chemical

IEnpiaeerills
sciclk?e,
lOS7.vol.6, pp.l!#Jto 181. puounonpnr Ltd.

The equations of change and the macroscopic mass, momentum,

and energy balances

R. BYRON BIRD
Department of Chemical Engineering, University of Wlsconsln, Bfadison, Wllnsin

(Accepted fewpublic& in revi&dform 6 SqM 1956)

Abstract-It is well-known how the Bernoulli equation of nmthenmtic8l hydrodynamics is

obtained by forming the scalar product of the velocity vector with the Euler equation of motion
for an itwkcid fluid and integrating the rezurltingequation along a &ream&s (Sruxwrrm [a]). It
is here shown how the “engineering Bernoulli equation ” -containing the mechanic8l worh
term and the friction loss term - may be obtained by a similar integration of the N&cr-Stoke-s
equation of motion for a viscous fluid over the oelumeof a flow system. For the sahe of completeness
it is first shown how the macroscopic mass, momentum, and energy bahumes uBed in engineering
are obtained from the “ equations of change ” of theoretical physics. In these derivations the
role played by the movhrg surface8 is taken into account explicitly, and the fluid flowing in the
system may consist of several chemical species with chemical reaction occmring. The development
leads to the unsteady state expressions for the macroscopic balances and the Bernoulli equation.
The correct types of average velocities to be used in the macroscopic balances arise naturally
in the course of the derivations.
B&aum&L’obtention de I’tkpiation de BERNOULLIen mkanique des fluides est bien connue 8
park du prodult scalaire du vecteur vitesse par l’kquation d’EuLER du mouvement d’un fluidenon
visqueux que l’on intigrele long d’unelignede courant(Streeter8). L’auteurindique ici comment
on peut obtenir par une intigration 8nalogue de l’tkpkion de NAVIERSTOKEB, kpmtion de
mouvement d’un fluide visqueux, 1’6quation de BERNOCIILLI utllisable pratiquement, contenant
les termes de travail mk8nique et de perte de charge par frottement. Dans un souci de p&&ion
I’auteur montre comment il obtient B partir des equations d’&hange de la physique thkique,
les bilans massiques, les bilans des moments et lee bilans &wg6tiques. 11 tient compte aussi
dans ses cslculs ; de fapn explicite, du r81e joue per les surfaces en mouvement, et du fait que
le fluide qui s’dcoule peut contenir plusieurs espkes chimiques en reaction. Le developpement
conduit 8 des expressions d%tats de transition pour les bilans macroscopiques et l’dquation
de BERNOUILLI.
Les expressions correctes des vitessea moyennes dont on se sert dsns les bilans macroscopiques
appawissent naturellement en tours de calculs.

THE EQUATIONS OF CHANGE FOR A which moves with the local fluid velocity (BIRD
MULTICOMPONENT SINGLE-PHASE FLUID [I] and HIR~CHFELDER et al. [a].$)
THE differential equations describing the motion
Eqs. of Ccndnuitg :
of a fluid containing v chemical species am the
” equations of change ” which may be derived
from non-equilibrium statistical mechanics
Dp’=-pc(V’v)-(V*j)+r*
Dt i

(HIRSCHFELDERet al. [S]). These equations in the i = 1, 2, 8, . . . v w*

forms given here are applicable to both laminar ---
$ Explicit expressions for the various vector and tensor
and turbulent flow, and apply to non-Newtonian operations in carte&n coordinates are given at the end
as well as Newtonian fluids. They may be written of the artiele.
in two equivalent forms : In the first form they * Addition of all Yequations of the form of eq. (1) fives :
indicate how the mass density of the ith chemical DP
-= - P(V'V)
species pi, the velocity v, and the total energy per Dl
unit mass $ change in a small element of fluid which is the overall equation of continuity.

