Chapter 3: Equations of Change In the last chapter, we presented examples of microscopic balances in one or two dimensions for various elementary examples. In this chapter we present the general balance equations in multidimensional case. The balances, also called equations of changes can be written in cartesian, cylindrical or spherical coordinates. We will explicitly derive the balance equations in cartesian coordinates and present the corresponding equations in cylindrical and spherical coordinates. The reader can consult the books in reference for more details. Once the equations are presented we show through various examples how they can be used in a systematic way to model distributed parameter models. 3.1 Total Mass balance Our control volume is the elementary volume xyz shown in Figure 3.1. The volume is assumed to be fixed in space. To write the mass balance around the volume we need to consider the mass entering in the three directions x,y, and z. vz)z+z vy)y+y y x vx)x+x vx)x z vy)y z y vz)z x Figure 0-1 Total Mass balance in Cartesian coordinates 102 Mass in: The mass entering in the x-direction at the cross sectional area (yz) is (vx)|x yzt (3.1) The mass entering in the y-direction at the cross sectional area (xz) is (vy)|y xzt (3.2) The mass entering in the z-direction at the cross sectional area (xy) is (vz)|z xyt (3.3) Mass out: The mass exiting in the x-direction is: (vx)|x+x yzt (3.4) The mass exiting in the y-direction is: (vy)|y+y xzt (3.5) The mass exiting in the z-direction is: (vz)|z+z xyt (3.6) Rate of accumulation: The rate of accumulation of mass in the elementary volume is: ()|t+t xyz - ()|t xyz 103 (3.7) Since there is no generation of mass, applying the general balance equation Eq. 1.2 and rearranging gives: (|t+t − |t) xyz = vx|x −vx|x+x)yzt + vy|y −vy|y+y)xzt + vz|z −vz|z+z)xyt (3.8) Dividing the equation by xyzt results in: |t t |t vx |x vx |xx v y | y v y | yy vz |z vz |zz t x y z (3.9) By taking the limits as y,x,z and t goes to zero, we obtain the following equation of change: vx v y vz t x y z (3.10) Expanding the partial derivative of each term yields after some rearrangement: v v v vx vy vz ( x y z ) t x y z x y z (3.11) This is the general form of the mass balance in cartesian coordinates. The equation is also known as the continuity equation. If the fluid is incompressible then the density is assumed constant, both in time and position. That means the partial derivatives of are all zero. The total continuity equation (Eq. 3.11) is equivalent to: 0 ( vx v y vz ) x y z or simply: 104 (3.12) 0 vx v y vz x y z (3.13) 3.2 Component Balance Equation We consider a fluid consisting of species A, B … , and where a chemical reaction is generating the species A at a rate rA (kg/m3s). The fluid is in motion with mass-average velocity v = nt/ (m/s) where nt = nA + nB + … (kg/m2s) is the total mass flux and (kg/m3s) is the density of the mixture. Our objective is to establish the component balance equation of A as it diffuses in all directions x,y,z (Figure 3.2). nAy|y+y z nAz|z y nAx|x+x nAx|x z y x nAy|y nAz|z+z x Figure 0-2 Mass balance of component A Mass of A in: The mass of species A entering the x-direction at the cross sectional (yz) is: (nAx)|x yzt (3.14) where nAx kg/m2 is the flux transferred in the x-direction Similarly the mass of A entering the y and z direction are respectively: (nAy)|y xzt 105 (3.15) (nAz)|z xyt (3.16) Mass of A out: The mass of species A exiting the x, y and z direction are respectively (nAx)|x+x yzt (3.17) (nAy)|y+y xzt (3.18) (nAz)|z+z xyt (3.19) A|t+t xyz − A|t xyz (3.20) The rate of accumulation is: The rate of generation is: -rAxyzt (3.21) Applying the general balance equation (Eq. 1.3) yields: A|t+t − A|t) xyz = (nAx|x+x − nAx|xyzt + (nAy|y+y − nAy|yxzt + (nAz|z+z − nAz|zxyt +rAxyzt (3.22) Dividing each term by xyzt and letting each of these terms goes to zero yields: A n Ax n Ay n Az rA t t t t (3.23) We know from Section 1.11.1, that the flux nA is the sum of a term due to convection Av) and a term due to diffusion jA (kg/m2s): nA = Av + jA 106 (3.24) Substituting the different flux in Eq. 3.23 gives: A ( A v x ) ( A v y ) ( A v z ) j Ax j Ay j Az rA t x y z x y z (3.25) For a binary mixture (A,B), Fick’s law gives the flux in the u-direction as : j Au DAB wA u (3.26) where wA = A/Expanding Eq. 3.25 and substituting for the fluxes yield: v y v z A v A v x A x v y A v z A t y z x y z x DAB wA DAB wA DAB wA ( ) ( ) ( ) rA x y y z z x (3.27) This is the general component balance or equation of continuity for species A. This equation can be further reduced according to the nature of properties of the fluid involved. If the binary mixture is a dilute liquid and can be considered incompressible, then density and diffusivity DAB are constant. Substituting the continuity equation (Eq. 3.13) in the last equation gives: 2 A 2 A 2 A A A vx v y A vz A DAB ) rA 2 2 x 2 t x y z y z (3.28) This equation can also be written in molar units by dividing it by the molecular weight MA to yield: 2C A 2C A 2C A C A C A C A RA D AB v x vy vz x 2 x y z y 2 z 2 reaction accumulation C A t Convection Diffusion 107 (3.29) The component balance equation is composed then of a transient term, a convective term, a diffusive term and a reaction term. 3.3 Momentum Balance We consider a fluid flowing with a velocity v(t,x,y,z) in the cube of Figure 3.3. The flow is assumed laminar. We know from Section 1.11.2 that the momentum is transferred through convection (bulk flow) and by molecular transfer (velocity gradient). zx |z yx |y+y xx |x+x xx |x zx |z+z yx |y y x z Figure 0-3 Balance of the x-component of the momentum Since, unlike the mass or the energy, the momentum is a vector that has three components, we will present the derivation of the equation for the conservation of the xcomponent of the momentum. The balance equations for the y-component and the zcomponent are obtained in a similar way. To establish the momentum balance for its xcomponent we need to consider its transfer in the x-direction, y-direction, and zdirection. Momentum in: 108 The x-component of momentum entering the boundary at x-direction, by convection is: (vxvx)|x yzt (3.30) The x-component of momentum entering the boundary at y-direction, by convection is: (vyvx)|y xzt (3.31) and it enters the z-direction by convection with a momentum: (vzvx)|z xyt (3.32) The x-component of momentum entering the boundary at x-direction, by molecular diffusion is: (xx)|x yzt (3.33) The x-component of momentum entering the boundary at y-direction, by molecular diffusion is: (yx)|y xzt (3.34) and it enters the z-direction by molecular diffusion with a momentum: (zx)|z xyt (3.35) Momentum out: The rate of momentum leaving the boundary at x+x, by convection is: (vxvx)|x+x yzt 109 (3.36) and at boundary y+y,: (vyvx)|y+y xzt (3.37) (vzvx)|z+z xyt (3.38) and at boundary z+z: The x-component of momentum exiting the boundary x+x, by molecular diffusion is: (xx)|x+x yzt (3.39) (yx)|y+y xzt (3.40) (zx)|z+z xyt (3.41) and at boundary y+y: and at boundary z+z:: Forces acting on the volume: The net fluid pressure force acting on the volume element in the x-direction is: (P|x – P|x+x)yzt (3.42) The net gravitational force in the x-direction is: g|xxyzt Accumulation is: 110 (3.43) (vx|t+t − vx|t)xyz (3.44) Substituting all these equations in Eq. 1.5, dividing by xyzt and taking the limit of each term goes zero gives: ( v x ) ( v x v x ) ( v x v y ) ( v x v z ) P ( xx yx zx ) g x t x y z x y z x (3.45) Expanding the partial derivative and