MECH341 Week 5: Non-Reacting Gas Mixtures

Concept questions:
Q1) A tank contains a mixture of several gases of identical masses. Will all the mass fractions be
identical? How about the mole fractions?

Solution:
The mass fractions will be identical, but the mole fractions will not because the gases may
have different number of moles.

Q2) When can a gas be treated as ideal gas?

Solution:
When its p-V-T relationship obeys the ideal gas equation of state, this is if its reduced pressure
pR is significantly lower than 1 and/or its reduced temperature, TR greater than 2. In other words
at low pressure (relative to its critical pressure) or at high temperature (relative to its critical
temperature), a gas can be considered having p-V-T relation PV = mRT

Q3) What is the difference between the component pressure and the partial pressure? When are
these two equivalent?

Solution:
Component pressure is the pressure a component would exert if it existed alone at the mixture
temperature and volume. For an ideal gas, considering gas i,

𝑚𝑖 𝑅𝑖 𝑇𝑚 𝑁𝑖 𝑅𝑢 𝑇𝑚
𝑝𝑖 = =
𝑉𝑚 𝑉𝑚

Now, consider gas i as one of the gases in a mixture, its partial pressure pi ,

𝑝𝑖 𝑁𝑖
= = 𝑦𝑖
𝑝𝑚 𝑁𝑚

𝑁𝑖 𝑁𝑚 𝑅𝑢 𝑇𝑚 𝑁𝑖 𝑁𝑖 𝑅𝑢 𝑇𝑚
𝑝𝑖 = 𝑝𝑚 = =
𝑁𝑚 𝑉𝑚 𝑁𝑚 𝑉𝑚

So component pressure is equal to partial pressure for ideal gases.

Q4) Is the total internal energy of an ideal-gas mixture equal to the sum of the internal energies of
each individual gas in the mixture?

Solution:
Yes, internal energy, enthalpy and entropy are all extensive properties. The mixture properties can
be determined by summing the contributions of each constituent of the mixture.

Calculation questions
o
Q5) A rigid tank that contains 1 kg of N2 at 25 C and 300 kPa is connected to another rigid tank
o
that contains 3 kg of O2 at 25 C and 500 kPa. The valve connecting the two tanks is opened, and
o
the two gases are allowed to mix. If the final mixture temperature is 25 C, determine:

a) The volume of each tank (ans. 0.295 𝑚3 and 0.465 𝑚3)

b) The final mixture pressure (ans. 422.22 𝑘𝑃𝑎)

Solution:

The assumption. Under the specified conditions both N2 and O2 can be treated as ideal gases, and
hence the mixture can also be treated as ideal gas. This can be shown as follow. Given N2 pcr =
3.39 MPa Tcr = 126.2 K, and O2 Pcr = 5.08 MPa Tcr = 154.8 K, their reduced pressures at the
conditions are <<1 (two order lower), therefore our assumption is fine.

pR,N = p/pcr = 0.3/3.39 = 0.089 <<1 and pR,O = p/pcr = 0.5/5.08 = 0.098 <<1
2 2

The molar masses, MN = 28 kg/kmol and MO = 32 kg/kmol (Table A-1)

2 2

a) The volumes of each tanks are determined using ideal gas equation of
state

𝑚3
𝑚𝑅𝑇 (1 𝑘𝑔) (0.2968 𝑘𝑃𝑎. ) (298 𝐾)
𝑘𝑔. 𝐾
𝑉𝑁2 = ( ) = = 0.295 𝑚3
𝑝 𝑁2 300 𝑘𝑃𝑎
 𝑚3
𝑚𝑅𝑇 (3 𝑘𝑔) (0.2598 𝑘𝑃𝑎. ) (298 𝐾)
𝑘𝑔. 𝐾
𝑉𝑂2 = ( ) = = 0.465 𝑚3
𝑝 𝑂2 500 𝑘𝑃𝑎

b) One way to calculate the final mixture pressure is to use the equation of state

𝑚𝑚 𝑅𝑚 𝑇𝑚
𝑝𝑚 =
𝑉𝑚

We know the total volume of the mixture

𝑉𝑚 = 𝑉𝑁2 + 𝑉𝑂2 = 0.295 + 0.465 = 0.760 m3

and the total mass of mixture

𝑚𝑚 = 𝑚𝑁2 + 𝑚𝑂2 = 1 + 3 = 4 kg

We need to calculate Rm,

𝑅𝑢
𝑅𝑚 =
𝑀𝑚

Here the apparent molar mass, Mm is needed

𝑚𝑚
𝑀𝑚 =
𝑁𝑚

In the above equation we need the total number of mole of the mixture, Nm. This is calculated by
adding the number of mole of N2 and number of mole of O2.

