UNIVERSITY OF NIGERIA, NSUKKA

DEPARTMENT OF MECHANICAL ENGINEERING

ME 561 – Thermodynamics III

Lecture Notes on
Mixtures and Solutions
for 2018/2019 Session
(Part I)

Lecturer:
Howard O. NJOKU PhD

April 25, 2019

Contents
1 Chemical Equilibrium 2
1.1 The Third Law of Thermodynamics and Absolute Entropy . . . . . . . . . 2
1.2 Chemical Stoichiometry and Dissociation . . . . . . . . . . . . . . . . . . . 2
1.3 Chemical Potential and the Gibbs Function . . . . . . . . . . . . . . . . . 7
1.4 Chemical Equilibrium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.5 Further discussions on Dissociation . . . . . . . . . . . . . . . . . . . . . . 15
1.6 Examples of the use of the equilibrium constant . . . . . . . . . . . . . . . 17

1
1 Mixtures and Solutions
1. A non-reactive gas mixture is a multi-component system whose constituents do not
react chemically with one another.

2. A reactive mixture is a multi-component system whose constituents may react chem-

ically with one another.

The study of systems involving chemical reactions is an important topic in chemical

thermodynamics. It has three main aspects corresponding to the three laws in nature,
viz.:

ˆ The principle of conservation of matter;

ˆ The first law of thermodynamics; and

ˆ The second law of thermodynamics.

1.1 Mixtures of ideal gases

Basic definitions:

1. The total mass, m of a mixture is the sum of the masses of each component i.e.,
X
m = m1 + m2 + m3 + . . . = mi (1)
i

and
m1 m2 m3 X mi
1= + + + ... = (2)
m m m i
m
mi
The ratio is defined as the mass fraction of the ith component in the mixture, and
m
the analysis of gas mixtures on the basis of mass or weight is known as gravimetric
analysis.

2. The total number of moles, n, for a mixture is the sum of the number of moles of
the constituents, i.e.,
X
n = n1 + n2 + n3 + . . . = ni (3)
i

and
n1 n2 n3 X ni X
1= + + + ... = = xi (4)
n n n i
n i

where xi is called the molar fraction of the ith component, i.e., xi = nni , and the
analysis of gas mixtures on the basis of moles is known as molar analysis.

2
 For the ith component of a mixture,

mi = ni Mi (5)

This implies
X X
m= mi = ni Mi (6)
i

where Mi = molar mass or molecular weight of the ith component. Average molec-
ular weight, M , of the mixture is given as
P
m i ni Mi X
=M = = xi Mi (7)
n n i

Mi ni mi Mi
= = xi (8)
Mn m M

1.1.1 Dalton model

Consider a gas mixture of n moles occupying a volume, V at the equilibrium temperature

and pressure of T and P , and treat the gas mixture as ideal, then

P V = nR̄T (9)

ni . For any ith component,

P
where n = n1 + n2 + n3 + . . . = i

Pi V = ni R̄T (10)

where Pi is the partial pressure of the component in the mixture.

X
P = P 1 + P2 + P3 + . . . = Pi (11)
i

Equation (??) states the fact that the total pressure of the mixture is the sum of the
(partial) pressures which each component would exert if it alone occupied the whole volume
of the mixture at the same temperature. This is called Dalton’s rule of partial pressures.
Dividing Equation (??) by Eqn. (??) gives

Pi ni
= = xi
P n

or Pi = xi P (12)

This states that the partial pressure of a component of an ideal gas mixture is the product
of the mole fraction of that component and the total pressure of the mixture.

3
1.1.2 Amagat model (or the Amagat-Leduc model)

In the Amagat model, the properties of each component are considered as though each
existed separately at the pressure and temperature of the mixture, i.e.,

X X X
V = V1 + V2 + V3 + . . . = Vi = xi V = V xi = V (13)
i i i

P ni RT
where xi = 1 and Vi = so that dividing by the equivalent form of Eqn. (??)
P

Vi ni
= = xi
V n

This is the Amagat-Leduc rule of partial volumes.

