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APPLIED THERMODYNAMIC
CHAPTER 6
MIXTURE AND
PSYCHROMETRY
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 = ∑m i
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 Ex:1
• Jisim O2, mO2=(23.3/100)(1)=0.233kg
• mN2=(76.7/100)(1)=0.767 kg
• Dari persamaan RM=R’/M; RM=pemalar gas tertentu
• Pv=mRT; P=mR’T/Mv
• Pi=miR’T/Miv
“..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,
pAV pVA
mA = mA =
RAT and RAT
fig A fig B
pAV pVA
=
RAT RAT
pA
pAV = pVA or VA = V
p
• In general, therefore
pi
Vi = V
p
piV V
∑ Vi = ∑ p
= ∑ pi
p
9
• Since, p = ∑ pi therefore
V
∑V = p × p
i
V = ∑V i
“…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
∑ ( pV ) = ∑ ( m R T )
i i i
V ∑ p =T ∑mR
i i i
12
• Since p = ∑ pi
∑mR
pV = T i i = mRT
mR = ∑ m R i i
• 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
Ro
From equation R =
M
8.314 kJ
RO2 = = 0.2598
32 kg.K
8.314 kJ
RN2 = = 0.2969
28 kg.K
8.314 kJ 8.314 kJ
RAr = = 0.2079 RCO2 = = 0.1890
40 kg.K 44 kg.K
14
mi
From equation R = ∑ m Ri
mO2 mN2 mAr mCO2
R = × RO2 + × RN2 + × RAr + × RCO2
mmix mixm mixm mixm
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
Ro pM pi Mi pi
• With R = , we get =∑ , where M = ∑ Mi
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
a. mass of constituent and mixture
From equation m = n × M
mCO2=nCO2×M CO2
mCO2= 1 × 44 = 44kg
ni V
We know = i
nmix Vmix
VO2 VN2
nO2 = × nair = 0.21× 3.5 nN2 = × nair = 0.79× 3.5
Vair Vair
nO2 = 0.735kmol nN2 = 2.765kmol
19
mmixture=mCO2+mO 2+mN 2
mmixture= 44 + 23.55 + 77.5
mmixture= 145.05kg
20
c. molar mass and gas constant of mixture
ni
We know Mmix = ∑ × Mi
nmix
21
d. specific volume of the mixture.
We know pv = RT
RmixT mix 0.2581× (15 + 273)
v mix = =
pmix 100
m3
v mix = 0.7435
kg
22
6.5 THE SPECIFIC HEAT FO MIXTURE
• We know mu = ∑ miui (Gibbs- Dalton) and u = CVT
mi
• Combining both equation mCVT = ∑ miCViT or CV = ∑ CVi
m
• To obtain the specific enthalpy, h and entropy s we will use the
same approach to obtain
m
CP = ∑ i CPi
m
• From equation CP − CV = R
mi m
CP − CV = ∑ CPi + ∑ i CVi
m m
m
CP − CV = ∑ i (CPi − CVi )
m
m
CP − CV = ∑ i Ri
m
23
EXAMPLE 6.4
24
SOLUTION
Assumption: The amount of mixture is 1 kmol. This can be done since the
work and heat transfer is per unit mass.
VCO2 VO2 V
We know = 0.12, = 0.115and N2 = 0.765
v mix v mix v mix
Rmix (T 2 − T1 ) γ −n
w12 = andq12 = w12
1− n γ −1
V
Mmix = ∑ i × Mi
Vmix
25
VCO2 VO VN
M mix = × M CO2 + 2 × M O2 + 2 × M N 2
Vmix Vmix Vmix
Find Cpmix
mi
CPmix = ∑ × CP i
mmix
mCO2 mO2 mN2
CP mix = × CP CO2 + × CP O2 + × CP NO2
mmix mmix mmix
26
ni V
We know = i and n mixture is 1 kmol
nmix Vmix
VCO2 VO2
nCO2 = × 1 = 0.12kmol nO2 = × 1 = 0.115kmol
Vmix Vmix
VN2
nN2 = × 1 = 0.765kmol
Vmix
Since mi = ni × Mi
mCO2 = nCO2 × MCO2 = 0.12× 44 = 5.28kg
mO2 = nO2 × MO2 = 0.115× 32 = 3.68kg
mNO2 = nN2 × MN2 = 0.765× 28 = 21.4kg
27
5.28 3.68 21.4
CP mix = × 1.271 + × 1.11 + × 1.196
30.36 30.36 30.36
kJ
CP mix = 1.199
kg.K
We know CV = CP − R
CV mix = CP 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
T 2 = 782.6K
γ −n 1.296− 1.25
q12 = w12 = × 537.5
γ −1 1.296− 1
kJ
q12 = 83.53
kg
29
6.6 GAS AND VAPOUR MIXTURE
Dry and Atmospheric Air
30
• Therefore, the change of enthalpy will be ∆hdry air = CP ∆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 = partialpressureof dry air
pv = partialpressureof wet vapour
31
Specific and Relative Humidity of Air
mv 1
vv v a
ω= V = =
ma 1 vv
V v a
32
Specific and Relative Humidity of Air
Ro Ro
• We know that Rv = and Ra =
Mv Ma
paVMa p VM
• Therefore ma = and mv = v v
RoT RoT
pvVMV
RoT Mv pv
ω= = ×
paVMa Ma 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,φ where
mv p V RvT p pg = psat @T
φ= = v = v
mg pgV RvT pg
34
• Substituting the equation, we will get;
0.622φpg ωp
ω= φ=
( p − φpg ) ( 0.622+ ω ) pg
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 = Ha + Hv = maha + mv hv
37
SOLUTION
For water, at 25oC, psat=0.03166 bar and hg=2546.6 kJ/kg
pa = p − pv = 1 − 0.0237= 0.9763
pv 0.0237
ω = 0.622 = 0.622
( p − pv ) (1 − 0.0237)
kgH2O
ω = 0.0151
kg dry air
38
c. the enthalpy per unit mass of the dry air
h = ha + ωhg ≅ CPT + ωhv
( )
hv = 2500( kJ / k ) g + 1.88 kJ / kg.o C T = 2500+ 1.88( 25)
hv = 2547kJ / kg
Both dry air and water vapour fill the entire room completely.
