CHEM302 Lecture 3

January 12, 2024

Atmospheric Pressure
Partial pressure
Water vapour pressure
Humidity, Dew point

1
 Partial Pressure PX
PX = C X P

PX : Pressure that would be exerted by the molecules of X if all other gases

of the mixture were removed.

P : Total pressure

Dalton’s Law of Partial Pressures

The total pressure of a mixture of gases equals the sum of the pressures that
each would exert if it were present alone.

P = PA + P B + PC + · · ·

2
 Partial Pressure PX
Number density of molecule X
N X Av
nX = NX : Number of moles of X
V
C X N Av N : Total number of moles of air
=
V

Partial pressure of molecule X

nX
PX = RT
Av

3
Exercise. What is the partial pressure of oxygen at sea level for 1013 hPa.

4
 H2O H2O,SAT d

Phase Diagram for Water

At temperatures below freezing, one may also report the frost point
Tf corresponding to saturation with respect to ice.

100

WATER VAPOR PRESSURE, hPa

LIQUID
SOLID
10 (ICE)

1
GAS
(WATER VAPOR)

0.1

-40 -20 0 20 40
TEMPERATURE, °C
Figure 1-3 Phase diagram for water. The thin line is the saturation vapor pressure
above supercooled liquid water. 5
 (Td). The relative humidity is defined as:
Water Vapour Pressure
RH ( % ) =P100 O
P
H⋅ 2-------------------------------
- H2O
• • (1.14)
P (T ) H2O,SAT (b)
• •
The partial pressure of
so water
that cloud vapour
formation takes place when RH ≥ 100%. The dew
Figurethe
point is defined as the temperature at which 1-2air
Evaporation of be
parcel would water from a pan

Water Saturation Vapour Pressure H2 O,

The SAT P
saturated with respect to liquid water:
P H2O2 = molecules
H O P H2O,SAT ( T din
) the liquid are in (1.15)
constant motion. As a re
of this motion, H2O molecules at the surface of the pan evaporat
The pressure at whichAtwater vapor
temperatures below is in thermodynamic
freezing, one may also report the
the atmosphere. If we let this evaporation
equilibrium
frost point take place for a l
with its condensed state.
Tf corresponding enough
to saturation with
time, therespect to ice.dry out. Let us place a lid on top of
pan will
pan to prevent the H2O molecules from escaping (Figure 1-2b).
H2O molecules escaping from the pan bounce on the lid and m
100
At equilibrium (closed system)

WATER VAPOR PRESSURE, hPa

now eventually return to the pan; a steady state is achieved w
LIQUID
the rate at which molecules evaporate from the pan equals the
PH2 O = PH2 O, SAT at whichSOLID
water vapor molecules return to the pan by collision w
10 the liquid water surface. The collision rate is determined by
(ICE)
water vapor pressure PH2O in the head space. Equilibr
between the liquid phase and the gas phase is achieved whe
1 saturation vapor pressure PH2O,SAT is reached in the head space.
GAS
we increase the temperature of the water in the pan, the energ
the molecules at the (WATER VAPOR)
surface increases and hence the rate
evaporation increases. A higher collision rate of water va
0.1 molecules with the surface is then needed to maintain equilibri
Therefore, PH2O,SAT increases as the temperature increases.
-40 -20 0 20 40
Cloud formation in the atmosphere takes place when PH2
TEMPERATURE,
PH2O,SAT, and it is therefore °C 6
important to understand how PH2O
 Water Saturation Vapour Pressure PH2 O, SAT

A simple approximation
✓ ◆
T [ C]
PH2 O, SAT (T ) [Pa] = 610.78 ⇥ exp ⇥ 17.2694
<latexit sha1_base64="(null)">(null)</latexit>
T [ C] + 238.3

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 H2O H2O,SAT d

Relative Humidity RH(%)

At temperatures below freezing, one may also report the frost point
T corresponding to saturation with respect to ice.
f • • (a)

In general PH2 O  PH2 O, SAT

• •
100 (b)

WATER VAPOR PRESSURE, hPa

PH2 O •
LIQUID
•
RH(%) = ⇥ 100 Figure 1-2 Evaporation of water from a pan
PH2 O, SAT TheSOLID
H2O molecules in the liquid are in constant motion. As a result
10 (ICE)
of this motion, H2O molecules at the surface of the pan evaporate to
the atmosphere. If we let this evaporation take place for a long
enough time, the pan will dry out. Let us place a lid on top of the
pan to prevent the H2O molecules from escaping (Figure 1-2b). The
H2O molecules escaping from the pan bounce on the lid and must
1 now eventually return to the pan; a steady state is achieved when
GAS evaporate from the pan equals the rate
the rate at which molecules
at which water vapor(WATER VAPOR)
molecules return to the pan by collision with
the liquid water surface. The collision rate is determined by the
water vapor pressure PH2O in the head space. Equilibrium
0.1 between the liquid phase and the gas phase is achieved when a
saturation vapor pressure PH2O,SAT is reached in the head space. If
we increase the temperature of the water in the pan, the energy of
the molecules at the surface increases and hence the rate of
evaporation
-40 -20increases. 0 A higher20collision40rate of water vapor
molecules with the surface is then needed to maintain equilibrium.
PH2O,SAT increases as the°C
Therefore, TEMPERATURE, temperature increases.
Clouds are formed when Figure 1-3 Phase diagramCloud
for water. The thin
formation lineatmosphere
in the is the saturation vapor
takes place pressure
when PH2O ≥
above
P supercooled liquidimportant
, and it is therefore water. to understand how P
PH 2 O PH2 O, SAT
H2O,SAT
depends on environmental variables. From the phase rule, the
H2O,SAT

number n of independent variables determining the equilibrium of

c chemical components between a number p of different phases is
8
given by
 so that cloud formation takes place when RH ≥ 100%. The dew

Dew Point Td
point is defined as the temperature at which the air parcel would be
saturated with respect to liquid water:
P H2O = P H2O,SAT ( T d ) (1.15)
Dew point : Temperature where the water vapour pressure equals the saturation vapour pressure
At temperatures below freezing, one may also report the frost point
Tf corresponding to saturation with respect to ice.

100

WATER VAPOR PRESSURE, hPa

LIQUID
SOLID
10 (ICE)

1
GAS
(WATER VAPOR)

0.1

-40 -20 0 20 40
TEMPERATURE, °C
Figure 1-3 Phase diagram for water. The thin line is the saturation vapor pres
above supercooled liquid water.

9
Exercise. Calculate the relative humidity (RH) for T=20 °C and Td=10 °C.

10
Exercise. Calculate the current vapour pressure of water for T=20 °C and RH = 45 %.

11
 At temperatures below freezing, one may also report the frost point
Water Vapour Pressure
Tf corresponding to saturation with respect to ice.

100

WATER VAPOR PRESSURE, hPa

LIQUID

SOLID
10 (ICE)

1
GAS
(WATER VAPOR)

0.1

-40 -20 0 20 40
TEMPERATURE, °C
Figure 1-3 Phase diagram for water. The thin line is the saturation vapor pressure
above supercooled liquid water.

As the temperature increases, the saturation vapour pressure of water ( ),

and the relative humidity ( ).
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