MECE322 Gas Mixtures

Ideal Gas Mixtures
Today’s main concepts:

• Be able to describe ideal gas mixture composition in terms
of mass fractions and mole fractions.
• explain use of the Dalton model to relate pressure, volume,
and temperature and to calculate changes in U, H, and S for
ideal gas mixtures.
• Be able to apply mass, energy, and entropy balances to
systems involving ideal gas mixtures, including mixing
processes.
Describing Mixture Composition 3
Thus far we have been working with pure fluids

• Water • Nitrogen
• Air • Oxygen
• R22 • Ammonia
For gas mixtures, in addition to the normal parameters (T, p), we also
need to know the mixture composition.
Number of moles mi mass of i
ni  
M i Molecular Weight of i
Mass fraction mfi 
mi

mass of i where 1 
i mfi
mT total mass
ni moles of i
Mole fraction yi   where 1   yi
nT total moles i
Avg. Molecular Weight m total mass n M i i

M  T   i
  yi M i
nT total moles nT i
Relating P, V, and T for Ideal Gas Mixtures 4
Ideal gas pV  nRT This refers to the overall mixture, on average.

How do we describe the relationship between
p, V, and T for each component?
Dalton Model: Assumes that each component behaves as an ideal
gas at the specified T and V of the mixture. This assumes that the
gases do not interact with each other.
ni R T
Partial Pressure pi 
V
pi ni R T V ni
and    yi thus pi  yi p
p nT R T V n
Amagat Model: Assumes that each component behaves as an ideal

gas at the specified T and p of the mixture.
ni RT Vi  yiV
Partial Volume Vi  and
p
5
Example (12.6): Natural gas at 23°C, 1 bar enters a furnace with the
following molar analysis:
40% propane (C3H8), 40% ethane (C2H6), and 20% methane (CH4).
Determine
(a) The analysis in terms of mass fractions
(b) The partial pressure of each component, in bar
(c) The mass flow rate, in kg/s, for a volumetric flow rate of 20 m3/s.
i C3 H 8 C2H6 CH4 Total

T (°C) 23
p (bar) 1
yi 0.40 0.40 0.20 1.0 yi is the mole fraction of
Mi each component
mi
mfi
mi (kg/s)
6
Example (12.6):
40% propane (C3H8), 40% ethane (C2H6), and 20% methane (CH4).
(a) The analysis in terms of mass fractions
Molecular weights of each component are found in Table A-1:
i C33H88 C22H66 CH44 Total The mass of each component is

found m yM
T (°C) 23 i i i
p (bar) 1 On a 1 kmol basis then
yii 0.40 0.40 0.20 1.0
Mii 44.09 30.07 16.04 mP   0.4  44.09   17.636
mii 17.636 12.028 3.208 32.872 mE   0.4  30.09   12.028
mfii
mM   0.2 16.04   3.208
mii(kg/s)
mtotal   mi  32.872
Units are effectively kg/kmol, thus mt = M i
7
Example (12.6):
To find Partial Pressure:

pi  yi p
i C3H8 C2H6 CH4 Total p P   0.4 1bar   0.4bar

T (°C) 23 p E   0.4 1bar   0.4bar
p (bar) 1
yi 0.40 0.40 0.20 1.0 pM   0.2 1bar   0.2bar
Mi 44.09 30.07 16.04
mi 17.636 12.028 3.208 32.872
mfi 0.5365 0.3659 0.0976 1.0
mi(kg/s)
8
Example (12.6):
First convert volumetric
 
m
 AV 

 AV  P

 AV  p
flow rate to mass flow rate:
v RT R MT
(20m3 / s )(10 2 kN / m 2 ) kJ
m

 8.314kJ / kmol  K  kN  m
 32.872kg / kmol   296 K 
 
i C3H8 C2H6 CH4 Total
kg
T (°C) 23  26.71
p (bar) 0.40 0.40 0.20 1.0 s
yi 0.40 0.40 0.20 1.0
Mi 44.09 30.07 16.04
mi 17.636 12.028 3.208 32.872
mfi 0.5365 0.3659 0.0976 1.0
mi(kg/s)
9
Example (12.6):
Can also find the mass flow rate of each component
 i   mf i  m
m 
 P   0.5365   26.71kg / s 
m
kg
i C3H8 C2H6 CH4 Total  14.33
s
T (°C) 23
P (bar) 0.40 0.40 0.20 1.0
 E   0.3659   26.71kg / s 
m
yi 0.40 0.40 0.20 1.0 kg
 9.77
Mi 44.09 30.07 16.04 s
mi 17.636 12.028 3.208 32.872  M   0.0976   26.71kg / s 
m
mfi 0.5365 0.3659 0.0976 1.0 kg
 2.61
mi(kg/s) 14.33 9.77 2.61 26.71 s
Evaluating U, H, S and specific heats 10
The properties of U, H, S, and c of a mixture are additive.
Mass of system: mT  m1  m2  m3  ......   mi

