CITY AND GUILDS 9210

Level 6
Module - Unit 128 Applied Thermodynamics
OUTCOME 5 - TUTORIAL 1

GAS MIXTURES

This module has 5 Learning Outcomes. This is the first tutorial for outcome 5

Outcome 5 Apply the fundamental principles of mixtures of gases and vapours and of
combustion processes to solve practical problems
The learner can:

1. Analyse mixtures of gases and vapours and the relationship between specific and molar properties.

2. Determine the effects of mixtures of gases and vapours on the performance of:
a. cooling towers
b. condensers.

3. Analyse air-conditioning plant.

4. Use psychrometric charts.

5. Analyse combustion processes in terms of:

a. stoichiometric
b. internal energy of reaction
c. enthalpy of reaction and formation.

6. Apply First Law of thermodynamics to chemical reactions.

7. Explain chemical dissociation and determine its effect in reactions involving perfect gases.

Pre-Requisite Knowledge Requirement

In order to study this module you should already have a good knowledge of thermodynamics. If not you
should study the tutorials at www.freestudy.co.uk/thermodynamics2.htm before commencing this
module.

In this outcome you will study the following:

 Revise the UNIVERSAL GAS LAW

 Learn DALTONS LAW OF PARTIAL PRESSURES
 Apply these laws to mixtures of water vapour and air.
 Solve problems involving air conditioning plant.
 Solve problems involving cooling towers.
 Solve problems involving steam condensers.
 Use psychrometric charts.

Let's start by revising the Universal gas law and the law of partial pressures.

(c) www.freestudy.co.uk Author D. J. Dunn

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1.1 UNIVERSAL GAS LAW

mRoT
pV  ~
N

Ro is the universal constant 8314.4 J/kmol K

Ñ is the relative molecular mass which is 18 for water vapour treated as a gas and 28.96 for dry air treated
as a single gas.

1.2 PARTIAL PRESSURES

The pressure exerted by a gas on the surface of containment is due to the bombardment of the surface by the
molecules. The relative distance between molecules is very large so if two or more gases exist in the same
space, their behaviour is unaffected by the others and so each gas produces a pressure on the surface
according to the gas law above. Each gas occupies the total volume V and has the same temperature T. If
two gases A and B are considered, the pressure due to each is:
m RoT
p a  ~a
Na V
m b RoT
pb  ~
NVb

The total pressure on the surface of containment is p = pa + pb

This is Daltons Law of partial pressures.

Now let’s see how these laws are applied to mixtures of vapour and air.

(c) www.freestudy.co.uk Author D. J. Dunn

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2. AIR - VAPOUR MIXTURES

In the following work, water vapour is treated as a gas.

Consider a mixture of dry air and vapour. If the temperature of the mixture is cooled until the vapour starts
to condense, the temperature must be the saturation temperature (dew point) and the partial pressure of the
vapour ps must be the value of ps in the fluids tables at the mixture temperature.

If the mixture is warmed up at constant pressure so that the temperature rises, the vapour must become
superheated. It can be shown that the partial pressure of the vapour and the dry air remains the same as at
the saturation temperature.

Let condition (1) be at the saturation condition and condition (2) be at the higher temperature. p is constant
so it follows that :

V1 V2

T1 T2
m RoT1
The initial partial pressure of the vapour is: p s1  ~s
N s V1
m RoT2
The final pressure of the vapour is : p s2  ~s
N s V2
V1 V2
Since  then ps1 =ps2
T1 T2

By the same process it can be shown that pa1 = pa2

If p is constant then the partial pressures are constant and the partial pressure of the vapour may easily be
found by looking up the saturation pressure at the dew point if it is known.

When the air is contact with water, it will evaporate the water and the water will cool down until it is at the
saturation temperature or dew point. When stable conditions are reached, the air becomes saturated and
equal to the temperature of the water and so its temperature is the dew point (t s) in fluids tables.

WORKED EXAMPLE No.1

Moist air at 1 bar and 25oC passes over water and emerges at 1 bar and 18 oC. Calculate the partial
pressure of the air and vapour before cooling.

