Documente Academic
Documente Profesional
Documente Cultură
APPLIED THERMODYNAMIC
CHAPTER 6
MIXTURES
1
6.1 INTRODUCTION
2
6.2 DALTON’S LAW
3
Dalton law stated:
“..the pressure of a mixture of gases is equal to the sum of the partial pressure of
the constituents…The partial pressure of each constituent is that the pressure
which the gas would exert if it occupied alone that volume occupied by the mixture
at the same temperature…”
p pi
Note:
From the conservation of mass m mi
4
EXAMPLE 6.1
A vessel of volume 0.4 m3 contains 0.45kg of CO and 1 kg of air at 15oC.
Calculate the partial pressure of each constituent and the total pressure
in the vessel. The gravimetric analysis of air is to be taken as 23% O2,
76.7% N2. Take the molar mass of CO, O2 and N2 as 28,32 and 28
kg/kmol.
5
Solution 6.1
• Volume,V=0.4m3, T=15+273=288K
• Partial pressure for O2;
• PiO2=(0.233 x 8.3145 x 288)/(32 x 0.4) =43.59 kN/m2=0.4359 bar
• Partial pressure for N2;
• PiN2=(0.767 x 8.3145 x 288)/(28 x 0.4) = 163.99 kN/m2=1.6399 bar
• Partial pressure for CO
• PiCO=(0.45 x 8.3145 x 288)/(28 x 0.4) =(96.21 kN/m2=0.9621 bar
• Total pressure, Pm=Pi=0.436+1.640+0.962
• =3.038 bar
6
6.3 GIBSS-DALTON’S LAW
“..the internal energy, enthalpy and entropy of gaseous mixture are respectively
equal to the sum of the internal energies, enthalpies and entropies of the
constituents…Each constituent has that internal energy, enthalpy, and entropy
which it have if it occupied alone that volume occupied by the mixture at the
temperature of the mixture..”
7
6.4 VOLUMETRIC ANALYSIS OF GAS MIXTURE
8
• From fig B, the partial volume of each constituents will be VA, VB and
VC.
• From equation pV=mRT,
p AV pV A
mA mA
R AT and R AT
fig A fig B
p AV pV A
R AT R AT
pA
p AV pV A or VA V
p
• In general, therefore
pi
Vi V
p
piV V
Vi p
p
pi
9
• Since, p pi therefore
V
V p p
i
V Vi
“…Therefore, the volume of a mixture of gases is equal to the sum of the volumes
of individual constituents when each exist alone at the pressure and the
temperature of a mixture…”
10
• Looking back at fig. A;
The volume V at p and T will contains an
amount of substance n
n ni
11
6.5 THE MOLAR MASS AND SPECIFIC GAS
CONSTANT
• Molar mass is defined as mass of substance per its amount, n;
m
M
n
• Molar mass for carbon is 12kg/kmol.
• For n kmol, the mass of the substance is m = n x M kg
• 1.3 kmol of carbon will have 1.3 x 12 = 15.6 kg of carbon.
• From equation pV=mRT, since m = n x M, therfore pV=nMRT
Ro R
• Since R therefore pV nM o T and pV nRoT
M M
pV T mi Ri mRT
mR mi Ri
• Or
mi
R Ri
m
13
EXAMPLE 6.2
The gravimetric analysis of air is 23.14% oxygen, 75.53% nitrogen, 1.28
% argon, 0.05% carbon dioxide. Calculate the specific gas constant for
air and molar mass. Take the molar mass of oxygen, nitrogen, argon and
carbon dioxide as 32 kg/kmol, 28 kg/kmol, 40 kg/kmol and 44 kg/kmol
SOLUTION 6.2
Ro
From equation R
M
8.314 kJ
RO 0 .2598
2
32 kg .K
8.314 kJ
RN 2 0.2969
28 kg .K
8.314 kJ 8.314 kJ
RA r 0.2079 RC O 0.1890
40 kg .K
2
44 kg .K
14
mi
From equation R m Ri
mO2 mN 2 mA r mC O2
R RO2 RN 2 RA r RC O2
mmix mmix mmix mmix
R 0.2314 0.2598 0.7553 0.2969 0.0128 0.2079 0.0005 0.1890
kJ
R 0.287
kg .K
Ro
The molar mass can be calculated using R
M
Ro 8.314
M
R 0.287
kg
M 28.96
kmol
15
6.5 THE MOLAR ANALYSIS
16
m
• Another way to fine molar mass besides using formula M is as
n
below:
pV
• We have from Gibbs law; mi i (constitue nt)
RiT
pV
m (mixture)
RT
• Since m mi then pV p iV
RT
RT
i
R pM pM pi
• With R o , we get i i , where M M i
M Ro Ro p
• Since pi Vi ni M
pi
Mi
p V n p
V
M i Mi
V
n
M i Mi
n
17
EXAMPLE 6.3
A mixture of 1 kmol CO2 and 3.5 kmol of air is filled in a vessel at 1 bar
and 15oC. The volumetric analysis of air is to be 21% O2 and 79%
N2.Determine:
a. mass of constituent and mixture
b. % carbon in the mixture
c. molar mass and gas constant of mixture
d. specific volume of the mixture.