1.1.3 Internal energy, enthalpy and specific heats of an ideal gas mixture

Since each component of an ideal gas mixture behaves as if it occupies the volume of the
mixture alone at the temperature of the mixture, the internal energy of each component
may be given as
Ui = ni ūi (14)

ūi = molar internal energy of the ith component and defined by T and V , or equivalently
by T and P . Consider a mixture as a system consisting of several subsystem,
X X
U = U1 + U2 + U3 + . . . = Ui = ni ūi (15)
i i

Divide equation ?? by n,
U X
= ū = xi ūi (16)
n i

We can also go ahead to show that since

dū = c̄v dT (17)

then
X
c̄v = xi c̄v,i (18)
i

but this will be left as an exercise.

From the definition of enthalpy

Hi = Ui + Pi V (19)

4
Hence
X X X
Hi = Ui + V Pi
i i i
X X
= Ui + V Pi (20)
i i

P P
But i Ui = U and i Pi = P

X
∴ Hi = U + P V (21)
i

But by definition, H = U + P V , thus

X
H= Hi (22)
i

Now, Hi = ni h̄i . By Eqn. (??),

X X
H = nh̄ = Hi = ni h̄i (23)
i i

Dividing through by n,
X
h̄ = xi h̄i (24)
i

Noting once again that dh̄ = cp dT , it can be shown that

X
c̄p = xi c̄p,i (25)
i

The foregoing equations were obtained in terms of the mole fractions of the components.
In terms of the mass fractions of the components, they are re-stated as follows:
X
U= mi ui (26)
i

X mi
u= ui (27)
i
m
X mi
cv = cv,i (28)
i
m
X
H= mi hi (29)
i
X mi
h= hi (30)
i
m
X mi
cp = cp,i (31)
m

5
1.1.4 Entropy of an ideal gas mixture

Using the same line of reasoning used in arriving at the relation for internal energy, we
can express the entropy of a gaseous mixture in terms of the entropies of the mixture’s
components.
X X
S= Si = ni s̄i (32)
i i

Equation (??) represents the Gibbs’ rules which states that the entropy of an ideal gas
mixture is equal to the sum of the entropies that each component of the mixture would
have if it alone occupied the volume of the mixture at the temperature of the mixture.
Dividing Eqn. (??) by n,
S X
= s̄ = xi s̄i (33)
n i

dTi dPi
ds̄i = c̄p,i − R̄ (34)
Ti Pi
Substituting equation ?? into the differential form of equation ?? gives
X dTi X dPi
ds̄ = xi c̄p,i − xi R̄ (35)
i
Ti i
Pi

In terms of masses,
1 X dTi 1 X dPi
ds = mi cp,i − mi Ri (36)
m i Ti m i Pi

The pressure to be used in Eqns. (??) and (??) for each component is that determined
by its temperature and its total volume.

1.1.5 Concluding remarks

There are a number of ways defining a mixture of ideal gases. It is proposed to use the
following definitions:

i) The gas mixture as a whole obeys equation of state P V = nR̄T .

ii) The total pressure of the mixture is the sum of the pressures which each compo-
nent would exert if it alone occupied the whole volume of the mixture at the same
temperature.

iii) The internal energy, enthalpy and entropy of the mixture are respectively equal to
the sums of the internal energies, enthalpies and entropies which each component of
the mixture would have if each alone occupied the whole volume of the mixture at
the same temperature.

The first condition implies that the gas mixture acts as if it were a single component
ideal gas. While the last two conditions are the well known Gibbs-Dalton laws. The first

6
condition both indicates that the gas molecules are considered to move independently of
one another in the whole volume of the system.

1.2 Mixtures of ideal gases and vapour (Gas-vapour Mixtures)

Let us consider problems involving a mixture of ideal gases that is in contact with a solid
or liquid phase of one of the components. Most familiar example being a mixture of air
and water vapor in contact with liquid water or ice, such as the problems encountered in
air conditioning or drying.

Assumptions in analysis

1. The solid or liquid phase contains no dissolved gases.

2. The gaseous phase can be treated as a mixture of ideal gases.

3. When the mixture and the condensed phase are at a given pressure and temperature,
the equilibrium between the condensed phase and its vapor is not influenced by the
pressure of the other component. This means that when equilibrium is achieved,
the partial pressure of the vapor will be equal to saturation pressure corresponding
to the temperature of the mixture.