SOLUTION

When cooled 18oC must be the saturation temperature so the partial pressure of the vapour is ps in the
fluids tables and is 0.02063 bar.

The partial pressure of the vapour was the same before cooling so the partial pressure of the air must be
1 - 0.02063 = 0.97937 bar.

Now let's look at the definitions and use of humidity.

(c) www.freestudy.co.uk Author D. J. Dunn

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3. HUMIDITY

There are two ways to express humidity SPECIFIC AND RELATIVE.

3.1. SPECIFIC HUMIDITY 

 = mass of water vapour/mass of dry air

Starting with the gas law

~
pVN
m
RoT
~ ~
p s VRoT N s ps Ns ps 18 p
ω ~  ~  x  0.622 s
p a VRoT N a p a N a p a 28.96 pa
ps
ω  0.622
p  ps

This derivation is often requested in Examinations.

3.2. RELATIVE HUMIDITY 

 = mass of vapour/maximum possible mass of vapour

The maximum possible mass of water vapour which can be held by air is when the vapour is saturated and
the temperature of the mixture is the saturation temperature.

mass = Volume/specific volume = V/v

When saturated, v = vg at the mixture temperature.

ms V V v a
   
m g vs v a vs

Alternatively v = V/m

N s ps Np
vs  and v g  g g
RoT RoT
p
 s
pg

ps = partial pressure of the actual vapour

pg = partial pressure when saturated.

ps p
ω  0.622 and φ  s
p  ps pg
ωp  ps 

0.622p g

(c) www.freestudy.co.uk Author D. J. Dunn

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 WORKED EXAMPLE No.2

Moist air at 1 bar and 25oC is cooled to 18oC by passing it over water at 18oC. It emerges at 18oC and
1 bar with a relative humidity of 1.0. Assuming that there is no net water absorbed nor lost, calculate
the relative and specific humidity before cooling.

SOLUTION

This is the same as the previous problem so the dew point must be 18 oC and the partial pressure of the
vapour is ps at 18oC and is 0.02063 bar.

pa = 1 - 0.02063 = 0.97937 bar

pg at 25oC = 0.03166 bar

It follows that if no net water is gained nor lost then the specific humidity must be the same before and
after and is :

 = 0.622(ps/pa) = 0.0131

 = ps/pg =0.651

These are the humidity values which will result in no evaporation nor condensation.

If <0.651 then there will have been evaporation.

If >0.651 then condensation will have taken place on contact with the water and cooling also.

(c) www.freestudy.co.uk Author D. J. Dunn

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MASS BALANCE

Consider the worked example 2 again only this time suppose the relative humidity at inlet is 0.5. This
means that water is evaporated. Consider 1 kg of dry air passing through from inlet to outlet.

At outlet  = 1 and ps2 = pg at 18oC = 0.02063 bar.

pa2 = 1 - 0.02063 = 0.97937 bar

2= 0.622ps/pg= 0.0131 = ms/ma hence for 1 kg of dry air there must be 0.0131 kg of saturated vapour.

At inlet 1 = 0.5

This time the mass of the vapour at inlet and outlet are not the same so the specific humidity is different at
inlet.

1 = 0.5 = 1(p-ps)/(0.622pg) at 25oC.

Remember ps is the saturation pressure at the dew point (18 oC) and pg is the saturation pressure at the
actual temperature (25oC).

0.5 = 1(1-0.02063)/(0.622 x 0.03166) = 49.733 1

Hence 1 = 0.01 = ms1/ma

Since the air mass is 1 kg throughout, then the mass of vapour at inlet is 0.01 kg.

It follows that the mass of water evaporated is 0.0131 - 0.01 = 0.0031 kg

PSYCHROMETRIC CHARTS.