I28
 R. BYRON BIRD

Eg.OfMOth: The physical significance of the “ microscopic

Dv balances ” in eqs. (4), (5), and (6) is, term by
Pz-- - IV l *J + Pir, (2) term : The equdm of contdnuity states that the
local mass density of the ith species within a
Eq. of Energy : small region changes because of (i) the net influx
of mass of i across the. surface of the region by
Di!i
- (V l q) - (V l (m l v)) + P& Wt mass flow, (ii) the mass flux by diffusional pro-
p-Bi=
cesses (ordinary, thermal, pressure, and forced
In the second form, derivable from the first, the diffusion), and (iii) the production of the ith
equations are written so as to show them as laws species by chemical reaction. The equation of
of conservation of mass, momentum, and energy motion states that the momentum within a small
applied to a small volume element (fixed in space) region changes because of(i) the flux of momentum
through which the fluid is flowing : across the surfaces by mass flow, (ii) the flux of
momentum across the surfaces by pressure and
Eq. of Continuity : viscous forces, and (iii) the external body forces
(which are assumed to be the same for all species
;Pi = - (V rn{PiV + Jr)) + r* (4)
and derivable from a potential : P+ = - Vc).
Eq. of Motion : The equation of energy states that the total energy
within a small region changes because of (i) the
;pv=-(v’{pvv+~})+p~, (5) flux of energy across the surface by mass flow,
(ii), the work done by the fluid in the region on its
Eq. of Ewgy : surroundings (both pressure-volume work and
work asscociated with viscous forces), (iii) the flux
~tP~=-_(v*{PBv+(r*v)+q})+Pa(6) of energy entering the system by heat conduction,
radiation, and mass transfer, and (iv) the heat
t Several &.em&e and completely equivalent formula- produced within the fluid by nuclear radiations.*
tions of the equation of energy balance are available ; one Equations (4), (~9, and (6) are all of the form :
is in term of internal energy and the other in terms of
temperature : (Accumulation) = (Input - Output)
+ (Production)
De .
p-c - (V q) - (n : Vv) + id
l (3s) applied to a flxed differential volume element
M
through which the fluid is flowing.
A DT
0 D> = - (V * q) - (n : Vv) + p-44 The equations of change together with boundary
and initial conditions, the thermal equation of
state (P = P (P, T, pi)), and the caloric equation
‘Y ) of state (U = U (p, T, pi)) give the complete
description of the flow system. In order to calcu-
late concentration, velocity, and temperature
profiles, one has to substitute expressions for
in which the derivative 3p/>T is talcen at constant com- ji, T, and q in terms of the transport coefficients
position and volume, and D, and vi are partial molal
(coefficients of diffusion, viscosity, and thermal
quantities. For single component, constant pressure
systems eq. (3b) may be simplified to : conductivity) and the gradients of the macroscopic

pep g = - (V * q) - (7 : Vv) + & (3c) * The energy relesse accompanying chemical reaction
is not included as a separate contribution in eqs. (3) and
which is the basis for most engineering calculations. The (a), inasmuch as it is inherently included in the internal
term (T : Vv) is the heat produced by viscous dissipation energy contribution to I% The heat of reaction does
(LAMIS [4]) which may generally be neglected in flow appear explicitly when the energy equation is rewritten
problems. in terms of temperature (see ri$ terms in eq. (tb)).

124
 The equations of change and the macroscopic maw, momentum, and energy balances

properties (concentration, velocity, and tempera-

ture). The equations thereby obtained are useful
for laminar flow calculations
: the fixed wetted solid
surface in the system (S,), the movable wetted
surface which allows for the transfer of energy
between the macroscopic system and its sur-
roundings in the form of mechanical work (S,,,),
and the open end surfaces at the control surfaces
(S,, Ss). These different surfaces have to be
treated individually. Throughout it is assumed
that the fluid properties (e.g. density) do not vary
appreciably over the control surfaces S, and S,.
The control surfaces are chosen in such a way
that the flow velocity at S, and S, is, aside from
turbulent fluctuations, parallel to the pipe axis
and normal to the control surfaces. It is further
assumed that transport of mass, momentum, and
energy across S, and S, by molecular processes
may be neglected in comparison with the transport
by mass flow.