Terms used in the analysis of gas vapor mixture

Saturated Mixture: If the partial pressure of the water vapor corresponds to the satu-
ration pressure of water at the mixture temperature, the mixture is said to be saturated.
Saturated Air: Is a mixture of dry air and saturated water vapor.
Unsaturated Air: Is a mixture of dry air and superheated vapor.
Psychrometry: Is the study of steam-air mixtures and is particularly concerned with
the measurement of their properties. It is of special importance to heating, ventilation
and air conditioning (HVAC) engineers.
Dry-Bulb Temperature: The temperature registered by the thermometer wetted
by the wick is known as the wet-bulb temperature. This is normally lower than the dry-
bulb temperature. The difference between the two is a measure of the humidity of the
air.
Dew Point: The dew point of a gas-vapor mixture is the temperature at which the
vapor condenses or solidifies when it is cooled at constant pressure.

1.2.1 Humidity ratio or specific humidity, ω

This is the ratio of the mass of water vapor to the mass of dry air in a given volume of
mixture.
mv
ω=
ma

7
 D ry b u lb
u lb r
th e rm o m e te r e t b e te
W om
rm
th e

A ir H 2 O

M o is t w ic k

Figure 1: wet and dry bulb hygrometer

Assuming ideal-gas behaviour for both the dry air and vapor

Pv V
mv =
Rv T

and
Pa V
ma =
Ra T
R a Pv
∴ω=
Rv Pa
For an air-water vapor mixture, this reduces to

Pv
ω = 0.622
Pa

1.2.2 Relative humidity, φ

This is defined as the ratio of the mole fraction of the vapor in a mixture to the mole
fraction of the vapor in a saturated mixture at same temperature and total pressure

Pv
φ=
Pg

or from Fig. ??,

P1
φ=
Pg
Pv Pv P a ω Pa
φ= = · =
Pg Pa P g 0.622 Pg

8
 P g S a tu ra tio n

p.
p re s s u re a t
T

1 m
a t b te
D ry -b u lb

l
te m p .

bu
ry
P V, v a p o u r

D
p re s s u re a t 1
g
D e w p o in t
te m p . a t 1

d
S a tu ra te d s a t. v a p o u r lin e
liq u id lin e

Figure 2: Vapor Pressure, Saturation pressure , Dew point temperature and dry bulb
temperature. Dry-bulb temperature and Wet-bulb temperature.

or
Pg
ω = 0.622φ
Pa
Noting that Pv + Pa = Pg + Pa = P ,

Pg P − Pa
ω = 0.622φ = 0.622φ
P − Pg Pa

Also noting that for a saturated mixture, φ = 1,

Pg
ωsat = 0.622
Pa

1.2.3 Processes involving air-water-vapor mixture

The analysis of problems involving these kinds of processes will require the application
of;

1. The principle of conservation of energy (The energy equation);

2. The principle of conservation of mass (The mass balance equation):

3. The principle of air water-vapor mixtures.

4. Gibb-Dalton relationships:
P = P1 + P 2 + . . .

mh = m1 h1 + m2 h2 + . . .

9
 mu = m1 u1 + m2 u2 + . . .

ms = m1 s1 + m2 s2 + . . .

The terms of the right hand side of each expression have to be evaluated for each
component when that component is assumed to exist at the mixture’s volume and
temperature.

M
V
1 + 2 + ... T
P

T 1 2 P 2, U 2, h 2, S 2 T
P 1, U 1, h 1, S 1 V
V

Figure 3: MVTP

The air - H2 O - mixtures considered includes all phases of H2 O. For a single-phase

mixture, when only the gaseous phase is present i.e., the mixture is composed of air and
steam, the Gibbs-Dalton law is applicable without modification.

Example

0.01 kg of steam and 0.99 kg of air from a gaseous mixture at a pressure of 100 × 103
N/m2 and a temperature of 20‰. Determine

(a) The partial pressure of the steam and air.

(b) The specific volume of mixture and

(c) The enthalpy of the mixture.

Solutions (a) and (b) have to be solved simultaneously.

