Thermodynamics of dry air

• First law of thermodynamics

• Specific heats
• Special cases of the first law
• Potential temperature
• Adiabatic lapse rate
• Static stability
• Brunt-Vaisala frequency
 First Law of Thermodynamics
• Systems may have macroscopic kinetic and
potential energy
• Systems may also have internal energy due
to kinetic and potential energy of its
molecules
• Increases in internal kinetic energy in the
form of molecular motions are manifested
as increases in temperature, while changes in
potential energy of the molecules are caused
by changes in the relative configurations
Consider a unit mass of gas which takes in
a certain quantity of heat q (joules) by
radiation or thermal conduction.

As a result, the gas may do a certain

amount of external work w (joules). The
excess of the energy supplied to the gas
over and above the external work done by
the gas is q-w.
Therefore, if there is no change in
macroscopic energy, from the principle of
energy conservation there must be increase in
the internal energy by q-w. That is
q − w = u2 − u1
Where u1 and u2 are the internal energies of
the gas before and after the change
In differential form,
dq − dw = du
FIRST LAW OF
THERMODYNAMICS
 dq − dw = du

Differential Differential increase

Element of work in internal energy
Differential
Increment of heat
 State Variables
• The change in internal energy du depends
only on the initial and final states of the gas
• du is independent of the manner by
which the gas is transferred between these
two states
• Such parameters, like u, are called functions
of state
• Neither heat q nor work w are functions of
state as their values depend on HOW a gas
is transformed from one state from another
 Cylinder

Working
substance Piston
Distance, x
Consider a gas contained in a cylinder of fixed
cross-sectional area with a moveable, frictionless
piston

The volume V of the gas is proportional to the

distance D from the base of the cylinder as the
cross- sectional area is constant: V  d
 Cylinder

Working
substance Piston
Distance, x
If the piston is moved outwards through an
incremental distance dx, while its pressure remains
essentially constant, the work dw done by the gas
in expanding is equal to the force exerted by the
piston multiplied by the distance dx:
dw = Fdx
but pressure = force / unit area  p = F/A
 F = pA
  dw= pAdx
but Adx = dV  dw  pdV
 The work done by the gas when its volume increases
by a small amount is equal to the pressure of the gas
multiplied by the increase in volume of the gas
 pdV is called p – V work
 For a unit mass of gas we have: dw = pd

dq  du  dw  du  pd
First Law of Thermodynamics
 Joule’s Law

• Joule showed following a series of lab

experiments that when a gas expands without
doing external work, by expanding into a
vacuum, and without taking in or giving out heat,
that the temperature of the gas does not change
 Joule’s Law
•Implications:
 If a gas does not do external work: dw= 0
 If a gas does not take in or give out heat: dq= 0
 From the first law of thermodynamics => du= 0
=> internal energy of a gas is a function of temperature
only
=> the internal energy of an ideal gas is independent
of its volume if the temperature is kept constant
 Specific Heats
 Definition: the amount of heat required to change
the temperature of a unit mass of a substance by
1 degree
 Suppose a small amount of heat dq is given to a
unit mass of gas causing its temperature to
increase from T to T+ dT (without any phase
changes occurring) then the ratio:
dq / dT
is called the specific heat of the gas
 Specific heat can vary depending on how the gas
changes as it receives the heat
  Specific Heat at Constant Volume
If the volume of the gas is kept constant, then we define
the specific heat of the gas as:  dq 
cv   
 dT   const
But if the volume is constant
then dq = du + pd = du  c   du 
v 
 dT   const
Apply Joule’s law for an ideal gas:
u = u(T) only du
 cv 
dT
Whether or not there is a change in volume
dq  cv dT  pd First law of thermodynamics
  Specific Heat at Constant Pressure
If the pressure of the gas is kept constant we can define
the specific heat of the gas as: c   dq 
p
 dT  p const
We showed above that dq = cvdT + pd
= cvdT + d(p) - dp
From the equation of the state: p = RT  d(p) = RdT
 dq  cv dT  RdT  dp  (cv  R )dT  dp

 dq 
If p is constant then
dq = (cv + R)dT
    cv  R  c p
 dT  p const
 Specific Heat at Constant Pressure

 c p  cv  R
By substitution:
dq  c p dT  dp
First law of thermodynamics
 cv= 717 J K-1 kg-1 for dry air
 cp = 1004 J K-1 kg-1 for dry air
 cp = cv+R  R = cp - cv = 287 J K-1 kg-1 which
is the gas constant for dry air

Why is cp greater than cv?