18
SOLUTION 6.3
a. mass of constituent and mixture
From equation m n M
m C O n C O M C O
2 2 2
m C O 1 44 44kg
2
ni V
We know i
nmix V mix
VO VN
nO nair 0.21 3.5
2
nN 2
nair 0.79 3.5
2
Vair 2
Vair
nO 0.735kmol nN 2.765kmol
2
2
m O n O M O
2 2 2
m N n N M N
2 2 2
19
m mixture m C O m O m N
2 2 2
%m C 8.27%
20
c. molar mass and gas constant of mixture
ni
We know M mix Mi
nmix
nC O2 nO2 nN 2
M mix
M C O2
M O2 M N 2
nmix nmix nmix
1 0.735 2.765
M mix 44 32 28
4.5 4.5 4.5
kg
M mix 32.2
kmol
R Note:
We know Rmix o
M mix The M and R can also
8.314 kJ determine using solution as
Rmix 0.2581 in Example 6.2 (page 13)
32.2 kg .K
21
d. specific volume of the mixture.
We know pv RT
RmixT mix 0.2581 15 273
v mix
p mix 100
m3
v mix 0.7435
kg
22
6.5 THE SPECIFIC HEAT FOR MIXTURE
• We know mu mi u i (Gibbs - Dalton) and u CVT
mi
• Combining both equation mCVT mi CV iT or CV CV i
m
• To obtain the specific enthalpy, h and entropy s we will use the same
approach to obtain
m
C P i C Pi
m
• From equation C P CV R
mi m
C P CV C Pi i CV i
m m
m
C P CV i C Pi CV i
m
m
C P C V i Ri
m
23
EXAMPLE 6.4
24
SOLUTION 6.4
Assumption: The amount of mixture is 1 kmol. This can be done since the
work and heat transfer is per unit mass.
VC O VO VN
We know 0.12,
2
0.115 and
2
0.765
2
Rmix T 2 T1 n
w 12 and q12 w
1n 1 12
V
M mix i M i
Vmix
25
VCO VO VN
M mix 2 M CO2 2 M O2 2 M N 2
Vmix Vmix Vmix
Find Cpmix
mi
C Pmix CP i
mmix
m mO2 mN 2
C P mix C O C P C O
2
2
m C
P O2
m C P NO2
mmix mix mix
26
ni V
We know i and n mixture is 1 kmol
nmix V mix
VC O VO
nC O 1 0.12kmol
2
nO 2
1 0.115kmol
2
Vmix 2
Vmix
VN
nN 2
1 0.765kmol
2
Vmix
Since mi ni M i
mC O nC O M C O 0.12 44 5.28kg
2 2 2
mO nO M O 0.115 32 3.68kg
2 2 2
mmix mC O mO mN 2 2 2
27
5.28 3.68 21.4
C P mix 1.271 1.11 1.196
30.36 30.36 30.36
kJ
C P mix 1.199
kg .K
We know CV C P R
CV mix C P mix Rmix 1.199 0.274
kJ
CV mix 0.925
kg .K
V2
We know 7
V1
28
1.25 1
1
T 2 1000 273
7
T2 782.6K
n 1.296 1.25
q12 w 12 537.5
1 1.296 1
kJ
q 12 83.53
kg
29
6.6 GAS AND VAPOUR MIXTURE
Dry and Atmospheric Air
30
• Therefore, the change of enthalpy will be hdry air C P T
• It certainly will be convenient to treat the vapour as ideal gas since
at low temperature the error can be negligible.
