Non-Reacting Gas Mixtures
Reading Problems
13-1 13-3 13-52, 13-60
14-1 14-7 14-32, 14-35, 14-68, 14-71, 14-75
14-79, 14-103, 14-112
Introduction
homogeneous gas mixtures are frequently treated as a single compound rather than many
individual constituents
the individual properties of inert gases tend to be submerged, such that the gas behaves as a
single pure substance
eg. - air consists of oxygen, nitrogen, argon and water vapour. But dry air can be treated as
a simple gas with a molar mass of 28.97 kg/kmole
equations can be derived to express the properties of mixtures in terms of the properties of
their individual constituents
it is assumed that each constituent is unaffected by the other constituents in the mixture
P-V-T Relationships for Ideal Gas Mixtures
Amagat Model (law of additive volumes)
the volume of a mixture is the sum of the volumes that each constituent gas would occupy if
each were at the pressure, P and temperature, T, of the mixture
T, P T, P T, P
m
A
m
B
remove m
C
= m
A
+m
B
n
A
n
B
n
C
= n
A
+n
B
V
A
V
B
partition V
C
= V
A
+V
B
the volume that n
i
moles of a component i would occupy at P and T is called the partial
volume, V
i
V
i
=
n
i
RT
P
1
The volume of the gas mixture is equal to the sum of the volumes each gas would occupy if it existed
at the mixture temperature and pressure.
V =
j
i=1
V
i
Dalton Model (law of additive pressures)
the pressure of a mixture of gases is the sum of the pressures of its components when each
alone occupies the volume of the mixture, V , at the temperature, T, of the mixture
V, T V, T V, T
m
A
, n
A
, P
A
+ m
B
, n
B
, P
B
= m
C
= m
A
+m
B
n
C
= n
A
+n
B
P
C
= P
A
+P
B
for a mixture of ideal gases the pressure is the sum of the partial pressures of the individual
components
The pressure of a gas mixture is equal to the sum of the pressures each gas would exert if it existed
alone at T and V .
By combining the results of the Amagat and Dalton models i.e. (1) and (2), we obtain for ideal gas mixtures
P
i
P
=
V
i
V
=
n
i
n
Therefore, Amagats law and Daltons law are equivalent to each other if the gases and the mixture
are ideal gases.
2
Mixture Properties
Extensive properties such as U, H, c
p
, c
v
and S can be found by adding the contribution of each
component at the condition at which the component exists in the mixture.
U =
U
i
=
m
i
u
i
= m
X
i
u
i
= mu
=
n
i
u
i
= n
Y
i
u
i
= nu
where u is the specic internal energy of the mixture per mole of the mixture.
u =
X
i
u
i
h =
X
i
h
i
c
v
=
X
i
c
v
i
c
p
=
X
i
c
p
i
s =
X
i
s
i
Changes in internal energy and enthalpy of mixtures
u
2
u
1
=
X
i
(u
2
u
1
)
i
=
_
T
2
T
1
c
v
dT = c
v
(T
2
T
1
)
h
2
h
1
=
X
i
(h
2
h
1
)
i
=
_
T
2
T
1
c
p
dT = c
p
(T
2
T
1
)
s
2
s
1
=
X
i
(s
2
s
1
)
i
= c
p
ln
T
2
T
1
Rln
P
2
P
1
These relationships can also be expressed on a per mole basis.
Entropy Change Due to Mixing of Ideal Gases
when ideal gases are mixed, a change in entropy occurs as a result of the increase in disorder
in the systems
if the initial temperature of all constituents are the same and the mixing process is adiabatic
3
temperature does not change
but entropy does
S =
_
m
A
R
A
ln
P
A
P
+m
B
R
B
ln
P
B
P
+
_
=
j
i=1
m
i
R
i
ln
P
i
P
= R
j
i=1
n
i
ln Y
i
4
Psychrometrics
studies involving mixtures of dry air and water vapour
used in the design of air-conditioning systems, cooling towers and most processes involving
the control of vapour content in air
for T 50
C (P
sat
13 kPa) h h(T)
water vapour can be treated as an ideal gas
Denitions
Moist Air
a mixture of dry air and water vapour where dry air is treated as if it were a pure component
the overall mixture is given as P =
mRT
V
Total Pressure
P = P
a
+P
w
P
a
=
m
a
R
a
T
V
P
w
=
m
w
R
w
T
V
where P
a
is the partial pressure of air and P
w
is the partial pressure of water vapour. Typically
m
w
<< m
a
.