In order to use these charts you need to know the DRY BULB TEMPERATURES (DBT) and the WET BULB
TEMPERATURE (WBT) of the moist air. The dry bulb temperature refers to the actual temperature of the
air originally found with a glass thermometer in a shaded position. The wet bulb temperature refers to the
temperature you would get if the bulb was covered in a wet porous tube (e.g. muslin cloth) with the bottom
immersed in water that is drawn up the tube and evaporated. This temperature can be obtained more rapidly
by blowing air over the bulb to create evaporation. The wet bulb temperature is the lowest temperature that
can be achieved by evaporating water. The difference in the DBT and WBT depends on the moisture
content of the air and they would be the same if the relative humidity was 100%. Actual calculation of the
WBT is quite complicated and involves considering the heat transfer involved.

A psychrometer measures both temperatures. A sling psychrometer requires manual operation to create the
airflow over the bulbs, but a powered psychrometer includes a fan for this function. Knowing both
temperatures enables you to find the relative humidity from the psychrometric chart appropriate to the air
pressure. A HYGROMETER is an instrument for determining relative humidity and may incorporate the
DBT and WBT. Modern electronic tools for Heating, Ventilating and Air Conditioning will do all the
measurements and calculations.

A psychrometric chart enables you to determine the humidity and other properties of moist air. A simplified
chart is shown next. Simply locate the point pin pointed by the two temperatures and read off specific
humidity, the relative humidity, specific volume and specific enthalpy. In an examination the chart should
be provided. In practice you could use a calculator programme such as the one at this web link.
http://www.srh.noaa.gov/epz/?n=wxcalc_rh
(c) www.freestudy.co.uk Author D. J. Dunn
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 Figure No. 1

(c) www.freestudy.co.uk Author D. J. Dunn

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 SELF ASSESSMENT EXERCISE No.1

1. Repeat the worked example 2 but this time the relative humidity 0.8 at inlet. Is water condensed or
evaporated?

(ms1 = 0.01609 kg so water is condensed)

2. Define specific humidity  and prove that

 = psÑs/Ña(p - ps)

Humid air at 1 bar flows through an insulated vessel over a pool of water and emerges saturated. The
temperatures are 25oC and 18oC at inlet and outlet respectively. The mass of water is maintained
constant at 18oC all the time. Calculate the relative humidity at inlet assuming constant pressure
throughout.
(Ans. 0.651)

(c) www.freestudy.co.uk Author D. J. Dunn

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4. ENERGY BALANCE

Consider a simple air conditioner. Moist air is drawn in and cooled so that water condenses out. The air at
this point must be at the dew point.

Figure 2

Applying the law of energy conservation we get :

Ma ca1 + ms2 hs1 = mw cw 2 + ma ca 2 + ms2 hs2 + energy removed

The suffixes a, s and w refer to air, vapour and water respectively. Treating vapour as a gas, the accepted
value of the specific heat capacity is 1.864 kJ/kg K.

The enthalpy of steam relative to 0o C is then hs = hg + 1.864 (s - ts)

ts is the saturation temperature of the vapour.

It is probably best to use the thermodynamic tables or the h - s chart supplied in the exam whenever possible
to find the enthalpy of vapour at low pressures and temperatures.

WORKED EXAMPLE No.3

Moist air enters a conditioning unit at 25 oC and 1 bar with a relative humidity of 0.7. It is passed
through a cooler causing the temperature to fall to 18oC and condensate is formed.

Calculate the mass of condensate formed per kg of dry air and the energy removed per kg.

SOLUTION

Following the same method as in the previous examples, the mass of vapour at exit is:
ms2 = 0.0131 kg per kg of dry air.

The vapour pressure at inlet is 1.0 bar.

At inlet the relative humidity is 0.7 = 1 = 1(p - ps)/(0.622pg) at 25oC.

1 = 0.622 x 0.03166 x 0.7/(1- 0.02063) = 0.014075

The mass of vapour at inlet is then ms1 = 0.014075 kg/kg

(c) www.freestudy.co.uk Author D. J. Dunn

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 The condensate formed mw = 0.014075 - 0.0131 = 0.000975 kg

Conducting an energy balance:

1 x 1.005 x 25 + 0.014075 hs1 = 1x 1.005 x 18 + 0.0131 hs2 + mw w + 

hs1 = hg + 1.864 (s - ts) at 0.02063 bar.

hs1 = 2533.9 + (25 - 18)(1.864) = 2546.9kJ/kg

hs2 = hg at 18oC since it is saturated.

hs2 = 2533.9 kJ/kg

The balance becomes

1 x 1.005 x 25 + 0.014075 (2546.9) =
1x 1.005 x 18 + 0.0131 (2533.9)+ 0.000975x4.168x18 + 

 = 9.87 kJ per kg of dry air.

