figure 12. Solving for this quantity. the inlet concentration (c(0)) is manipulated. Figure 15. For this experiment. The graph on the top right shows the disturbance input (velocity d v). Servo control simulation results under proportional feedback and nonlinear feedforward control for Example 2. Figure 14 shows the results. whether the system was inﬂuenced by a proportional controller or a proportional integral controller. Using a local storage function con- Figure 13. Therefore. The concentration proﬁles are shown in Figure 15. 51. 12 AIChE Journal .61 In other words. Figure 13 shows the response of the system under this control strategy. The graph on the top left shows the controlled output (Inventory y MA). In practice. This is expected since we cannot control the concentration when there is no ﬂow. In this case we loose controllability as the velocity decreases toward zero. Servo control simulation results under proportional integral feedback and nonlinear control for Example 1. Example 2: We now manipulate the inlet boundary condition (c(0)) instead of the transport velocity. biochemical and metallurgical process engineering. the inﬁnite dimensional system is stabilized PID type inventory control. The graph on the left shows the controlled output (Inventory y MA). To maintain a constant inventory set point. The graph on the bottom left shows the manipulated input (inlet concentration u c(0)). the control law now becomes 1 v L Figure 14. This ﬁgure shows that different internal conditions can give the same macroscopic holdup. In all three examples. however. 3162 December 2005 Vol. the choice of a control strategy may be limited by the availability of control variables and other equipment constraints. Conclusions In this article we have proposed a method to integrate physics and process control by developing a thermodynamic based approach to passivity based control of transport-reaction systems. it was able to converge to a stable stationary point.

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Acknowledgments This research was generously supported by the National Science Foundation (CTS-9316572).26:1037-1048. Feedback Systems: Input-Output Properties. Process systems and inventory control. Sontag ED. Willems JC. Buckley PS. Wang F. 21.26:1023-1036. No. Deane AE. Phys Fuids A.

1986. 57. New York: Springer Verlag. 1990. Network theory for chemical processes. 2003. Mineola. 14 we get s t wT f x From which we get the conservation law for the entropy s t w Tf x Entropy Flux fT w x wT (A1) Entropy Generation The second law of thermodynamics stated in the local form is easily derived from Eq. Chemical Engineering. Onsager and Prigogine were both awarded Nobel prizes for contributing to LIT: Onsager for having established symmetry of the conductance parameters using microscopic reversibility. A1 and inequality (Eq. Gilles ED. 1981. Englewood Cliffs. NJ: Prentice Hall Professional Technical 1996.34:683-696. 59. Ruskowski M. Prigogine I. Phys Rev. Amsterdam: Elsevier. Alonso AA. Studies in Network Thermodynamics. Process networks. Astarita G. AIChE J. this does not imply linearity since we still allow for nonlinear phase behavior as given by for example by the Peng-Robinson equation of state. 50. 18 we have ˆ U ˆ V ˆ M1 ˆ M2 T f T conv X u d dx 1/T P/T 1 /T 2 /T By writing this expression out term by term and using the fact ˙ M we get that u T f convX m U ˙ ˆ d 1 dx T ˆ V d P dx T ˆ M1 d 1 dx T ˆ M2 d 2 dx T Vol. Wei J.24. 1999. Hoboken. New York: Academic Press. Machlup S. 61. Ind and Eng Chem. 56. 63. 58. Nonequilibrium Thermodynamics and its Statistical Foundations. 12 AIChE Journal . 65. 1998. Applications to Nonlinear Partial Differential Equations and Hamiltonian Systems. 54. sipation. and nonlinear convection.47. Khalil K. Hangos KM. Berlin: Springer-Verlag. Peusner L. 64. Physica.21:121-132. 2005. Thermodynamics: an advanced textbook for chemical engineers. 1963. 67. Oxford: Clarendon Press. 60. Gelfand IM. Ydstie BE. Prigogine for having established the principle of minimum entropy production using Onsager symmetry as his point of departure. Calculus of variations. 1995. 2005 51. Carnegie Mellon University. Comp Chem Eng. Non-Equilibrium Stability Theory.91. 2001. No. Appl Math Sci Ser. Modern thermodynamics: From heat engines to dissipative structures. 62. 1970. Process Modeling and Model Analysis.58:55-60. Ydstie BE. Passivity Based Control of Transport-Reaction Systems: Application to Silicon Production. Ottinger HC. It states that the rate of entropy generation is positive so that S f TX wT 0 (A2) Appendix: Review of Classical Irreversible Thermodynamics and Symmetry of the Linear Laws In this appendix we revisit two classical problems in linear irreversible thermodynamics (LIT). Variational methods. 52.36 By using the ﬂow decomposition (Eq. Robust inventory control of process systems. New York: Springer Verlag. The second problem concerns the question of whether or not steady-state thermodynamics can be formulated via a variational principle. 55. 1998. Mathematical Control Theory. Distributed decision making in complex networks: The adaptive enterprise. 1992. as well as chemical reaction are assumed to be linear. NY: Dover Publications. 1966. Nonlinear Systems. JJ Slotine. Onsager L. Inc. Ydstie BE. 53. 49. A2). On contraction analysis for nonlinear systems.63 The entropy density is deﬁned so that for any nonempty volume V S V sdV We can now use HLE write s t s z z t wT z t By using the transport Eq. Prigogine I. Kondepudi DK. NJ: Wiley Interscience. 51. Praha. Glansdorff P. By combining Eq. Irreversible thermodynamics in engineering. 1990. The ideas are closely related to the principles of le Chatelier-Braun and Maxwell’s theorem of minimum heat dis3164 December 2005 where the thermodynamic forces X are deﬁned in Eq 18.46:344-366. 15) we have from Assumption A2 S T f convX T fdiffX wT 0 Using the deﬁnition of the forces in Eq. Cameron IT. Straughan B. Sontag ED. 1953. Struwe M. Fomin SV. Automatica. PhD. stability. Jillson KR. New York : John Wiley & Sons. 45:802-816. Paper to be presented in IFAC World Congress: Czech Republic. The ﬁrst problem concerns the issue of stability. The energy method. Perkins JD. Chem Eng Tech. Ydstie BE. 66. 48. Boston: American Control Conference. Hangos K. Wang J. 2004.91:1301-1308. Texts in Applied Mathematics 6. A very readable account of these ideas can be found in the book by Kondepudi and Prigogine (1995). Lohmiller W. Note that while the constitutive laws for heat and mass transport. Thermodynamic approach to the structural stability of process plants. Beyond equilibrium thermodynamics. A1. 2005. 1992. Fluctuations and irreversible processes. Kreuzer HJ. New York: Plenum Press. and integrating we obtain the celebrated Clausius-Planck inequality which was used as the starting point for the stability theory by Ydstie and Alonso (1997).