2. MACROSCOPIC MASS BALANCE

Integration of eq. (4) over the volume of the
mactipscoic flow system V gives :*

-
V
s (V*py)dV-
V
f (v*jJ&v+
v
s
r,dV (7)

The first two integrals on the right hand side

(0) b) (4
FIG. 1. Macroscopic flow system with mechanisms for (a)
the addition of heat &through fixed surfaoe St and volume
heat ~)urce f& resulting from subatomic radiations, (b)
transfer of mechanical work 6’ to surroundings by means
of motig surface S,,,, and (c) both homogeneous chemical
reaotions iii, and heterogeneous (catalytic) reaotions &.
may be transformed into surface integrals by
means of the divergence theorem. The integral
on the left hand side may be rewritten by taking
the time derivative outside the integral sign. In
so doing, however, one must remember that
because of the moving parts within the flow
system, the shape of the volume V is changing
with time, and hence a term must be subtracted
which accounts for the local gain or loss of mass
by virtue of the motion of the surface. One there-
by obtains :

In the integration of the equations of change
use is made of the Gauss divergence theorem
change the integration over the volume (V)
the divergence of a vector to an integral of the
normal component of the vector over the system
+ The mass flux Ji is the local flux of component i in
to gmacrnea se& referred to a co-ordinate system which in
moving with the local mass average velocity v. The
of
relation of thin flux to other flues (including the flux N,
more usual in chemical engineering) is given in ref. [l],
Table III.

125
 R. BYSONBUD

with the first term which represents mass trans-

port of the ith species by the overall flow motion.
The integrals 8, and k, are the net rates of
production of the ith species by surface reactions
on Sr and by homogeneous reactions in the fluid

Here v,, is the velocity of the Jluid normal to the phase respectively. If now k, = k~ + R<+ and
surface of the system, and v,,,, is the component
of the velocity of the moving surfme which is
4, = PiAS,
normal to the surface (see Fig. 2). Hence eq. (8) it&= i = 1,2,. . .Y
-A&& w-0
becomes. :
______
_______-
__-__
n
where Aj, = j, - j,, Addition of all the v
equations represented by eq. (10) gives :
A __ __________--_----
dsdf;na
&f=-Aj (11)

Equations (10) and (11) are the familiar macro-

scopic mass balances for individual chemical
species and for the fluid as a whole. For steady
state operations i&, and i$f are zero.

8. MACROSCOPIC MOMENTUM BALANCE

Fro. 2. A differentis element of surfaoe.dS of the moving Integration of eq. (5) over the volume gives :*
surface of the macroscopic system moves with an lnstant-
aneous velocity vm ; the component of v, normal to dS
ls %a*
v
s EdV=
‘3t
-
s
V
(V*pw)dV-
s
V
VpdV-

(12)
.
ill,= -
s
S
Pi (%I- %wJds V
s
(V. T)~V+

The left hand side may be transformed as des-

V
s
,&dV

cribed in Section 2. And the first three volunne

integrals on the right hand side may be trans-
formed into surface integrals by means of modi-
fications of the divergence theorem (MILNE-
THOMSON[5], MOIWE and FESEBLCEI[6]).

* The element w3/ of the second-order pressure tensor

In the first term on the right hand side use has w is the force per unit area acting in the x-direction on an
been made of the assumption that pi is constant elemental fluid surface perpendicuhxr to the @rection.
The diagonal elements Q,,, ~4, W, correspond to normal
over the cross-section S, and Se. The integral of
forces, and the non-diagonal elements w,_, = wW
j,,, over Si and S, may be neglected in comparison na = r=, and ‘II p = wsi,correspond to shearing forces.
_ - -. The diagonal elements include both hydrostatic pressure
t In what followswe use o, va, v* for averages over a forces and viscous forces : ra = p + T= ; the non-
cross-sectional area ; specifically for a circular tube these diagonal element.43include only viscous forces : wW = 7isr
are detlned by This is summarked by the tensor relation v = p8 + 7,
an R au R
in which S is the unit tensor (S,, = &, = 8, = 1, all
F= ZPrdrde rlfrde other components are zero). In eq. (12) w is split up into
IS 1, s
0 0 0 0 pandranduse~lsmadeofthefactthat(V:a)=Vp+
where n is 1,2, or 8. (V : 7).

