A derivation of the first law of thermodynamics

A derivation of the first law of thermodynamics for a fluid is presented here. The basic
elements of the derivation presented here follow the arguments given in Holton, An In-
troduction to Dynamic Meteorology, 2004. Consistent with our earlier description of fluid
mechanics, 1d fluid flow is assumed. (The corresponding derivation in 3d is more narural,
but requires a good knowledge of vector calculus.)
We begin with a restatement of the equations of motion of fluid mechanics in 1d. Mass
conservation is expressed by the equation
dρ ∂v
+ρ = 0. (1)
dt ∂x
For convenience the variable A used earlier to denote the cross-sectional area of the pipe or
duct is assumed to be constant, and therefore has been factored out. This assumption puts
the focus on the compressibility of the fluid, which is of central importance in thermody-
namics. Newton’s second law for an inviscid (frictionless) fluid in 1d is

dv ∂p
ρ =− .
dt ∂x
After multiplication by v, this equation can be written
d 1 2 ∂p
 
ρ v = −v . (2)
dt 2 ∂x
Consider the product pv, whose dimensions are N/m2 × m/s = (N × m/s)/m2 = (J/s)/m2 .
This quantity is related to the time rate of change of work done per unit area. Specifically,
the local change in this quantity is the local time rate of change of work done by the fluid
per unit area. Thus
" #
dWork ∂(pv) ∂(pv)
= [(pv)x+δx − (pv)x ]δyδz = δx δyδz = δV. (3)
dt ∂x ∂x

Here δxδyδz = δV is a small element of volume.

The general form of the equation describing the time rate of change of the total energy
of a small element of mass ρδV , including an unspecified source/sink term, is

dE dWork dq
+ = . (4)
dt dt dt
Here E is the sum of all contributions to the energy of the fluid that do not contribute to
the work done, Work is the work done by the fluid and q is the heat added to or taken
from the the fluid. (Heat exchange mechanisms are radiation, conduction and latent heat
exchange, i.e., heat exchange associated with phase changes.) Let e0 denote the internal (or
microscopic) energy per unit mass of the fluid. The external (or macroscopic) energy per
unit mass of the fluid is v 2 /2. Thus E = ρδV (e0 + v 2 /2). Let q 0 denote the heat gained or
lost by the fluid per unit mass, so q = ρδV q 0 . Then, combining Eqs. (4) and (3) gives

de0 v2 dq 0
" !#
d ∂
ρδV + + δV (pv) = ρδV . (5)
dt dt 2 ∂x dt
Note that ∂(pv)/∂x = p ∂v/∂x + v ∂p/∂x. Dividing Eq. (5) by ρδV and subtracting Eq. (2)
gives
de0 p ∂v dq 0
+ = . (6)
dt ρ ∂x dt
Substituting ∂v/∂x = −ρ−1 dρ/dt [from Eq. (1)] gives

de0 p dρ dq 0
− 2 = . (7)
dt ρ dt dt
This equation is a statement of the first law of thermodynamics. Had we included gravity in
our derivation, the final result, Eq. (7), would have been unchanged; gravitational potential
energy would have been included in Eqs. (2) and (5), but those terms would have cancelled
in Eq. (6).
The first law, Eq. (7), is written in a slightly different the form in your textbook. In that
book – and most introductory textbooks – the time dependence of thermodynamic processes
is not considered. Multiplication of Eq. (7) by dt puts the emphasis on changes in the
thermodynamic variables. Also, to simplify the treatment of enclosed systems whose volume
may change, we multiply Eq. (7) by mass m, introduce e = me0 , q = mq 0 , and note that
because ρ = m/V , ρ−2 dρ/dt = −m−1 dV /dt. With these trivial changes, Eq. (7) becomes

de + pdV = dq. (8)

Note that +pdV is the work done by the system, while −pdV is the work done on the system.
The preceding derivation should make clear that e is the internal energy of the fluid asso-
ciated with random motions of the molecules that comprise the fluid, while the source/sink
term dq is the heat added to or lost from the fluid. Consistent with kinetic theory, the
internal energy e depends only on the temperature of the fluid. For example, if the fluid is
at rest, it has zero macroscopic kinetic energy because the mean velocity of the molecules in
the fluid is zero, but an increase in temperature of the fluid increases rms molecular speeds,
thereby increasing the internal – or microscopic – energy of the fluid.