• As a result we can say that it will obey pv RT
• From Dalton Law, if dry air is mix with water vapour at T and V, the
total pressure P can be written as; p pa pv
where;
pa partial pressure of dry air
pv partial pressure of wet vapour
31
Specific and Relative Humidity of Air
mv 1
V vv v a
ma 1 vv
V v a
32
Specific and Relative Humidity of Air
pvVMV
RoT Mv pv
p aVM a M a pa
RoT
33
• By definition, dry air contains no water vapour and thus its specific
humidity is zero.
• Let us add some water vapour, the specific humidity will increase
until it the air can hold no more moisture.
• At this point it will be the maximum amount of moisture the air can
hold and is called the saturated air.
• Any moisture introduce into saturated air will condense.
• The amount of moisture in the air has a definite effect on how
comfortable we feel in an environment.
• However, the comfort level depends more on the amount of
moisture the air holds, mv relative to the maximum amount of
moisture the air can hold, mg (saturated condition)
• The ratio is called relative humidity, where
mv p V RvT p p g p sat @T
v v
mg p gV RvT pg
34
• Substituting the equation, we will get;
0.622p g p
p p g 0.622 p g
35
Specific Enthalpy and Specific Heat Capacity
• The total enthalpy (extensive property) of the atmospheric air is the
sum of the enthalpy of the enthalpies of dry air and water vapour;
H H a Hv ma ha mv hv
ma ha mv
• Dividing with mass of dry air; h hv and h ha hv
ma ma
kJ
• h is actually the mixture enthalpy per unit dry air kg dry air
where the value 2500 kJ/kg is the enthalpy at 0oC and 1.88kJ/kg.oC
is the value of average specific heat capacity of water vapour.
37
SOLUTION 6.5
For water, at 25oC, psat=0.03166 bar and hg=2546.6 kJ/kg
pv 0.0237
0.622 0.622
p pv 1 0.0237
kg H2O
0.0151
kg dry air
38
c. the enthalpy per unit mass-of-dry-air
hv 2500kJ / kg 1.88 kJ / kg.o C T 2500 1.8825
hv 2547kJ / kg
Both dry air and water vapour fill the entire room completely.
Vmix Va Vv 5 5 3 75m 3
39
So the mass of dry air will be;
p aV mix 97.63 75
ma
RaT mix 0.28725 273
ma 85.53kg
40
Dew-Point Temperature
• Every morning, we can see that the grass T
is always wet although it did not rain. This
is because the excess moisture in the air 1
simply condensed on cool surface forming
what we call dew.
• What happen is that, when the
temperature falls at night, so does the 2
moisture capacity of air, which is the
maximum amount of moisture can hold. s
After a while the moisture capacity will be
equal to the moisture content ( = 100%). Example:
Any further in temperature drop will result
Droplet on cold can is result by:
in condensation, and this is the beginning
of dew formation. T water in can < Tdp (of surrounding air)
41
Adiabatic Saturation and Wet Bulb Temperature
• It is easy to obtain water vapour pressure Unsaturated
if we know the dew-point temperature but Saturated air
air
T2,2
it is not practical. T1, 1, 1 2
2 = 100%
• Another way to determine the relative and 1
Liquid water
specific humidity is using the
Liquid water
understanding of an adiabatic saturation
at T2
process.
• The system consist of a long insulated
channel that contains a pool of water.
• A steady stream of unsaturated water with
Adiabatic saturated
1 and T1 is passed through this channel. T temperature
• As the air flows, some water evaporates
resulting in temperature decrease and
increase of moisture content ( increase). 1
• If the channel is long enough, will
become 100% at T2(adiabatic saturated
temperature.