Vmix = Va = Vv = 5 × 5 × 3 = 75m3
39
So the mass of dry air will be;
paVmix 97.63× 75
ma = =
RaT mix 0.287( 25 + 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 (φ = 100%).
Any further in temperature drop will result Example:
in condensation, and this is the beginning Droplet on cold can is result by:
of dew formation.
T water in can < Tdp (of surrounding air)
• Dew temperature, Tdp is defined as the
temperature of which begin when air is
cooled at constant pressure.
T dp = T s @ p
V
41
Adiabatic Saturation and Wet Bulb Temperature
• It is easy to obtain water vapour pressure
Unsaturated
if we know the dew-point temperature but air
Saturated air
it is not practical. T1, ω1, 1 2 T2,ω2
• Another way to determine the relative and φ2 = 100%
φ1
Liquid water
specific humidity is using the
understanding of an adiabatic saturation Liquid water
process. at T2
• The system consist of a long insulated
channel that contains a pool of water.
• A steady stream of unsaturated water with
ω1 and T1 is passed through this channel. Adiabatic saturated
• As the air flows, some water evaporates T temperature
resulting in temperature decrease and
increase of moisture content (φ increase).
1
• If the channel is long enough, φ 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
flow process. 2 T2,ω2
T1, ω1, 1
φ2 = 100%
• From the principle of mass; φ1
Liquid water
a = m
m a ( no massaddedfor dry air)
a = m Liquid water
1 2 at T2
mv + m f = m v or
1 2 2
a ω1 + m
m f = m a ω2 thus
1 2 2
mf = ma ( ω2 − ω1 )
2
Adiabatic saturated
T temperature
∑ m hin in = ∑m
outhout
ah1 + m
m f hf = m
ah2 or
2 2
1
m a ( ω2 − ω1 ) hf = m
ah1 + m ah2
2
Dividing by m a gives 2
h1 + ( ω2 − ω1 ) hf = h2 Dew-point
(CPT1 + ω1hg ) + (ω2 − ω1 )hf = (CPT 2 + ω2hg
1 2 2
) temperature
s
43
Rearrange the formula will give; Unsaturated
Saturated air
air
T2,ω2
CP (T 2 − T1 ) + ω2hfg2 T1, ω1, 1 2
φ2 = 100%
ω1 = φ1
hg1 − hf2 Liquid water
ω1p2
φ1 =
( 0.622+ ω1 ) pg1
• The process discuss above involve long channel.
• A more practical approach is to use a sling
psychrometer which have the dry bulb thermometer
and a wet bulb thermometer which is soak with
water
44
• Comparison with the system used before: CP (T 2 − T1 ) + ω2hfg2
ω1 =
hg1 − hf2
The dry bulb thermometer will give the temperature
at the inlet, that is T1. pg2
ω2 = 0.622
From the value of T1, we can get the value of pg , hg
1 1
(p 2 − pg2 )
The dry bulb temperature will give the desired ω1
that we want to find. ω1p2
φ1 =
( 0.622+ ω1 ) pg1
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
From the table:
pg2 = psat @15o C = 0.01704bar hf2 = hf @15o C = 62.9kJ / kg pg1 = psat @25o C = 0.03166bar
hfg2 = hfg @15o C = 2465.5kJ / kg hg1 = hg @25o C = 2546.6kJ / kg
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 its not my job to give to
you…..
49
PSYCHROMETRIC CHART
50
EXAMPLE 6.6
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
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 6.7
• 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.
• Example 6.8
• A small-size cooling tower is designed to cool 5.5 liters of water per
second, the inlet temperature of which is 44ºC. The motor-driven fan
induces 9 m3/s of air through the tower and the power absorbed is
4.75 kW. The air entering the tower is at 18ºC, and has a relative
humidity 60% and its temperature is 26ºC. Assuming that the
pressure thought the tower is constant at 1.013 bar, and make-up
water is added outside the tower, Calculate:
• (i) the mass flow rate of make-up water required;
• (ii)the final temperature of the water leaving the tower.
55
Cooling Tower
Solution 6.7
2 T2=30ºC;ø2=100%
Air
Exit Assumption:
• m’ dry air in~out are constant-
T3=35ºC;
Fan • Dry air and water vapor is ideal gas
m3=100kg/s 3 • K.E and P.E ~Δ are Neglecting
Hot • 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 =Σm e he
. . . .
m a1 h1 +m3 h3 =m a 2 h2 +m a 4 h4
. . . .
hence m3 h3 =m a (h2 −h1) +(m3 −m makeup water )h4
•To define volume flow rate of air into the cooling tower
V1=mav1
=(96.9 kg/s)(0.842 m3/kg)
=81.6m3/s
Packing
m1=m2=5.5 liter
Tw2=? 2 1
m’w2hw2 Cold
Water Out
Air Inlet
1 atm;Ta1=18ºC;
ø1=60%;m’aha1
Make-up water
m’s1hs1
59
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
60
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] 61
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
62