In air conditioning it is normal to heat the air to the required temperature before it leaves the unit.

Figure 3

Suppose the air is heated to 22oC before leaving. What is the heat transfer required in the heater? The
masses are unchanged so we only need an energy balance between 2 and 3.

1x 1.005 x 18 + 0.0131 hs2 +  = 1 x 1.005 x 22 + 0.0131 hs3

hs3 = hg + 1.864 (s - ts) at 0.02063 bar. ts = 18oC

hs3 = 2533.9 + 1.864 (22 - 18) = 2541.3 kJ/kg

hs2 = 2533.9 kJ/kg

1 x 1.005 x 18 + 0.0131 x 2533.9 +  = 1 x 1.005 x 22 + 0.1031 x 2541.3

51.28 +  = 55.27

 = 4.11 kJ

(c) www.freestudy.co.uk Author D. J. Dunn

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 SELF ASSESSMENT EXERCISE No. 2

Air having a pressure, temperature and relative humidity of 1 bar, 26 oC and 0.65 respectively, flows
into an air conditioner at a steady rate and is dehumidified by cooling and removing water from it. The
air is then heated to produce an outlet temperature and relative humidity of 24oC and 0.359
respectively. The pressure is constant throughout. Determine the heat transfers in the cooler and heater
per kg of conditioned air at exit. Draw up a complete mass balance.

(36.22 kJ/kg and 16.24 kJ/kg)

(c) www.freestudy.co.uk Author D. J. Dunn

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5. COOLING TOWERS

Cooling towers fall into two types, dry and wet. Dry cooling towers are no more than very large air
conditioners and the theory is the same as already outlined.

Wet cooling towers work on the principle of spraying warm water downwards so that heat and vapour is
passed to the air which rises and carries away latent heat leaving the water at a lower temperature to collect
in a pool at the bottom of the tower. The water is then recycled from the pool. The moist air leaves the top
of the tower as a plume. The tower has a venturi shape to assist the process by causing a slight pressure
reduction in the spray area followed by resurgence as the top widens. This causes condensation to form and
make the plume visible. Some of the condensate rains down into the pool. We can say with certainty that
the air leaves the tower with 100% humidity.

The best way to understand the problem is to do a worked example as follows.

WORKED EXAMPLE No.4

A cooling tower must cool 340 kg of water per minute. The water is supplied at 42 oC and it is sprayed
down into the column of air which enters the bottom of the tower at a rate of 540m 3/min with a
temperature of 18oC and relative humidity of 60%. The moist air leaves the top of the tower saturated
at 27oC. The whole process occurs at a constant pressure of 1.013 bar. Determine the temperature of
the cooled water in the pool and the rate at which make up water must be supplied to replace that
evaporated.

Figure 4

(c) www.freestudy.co.uk Author D. J. Dunn

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 SOLUTION

R = 287 J/kg K for air and 462 J/kg K for vapour.

INLET AIR

pg1 = 0.02063 bar at 18oC 1 = 0.6 = ps1/pg1 ps1 = 0.012378 bar

hence pa1 = 1.013 - 0.012378 = 1 bar

ma = pV/RT = 1 x 105 x 540/(287 x 291) = 646.6 kg/min

ms1 = pV/RT = 0.012378 x 105 x 540/(462 x 291 ) = 4.971 kg/min

OUTLET AIR

2 = 1 ps2 = pg2 = 0.03564 bar hence pa2 = 0.9774 bar

2 = 0.622 x 0.03564/0.9774 = 0.02268

ms2 = 0.02268 x 646.6 = 14.66 kg/min

Water evaporated = 14.66 - 4.971 = 9.693 kg/min

Make up water = 9.693 kg/min

mw2 = 340 – 9.693 = 330.3

ENERGY BALANCE

In this example enthalpy values from the steam tables and chart will be used.