2
Dew-point
temperature
s
42
• If makeup water is supplied at the rate of Unsaturated
the evaporation, it will become a steady Saturated air
air
T2,2
flow process. T1, 1, 1 2
2 = 100%
• From the principle of mass; 1
Liquid water
m a 1 m f m a 2 thus
1 2 2
m f m a 2 1
2
Adiabatic saturated
T temperature
m inhin m out hout
m a h1 m f hf m a h2 or
2 2
1
m a h1 m a 2 1 hf m a h2 2
Dividing by m a gives 2
h1 2 1 hf h2 Dew-point
C PT1 1hg 2 1 hf C PT 2 2hg
1 2 2
temperature
s
43
Rearrange the formula will give; Unsaturated
Saturated air
air
T2,2
C T T 2hfg T1, 1, 1 2
2 = 100%
1 P 2 1 2
1
hg hf 1 2
Liquid water
1p 2
1
0.622 1 p g 1
44
• Comparison with the system used before: C P T 2 T1 2hfg
1 2
hg hf
1 2
The dry bulb thermometer will give the temperature
at the inlet, that is T1. pg
2 0.622
p p g2
2
45
EXAMPLE 6.6
The dry-wet bulb temperature of atmospheric pressure at 1 atm are
measured with sling psychrometer and determined to be 25oC and 15oC
respectively. Determine:
a. the specific humidity
b. the relative humidity
c. the enthalpy per unit dry air.
46
SOLUTION 6.6
From the table:
p g psat @15o C 0.01704bar
2
hf hf @15o C 62.9kJ / kg
2
p g psat @ 25o C 0.03166bar
1
2 1.01325 0.01704
2 0.0106 kgH2O/kg dry air
hg hf
1 2
1546.6 62.9
1 0.00648 kgH2O/kg dry air
1 0.33 or 33%
47
c. the enthalpy per unit dry air
48
Psychrometric Chart
• The state of atmospheric air at a
specific pressure is completely
specified by two independent intensive
properties.
• Since calculations create tedious jobs,
using chart is much more simpler……..
but we have to compromise with
accuracy.
• Psychrometric chart is introduce to
ease all the scientist and engineering
so that fast result can be obtained and
it is used extensively in air-conditioning
application.
• The chart given is the chart for 1 atm
only. Charts for other pressure are also
available.
49
PSYCHROMETRIC CHART
50
EXAMPLE 6.7
Considered a room that contains air at 1 atm, 35oC and 40% of relative
humidity. Using the psychrometric chart , determine:
a. the specific humidity
b. the enthalpy
c. the wet-bulb temperature
d. the dew-point temperature
e. the specific volume of the air.
51
a. the specific humidity
b. the enthalpy
c. the wet-bulb temperature
d. the dew-point temperature
e. the specific volume of the air
Specific humidity
Dew temp
52
COOLING TOWER
• A device to use water as a cooling which in the
cycle cooling systems the heat from the
component are remove.
• Two types of the cooling tower
• i. Induced-draught cooling tower
• Ii. Natural draught cooling tower
53
COOLING TOWER
Air
Exit
Air Exit
Fan
Hot
Water In
Packing
Hot Water In
Cold
Air Inlet
Water Out Air In
Schamatic Diagram of Cooling Tower: (a) Induced-draught and (b) Natural Draught
54
Cooling Tower
• Example 6.8
• The cooling water from condenser of the power plant
enters a cooling tower at 35ºC at the rate of 100 kg/s.
The water is cooled to 22ºC in the cooling tower by air
that enters the tower at 1 atm, 20ºC, and 60 % relative
humidity and leaves saturated at 30ºC. Neglecting the
power input to the fan. determine:
• (i) the volume flow rate of air into the cooling tower
• (ii) the mass flow rate of the required makeup water.
55
Cooling Tower
Solution 6.8
2 T2=30ºC;ø2=100%
Air
Exit Assumption:
1. m’ dry air in~out are constant-
T3=35ºC;
Fan 2. Dry air and water vapor is ideal gas
m3=100kg/s 3
3. K.E and P.E ~Δ are Neglecting
Hot 4. Cooling Tower is adiabatic
Water In
Packing
m3=m4=100kg/s;
T4=22ºC 4 1
Cold
Air Inlet
Water Out
1 atm;T1=20ºC;
ø1=60%;v1=?
