2.4 The Microscopic Mass Balance Equations in Thermodynamics and Fluid Mechanics A2.

4-1

2.4 THE MICROSCOPIC MASS BALANCE EQUATIONS

IN THERMODYNAMICS AND FLUID MECHANICS1
The balance equations we have developed thus far are those commonly used in engi-
neering thermodynamics. An important characteristic of these equations is that they
are balances for large, black-box systems2 and: therefore, yield information only about
the total mass or the rate of change of mass in the system. Frequently, it is useful to
have information not about the total mass, but about the mass density at each point in
the system. To get a balance equation for mass density at any point in the system, we
must start with a system of microscopic (or differential) size. There is some advantage
to developing the microscopic balance equations here. First, it exposes the essential
similarity between thermodynamics and uid mechanics, and, second, these equations
will be of use in the following chapters. However, since the formulation of these equa-
tions requires a greater degree of mathematical complexity than has been used hereto-
fore, and since these equations are of only peripheral interest in our development of
thermodynamics, you may wish to proceed directly to Chapter 3.
To obtain the microscopic equations of uid mechanics and thermodynamics, we
apply the general balance equation, Eq. 2.1-4, to the small stationary volume element of
Fig 2.4-1. This volume element, of dimensions Δx, Δy , and Δz , is part of a much larger
uid system, so the boundaries are not physical boundaries and mass can ow across
each of its faces. Finally, since this volume element is of innitesimal size (our interest
is in the case in which Δx, Δy , and Δz simultaneously go to zero), the properties within
it can be assumed to be uniform. Thus, the mass contained within the volume element
is ρ Δx Δy Δz where ρ is the mass density within the innitesimal volume element.
With this introduction we can now make the following identications in Eqs. 2.1-4:
 
Rate of change of mass in ∂ρ
= Δx Δy Δz (2.4-1a)
the volume element ∂t
( )
Net rate at which
mass enters the = ρυx Δy Δz |x − ρυx Δy Δz |x+Δx
volume element + ρυy Δx Δz |y − ρυy Δx Δz |y+Δy
+ ρυx Δx Δy |z − ρυz Δx Δy |z+Δz (2.4-1b)

where x, y , and z are the rectangular coordinate directions and υi is the uid velocity
in the ith coordinate direction. The interpretation of the terms in Eq. 2.4-1b is as fol-
lows. The mass ow into the volume element across the face of the volume element
perpendicular to the x-axis at x is

ρυx Δy Δz |x
where Δy Δz is the area of the face and ρυx is the ow rate in the x direction per unit
area. Similarly, the term
−ρυx Δy Δz |x+Δx

1 Thissection is optional—only for graduate and advanced undergraduate students.

2 Herethe term black box is being used to indicate that we did not consider the exact details of what was inside
the box or system for which we were writing the balance equation. That is, we were concerned only with the total
mass in the system, not the details of how it was distributed within the system or the mass density at every point.
A2.4-2 Chapter 2: Conservation of Mass

Δz

Δy
Δx
x

Figure 2.4-1 Volume element for a microscopic

y balance equation.

is the mass ow out of the volume element at the face perpendicular to the x-axis at
x + Δx and therefore has a negative sign. The remaining terms in Eq. 2.4-1b represent
the mass ows into and out of the other faces of the volume element.
Using Eqs. 2.4-1 in Eq. 2.1-4 yields
∂ρ
Δx Δy Δz = ρυx Δy Δz |x −ρυx Δy Δz |x+Δx + ρυy Δx Δz |y −ρυy Δx Δz |y+Δy
∂t
+ ρυz Δx Δy |z −ρυz Δx Δy |z+Δz

Now, dividing by Δx Δy Δz and taking the limit as Δx, Δy , Δz go to zero gives

∂ρ ρυx |x −ρυx |x+Δx ρυy |y −ρυy |y+Δy ρυz |z −ρυz |z+Δz

= lim + lim + lim
∂t Δ x→ 0 Δx Δy →0 Δy Δz →0 Δz
(2.4-2)
Finally, using the denition of the partial derivative, that is

∂F (x, t) F (x + Δx, t) − F (x, t)

= lim (2.4-3)
∂x Δx→0 Δx
we obtain
∂ρ ∂(ρυx ) ∂(ρυy ) ∂(ρυz )
= − −
∂t ∂x ∂y ∂z
or, in vector notation,
∂ρ
Continuity equation = −∇ · (ρv) (2.4-4)
∂t
Equation 2.4-4 is the mass conservation equation for a stationary differential volume
element; in uid mechanics it is called the continuity equation. This equation can be
rearranged to yield
∂ρ
= −ρ∇ · v − v · ∇ρ
∂t
or
∂ρ Dρ
+ v · ∇ρ ≡ = −ρ∇ · v (2.4-5)
∂t Dt
2.4 The Microscopic Mass Balance Equations in Thermodynamics and Fluid Mechanics A2.4-3

vΔ t

r
r + Δ r = r + vΔ t
x

Figure 2.4-2 Positions of a moving volume element

y at t and at t + Δt.

Here we have introduced the notation D/Dt = ∂/∂t + v · ∇, where D/Dt is the
convected derivative; it is the derivative with respect to time in a volume element mov-
ing with uid velocity v. To see this, consider the moving volume element shown in
Fig. 2.4-2. The position vector of the center of this volume element is r at time t, and
r + Δr at time t + Δt, where Δr = vΔt. The time derivative of any function F taken
in this moving differential volume, DF/Dt, is dened, in analogy with Eq. 2.4-3, as
{ }
DF F (r + Δr, t + Δt) − F (r, t)
= lim
Dt Δt→0 Δt
{ }
F (r + Δr, t + Δt) − F (r + Δr, t) F (r + Δr, t) − F (r, t)
= lim +
Δt→0 Δt Δt
{ }
F (r + Δr, t + Δt) − F (r + Δr, t) Δr F (r + Δr, t) − F (r, t)
= lim + ·
Δt→0 Δt Δt Δr
or
DF ∂F
= + v · ∇F (2.4-6)
Dt ∂t
where we have used the fact that limΔt→0 Δr/Δt = v, and Δr → 0 as Δt → 0.
Equation 2.4-4 can be integrated over a nite volume element to obtain Eq. 2.2-1b.
Since this requires the use of certain mathematical theorems that may be unfamiliar to
you, this integration will not be pursued here except to point out that for a stationary
system (υ = 0) we can integrate the left side of Eq. 2.4-4 over the volume V to obtain
∫ ∫
∂ρ d dM
dV = ρ dV =
∂t dt dt

which is equal to the left side of Eq. 2.2-1b. A similar correspondence exists between
the right sides of Eqs. 2.2-1b and 2.4-4, but this is more difcult to prove. This analy-
sis does establish a very important general relationship; the black-box thermodynamic
equations developed in Sec. 2.2 can be obtained by an integration over volume of the
more detailed microscopic equations.
At this point, it is useful to reect on the three levels of description used in this book.
First, the microscopic equations, of which the mass conservation equation developed
here is only the rst, require detailed information about the internal structure and in-
ternal ows in any macroscopic system in order to be of use. Next, by integration over
A2.4-4 Chapter 2: Conservation of Mass

a nite volume element these microscopic equations result in an equation for the time
rate of change for the black-box description of the system. For these equations to be
of use, only information about ow rates into and out of the system as a function of
time is needed. Finally, by integration over time of the time rate-of-change equations,
we obtain equations for the change over an interval of time of various properties of the
black-box system. For these last equations to be useful, one merely needs information
about the total ows into and out of the system over the time interval, and not a history
of how these ow rates varied with time.