P = 100 × 103 N/m2 = Psteam + Pair

For air,
Rair T 287 × (293)
Pair = = (37)
vair vair
where Rair = 8314.5 J/(kmol K) ÷ 28.96 kg/kmol ≈ 287 J/(kg K) is the gas constant for
air. For steam, Psteam is related to vsteam by the data presented in the superheated steam
table. Also,

10
 X
V = mi × v = (msteam + mair ) × v = msteam × vsteam = mair × vair (38)

where V and v are the volume and specific volume of the mixture, respectively.

1 × v = 0.001 × vsteam = 0.99 × vair

NB: Examination of the superheated steam table shows that it does not extend into
the low pressure region which is required. Therefore we assume that at low pressure,
steam can be treated as an ideal gas.

Rsteam T 462 × 293

∴ Psteam = (39)
vsteam vsteam

where Rsteam = 8314.5 J/(kmol K) ÷ 18.015 kg/kmol ≈ 462 J/(kg K) is the gas constant
for H2 0. Dividing Eqn. (??) by Eqn. (??) gives

Psteam 462 vair 462 0.01

= × = × = 0.01626
Pair 287 vsteam 287 0.99

or
Psteam
Pair =
0.01626
But Psteam + Pair = 100 × 102 N/m2 ,

Psteam
∴ Psteam + = 100 × 102
0.01626

and so
0.01626
Psteam = × 100 × 102 = 1.60 × 103 N/m2
1 + 0.01626
Pair = P − Psteam = 100 × 103 − 1.60 × 103 = 98.40 × 103 N/m2

From Eqn. (??),

462 × 293
vsteam = 3
= 84.4 m3 /kg
1.60 × 10
From Eqn. (??),
V = 0.01 × 0.846m3 /kg of air

Note: A solution by means of steam tables would b ea trial and error process. The
steps are as follows:

i) Select a value of Psteam ;

ii) From the steam table, at T = 20 ‰, look up the corresponding value of vsteam ;

iii) Evaluate Pair from P = Psteam + Pair ;

iv) Evaluate vair from the ideal gas rule;

11
 v) The values of vsteam and vair have to satisfy

mv = mair vair + msteam vsteam

i.e 0.01vs = 0.99va

Select values of Psteam until agreement is reached.

Solution (c):

mh = msteam hsteam + mair hair = 0.01hsteam + 0.99hair

Since the supersaturated-steam table does not extend to the value of Ps , take hs equal
to hg at 20‰, in conformity with our ideal gas assumption that h = f (T ). For air let cp =
1.0 kJ/Kg K. Note that for our selected approach for determining the specific enthalpies,
the datum state (i.e., zero values of enthalpy) for saturated water is at the triple point,
while for air it is at T = 0.01‰.

1 × h = (0.01 × 2537.5) + (0.99 × 1.0 × 283.15) = 305.6935 kJ/kg

Note that an inconsistency arises because of the different datums for the air and
steam and the final quantity obtained has no physical meaning. This is not a problem in
practice because what is usually required is not the specific enthalpy a given state but the
enthalpy change as the mixture undergoes processes between two states. When this is so,
a consistency should be maintained in the method for obtaining the specific enthalpies of
the air and steam.

Example

A sample of atmospheric air contains 0.012 kg of water and 1.0 kg of dry air at 22‰and 95
kPa. During the night, the temperature drops to 10‰ at the same pressure. Determine

(a) the initial relative humidity;

(a) the initial dew point, and

(a) the mass of water condensed per unit mass of dry air.

Solution:
P = 95 kPa, T1 = 22‰, T2 = 10‰
P
mi Mi ni = mi /Mi y i = ni / ni
H2 O 0.012 18 0.000667 0.0191
Air 1.0 28.97 0.0345 0.981
P
ni = 0.035167

12
(a)
Pv
φ=
Pg
Pv = yi × P = 0.0190 × 95 kPa = 1.805 kPa ≡ 0.01805 bar

Pg = Psat @ 22‰ = 0.02645 bar. Hence

0.01805
φ= = 0.682
0.02645

(b) By interpolation from the steam tables,

0.01805
Tdew − 15 0.0805 − 0.01705
=
16 − 15 0.01818 − 0.01705

From which we obtain Tdew = 15.885‰.