rearranging: v y v x v z v x x y z t ( v x v x v x v x t v x x v y y v z z (3.46) yx xx zx P ) g x x y z x Using the equation of continuity (Eq. 3.10) for incompressible fluid, Equation (3.46) is reduced to: v x v v v P v x x v y x vz x ( xx yx zx ) g x x y z x y z x t (3.47) Using the assumption of Newtonian fluid, i.e. xx v x , x yx v x , y zx v x z (3.48) Equation 3.47 yields: 2v v v x v v 2v 2 v P v x x v y x v z x 2x 2x 2x g x t x y z x y z x accumulation generation transport by bulk flow transport by viscousforces 111 (3.49) The momentum balances in the y-direction and z-direction can be obtained in a similar fashion: 2 v y 2 v y 2 v y P v y v y v y v x vy vz g y 2 2 2 t x y z x y z y accumulation (3.50) 2 v z 2 v z 2 v z P v z v z v z v z vx vy vz g z 2 2 2 t x y z x y z z accumulation generation (3.51) v y transport by bulk flow transport by viscousforces transport by bulk flow generation transport by viscousforces These equations constitute the Navier-Stock’s equation. 3.4 Energy balance In deriving the equation for energy balance we will be guided by the analogy that exists between mass and energy transport mentioned in Section 1.11.3 We will assume constant density, heat capacity and thermal conductivity for the incompressible fluid. The fluid is assumed at constant pressure (Fig 3.4). The total energy flux is the sum of heat flux and bulk flux: e = q + CpTv (3.52) Therefore, the energy coming by convection in the x-direction at boundary x is: (qx + CpTvx)yzt (3.53) Similarly the energy entering the y and z directions are (qy + CpTvy)xzt (3.54) (qz + CpTvz)xyt (3.55) 112 The energy leaving the x,y and z directions are: (qx + CpTvx)|x+x yzt (3.56) (qy + CpTvy)y+yxzt (3.57) (qz + CpTvz)|z+z xyt (3.58) The energy accumulated is approximated by: CpT|t+t −CpT|txyz (3.59) q y |y qz |z+z y x qx |x+x qx |x z qy |y+y q z |z Figure 0-4 Energy Balance in Cartesian coordinates The rate of generation is H where H includes all the sources of heat generation, i.e. reaction, pressure forces, gravity forces, fluid friction, etc. Substituting all these terms in the general energy equation (Eq. 1.7) and dividing the equation by the term xyzt and letting each of these terms approach zero yield: ( CpT ) ( CpTvx ) ( CpTv y ) ( CpTvz ) qx q y qz H t x y z x y z 113 (3.60) Expanding the partial derivative yields: v v y vz qx q y qz T T T T Cp vx v y vz CpT x H x y z x y z x y z t t (3.61) Using the equation of continuity (Eq. 3.10) for incompressible fluids the equation is reduced to: T T T T qx q y qz Cp vx vy vz H x y z x y z t (3.62) Using Fourier's law: qu k (3.63) dT du into the last equation gives: 2T 2T 2T T T T T Cp Cp vx vy vz H k x 2 y 2 z 2 t x y z generation accumulation Transport by bulk flow (3.64) Transport by thermal diffusion The energy balance includes as before a transient term, a convection term, a diffusion term, and generation term. For solids, the density is constant and with no velocity, i.e. v = 0, the equation is reduced to: 2T 2T 2T T Cp k 2 2 2 H t x y z generation accumulation Transport by thermal diffusion 114 (3.65) 3.5 Conversion between the coordinates So far we have shown how to derive the equation of change in Cartesian coordinates. In the same way, the equations of change can be written other coordinate systems such as the cylindrical or spherical coordinates. Alternatively, one can transform the equation of change written in the Cartesian coordinates to the others through the following transformation expressions. The relations between Cartesian coordinates (x,y,z) and cylindrical coordinates (r,z,) (Figures 1.3 and 1.4) are the following: x = rcos(), z=z (3.66) y tan 1 ( ) x (3.67) y = rsin(), Therefore; r x2 y 2 , The relations between Cartesian coordinates (x,y,z) and spherical coordinates (r,,) (Figures 1.3 and 1.5) are: x r sin( ) cos(), y r sin( ) sin( ), z r cos() (3.68) Therefore; r x y z , 2 2 2 x2 y 2 tan ( ), z 1 y tan 1 ( ) x (3.69) Accordingly, we list the following general balance equations in the three coordinates. These equations are written under the assumptions mentioned in previous sections. For the more general case, where density is considered variable the reader can consult the books listed in the references. 