i
Internal energy U T  U1  U 2  U 3  ......   U i

i
muT  m1u1  m2u 2  m3u3  ......   mi ui
i
nuT  n1u1  n2u 2  n3u3  ......   ni ui
uT  y1u1  y2u2  y3u3  ......   yi ui
i
i
Where a similar set of equations can be written for H and S
For specific heat cP  y1cP ,1  y2 cP , 2  y3cP ,3  ......   yi cP ,i

i
cV  y1cV ,1  y2 cV , 2  y3cV ,3  ......   yi cV ,i
i
Analyzing Systems Involving Mixtures 11
For mixtures with constant

composition (no chemical reaction):
U 2  U1   ni  ui  @ T2   ui  @ T1  
i
u   yi  ui  @ T2   ui  @ T1  
i
For constant specific heats,

u  cv  T2  T1 
with ui  cv ,i  T2  T1 
Equations for enthalpy (H) are similar to those for internal energy (U), but
uses cp.
Analyzing Systems Involving Mixtures 12
For entropy, is also dependent upon pressure changes.

S 2  S1   ni si  @ T2 , pi ,2   si  @ T1 , pi ,1 
i


s   yi si  @ T2 , pi ,2   si  @ T1 , pi ,1 
i

 pi ,2   yi p2 
si  s i  @ T2   s i  @ T1   R ln   s i  @ T2   s i  @ T1   R ln 
 p  y p

 i ,1   i 1
For constant specific heats,
 T2   p2 
s  cP ln    R ln  
 T1   p1 
 T2   p2 
with si  cP ,i ln    R ln  
 T1   p1 
or
T  V 
s  cV ln  2   R ln  2 
 T1   V1 
 T2   V2 
with si  cV ,i ln    R ln  
 T1   V1 
13
Example (12.17): A mixture of 2 kg of H2 and 4 kg of N2 is compressed in a

piston-cylinder assembly in a polytropic process for which n = 1.2. The
temperature increases from 22 to 150°C. Using constant values for the
specific heats, determine
(a) The heat transfer, in kJ.
(b) The entropy change, in kJ/K.
Principles to be applied:
Closed Ideal Gas system: pV  nRT and piV  ni RT
1st Law of Thermodynamics: U  U 2  U1  Q12  W12
2 mR  T2  T1 
where for polytropic process W12   pdV 
1 1 n
2
Q
2 Law of thermodynamics:
nd S  S 2  S1   
1
T
14

Find the moles of each component and the Mixtures Molecular Weight:
mH 2 2kg mN 2 4kg
nH 2   nN 2  
M H2 2.018kg / kmol M N2 28.01kg / kmol
 0.991kmol  0.143kmol
nH 2 0.991kmol nN 2 0.143kmol
yH 2   yN2  
ntotal (0.991  0.143)kmol ntotal (0.991  0.143) kmol
 0.874  0.126
Molecular
Weight: M  yH 2 M H 2  yN2 M N2   0.874   2.018    0.126   28.01  5.29
15

To Evaluate work for a polytropic process.
mR T2  T1  m R M   T2  T1 
W12  
1 n 1 n
 8.314kJ / kmol  K 
 2  4  kg    150  22  K
 5.29kg / kmol 

 1  1.2 
 6035.1kJ
16
Example (12.17):
Evaluate change in internal energy
Assuming constant heat capacity from Table A-20 at average temperature (359 K)
U  mH 2 cv , H 2  T2  T1   mN2 cv , N2  T2  T1 
  2kg   10.311kJ / kg  K   150  22  K
  4kg   0.745kJ / kg  K   150  22  K
 3021.1kJ
Then using the energy balance to evaluate Q
Q12  U12  W12
 3021.1  6035.1   3014kJ