(c) Since 10‰ is below the dew point, condensation will occur. At 10‰ φ = 1 (100%),
and thus Pv,2 = Pg @ 10‰ which is 0.01228 bar (≡ 1.228 kPa). The molar fraction
of the steam at 10‰ is

Pv,2 1.228 kPa

yv,2 = = = 0.0129
P 95 kPa

The molar fraction of air at 10‰ will be

ya,2 = 1 − yv,2 = 1 − 0.0129 = 0.9871

The total number of moles in the mixture @ 10‰ is

X na 0.03495
ni,2 = = = 0.03495
ya,2 0.9871

Thus the number of moles of water vapour @ 10‰ is

X
nv,2 = ni,2 − na = 0.03495 − 0.0345 = 0.000451

and the mass of water vapour in the mixture @ 10‰ is

mv,2 = nv,2 × MH2 O = 0.000451 × 18 = 0.008118 kg

Finally the mass of water condensed is

mv,1 − mv,2 = 0.012 − 0.008118 = 0.003882 kg

13
 T
(T e m p )

C lo c k [tim e (t)]

C o ld b o d y

1.2.4 Constant-pressure cooling experiments

Figure ?? above shows temperature-time curves for air-H2 O mixtures cooling at atmo-
spheric pressure.

1.2.5 The enthalpy-composition diagram

The composition of a mixture, f is given as

mass of H2 0 mH2 0
f= =
mass of mixture mair + mH2 0

Thus f = 1 denotes pure water, while f = 0 denotes pure air. Alternatively, if the
composition is given in terms of the mass of air, i.e.,

mass of air
f=
mass of mixture

then f = 1 denotes pure air and f = 0 denotes pure H2 0. It is thus important to note that
composition is another property to be specified while dealing with the type of problem.
Since steam-air mixture is not a pure substance, three properties are needed to fix its
state viz, temperature, specific volume and composition.

1.2.6 Application of the first law to mixtures

In applying the first law of thermodynamics to gas-vapor mixtures. It is helpful to realize

that because of our assumption that ideal gas are involved, the various components can
be treated separately when calculating changes of internal energy and enthalpy. When
dealing with air-water vapor mixtures, the changes in enthalpy and internal energy of the
water vapor can be found from the steam tables and the ideal gas relations can be applied
to the air.

14
 a (a ir) b c d e p = 1 a tm
T

1 0 0 % H 2O
o
100 C

A +S +W
T
Tem p A +S A +S
T C1 W
C1

on
0
a ir
10

o rti
o p re
%

p r x tu
g i
in m
e as 2O
cr f H
In o

L1
C2C3 d2 d3
0 oC
Hoar t
dew tim e
fro s t

Figure 4: Constant pressure cooling for air-H2 O mixture.

a 100 % air
mH2 O
b Small ratio mair
(air + superheated steam)
m H2 O
c Large ratio mair

d 100% H2 0

Sample Problem

A rigid insulated vessel of 1 m3 capacity contains pure hydrogen at a pressure of 104 ×102
N/m2 and a temperature of 16‰. It is connected to a compressed-air main in which the
air at a guage pressure of 280 ×103 N/m2 and a temperature of 25‰. Air enters the vessel
until the pressure in the main and in the vessel are equal. What is the final temperature
of the mixture in the vessel?
Note: This problem is important because if a mixture of hydrogen and air becomes
hot enough, it will explode.
Data needed:
For air, R = 287 J/kg K, cv = 717 J/kg K
For hydrogen, R = 4160 J/Kg K, cv = 1008J/kg K.

15
Sample Problem

0.1 kmol of CO2 initially at 2 bars and 27‰ is mixed adiabatically with 0.2 kmol of O2
initially at 5 bars and 152‰. during the constant-volume mixing process, electric energy
equal to 670 kJ/kmol of the mixture is added. Determine

(a) the final temperature of the mixture, in ‰, using tabular data and

(b) the final pressure in bars.