126
 The equatiouaof changetid the macroscopic
mans,momentum,and energybslaneea

$
V
s spvdV=-
S
PV hl - V,“) ds -
s
!!!?$,,=
1 sl V

c
pndS-
c(7=n )a + fP+q
(18)
-
V
(V pkv)dV-
J’
V
(V*(lr*V))dV (16)

Here n is the normal unit vector directed out-

wardly from the system surface. The left hand
side is the time rate of change of the total
s -
I
(V*q)dV+
Ip&dV
V

momentum P of the fluid in the system. The
first term on the right hand side vanishes on all
solid surfaces ; the contribution at S, and S’s
represents the rate of flow of momentum into
and out of the system by virtue of fluid flow
alone. The second term on the right gives a
contribution to the influx and efflux of momentum
due to pressure forces at S, and S’s, and also a
contribution to the drag force on the equipment
on Sf and S,,,. The third term also contributes
to the drag force on the equipment due to viscous
forces on the solid surfaces S, and S, ; in addition
this term includes momentum transport into and
out of the system at S, and S, by viscous action -
a contribution almost always safely neglected. The
fourth term gives the total force exerted on the
fluid in the system by external body forces such
as gravity. Hence one obtains finally ‘the macro-
scopic momentum balance :
@=-A(,&++S)-FFdnO+Fut (14)
or in terms of the mass rate of flow :
The first three volume integrals on the right hand
side may be transformed into surface integrals as
before.
1 p$dV=
s
V
The left hand side is the rate of change of the
total energy in the system. On the right hand
side the first integral is zero except on S, and S,
and represents the energy flowing in and out with
the fluid. The second integral vanishes on S, ; its
value on S, gives the rate at which work is done
on the external surroundings, I$, resulting from
both pressure and viscous forces on the moving
parts : on S, and S’s it contains a term pv,, (the
pressure-volume work) and a term (T v), (the l

shear work), the latter being generally neglected.

i=-A~j+pS)--Fhg+Fext (15)
Here S indicates a vector whose magnitude is the
surface area of the cross section and whose direc-
tion is normal to the cross-section (chosen to point
in the direction of flow!). The vector b is the
mass rate of flow vector similarly defined. The
negative of Fdrae is just the “ reaction force ”
offered by the equipment. Note that the average
value of the square of the velocity appears
properly in the momentum balance (ROUSE and
HOWE [7]).
The third integral gives the heat added to the
system over the solid surface @; there is also a
contribution at S, and Ss which represents the
heat input and outflow by conduction in the fluid
stream, this contribution generally being quite
small in comparison with the heat transport by
bulk flow. Finally the fourth integral represents
the volume heat production &, The surface
integral over I? can be shown as being made up
of internal energy Z?, kinetic energy )v”, and
potential energy d (all on a per unit mass basis).
Then eq. (17) finally becomes :

4. MACROSCOPIC ENERGY BALANCE jj= - A (&ES + &$S + pi) $S + p-S)

Integration of eq. (6) over V gives :

127
 R. BYEONBnm

in which & =6+8+d,andC&f&+Q+.0r, This equation is next integrated over V to give :

in terms of the mass rate of flow, the macroscopic
energy balance is :
Term (a) :

k=-A(fi+#++(~~)+&$j+

Here it is seen that the average value of the cube

&-ti(l9)*
s
v
3(tpvB)dV=
8

of the velocity enters quite naturally (ROUSE and (22)

HOWE [7]). V 8

5. THE “ ENCJINEERING BERNOULLI

= B-
I
8m
(#PUS)v,, ds

J
EQUATION ” Here Z? is the rate of change of the total
The formation of the scalar product of v with kinetic energy within the system
eq. (2) gives (STREETER[S]) after some manipu-
lation :
Term (b) :

p&(4$)=
-(v-W
- (v l (V l T)) + p (v l i+,, I @O)
-
V
(V l tpv*v> d v =
s
81 Pa
&sv%,ds

1
This is an energy equation involving only mech- 9m
anical terms - that is, heat and internal energy
do not appear. The left hand side may be re-
written by using the equation of continuity to
= - A(ipi?S) -
s
&a
~pv%,,dS
(28)

give terms (a) and (b) below ; and the second

term on the right hand side may be split up into
= -A($+~~pv=v,,,,,dS 1
two terms (d) and (e), provided that use is made Sm J
of the fact that T is a symmetric tensor. Thereby
one obtains : The integral over S, just cancels the same
integral in eq. (22) ; the other term gives the
input of kinetic energy at surface 1 minus the
output at surface 2.
(0) (W (4
(21)
- (V (T v)) + (T : Vv) + p (v
l l * 6,)
(a) (Cl U)
.
- (V+*V))dV= - (T l v),ds = - w, (24)
.* For &ad@& jl = 3% and eq. (19) can be written s
V Sm
on a per unit maw basis by dividing through by j.