51. get nr S f diff X T X i 1 i T i 2 1 T u x 2 0 0 and that the eigenvalues of L and K are sufﬁcient that nonnegative since T is positive7. say B. the result does not say anything about ﬂuid ﬂow stability since the Lyaponov function(al) does not include the momentum... A8 and A9. 16 we have u 1 P T x 1 u P T x nr i i 1 wT T i 2 1 T u x 2 The ﬁrst two terms represent reversible work and they cancel. and reaction where 1 nr m T . . necessary and AIChE Journal December 2005 Vol. We note that while the dissipation due to ﬂuid ﬂow has been included. A5 and A6) and constant boundary conditions is stable. Proof: This follows immediately from Result R3 since Assumption A3 is satisﬁed. No. T 2A B7C The ﬁrst term in expression (Eq. We now want to address the issue of Onsager reciprocity (symmetry of L) and see how symmetry is related to Prigogine’s “principle of minimum entropy production”.63 showed that chemical reactions (not necessarily equilibrium reactions) can be modeled using afﬁnities. r (A9) and for the reactive terms we get R Km (A6) The afﬁnity is equal to zero if reaction j is at equilibrium (Sandler. write the entropy production as a quadratic form X TLX mT Km 1 T u x 2 v kjk jA j j 1 v kjk j v ij i T This we can write on the vector matrix form 0 (A7) 7 Any square matrix. From expression (Eq. therefore. Strict positivity of L implies that the resistance matrix R L 1 is bounded which it means that the medium has some conductivity. S 2 In order to satisfy the second law for all possible variations in forces and intensive variables it is. de Donder (Kreuzer. and write the expression for the reaction rate for component k so that nr k j 1 nr where L and K are constant matrices. It follows that inequality (A7) doesn’t imply symmetry. . therefore.Using the Gibbs-Duhem Eq. LIT assumes that the constitutive equations for diffusive ﬂow and chemical reaction are linear. be written S f diff X T X wT 0 (A3) By using the expression Eq. We review this theory very brieﬂy here. For example if we have n 3 and r 1. Kondepudi and Prigogine. therefore. A4) represents entropy generation due to heat conduction and diffusion.45 de Donder. Consider a system with n species and r chemical reactions. therefore. We write this decomposition so that B A S. j 1. proposed to set the reaction rate proportional to the afﬁnity so that for reaction rj kjAj. . A3 we. We can then combine Eqs. . 1 2 and 3 The afﬁnity of reaction j is deﬁned so that n Aj i 1 v ij i T j 1. therefore. therefore. can be decomposed into a symmetric matrix S and an antisymmetric matrix A where A has zeros on the diagonal. since gradients cannot be sustained at all. A4) we can. We therefore have xTBx xTSx for any vector x. The second term represents entropy generation due to chemical reaction. 2. We then have n We can. 1995)48. This gives f diff LX (A5) then we have 1 1. Superconducting materials have the best stability as might be expected. A2) can. . r (A8) m 1 2 T u x 2 i 1 0 (A4) where ij is the stochiometric coefﬁcient of species si as it enters in reaction j. 3 we conclude that T f convX 0 Inequality (Eq.. From Eq. 12 3165 . and the third term represents entropy generation due to viscous dissipation. 1981. .. 0 The stationary state of a process system with linear laws (Eqs. Result A1: Suppose that L has eigenvalues i 0. . 1996). write the local form of the second law so that f diff X T X T R v jis i S 0. .