1.2.7 Adiabatic saturation process

1 2

U n s a tu ra te d a ir
S a tu ra te d a ir

W a te r
m akeup

An important process involving an air-water vapor mixture is the adiabatic satura-

tion process, in which an air-vapor mixture comes in contact with a body of water in a
well insulated duct. An unsaturated air of dry bulb temperature T1 enters an insulated
chamber containing a body of water. It leaves as saturated air with a temperature of T2
. When the unsaturated air passes over the water surface, some of the water is evapo-
rated. The energy for evaporation comes from both the moist air and the water in the
chamber. Since the system is insulated, the temperature of the air decreases. Therefore
T2 will be lower than T1 . If the water being added to the air is equal to T2 , the final
equilibrium temperature is called the thermodynamic wet bulb temperature, also known
as the adiabatic saturation temperature.
The energy balance for the adiabatic saturator is stated as

ṁa,1 h1 + ṁw,3 hw,3 = ṁa,2 h2

But h = ha + ωhv

∴ ṁa,1 (ha + ωhv )1 + ṁw,3 hw,3 = ṁa,2 (ha + ωhv )2 (a)

16
 p.
1 m
a t b te
T

l
bu
ry
D
P V, v a p o u r
p re s s u re a t 1
g 1

3
2

d
D e w p o in t
te m p . a t 1

Figure 5: Adiabatic saturation process.

From mass conservation,

ṁa,1 = ṁa,2 = ṁa

and
ṁv,1 + ṁw,3 = ṁv,2 =⇒ ṁw,3 = ṁv,2 − ṁv,1

Since ω = ṁv /ṁa =⇒ ṁv = ω ṁa ,

ṁw,3 = ω2 ṁa − ω1 ṁa = ṁa (ω2 − ω1 )

Substituting these into Eqn. (??),

ṁa (ha + ωhv )1 + ṁa (ω2 − ω1 )hw,3 = ṁa (ha + ωhv )2

Dividing through by ma

ha,1 + ω1 hv,1 + (ω2 − ω1 )hw,3 = ha,2 + ω2 hv,2

Rearranging,

ω1 (hv,1 − hw,3 ) = ha,2 − ha,1 + ω2 (hv,2 − hw,3 )

ha,2 − ha,1 + ω2 (hv,2 − hw,3 )
⇒ ω1 =
(hv,1 − hw,3 )
cp,a (T2 − T1 ) + ω2 (hg,2 − hw,3 )
≈ (40)
(hg,1 − hw,3 )

17
Earlier, it had been stated that T2 ≡ Tad,1 , the specific enthalpy of the make-up fluid is
the saturation enthalpy at T3 = T2 , i.e., hw,3 = hf,2 thus hg,2 − hw,3 = hf g,2 . Substituting
these into Eqn. (??),
cp,a (T2 − T1 ) + ω2 (hg,2 − hw,3 )
ω1 = (41)
(hg,1 − hw,3 )

1.2.8 The mixing rule

hy y

hz z

x
hx

0
fx fz fy f

If X and Y are the state-points of two air–H2 O systems on an h − f diagram and these
two systems are mixed together adiabatically at constant pressure in the mass proportions
mx to my , the state point, Z for the resultant system lies on the line XY and divides it
so that
ZY mx
=
XZ my
Proof: Applying first law,
Q − W = ∆U

Since the mixing process is adiabatic, Q = 0,

0 − W = ∆U

For constant pressure, this equation reduces to

∆H = 0

i.e., Final H = Initial H

(mx + my )hz = mx hx = my hy

18
 fx
mx X hx

mz= mx + my
Z

f z, hz
my
Y

mx hy − hz
=
my hz − hx
Applying the conservation of mass, the principle of conservation of mass applied to
H2 O in the process
(mH2 O )z = (mH2 O )x + (mH2 O )y

mz fz = mx fx + my fy
mx fy − fz
=
my fz − fx
These show that we have a straight line relationship between enthalpy and composi-
tion.

1.2.9 Adiabatic saturation on a h − f diagram

G represents the initial state the air-steam mixture while W represents the state of the
water which is to be mixed with it. How much water must be added to produce S?
The mixing rule shows that the state point for the resultant mixture must lie on the
line W G. But it must also lie on the saturation line. The required state point is S where
W G cuts the saturation line.
mw SG
=
mg WS

Example

The pressure of the mixture entering and leaving the adiabatic saturation in 1 bar, the
entering temperature of 30‰ and the temperature of mixture leaving is 20‰ which is the
adiabatic saturation temperature. Calculate the humidity ratio and relative humidity of

19
 h

TG

G
Tw s

Ts
w

0
f

the air-water vapor entering the saturator.