115 3.5.1 Balance Equations in Cartesian Coordinates Mass Balance ( vx v y vz )0 x y z (3.70) Component balance for component A in binary mixture with chemical reaction rate RA: 2C A 2C A 2C A C A C A C A C A D AB v x vy vz ) R A 2 2 2 t x y z x y z (3.71) Energy balance Cp T T T T 2T 2T 2T Cp(v x vy vz ) k( 2 2 2 ) H t x y z x y z (3.72) Momentum balance x component vx vx vx vx 2vx 2vx 2vx P (vx vy vz ) ( 2 2 2 ) g x t x y z x y z x (3.73) y component: v y t (vx v y x vy v y y vz v y z ) ( 2v y x z component 116 2 2v y y 2 2v y z 2 ) P g y y (3.74) vz vz vz vz 2vz 2vz 2vz P (vx vy vz ) ( 2 2 2 ) g z t x y z x y z z (3.75) 3.5.2 Balance Equations in Cylindrical Coordinates Mass balance ( 1 rvr 1 v vz )0 r r r z (3.76) Component balance for component A in binary mixture (A-B)with reaction rate RA: 1 C A C A C A C A 1 C A 1 2 C A 2 C A vr v vz (r ) 2 ) RA D AB r r t r r z r r 2 z 2 (3.77) Energy balance Cp T T 1 T T 1 T 1 2 T 2T Cp(vr v vz ) k( (r ) 2 ) H t r r z r r r r 2 z 2 (3.78) Momentum balance r component v v r v2 v r v v (v r r vz r ) t r r r z ( 2 2 1 rv r 1 vr 2 v v r P ( ) 2 ) g r 2 2 2 r r r r r r z component: 117 (3.79) vv v v v v v (vr r vz ) t r r r z ( (3.80) 1 rv 1 2v 2 vr 2v P ( ) 2 2 ) g r r r r 2 r 2 z z component v v vz v v 1 vz 1 2vz 2vz P (vr z z vz z ) ( (r ) 2 2 ) g z t r r z r r r z r 2 z (3.81) 3.5.3 Balance Equations in Spherical Coordinates Mass Balance 1 (r 2 v r ) 1 (v sin( )) 1 v 2 r r sin( ) r sin( ) r 0 (3.82) Component balance for component A in binary mixture (A-B) with reaction rate RA : C A C A v vr t r r 1 D AB 2 r v C A C A r sin( ) 2 C A 1 C 1 2C A (r ) 2 (sin( ) A ) 2 2 ) RA r r r sin( ) r sin ( ) 2 (3.83) Energy balance Cp v T T v T T Cp v r t r r sin( ) r 1 T 1 T 1 2T H k 2 ( r 2 ) 2 (sin( ) ) 2 2 r r sin( ) r sin ( ) 2 r r Momentum balance r component 118 (3.84) 2 2 v v v v vr vr v v vr r r r t r r sin( ) r 1 2 r r 2 2 ( r 2 vr ) v 1 2 vr (sin( ) r ) 2 2 r sin( ) r sin ( ) 2 1 2 P g r r (3.85) component: 2 v v v v v v vr v v cot( ) vr r t r r sin( ) r r 1 2 v sin( )v 2v 1 1 ( r ) (sin( ) ) 2 r r 2 r 2 sin 2 ( ) 2 r r 2 v cos( ) v 1 P 2 r g r sin 2 ( ) r (3.86) component v v v v v vr v v v cot( ) vr r t r r sin( ) r r v 1 2 v 2v 1 1 sin( )v 1 ( r ) ( ) r 2 r r r 2 sin(θ ) r 2 sin 2 ( ) 2 (3.87) 2 vr 2 cos( ) v 1 P 2 2 2 r sin( ) g r sin( ) r sin ( ) 3.6 Examples of Application of Equations of change Practically all the microscopic balance examples treated in the previous chapter can be treated using the equations of change presented in this chapter. In this section we review some of the previous examples and present additional applications. 3.6.1 Liquid flow in a Pipe To model the one dimensional flow through the pipe of an incompressible fluid (Example 2.2.1) we may use the continuity balance. For constant density we have the continuity equation in cylindrical coordinates (Eq. 3.76). 