Why is cp greater than cv?
 when the volume is constant, no p-V work can be
done
 when the pressure is constant, a certain amount of
the heat added to the gas will be used to do work
as the gas expands against its environment
 therefore more heat must be added to the gas to
raise its temperature by a given amount if the
pressure is constant compared to when the volume
of the gas is kept constant
 Some Definitions and Concepts

1. Adiabatic: if a gas undergoes a change in

its physical state (p, V, T) without any heat
being added to it or being taken away from
it, the change is said to be adiabatic
For adiabatic processes dq= 0
 du = - dw
 Some Definitions and Concepts

2. Air parcel:
To gain some insights into vertical mixing and
stability it is useful to consider the behavior of an
infinitely small parcel of air that is assumed to be:
 Some Definitions and Concepts (cont’d)
 thermally insulated from its environment so that
heat is not added to or taken away from the parcel
(adiabatic)
 at exactly the same pressure as the environmental
air at the same level (the parcel immediately adjusts
to the hydrostatic pressure at that level)
 moving slowly enough so that its macroscopic
kinetic energy is small (negligible fraction of the
total energy)
 Potential Temperature
Consider an adiabatic process:
From the first law of thermodynamics:
dq  c p dT  dp  0 (for adiabatic process dq = 0)
Rearrange the Equation of State:
p = RT   = RT / p
RT
Substituting for :  c p dT  dp  0
p
or c p dT dp
 0
R T p
cp
 d ln T  d ln p  0
R
 Potential Temperature (cont’d)
cp
d ln T  d ln p  0
R
Integrating from p0 (typically 1000 hPa) where by definition we let
T =  to p: c  p
c
T   p
 d ln T   d ln p  ln   ln 
p p

R  p0
R   p0 
Taking antilogs:
cp R
Poisson’s Equation
T  R  p
    
 p0  cp
   T   θ is potential
  p0   p temperature

For dry air R=Rd=287 J K-1 kg-1 and cp=1004 J K-1 kg-1 ,
Therefore R/cp=0.286
 The potential temperature () of an air parcel
is the temperature that the air parcel would
have if it were compressed or expanded
adiabatically from its initial level (p, T) to a
standard pressure level p0 (usually taken to
be 1000 hPa)
 Potential temperature is conserved for
adiabatic transformations
 Many atmospheric processes are close to
adiabatic, so potential temperature is a useful
parameter
 Potential temperature can be used as a tracer
under adiabatic conditions
Contents to read:

Enthalpy
latent heats:
latent heat of fusion,
latent heat of vaporization,
latent heat of condensation
 Dry adiabatic lapse rate
For dry air undergoing an adiabatic motion,
the potential temperature is conserved, that is,
R
d  p0  cp
0 But   T  
dz  p
Taking natural logs and differentiating with
respect to z: 1 d 1 dT R 1 dp
  0
 dz T dz c p p dz
 Dry adiabatic lapse rate (cont’d)
As the pressure of the parcel adjusts to the
hydrostatic pressure at any level (hydrostatic
equilibrium), dp   g
dz
dT RT g
So we have 
dz p cp
dT g
Using the ideal gas law we get: dz   c  d
p
 Dry adiabatic lapse rate (cont’d)
dT g
  d
dz cp

where d is referred to as the Dry adiabatic lapse

rate (the rate at which temperature falls off with
height in the process of dry adiabatic ascent)
 Dry adiabatic lapse rate (cont’d)
d  g  9.8 K km-1
cp
NOTE d is the rate of change of temperature
following a parcel of air which is being raised
or lowered adiabatically.
The actual lapse rate of temperature, which
we will indicated by , in the atmosphere, as
measured by a radiosonde, averages 6-7 K
km-1 in the troposphere but it takes on a wide
range of values at individual locations.
An example:

An air parcel with temperature of

25oC is initially at the surface.What
is its temperature if it is lifted
adiabatically to a height of 2 km?
Static stability for dry and unsaturated air
Buoyant force on a parcel of air:
The vertical equation of motion is given by
dw 1 dp
 g
dt  dz
So the vertical motion is due to imbalance
between the pressure gradient force and the
acceleration due to gravity. Now if we assume
that the environmental air is in hydrostatic
balance, then  dp 
    g
env
 dz  env
 dw 1  dp 
But for an air parcel:    g
dt  par  dz  par
Now if we assume that the vertical pressure
gradient acting on a parcel is the same as the
environmental vertical pressure gradient at that
level, then  dp   dp  dp
    
 dz  par  dz  env dz
Therefore, we can get
dw 1  dp  1
   g  (  env g )  g
dt  par  dz  env  par
 dw   env   par  This is the Buoyant force
or  g 
dt   par  per unit mass.
dw
• If  env   par then  0 : under this force a
dt
parcel starting at rest will accelerate upward if
it is less dense than the surrounding air
dw