Solution:
Since the water leaving is saturated,

Pv 2 = Pg 2

and ω2 can be calculated from

2.339
ω2 = 0.622 × ( ) = 0.0149
100 − 2.34

cpa (T2 − T1 ) + ω2 hf g,2

ω1 = (42)
hv,1 − hf,2
1.0035(20 − 30) + 0.0149 × 2454.1
= = 0.0107 (43)
2556.3 − 83.96

 
Pv,1
ω1 = 0.0107 = 0.622 ×
100 − Pv,1
Hence Pv,1 = 1.691 kPa
Pv,1 1.691
φ= = = 0.398
Pg,1 4.246

1.2.10 Psychrometric chart

The numerous property data for air-water vapour mixtures have been presented graphi-
cally in the psychrometric chart for ease. The chart is widely used for HVAC applications
as well as drying applications. The dry-bulb temperature is represented on the absissa of

20
 In s u la tio n

A ir + s a tu ra te d s te a m
A ir + s u p e rh e a te d s te a m S s ta te
C s s ta te

liq u id w a te r
W s ta te

the chart while humidity ratio is represented on the ordinate. Other properties include the
specific volume, relative and specific humidities, vapour pressures, and specific enthalpy.
The specific enthapy is defined in terms of the mass of air, i.e.,

H = ma h = ma ha + mv hv

∴ h = ha + ωhv

A sample of the psychrometric chart is presented in the figure below.

Exercises
1. (A) A mixture at 300 K and 160 kPa has the following volumetric analysis: O2 , 60
%; CO2 , 40 %. Compute (a) the mass analysis, (b) the partial pressure of O2 , in
kPa, (c) the apparent molar mass, and (d) the volume occupied by 0.13 kg of the
mixture, in m3 .
(B) A gas mixture at 120 kPa and 0.063 m3 has the following gravimetric analysis:
O2 , 32%; CO2 , 56 %; He, 12 %. Determine (a) the volumetric analysis, (b) the
apparent gas constant in kJ/(kg K), and (c) the temperature of 0.050 kg of the
mixture, in K.

2. A gas mixture is made up of 64% O2 and 36 % H2 , by mass. The total pressure is 3

bars, and the volume is 0.10 m3 . Determine (a) the partial pressure of hydrogen, in
bars, (b) the apparent molar mass in kg/kmol, (c) the gas constant, in kJ/(kg K),
and (d) the temperature, in K, if the mass of the mixture is 0.052 kg.

3. A gas at 77‰ and 100 kPa has the following volumetric analysis: H2 , 4 %; CO, 12

21
 %, CO2 25 %; and N2 , 59 %. The initial mixture passes at 20 m3 /min through a
steady-flow heat exchanger until the temperature reaches 227‰. Determine (a) the
gravimetric analysis, (b) the heat transfer based on tabular ideal-gas tables, (c) the
heat transfer based on average specific-heat data, in kJ/kg and (d) the heat transfer
rate in kJ/min.

4. Carbon monoxide and argon in separate streams enter an adiabatic mixing chamber
in a 2:1 ratio. At the inlet the CO is at 120 kPa and 300 K, and the Ar is at 120 kPa
and 450 K. The mixture leaves at 110 kPa. Determine (a) the final temperature of
the mixture in K, and (b) the entropy production for the process, in kJ/K per kmol
of mixture.

5. Hydrogen and nitrogen in separate streams enter an adiabatic mixing chamber in a

3:1 molar ratio. At the inlet the H2 is at 2 bars and 77‰, and the N2 is at 2 bars
and 277‰. The mixture leaves at 1.9 bars. (a) Determine the final temperature of
the mixture, in K. (b) Compute the entropy production of the overall process, in
kJ/(kmol K).

6. (A) A rigid tank with a volume of 300 L initially contains 0.34 kg of dry air at
60 ‰. Water vapor is added until the gas is saturated at the same temperature.
Determine (a) the mass of water added, in kg, and (b) the final total pressure, in in
kPa.
(B) Atmospheric air at 1 bar has dry-bulb temperature of 25‰ and a relative hu-
midity of 50 %. Use a psychrometric chart to estimate (a) the wet-bulb temperature,
(b) dew point, (c) specific humidity and (d) specific enthalpy.