A(&++)(~,&)+$)=&-6 The contributions of the surface integral over S,

(IW
ant S, are neglected as was done in going from
It should be noted that 4 doee not include the heat pro-
eq. (17) to eq. (IS) ; 6’,, is the rate of transferring
duced by. chemical reaction inasmuch aa that effect is
autmnatically included in the calculation of the iutemal mechanical energy to the surroundings because
energies fr, and & of the inlet and outlet streams. of the viscous forces.
 The equations of change and the macroscopic mass, momentum, and energy balancea

Term (e) :
P
- 1 (v.Vp)dV
+ (r:Vv)dV= - 8, (25) YJ
I
s
V =- (pV*' W dV
P
!l’his the total rate of energy loss by viscous
is V
dissipation within the system (LAMB [4]) - that
is, the friction losses resulting from the degrada-
tion of mechanical energy into heat.
= -~pv,,&W- j%$dV
Term (f) may be evaluated by introducing the V
potential energy, which is related to
=-
S
s pv, iids - &
s
V
pi&V
+ (27)

V V

=-
s
V
(V.&)dV+
s
V
&V.pv)dV

The first of these integrals may be transformed

by using the divergence theorem and the second V S
may be rewritten by using the equation of = -A(pihs)-fL-_p
continuity (and the fact that & is time-
independent) : =-A&i)-k-ti,, J

- ,$&.S -l$$dV The first term gives the rate of influx and efflux
S of 6 ; the second term is the time rate of change
=- of the Helmholtz free energy A = G - p V for
PDF
I the whole system ; and the third term is the work
S
done by pressure forces on the moving parts.
Combination of the results of eqs. (21) through
(27) gives then finally :

=-
S
s p~(v,-vm)ds- b IL+&-k= - *( +;+;+q LJk-E,

where I@ = wO + I#‘r. This is the unsteady state

(28)

=- A(pi&) - cii
engineering Bernoulli equation for an isothermal
=- A@) - b system of constant chemical composition.
For an isentropic system of constant composi-
The first term is just the influx and efflux of tion, term (c) is evaluated by noting that
potential energy, and b is the rate of change of (l/p)dp = da. A similar procedure leads to the
the potential energy of the entire system. result