• If env   par then  0 : a parcel at rest will
dt
stay at rest and a parcel in motion will continue
to move at constant speed

• If env   par then
dw
 0 : under this force a
dt
parcel starting at rest will accelerate downward
if it is denser than the surrounding air
Using the ideal gas law, the buoyant force can
also be expressed in terms of temperature as
dw  T par  Tenv 
 g 
dt  Tenv 
or in terms of potential temperature as
dw  par   env 
 g 
dt   env 

The buoyant force will be positive (negative) if

the parcel is warmer (colder) than the ambient
air.
 Static stability of the atmosphere:

One of the use of the dry adiabatic lapse rate is to

assess the stability of atmospheric layers with respect
to the vertical displacement of an air parcel.
Static stability of the atmosphere:

If after a small vertical displacement the parcel at a

given level is subject to a restoring force, which tends
to accelerate it towards the original position, the
atmosphere at that level is said to be stable
• If after a displacement the parcel is subject to a force
in the direction of the displacement, the atmosphere
at that level is said to be unstable
• The stability condition depends on the ambient lapse
rate, that is the decrease of temperature with height
at the level of the air parcel tested
 Lapse rate:
Consider a parcel of air with the ambient
temperature T initially. If it is lifted adiabatically
a small distance z, it cools by the amount d z
and its temperature is reduced toT  d z .
Let us denote the ambient lapse rate by ,
that is,   T    (which should not be confused
 z  with the adiabatic lapse rate!).
Lapse rate:

At height z above the initial position of the

parcel, the ambient temperature is T  z .
So the excess temperature of parcel over ambient
air is
T  d z  (T  z )  z (  d )
• When z (  d )  0 , the parcel is warmer than
its surroundings and therefore is accelerated
upwards. Consequently the air is unstable
whenever   d  0
• Conversely, the parcel is subject to a restoring
force (downward) whenever (  d )  0 .
• For the special case   d , the displaced parcel
experiences zero buoyant force, and the air is
said to be neutral.
The stability criteria for dry air may thus be
summarized as
  d stable
  d neutral
  d unstable
Using the definition of potential temperature,
taking logs and partial differentiation with
respect to height z, and with the definitions for
 and d, we can obtain
1  1
 (d  )
 z T
Equivalently, the stability conditions may be
described by

 0 stable
z

 0 neutral
z

 0 unstable
z
Brunt-Vaisala frequency
The stability conditions can also be obtained
from dw d 2 z  Tpar  Tenv 
 2  g  
dt dt  Tenv 
By expending Tpar(z) and Tenv(z) as Maclaurin’s
Series in z, and neglecting the higher order
terms, the above equation
2
is reduced to
d z g
2
  (d  ) z
dt T
1  1
Using  z  T (d  )
Brunt-Vaisala frequency (cont’d)

2
d z g 
  ( )z  N z
2

dt 2
 z

1
 g   2
where N   has unit of s-1 and
  z 
is called the Brunt-Vaisala frequency.
 1
 g   2
N  
  z 
• For N2=0, the displaced parcel is in neutral
equilibrium and there is no restoring force.
• For N2>0, the equilibrium is stable and the
parcel undergoes oscillatory motion about its
initial position. A typical value of N in the
atmosphere is about 1.210-2 s-1, so that the
period of oscillation is about 8 min.
• For N2<0, the equilibrium is unstable and the
displacement grows exponentially.
Therefore, the stability conditions based on N2
are the same as those by  .
z

Maclaurin’s Series:
x2 x n (n)
f ( x)  f (0)  xf (0)  f (0)    f (0)  Rn ( x)
2! n!
n 1
x
Rn ( x )  f ( n 1)
( x ) 0  1
(n  1)!
Summary:

1. How the first law of thermodynamic is derived?

2. What does it mean by air parcel, potential temperature,
dry adiabatic lapse rate?
3. Under what conditions the atmosphere is said to be stabe,
unstable and neutral? Describe the stability conditions
based on temperature, potential temperature and Brunt-
Vaisala frequency.
Problems:
Assume that the air close to the ground is at
a pressure p0 =1000 hPa and a temperature
T0 = 25oC. The temperature decreases with
height at a constant lapse rate, so that at 500
m it reaches 19oC.
1. Find the pressure p at 500 m level.
2. Compute the potential temperature  at the
ground and at 500 m level.
3. Explain whether the air is stable or not, and
in the latter case, what will happen.
4. State the stability conditions in terms of the
Brunt-Vaisala frequency.