119 1 rvr v vz 0 r r r z (3.88) The plug flow assumptions imply that vr = v = 0, and the continuity balance is reduced to: vz 0 z (3.89) 3.6.2 Diffusion with Chemical Reaction in a Slab Catalyst To model the steady state diffusion with chemical reaction of species A in a slab catalyst, (Example 2.2.3) we use the equation of change (Eq. 3.71). The fluid properties are assumed constant, C A C A C A C A 2C 2C A 2C A vx vy vz D A ( 2A ) RA t x y z x y 2 z 2 Since the system is at steady state we have C A 0. t (3.90) If we assume that there is no bulk flow then vx = vy = vz = 0. For diffusion in the z-direction only, the following holds: 0. x y The equation is then reduces to: d 2C A DA RA dz 2 3.6.3 Plug Flow Reactor 120 (3.91) The isothermal plug flow reactor (Example 2.2.5) can be modeled using the component balance equation (3.77). The plug flow conditions imply that vr = v = 0 and 0. r Equation (3.77) is reduced to: C A C A 2C A v z DAB RA t z z 2 (3.92) For the non-isothermal plug flow reactor (Example 2.2.6), the energy balance is obtained by using Eq. 3.78. For fluid with constant properties and at constant pressure, we have: Cp T T v T T 2T 1 T 1 2T 2T Cp(vr vz ) k( 2 ) H t r r z r r r 2 2 z 2 r Using the plug-flow assumptions, vr = v = 0 and 0, r (3.93) and neglecting the viscous forces, the term H includes the heat generation by reaction rate RA and heat exchanged with the cooling jacket, htA(T –Tw). Equation (3.93) is reduced to: Cp T T 2T D Cpv k 2 H r ko e E / RT C A ht (T Tw ) t z z A (3.94) 3.6.4 Energy Transport with Heat Generation Consider the example of a solid cylinder of radius R in which heat is being generated due to some reaction at a uniform rate of H (J/m2s). A cooling system is used to remove heat from the system and maintain its surface temperature at the constant value Tw (Figure 3.5). Our objective is to derive the temperature variations in the cylinder. We assume that the solid is of constant density, thermal conductivity and heat capacity. Clearly this is a distributed parameter system since the temperature can vary with time and with all positions in the cylinder. We will use then the equation of change (Eq. 3.78) in cylindrical coordinates for a solid: 121 T k 2T 1 T 1 2T 2T ( 2 2 2 2 ) H t Cp r r r r z Cp (3.95) T (r = R) R -R T (r = -R) Figure 0-5 Cylindrical solid rod A number of assumptions can be made: The system is at steady state i.e. T 0 t The variation of temperature is only allowed in radial directions. Therefore, the terms 2T 2T and are zero. z 2 2 The energy balance is reduced to: 0 k d 2T 1 dT ( 2 ) H Cp dr r dr Cp (3.96) Or equivalently: ( d 2T 1 dT ) H 2 dr r dr k with the following boundary conditions: The temperature at the wall is constant: 122 (3.97) T (r R) Tw (3.98) The maximum temperature will be reached at the center ( r = 0), therefore: dT 0 dr at r 0 (3.99) Note that Equation (3.97) can also be written as follows: 1 d dT (r ) H r dr dr k (3.100) since qr = −k dT/dr, this equation is equivalent to: 1 d (rqr ) H r dr (3.101) The left hand side is the rate of diffusion of heat per unit volume while the right hand side is the rate of heat production per unit volume. 3.6.5 Momentum Transport in a Circular Tube We revisit example 2.2.2 where we derived the steady state equations for the laminar flow inside a horizontal circular tube. We will see how the model can be obtained using the momentum equation of change. We assume as previously that the fluid is incompressible and Newtonian. The momentum equations of change in cylindrical coordinates are given by Eqs. (3.79-3.81). A number of simplifications are used: The flow has only the direction z, i.e. vr = v = 0. The flow is at steady state, v z 0 t The momentum equation in cylindrical coordinates Eq. 3.81 is reduced to: 123 vz 2v 1 vz 1 2vz 2vz P vz 2z g z z r r r 2 2 z 2 z r (3.102) Using the continuity equation (Eq. 3.76), and since vr = v = 0 gives: dv z 0 dz (3.103) We also note that because the flow is symmetrical around the z-axis we have necessarily no variation of the velocity with , i.e. 2vz 2 0 (3.104) Equation 3.102 is then reduced to d 2 v z 1 dv z dP 2 dr r dr dz Since the left hand side depends only on r, this equation suggests that (3.105) dP is