67 Another important problem with LIT is that it does not address input-output behavior.48. Kreuzer. Lars Onsager (Onsager and Machlup.48 This property prompted Prigogine to propose the principle of minimum entropy production at steady state. has limited scope for practical application (Wei. 8. to develop theory that can (1) deal with instabilities that arise due to nonlinear phenomena. 1953). Suppose now that KL 1 (L LT ) 0. heat conduction and many other phenomena that can be modeled using linear rate expressions. 1998). It is also satisﬁed for nonreacting systems since we then have K 0. 1984). therefore. . therefore.63 This theory was quite successful for diffusion.nr k j 1 Using the steady-state equation A12 with A13 and A14. In order to make use of the formalism for control it is necessary. is a more general principle than symmetry. A12 we get nr K j 1 kj vj vjT (A11) d dx S S X w 1 w TKL LT ) S 1 L LT (A15) Equation A10 now has the form given in Eq. The use of linear reaction is especially troublesome and LIT. we get kvv m T j j j (A10) d dx S S X w dX TL dx wT K where vj (v 1j . He was able prove the generality of the principle using example problems. Proof: We have shown above that the rate of entropy production is independent of the center of mass velocity since the Gibbs-Duhem orthogonality allows us to write X T vz 0. therefore. therefore. A15 is not equal to zero. 1966). 12 AIChE Journal . The linear theory was not successful for the analysis of systems far from equilibrium. The E – L gives the necessary and sufﬁcient conditions for an extremum for this problem (Gelfand and Fomin.65 and it follows. . Result A2: Consider an LIT system. 51. That the extremum indeed is a minimum follows from the fact that the entropy production with linear laws is convex according to constraint (Eq. 2005. 1963). Later. Minimum entropy production. A6. argued that in LIT L must also be symmetric due to microscopic time reversibility (Kreuzer. by showing that in the linear case minimum entropy production and symmetry are equivalent. we get 0 S X w By differentiating (A7) with respect to X we have S X hence d dx Likewise S S X TL LX T d X TL dx LX T X (A13) However. The functional L 0 is minimized at steady state if and 0 S (w. 2004. Kondepudi and Prigogine. .64 however. w w TK Kw T (A14) 3166 December 2005 Vol. We can now write Using the symmetry of K and the steady-state Eq. Manuscript received July 30. Without losing generality. these are the Euler-Lagrange equations for the functional and it follows that is at an extremum. At steady state we then have d LX dx Kw (A12) Using the assumption KL d dx (L 0. Prigogine developed a local stability result by using the second-order variation of the entropy as a Lyapunov function and looked at small deviations from equilibrium steady states (Glansdorff and Prigogine. We see that the condition of Result A2 is satisﬁed if L is symmetric. t)dx only if KL 1 (L LT ) 0. 1981.66. It follows that K automatically is symmetric. we set u 0. that the functional is not minimized for general w. and (2) address the input output behavior as we have done is the main body of this article. we generalize the results due to Onsager and Prigogine. X. and revision received Mar. Then there exists w so that the right hand side of Eq. . x. 1970. v nj ) T . No. A7).

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