hw1 = hf @ 42oC = 175.8 kJ/kg

hw2 is unknown

ha1 = 1.005 x 27 kJ/kg

hs1 = h @ 0.012378 bar & 18oC = 2530 kJ/kg (from h-s chart)

hs2 = hg @ 27oC = 2550.3 kJ/kg

Balancing energy we get

(340 x175.8) + {646.6 x 1.005 x (18-27)} + {4.971 x 2530) – (14.66 x 2550.3)

= 330.3 hw2

hw2 = 123.5 kJ/kg and from the tables the temperature must be 29.5 oC.

The temperature of the cooled water is 29.5 oC.

(c) www.freestudy.co.uk Author D. J. Dunn

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 SELF ASSESSMENT EXERCISE No. 3

1. Derive the expression for specific humidity

 = 0.622(ps/pa)

Water flows at 5 000 kg/h and 40oC into a cooling tower and is cooled to 26 oC. The unsaturated air
enters the tower at 20oC with a relative humidity of 0.4. It leaves as saturated air at 30 oC. The pressure
is constant at 1 bar throughout.

Calculate

i. the mass flow of air per hour. (4 636 kg/h)

ii. the mass of water evaporated per hour. (100.5 kg/h)

2. The cooling water for a small condenser is sent to a small cooling tower. 7 m 3/s of air enters the
tower with a pressure, temperature and relative humidity of 1.013 bar, 15 oC and 0.55 respectively. It
leaves saturated at 32oC. The water flows out of the tower at 7.5 kg/s at 13oC. Using a mass and energy
balance, determine the temperature of the water entering the tower.
(Answer 33.9oC)

3. A fan supplies 600 dm3/s of air with a relative humidity of 0.85, temperature 30oC and pressure 1.04
bar into an air conditioner. Moisture is removed from the air by cooling and both the air and
condensate leave at the same temperature. The air is then heated to 20 oC and has a relative humidity of
0.6. Determine the following.

i. The mass of dry air and water at entrance to the conditioner.

(0.6927 kg/s and 0.01546 kg/s)

ii. The mass of water vapour delivered at exit.

(0.00588 kg/s)

iii. The mass of water extracted from the cooler.

(0.00958 kg/s)

iv. The temperature at exit from the cooler.

(12oC)

v. The heat transfer in the cooler.

(c) www.freestudy.co.uk Author D. J. Dunn

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6. CONDENSERS

It is inevitable that air will be drawn into steam condensers operating with a vacuum. The effect of this is to
reduce the saturation pressure and temperature of the steam resulting in a colder condensate that would
otherwise be obtained. This in turn means more heat required to turn it back into steam in the boiler and a
reduced thermal efficiency for the power plant.

The air must be removed from the condenser in order to keep the partial pressure as small as possible. This
is done with an extractor pump. Some vapour will be removed with the air but this loss is tolerable because
of the energy saved.

Figure 5

The solution to problems on condensers is similar to that for cooling towers and requires mass and energy
balances. It is normal to neglect the partial pressure of the air at inlet as it makes little difference to the
answers.

SELF ASSESSMENT EXERCISE No. 4

a. Discuss the reasons why air mixed with steam in a condenser is not desirable.

b. Wet steam with a dryness fraction of 0.9 enters a condenser at 0.035 bar pressure at a rate of 10 000
kg/h. The condensate leaves at 25oC. Air also enters with the steam at a rate of 40 kg/h. The air is
extracted and cooled to 20oC. The partial pressure of the air at inlet is negligible and the process is at
constant pressure. The cooling water is at 10oC at inlet and 21oC at outlet.

i. Determine the mass of vapour extracted with the air. (50 kg/h)

ii. Calculate the flow rate of the cooling water required. (475 484 kg/h)

(c) www.freestudy.co.uk Author D. J. Dunn

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