DEPARTMENT OF CHEMICAL ENGINEERING CH 503 TRANSPORT PHENOMENA EQUATIONS OF CHANGE IN MULTICOMPONENT SYSTEMS

Transport of momentum, heat and mass is widely described using "equations of change". The development of these equations is based on several assumptions. The mathematical description that is sought is a functional relation between the dependent variables - i ( i=1.....n), T and v - and the independent variables - r and t. The development is conveniently divided into two parts: the "Phenomenological Theory" describes phenomena without any special reference to the nature, geometry of the specific system of interest and its interaction with the surroundings. Such a description introduces into the equations, formally and necessarily, additional unknowns usually refered to as "fluxes": p, , q and ji. These fluxes are then related to the variables through empirical "constitutive relations" that describe the nature of individual systems. The geometry of the system and its interactions with the surroundings are conveniently described by a suitable choice of coordinates and a specification of "boundary conditions".

There are a total of n+4 dependent variables in an n-component system. The law of conservation of mass provides n equations ( one for each component) and

Newton's law provides three equations for the three components of the momentum and the first law of thermodynamics provides an equation for the energy. Thermodynamics also provides a `constitutive relation' for the pressure in the form of an equation of state. It is implicitly assumed here that the equilibrium relations of thermodynamics continue to hold in these systems in a localised manner. For example the pressure in the fluid element of volume dr about r is the same function of i(r,t) and T (r,t) as in the fluid at equilibrium. The second law of

thermodynamics, being an inequality under non-equilibrium conditions plays only a "supervisory" nonetheless important role: it sets constraints that constitutive relations have to satisfy.

The laws are conveniently formulated for the Lagrangian observer, one who moves with the centre of mass of the system of interest. The system is conveniently chosen as one of constant total mass: thermodynamically "closed". Experimental observations are conveniently made by an Eulerian observer in laboratory-fixed coordinates. The mathematical transformations relating the rates of change of physical quantities as seen by the two observers is described by the "Reynold's transport theorem. In the equations that follow the Lagrangian derivatives are denoted as D/Dt. The Eulerian derivatives are written appropriately as partial derivatives.

General form of equation of change:

D( g) ( g) g = + . v.g = + v. g = - . j + g g t Dt t
The equalities are successively from the Reylond's transport theorem, the continuity equation and the form of the phenomenological law. Notation: g jg g i v b k q u Mi Hi Vi Si : : : : : : : : : : : : : : property per unit mass = G/mass of system flux of G relative to CM generation of G per unit volume mass density of species i velocity of centre of mass body force per unit mass mass stoichiometric coefficient of species k deviatoric shear stress heat flux internal energy Molecular mass of i partial molal enthalpy/Mi partial molal volume/Mi partial molal entropy/Mi
D = + v. Dt t

D/Dt is denotes the substantive derivative:

Some identities: (a) (b) .p I = p

.( p v ) = p .v + v . p

(c) (d) (e) (f)

v . v = ( v 2 / 2 ) v x ( x v ) v.( v. v ) = v. ( v 2 / 2 )
. ( .v ) = v. . + : v .v = v.
.( q / T ) = q T
2

f or sym m et r ic
T + 1 . q T

(g)

Specific equations of change (1)

R dk / Dx i / = . j + i k i Dt dt k =1

/ Com pon ent i

g = xi
g =1 g=v

(2)

D = .v Dt

/ 1 / Con t u n it y

(3)

r Dv = p . + i b i Dt i =1

/ 2 ,a / Mom en t u m

(4)

D ( v 2 / 2 ) = . p v . ( .v ) + i v i . b i Dt + p .v + : v / v, 3 ,b,d,e/ Mech . En er gy

g = v2 / 2

(5)

r De = . p v .( .v ) . q .( j i H i ) Dt L =1 + i v i . b i / 2 ,e/ Tot al en er gy g = e = u + v 2 / 2

(6)

Du = p .v v .q . ( j H i ) i Dt j . bi / 5 4 / I nt er n al ener gy
i

g=u

(7)

Ds = .( q / T ) .( j Si ) i Dt

+ s

/ Ent r opy g = s

(8)

Dx i P D Ds Du = i Dt T Dt Dt T Dt T

/ Fir st and Second law

(9)

Ts =

Dx i Du D P/ i + .q. Dt Dt Dt q. ln T + T .( j Si ) / 7 ,8 ,g / En t r opy gen er at ion

i

Explicitly
T s = q . l n T j .( H i b i T S i )
i

( . j ) ( H i i TSi ) : v
i

Gk ( d / k / dt )
k =1

Thermodynamic identities
H i = i + TSi ; H i = i + T Si + Si T ; T i / i b i + Si T

Entropy generation rate per unit volume (g) (10) s =

R d/ k 1 {q. lnT + j. T i / + : v + G k } i T k =1 dt

Conjugate fluxes and forces Force: Flux q

ln T Fouriers law Soret effect x x

T i /

G k

Dufour effect Ficks law x x

x x Newtons law ?

x x ? ?

ji d/k/dt

x: denotes that, in isotropic systems, contribution to flux from force possible only when tensorial orders differ by an even number.

Remarks: `System has constant total mass. Observer moves with CM of system.

Hence all fluxes are relative to CM motion. Thermodynamic quantities are per unit

mass = (partial molal property)/Mi. Gk is per mole. Hk will not appear explicitly in 5 or 6. It appears in T equation only. q here is the same as qc in BSL. Equation for T from basic equation for internal energy. Dx i p p 1 D Du DT = p T Vi + Cv + H i T T Dt Dt T Dt Dt

(10)

r p p dk / DT k/ C v =T ( . v ) + H l T V l . j i i Dt T T dt l =1

.q . j H i : v + j .b i i i

..../1,2,6,j,k/ Energy equation in terms of temperature. Equations 1, 3 and 10 plus equation of state give r + 5 equations for unknowns i, v, T, p. Variables , ji, q are related to these quantities through `constitutive relations Independent variables are r,t. The second law of thermodynamics requires that s0. Constitutive relations are usually obtained empirically.

The tables below are from Bird, Stewart and Lightfoot, Transport Phenomena Table I: The equation of continuity in several coordinate systems

(A)

(B)

(C)

Table II (a): The equation of motion in rectangular coordinates (x, y, z)

(A)

(B)

(C)

(D)

(E)

(F)

Table II (b) : The equation of motion in cylindrical coordinates (r, , z)

In terms of : r-componenta

-componentb

z-component

In terms of velocity gradient for a Newtonian fluid with constant and : r-componenta

-componentb

z-component

Table II (c): The equation of motion in spherical coordinates (r, , )

(A)

(B)

(C)

In terms of velocity gradients for a Newtonian fluid with constant and :

r-component

-component

-component

Table III: Components of the stress tensor for Newtonian fluids (a) Rectangular coordinates (x,y,z) (b) Cylindrical coordinates (r, , z)

(A)

(A)

(B) (C) (D)

(B)

(C) (D) (E) (F)

(E) (F)

(G)

(G)

(c) Spherical coordinates(r, , )

(A) (B)

(C) (D) (E) (F) (G)

Table IV: The function ( : v) = v for Newtonian fluids

Rectangular

Cylindrical

Spherical