7. (A) A tank contains 10 kg of dry air and 0.15 kg of water vapour at 26‰ and 100
kPa. Determine (a) the specific humidity, (b) the relative humidity, and (c) the
volume of the tank in m3 .
(B) Atmospheric air at 1 bar has dry-bulb and wet-bulb temperatures of 25 and
20‰. By use of a psychrometric chart, estimate the values of (a) relative humidity,
(b) dew point, (c) specific humidity, and (d) specific enthalpy.

8. (A) Atmospheric air initially at 20‰, 1 bar, and 70 % relative humidity is com-
pressed isothermally until the pressure reaches 2 bars. (a) Show that condensation
must occur. (b) Determine the amount of water condensed, in kg of H2 O / kg of
dry air.
(B) Atmospheric air at 1 bar has dry-bulb temperature of 28‰ and a specific hu-
midity of 0.0090 kg H2 O/kg dry air. Use a psychrometric chart to estimate (a)
the wet-bulb temperature, (b) relative humidity, (c) dew point, and (d) specific
enthalpy.

22
 9. If the partial pressure of water vapour in atmospheric air at 1 bar is 30 mbars at
30‰, calculate (a) the relative humidity, (b) the dew-point temperature, (c) the
humidity ratio, (d) the enthalpy, kJ/kg (based on h = 0 at 0‰for both dry air and
water), and (e) the specific volume of the mixture, in m3 /kg dry air. Use steam-table
data where necessary.

10. (A) Atmospheric air at 22‰ and 99 kPa has an enthalpy of 40.0 kJ/kg dry air
(based on h = 0 at 0‰for dry air). Calculate (a) the specific humidity in kg/kg, (b)
the vapour pressure of water, in kPa, (c) the relative humidity, and (d) the specific
volume, in m3 /kg dry air.
(B) Atmospheric air at 1 bar has dry-bulb temperature of 26‰ and a specific en-
thalpy of 65 kJ/kg dry air. Use a psychrometric chart to estimate (a) the wet-bulb
temperature, (b) relative humidity, (c) specific humidity, and (d) the specific vol-
ume.

11. A gas mixture is made up of 50% O2 and 50 % H2 , by mass. The total pressure is 3
bars, and the volume is 0.10 m3 . Determine (a) the partial pressure of hydrogen, in
bars, (b) the apparent molar mass in kg/kmol, (c) the gas constant, in kJ/(kg K),
and (d) the temperature, in K, if the mass of the mixture is 0.052 kg.

23
 120 125 130 135 140 145
115

0,36
Carrier 35 40 45 50 55
0,033
110

0,032
0,031
105

PSYCHROMETRIC CHART 0,030 0,40

100

0,029

%
NORMAL TEMPERATURES 0,028
95

90
30
0,027
SI METRIC UNITS
90

0,45

%
0,026

80
Barometric Pressure 101,325 kPa
0,025
85
SEA LEVEL

%
0,024

70
80
0,023 0,50

y
idit
0,022

m
%
75

Hu
60

ive
0,021

lat
0,55

Re
70
0,020

25

%
50
0,019

n k J /k g d ry a ir
65
0,60
Air
0,018
g Dry
0,017

60
kJ/k
0,65

%
40

24
0,016

on

–1,0 E n th a lp y d e vi a tio
0,95

rati

55
0,015 0,70

atu

20

Sensible Heat Factor

at s
0,014

50
0.75

py
%

hal
30 0,013

Ent
0,80
40

45
0,012

–1,2
0,85

–0,8
–0,6
0,011
35

40
0,90

–0,4
15

,2
5
,0

–0
,1
–0 0,010
25

0,95

–0
20%

30
1,00
0,009
°C
re
20

atu 10 0,008
per

25
n Tem 0,007
atio

Moisture content kg/kg Dry Air

15
10

tur
r Sa 0,006
lb o 5
t Bu 10%
We
5

10

0,005
0 0,004
0

0,003
–5
–5

0,002
0

0,001
–1

0,00
–10 –5 0 5 10 15 20 25 30 35 40 45 50 55
Dry Bulb Temperature °C
0,75 0,80 0,85 0,90
Volume m3 /kg dry air
Below 0°C, Properties and Enthalpy Deviation Lines Are For Ice