Term (c) requires special consideration. If the &+&+ti= -A $+$+g j-#--E, (29)
fluid is of constant temperature and composition, ( 1
then use can be made of the fact that (l/p)dp=d& For a system which is neither isothermal nor
and the development parallels the treatment of isentropic or in which chemical reactions are
term (f) : taking place no such simple results may be
 R. BYRONBIRD
written down. The two cases described by eqs.
(28) and (29) are those usually considered in
engineering text (COULSONand RICHARDSON[2]).
For steady state operation j, = js = j, and
the engineering Bernoulli equation may be
written on a per unit mass basis by dividing
through by j to obtain :
A 4-f+ A6 + (30)
For the isothermal, eonstant-composition process
the line integral reduces to A& ; for the isentropic,
constant-composition process the line integral is
Afi. For any other process the best one can do
is to evaluate the line integral over the succession
of thermodynamic states encountered in the flow
NOTATION
A = Hehnholtz free energy
CP = heat capacity at constant pressure
C, = heat capacity at constant volume
E = total energy
En = energy losg due to friction
F+ = volume force = - V0
F at = total external force
Fk = total drag force
G =Glbbsfreeenergy = A +pY
H = enthalpy
ji = mass gux of ith component with respect to the
mass average flow velocity ( Zji = 0)
~=massrateofflow
K = total kinetic energy of macroscopic system
M = total mass of fluid in macroscopic system
M, = mass of the ith species in the macroscopic flow
system
n = outwardly directed normal unit vector
p = static pressure
P = tot.4 momentum of system
q = heat flux vector
qa = normal component of q
Q, = heat transferred across surface of macroscopic
system
Q,, = volume heat source in macroscopic system
ri+ = mass of ith chemical species produced by homo-
. eneous chemical reaction (Zr( = 0)
Ri = total rate of production of mass of the ith species
in the macroscopic system
S = surface of flow system
S/, S, = Axed and moving surfaces of the system
S,, Ss E cross-sectional area of flow system at 1, 2
t = time
from S, to Ss, the integration being performed
over some representative streamline in the
system. This implies that one know, for example,
how p varies with p, T, and composition (specifi-
cation of the equation of state) and how T and
the composition vary with p (specification of the
path of the line integral).
A&u&e--The author wishes to
acknowledge the Wisconsin Alumni Research
Foundation for financial support during the course
of this work. He also desires to thank Professor
C. F. CURTISSand Mr. L. B. ROTHFELD(University
of Wisconsin), Professor J. M. SMITH (Purdue
University), Professor H. G. DRICKAMER(Uni-
versity of Illinois), and Professor W. E. RANZ
(Pennsylvania State University), for reading the
manuscript and offering numerous suggestions.
U = internal energy
v = velocity
%I = normal component of v
V = volume of flow system
0 = velocity averaged over a cross-section
vm = velocity of surface of a moving part
u?lm= normal component of var
W = work done by system on its surroundings
Wv = work resulting from pressure. forces, viscous
forces on movhrg parts of the equipment
A = quantity evaluated at Sa minus quantity evalu-
ated at S,
I=unittensor
n =pi+7 = pressure tensor
p= mass density = (l/e) = Xpt
pi = mass density of ith chemical species
7 = shear stress tfmor
Q, = potential energy
Marks above qmbok :
A = quantity per unit mass of fluid
- -5 quantity averaged over cross-section of flow
system
- = time rate of change of quantity, pertaining to
the macroscopic system
&bb8CTipte :
f = quantity associated with tlxed surface
m. = quantity associated with moving surface
4 = quantity associated with the fluid
n = normal component of a vector
v= quantity associated with viscous effects
p = quantity associated with pressure effects
i = ith chemical species
 The equations of change and the macmscopic mass, momentum, and energy balances

Vector and Tensor Operationa in Cariesian Co-ordinaics* 8 = second order unit tensor with three compo-
Seabus are indicated by light face symbols nents &i = 1 and six components $, = 0
(i =i=j)
Vectors are indicated by bold face Roman symbois
Tensors are indicated by bold face Greek symbols Vp&!! + k:s =the “gradient of p”
dafj$
i, j, k = unit vectors in s, Q, a directions
v = iv, + ju, f kv, = vector with 8 components (V . v) = ?!! + ‘“# + ‘3 = the “ divergence of v ”
3x ay 32
cs, f, c*
T = second order tensor with 9 components rsr,
(V . s)= = %dl
-~ +%$+2
I-, I=, etc.?
w = dyadic product with 9 components v#e, v&,,
og,, etc. (V * P-% = $ P,v, + $ P*“al+ ; Pwz
v* = (v * v) = fl*= + v = + v 3
(v ’ w) = y#Jz + upp + v:wz = z&alarproduct of two (v l qp = (v : Vp) = we g + ov $ + D‘ g
vector8
(T * v)= = Tda + T@#t&+ ‘I&* (T : Vv) = c c r,p (bv,/iJiq (u, B = d, 1y.2)
Vv = t&&c product with nine components 30,/3x,
* See ref. [l] for a tabulation of the more difhcuit
operations in cyclindrical and spherical co-ordinates. WV/&r, W&x, &/3y, etc.
7 All tensors used in this article are %ymmetric” - that Dp = G
@J+ (v - V)p = the “ substantial derivative
is 7.J = Tji* m of p ”

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PI HIRSCHFELDERJ. O., CURTISS C. F., and BIRD R. B. Molecule Theoq of Gaacs and Liquids, Wiley, New York
(1954) Sections 7.2e, Q&l, ll.lb.
PI LAMB H. F&drcd~namics, Cambridge University Press, 0th ed. (1982) 579-581.
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181