constant. dz Therefore: dp P dz L (3.106) where P is the pressure drop across the tube. Equation 3.105 is equivalent to: d 2 vz 1 dvz P 2 r dr L dr (3.107) with the following conditions identical to those in Example 2.2.2. Note also that Eq. 3.107 can also be written as: 124 d rv z P ( ) dr dr L (3.108) d ( r rz ) P rdr L (3.109) which is also equivalent to: where rz is the shear stress. The left term is the rate of momentum diffusion per unit volume and the right hand side is in fact the rate of production of momentum (due to pressure drop). Note then the similarity between Eq. 3.109 for momentum transfer with Eq. 3.101 for heat transfer. 3.6.6 Unsteady state Heat Generation We reconsider Example 3.6.4 but we are interested in the variations of the temperature of the reactor with time as well. This may be needed to compute the heat transferred during start-up or shut-down operations. Keeping the same assumptions as Example 3.3.4 (except the steady state assumption), the energy balance in cylindrical coordinates yields: Cp T 1 d dT k (r ) H t r dr dr k (3.110) with the initial and boundary conditions: T ( R , t ) Tw (3.111) dT | r 0 0 dr T ( r ,0) Tw (3.112) 3.6.7 Laminar Flow Heat Transfer with Constant Wall Temperature 125 (3.113) We consider a fluid flowing at constant velocity vz into a horizontal cylindrical tube. The fluid enters with uniform temperature Ti. The wall is assumed at constant temperature Tw. We would like to model the variations of the fluid temperature inside the tube. To apply the energy equation of change (Eq. 3.78) we will assume that the fluid is incompressible, Newtonian and of constant thermal conductivity. Since the system is at steady state d/dt = 0 and the flow is one-dimensional vr = v = 0, the energy equation in cylindrical coordinates Eq. 3.78 is reduced to: Cpv z T 2T 1 T 1 2T 2T k( 2 ) t r r r 2 2 z 2 r (3.114) Tw Tb(z) T(r,z) r Tb(0) Figure 0-6 heat transfer with constant wall temperature Since the temperature is symmetrical then the conduction term 2T z 2 2T T = 2 = 0. In some cases we can neglect compared to the convective term v z described by the following energy and momentum equations: 126 T . The system is then z Cpv z T 2T 1 T k( 2 ) t r r r d rv z P ( ) dr dr L (3.115) (3.116) These two equations are therefore coupled by vz, with the previous boundary conditions for vz, At r = R, vz = 0 (3.117) At r = 0, dvz/dr = 0 (3.118) At z = 0, T = Ti (3.119) At r = 0, dT/dr = 0 (3.120) At r = R, T = Tw (3.121) 3.6.8 Laminar Flow and Mass Transfer We consider the example of a fluid flowing through a horizontal pipe with constant velocity vz. The pipe wall is made of a solute of constant concentration CAw that dissolved in the fluid. The concentration of the fluid at the entrance z = 0 is CAo. The regime is assumed laminar and at steady state. The fluid properties are assumed constant. We would like to model the variation of the concentration of A along the axis in the pipe. The component balance for A (Eq. 3.77) is: vr C A C A C A v vz D AB ( r z C A ) 2 2 r C A C A ) rr r 3 2 z 2 (r (3.122) Since vr = v = 0, the balance equation becomes: C A vz D AB ( z C A ) 2 r C A ) rr z 2 (r 127 (3.123) If the diffusion term vz C A z 2C A z 2 in the z-direction is negligible compared to convection term then the last equation reduces to: C A ) (r C A r vz D AB rr z (3.124) The equation (Eq. 3.116) is unchanged. The two equations are coupled through vz. The boundary conditions are analogous to the previous example: At r = R, vz = 0 (3.125) At r = 0, dvz/dr = 0 (3.126) At z = 0, CA= CAo (3.127) At r = 0, dCA/dr =0 (3.128) At r = R, CA= CAw (3.129) Note the similarity between this example and the heat transfer case of the previous example. 128 102
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