17
Example (12.17):
1  n 1
  T2   V2     T2   T2  
s  cV ln    R ln     cV ln    R ln   
  T1   V1     T1   T1  
  T2  R  T2    R   T2 
 cV ln    ln      cV   ln  
  T1   n  1  T1     n  1   T1 
Using M = 5.29 kg/kmol,
The mixture’s cv (avg. heat capacity) needs to be found.
cV   mf i cV ,i  mf H 2 cV , H 2  mf N 2 cV , N 2
i
 2kg   4kg 
   10.311kJ / kg  K      0.745kJ / kg  K   3.933kJ / kg  K
 6kg   6kg 
so cV
cV 
M
cV  cV M  (3.933kJ / kg  K )(5.29kg / kmol )
 20.8kJ / kmol  K
18
Example (12.17):
Therefore:
 R   T2 
s  cV   ln  
  n  1   T1 

  20.8kJ / kmol  K  
 8.314kJ / kmol  K    423K 
 ln  
 (1.2  1)   295 K 
 7.49kJ / kmol  K
s 7.49kJ / kmol  K
s    1.42kJ / kg  K
M 5.29kg / kmol
S  ms  (6kg )(1.42kJ / kg  K )  8.49kJ / K

Mixing of Ideal gases 19
The previous example considered a mixture that had already been formed.
How is a process different when a mixture is formed from two individual

gases which might originally be at different temperatures and pressures?
Whenever two highly ordered substances are mixed, entropy is expected to

increase. This is because
-- Gases are initially at different temperature.
-- Gases are initially at different pressures
-- Gases are distinguishable from one another.
irrev.
process
Example 3:
Consider a canister that is initially divided into two sections.
One side contains 2 lbmol of Nitrogen (N2) at 500°R and 2 atm
One side contains 3 lbmol of Oxygen (O2) at 300°R and 1 atm.
Determine final temperature, pressure, and entropy production when mixed.
Start with Energy Balance: Assume no heat lost from system

No change of total volume  no work
U  Q  W  0
where U1  nN2 u N2 (TN2 )  nO2 uO2 (TO2 )
U 2  nN2 u N2 (T f )  nO2 uO2 (T f )
so
  
0  nN 2 u N 2 (T f )  nO2 uO2 (T f )  nN2 u N2 (TN2 )  nO2 uO2 (TO2 ) 
or
0  nN2 u N2 (T f )  u N2 (TN2 )   nO2 uO2 (T f )  uO2 (TO2 ) 
Assuming constant specific heat, cv _ N2 and cv _ O2
0  nN 2 cv _ N2 (T f  TN2 )   nO2 cv _ O2 (T f  TO2 ) 

Example 3:
Consider a canister that is initially divided into two equal sized sections. One
side contains 2 lbmol of Nitrogen (N2) at 500°R and 2 atm
Solving for final temperature Tf
nN2 cv _ N 2 TN2  nO2 cv _ O2 TO2

Tf 
nN2 cv _ N 2  nO2 cv _ O2
A good choice to use for the temperature to find the cv is the average
temperature of the initial gases (Tave = 400 R). From Table A-20E.
cv _ N2 (@ 400o R )  0.180 Btu / lbm  R M N2  28.01lbm / lbmol
and cv _ O2 (@ 400o R)  0.168 Btu / lbm  R M O2  32.0lbm / lbmol
so
cv _ N2  cv _ N2 M N 2  (0.180 Btu / lbm  R )(28.01lbm / lbmol )  5.042Btu / lbmol  R
cv _ O2  cv _ O2 M O2  (0.168 Btu / lbm  R)(32.0lbm / lbmol )  5.376Btu / lbmol  R
Example 3:
therefore:
nN2 cv _ N 2 TN2  nO2 cv _ O2 TO2

Tf 
nN2 cv _ N 2  nO2 cv _ O2
(2lbmol )(5.042 Btu / lbmol  R)(500 R)  (3lbmol )(5.376 Btu / lbmol  R )(300 R)

(2lbmol )(5.042 Btu / lbmol  R)  (3lbmol )(5.376 Btu / lbmol  R )
 377 o R
Example 3:
To find the final pressure first find the volume of the total original gases.
V  VN2  VO2
where
pN 2VN2  nN2 RTN2 pO2VO2  nO2 RTO2
nN 2 RTN2 nO2 RTO2
VN 2  VO2 
pN 2 pO2
(2lbmol )(1.986 Btu / lbmol  R)(500 R) 1 ft 2 778lbf  ft (3lbmol )(1.986 Btu / lbmol  R)(300 R ) 1 ft 2 778lbf  ft
 
29.4lb f / in 2 144in2 Btu 14.7lb f / in 2 144in 2 Btu
 365 ft 3  657 ft 3
total volume is then
V  VN 2  VO2  365  657  1022 ft 3
Example 3:
Consider a canister that is initially divided into two equal sized sections. One
side contains 2 lbmol of Nitrogen (N2) at 500°R and 2 atm
The mixed gases have a combined Molecular weight given by