Relative Humidity -
=
P
w
(T)
P
sat
(T)
=
vapour pressure at the prevailing T
saturation pressure at the prevailing T
If P
w
= P
sat
(T) the mixture is said to be saturated.
Specic Humidity (Humidity ratio) -
=
m
w
m
a
=
mass of water vapour
mass or air
5
=
M
w
n
w
M
a
n
a
=
M
w
(P
w
V/RT)
M
a
(P
a
V/RT)
=
M
w
M
a
_
P
w
P
a
_
= 0.622
_
P
w
P
a
_
In addition can be written as
= 0.622
_
P
w
P
a
_
= 0.622
_
P
w
P P
w
_
= 0.622
_
P
sat
P P
sat
_
which can be rearranged in terms of relative humidity
=
P
P
sat
M
w
M
a
=
P
P
sat
( + 0.622)
Dry Bulb Temperature - the temperature measured by a thermometer placed in a mixture of air
and water vapour
Wet Bulb Temperature
6
thermometer surrounded by a saturated wick
if air/water vapour mixture is not saturated, some water in the wick evaporates and diffuses
into the air cooling the water in the wick
as the temperature of the water drops, heat is transferred to the water from both the air and
the thermometer
the steady state temperature is the wet-bulb temperature
Sling Psychrometer - a rotating set of thermometers one of which measures wet bulb temperature
and the other dry bulb temperature. T
DB
and T
WB
are sufcient to x the state of the mixture.
The Psychrometric Chart
where the dry bulb temperature is the temperature measured by a thermometer place in the mixture
and the wet bulb temperature is the adiabatic saturation temperature.
7
An Adiabatic Saturator
How can we measure humidity?
the adiabatic saturator is used to measure humidity
two inlets, single exit device through which moist air passes
air-water mixture of unknown humidity enters at a known pressure and temperature
if air/water mixture is not saturated, ( < 100%), some water from the pool will evaporate
the energy required to evaporate the water comes from the moist air mixture temperature
decreases
for a sufciently long duct, the moisture exits with
3
= 1
the temperature of the exiting mixture is called the adiabatic saturation temperature
Adiabatic Saturator Analysis
Conservation of Mass
m
a,1
= m
a,3
air (1)
m
w,1
+ m
w,2
= m
w,3
water (2)
Conservation of Energy
( mh)
a,1
+ ( mh)
w,1
+ ( mh)
w,2
= ( mh)
a,3
+ ( mh)
w,3
(3)
8
By denition
1
=
_
m
w
m
a
_
1
(4)
3
=
_
m
w
m
a
_
3
(5)
From (2) and (1)
_
m
w,2
m
a,1
_
=
m
w,3
m
a,1
. .
m
a,3
_
m
w,1
m
a,1
_
=
3
1
Dividing (3) by m
a,1
and noting m
a
1
= m
a
3
and
m
w
2
m
a
1
=
3
1
h
a,1
+
1
h
w,1
+ (
3
1
) h
w,2
= h
a,3
+
3
h
w,3
(6)
1
=
(h
a,3
h
a,1
) +
3
(h
w,3
h
w,2
)
(h
w,1
h
w,2
)
9
If we assume:
i) air is an ideal gas and (h
a,3
h
a,1
) = c
pa
(T
3
T
1
)
ii) (h
w,3
h
w,2
) = h
g
h
f
= h
fg
(T
3
)
iii) h
w,1
h
g
(T
1
)
iv) h
w,2
= h
f
(T
2
) = h
f
(T
3
)
then we can write
1
as a function of T
1
and T
3
only
1
=
c
pa
(T
3
T
1
) +
3
h
fg
(T
3
)
h
g
(T
1
) h
f
(T
3
)
Aside: Since h
f
<< h
g
very little is lost if the denominator is approximated as h
fg
(T
1
)
During the adiabatic saturation process, the vapour pressure increases and the temperature de-
creases; so the adiabatic saturation temperature is higher than the dew point temperature and lower
than the dry bulb temperature. For the limiting case of a saturated mixture, the dry bulb, dew point
and adiabatic saturation temperature are the same.
Equation 6 can be written as
h
1
+ (
3
1
)
. .
negligible
h
,2
= h
3
where
h
= h
a
+ h
w
Therefore h
1
h
3
(T
wb
). The lines of wet bulb temperature and h
coincide on the psychromet-
ric chart. Since h
3
is solely a function of T
wb
, lines of h
1
are proportional to T
wb
.
10