Make-up water
56
Cooling Tower
• From assumption:
• Dry air mass balance;
• m’a1=m’a2=m’a
• Water mass balance;
• m’3=m’aω1=m’4+m’a2 ω2
• Or m’3-m’4 =m’a (ω2-ω1) = m’makeup water
• Energy balance;
. .
mi hi me he
. . . .
ma1 h1 m3 h3 ma 2 h2 m4 h4
. . . .
hence m3 h3 ma (h2 h1) (m3 mmakeup water )h4
59
Cooling Tower
Solution 6.9 Ta2=26ºC;ø2=100%
2 m’aha2;m’s2hs2
Air
Exit
m’w1hw1; Tw1=44ºC Assumption:
m1=5.5 liter 1. m’ dry air in~out are constant-
Fan 2. Dry air and water vapor is ideal gas
1 3. K.E and P.E ~Δ are Neglecting
Hot 4. Cooling Tower is adiabatic
Water In
Packing
m1=m2=5.5 liter
Tw2=? 2 1
m’w2hw2 Cold Air Inlet
Water Out
1 atm;Ta1=18ºC;
ø1=60%;m’aha1
Make-up water
m’s1hs1
60
Cooling Tower
• i. At air inlet @18ºC
• Ø=Ps/pg and Pg@18ºC=0.02063 bar
• Ps1=(0.6)(0.02063)=0.01238 bar
• Pa1=P-Ps1
• =1.013-0.01238=1.0006 bar
• m’a=(105 x 1.0006 x 9)/(103x 0.287)(18+273)=10.78 kg/s
• And
• m’s1=(105x0.01238 x 9)/(103x 0.4618 x 291)=0.0829
kg/s
• At air Exit@ 26ºC
• Pg=0.03360 bar and ø=1
• Ps2=Psg=0.03360 bar
• From equation ω2=0.622[(Ps2)/(P-Ps2)]
• =(0.622 x 0.0336)/(1.013 – 0.0336)
• =0.02133
61
Cooling Tower
• From equation m’s2=10.78 x 0.02133 [ω2=ms2/ma]
• m’s2=0.23 kg/s
• Hence makeup water required is, mmakeup=m’s2-m’s1
• =0.23-0.0829=0.1471 kg/s
• Ii. Water
• m’w1=5.5 x 1 =5.5 kg/s and
• m’w2=m’w1-m’makeup
• =5.5 – 0.1471
• =5.353 kg/s
• From SFEE with Δ K.E and P.E are Neglecting and all of losses heat
• W’+m’w1hw1+m’a1ha1+m’s1+hs1=m’a2ha2+m’s1hs2+m’w2hw2 …..(1)
• But given W’=4.75 kW=4.75 kJ/s
• Evaluating the enthalpies from a datum of 0ºC we have;
• hw1=hf @ 44ºC=184.2 kJ/kg
• ha1=1.005(18-0)ºC=18.09 kJ/kg [CpΔT]
• hs1=2519.4 + 1.86(18-10.3)=2534 kJ/kg [Patm)
• hs2=hg @ 26ºC = 2548.4 kJ/kg
• ha2=1.005(26-0)=26.13 kJ/kg [CpΔT] 62
Cooling Tower
• The vapor is superheated at 1, being above @10.13ºC,
the saturation temperature corresponding to 0.01238
bar;
• Substituting in (1)
• 4.75 +(5.5 x 184.2)+10.78 x 18.09) + (0.0828 x 2534) =
(10.78 x 26.13) + (0.23 x 2548.4) + 5.353hw2
• 5.353hw2=556.3
• Hw2=104 kJ/kg=hf
• By interpolotion
• Hf Ts
• 101 24.1
• 104 Tw2
• 112 26.7
• Tw2=[(104-101)/(112-101)] [26.7-24.1] +24.1=24.80ºC
• =temperature of water leaving tower
63