M  y N2 M N 2  yO2 M O2
2lbmol 3lb
 (28.01lbm / lbmol )  mol (32.00 lbm / lbmol )  30.40 lbm / lbmol
5lbmol 5lbmol
using Ideal Gas equation:
nt RT f (5lbmol )(1.986 Btu / lbmol  R )(377 R ) 778lb f  ft 1 ft 2

pf  
V 1022 ft 3 Btu 144in 2
 19.79 psi  1.346atm

Example 3:
To find the change in entropy: 0
f
Q
S  S f  S1   
1
T
where
S1  nN2 sN2 (TN2 , pN2 )  nO2 sO2 (TO2 , pO2 )
S f  nN2 sN2 (T f , y N2 p f )  nO2 sO2 (T f , yO2 p f )
therefore
  nN 2  sN2 (T f , yN2 p f )  sN 2 (TN2 , pN2 )   nO2  sO2 (T f , yO2 p f )  sO2 (TO2 , pO2 ) 
then using the form based on ideal gas behavior with constant specific heat
  Tf   y N2 p f    Tf   yO2 p f 
  nN 2  c p _ N2 ln    R ln     nO2  c p _ O2 ln    R ln   
 TN 
  2   pN2     TO2   pO2  
Example 3:
To find the change in entropy:
  Tf   yN2 p f    Tf   yO2 p f 
  nN2 c p _ N 2 ln    R ln     nO2  c p _ O2 ln    R ln   
 TN 
  2   pN 2    T
 O2   pO2  
  377   (0.4)(1.346atm)  
 2lbmol  (5.042 Btu / lbmol  R ) ln    (1.986 Btu / lbmol  R ) ln  
  500   2atm 
  377 K   (0.6)(1.346atm)  
 3lbmol (4.376 Btu / lbmol  R) ln    (1.986 Btu / lbmol  R ) ln  
  300 K   1atm 
 2.365  4.272  6.637 Btu / R

27
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MECE322 Gas Mixtures

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MECE322 Gas Mixtures

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Ideal Gas Mixtures

Today’s main concepts:

Thus far we have been working with pure fluids

Avg. Molecular Weight m total mass n M i i

Ideal gas pV  nRT This refers to the overall mixture, on average.

Amagat Model: Assumes that each component behaves as an ideal

i C3 H 8 C2H6 CH4 Total

Molecular weights of each component are found in Table A-1:

i C33H88 C22H66 CH44 Total The mass of each component is

To find Partial Pressure:

i C3H8 C2H6 CH4 Total p P   0.4 1bar   0.4bar

Can also find the mass flow rate of each component

The properties of U, H, S, and c of a mixture are additive.

Mass of system: mT  m1  m2  m3  ......   mi

Internal energy U T  U1  U 2  U 3  ......   U i

For specific heat cP  y1cP ,1  y2 cP , 2  y3cP ,3  ......   yi cP ,i

For mixtures with constant

For constant specific heats,

For entropy, is also dependent upon pressure changes.

Example (12.17): A mixture of 2 kg of H2 and 4 kg of N2 is compressed in a

Closed Ideal Gas system: pV  nRT and piV  ni RT

1st Law of Thermodynamics: U  U 2  U1  Q12  W12

Example (12.17): A mixture of 2 kg of H2 and 4 kg of N2 is compressed in a

Example (12.17): A mixture of 2 kg of H2 and 4 kg of N2 is compressed in a

To Evaluate work for a polytropic process.

Q12  U12  W12

 3021.1  6035.1   3014kJ

S  ms  (6kg )(1.42kJ / kg  K )  8.49kJ / K

How is a process different when a mixture is formed from two individual

Whenever two highly ordered substances are mixed, entropy is expected to

Start with Energy Balance: Assume no heat lost from system

0  nN 2 cv _ N2 (T f  TN2 )   nO2 cv _ O2 (T f  TO2 ) 

Solving for final temperature Tf

nN2 cv _ N 2 TN2  nO2 cv _ O2 TO2

nN2 cv _ N 2 TN2  nO2 cv _ O2 TO2

The mixed gases have a combined Molecular weight given by

nt RT f (5lbmol )(1.986 Btu / lbmol  R )(377 R ) 778lb f  ft 1 ft 2

 19.79 psi  1.346atm

 2.365  4.272  6.637 Btu / R

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