𝑚𝑁2 1 𝑘𝑔
𝑁𝑁2 = = = 0.03571 𝑘𝑚𝑜𝑙
𝑀𝑁2 28 𝑘𝑔/𝑘𝑚𝑜𝑙

𝑚𝑂2 3 𝑘𝑔
𝑁𝑂2 = = = 0.09375 𝑘𝑚𝑜𝑙
𝑀𝑂2 32 𝑘𝑔/𝑘𝑚𝑜𝑙

𝑁𝑚 = 𝑁𝑁2 + 𝑁𝑂2 = 0.03571 + 0.09375 = 0.1295 𝑘𝑚𝑜𝑙

which gives

𝑚𝑚 4
𝑀𝑚 = = = 30.8880 𝑘𝑔/𝑘𝑚𝑜𝑙
𝑁𝑚 0.1295
Given Ru = 8.314 kPa.m3/kmol.K, Rm is calculated

𝑅𝑢 8.314
𝑅𝑚 = = = 0.2692 𝑘𝑃𝑎. 𝑚3 /𝑘𝑔. 𝐾
𝑀𝑚 30.8880

Now

𝑚𝑚 𝑅𝑚 𝑇𝑚 (4 ) (0.2692) (25 + 273)

𝑝𝑚 = = = 422.22 𝑘𝑃𝑎
𝑉𝑚 0.760

Alternatively

𝑁𝑚 𝑅𝑢 𝑇𝑚 (0.1295) (8.314) (25 + 273)

𝑝𝑚 = = = 422.22 𝑘𝑃𝑎
𝑉𝑚 0.760

Q6) The combustion of a hydrocarbon fuel with air results in a mixture of products of combustion
having the composition on a volume basis as follows: 4.89% CO2, 6.5% water vapor, 12.2% O2,
and 76.41% N2. Determine:

a) the average molar mass of the mixture; the average specific heat at constant pressure of the
mixture at 600 K, in kJ/kmol.K; and (ans. 28.632 kg/kmol, 31.6069 kJ/kmol.K)
b) the partial pressure of the constituents in the mixture for a mixture pressure of 200 kPa. (ans.
9.780 kPa, 24.2 kPa, 152.82 kPa, 13 kPa)

Solution:

The assumption. Under the specified conditions N2, O2, H2O and CO2 can be treated as ideal gases,
and hence the mixture can also be treated as ideal gas. This can be shown as follow. Given N2 pcr =
3.39 MPa Tcr = 126.2 K, O2 Pcr = 5.08 MPa Tcr = 154.8 K, H2O Pcr = 22.06 MPa Tcr = 647.1 K, and
CO2 Pcr = 7.39 MPa Tcr = 304.2 K, their reduced temperatures at the conditions are all > 2 or
reduced pressure << 1, hence our assumption is fine.

TR,N = T/Tcr= 600/126.2 = 4.754 >2 TR,O = T/Tcr = 600/154.8 = 3.8760 >2
2 2

PR,H = p/pcr= 0.2/22.06 = 0.0091 <<1 PR,CO = p/pcr = 0.2/7.39 = 0.0271 << 1
2O 2

Note in the water and CO2 reduced pressures calculations, we use the pm, which is larger than the
actual partial pressure of water and CO2. This results in a slight overestimation of the actual
reduced pressure.

a) The average molar mass of the mixture is calculated using

𝑚𝑚
𝑀𝑚 =
𝑁𝑚
Since we do not know the total mass or the total number of mole but knowing the volume fraction
of each gas constituents, we can calculate the number of mole, Ns of each gas for number of mole
in the mixture. So let us work on the basis of 100 kmole in the mixture.
𝑉𝑖 𝑁
𝑉𝑚
= 𝑁 𝑖 = 𝑦𝑖  𝑁𝑖 = 𝑦𝑖 𝑁𝑚
𝑚

Using this relation, we can calculate

𝑁𝐶𝑂2 = (4.89%)(100) 𝑘𝑚𝑜𝑙𝑒 = 4.89 𝑘𝑚𝑜𝑙𝑒

𝑁𝑂2 = (12.20%)(100 𝑘𝑚𝑜𝑙𝑒) = 12.20 𝑘𝑚𝑜𝑙𝑒

𝑁𝐻2𝑂 = (6.50%)(100 𝑘𝑚𝑜𝑙𝑒) = 6.50 𝑘𝑚𝑜𝑙𝑒

𝑁𝑁2 = (76.41%)(100 𝑘𝑚𝑜𝑙𝑒) = 76.41 𝑘𝑚𝑜𝑙𝑒

The masses of each constituent in 100 kmole of mixture are calculated using

𝑚𝑖 = 𝑀𝑖 𝑁𝑖

and the gasses molar masses, Ms from Table A-1

𝑘𝑔
𝑚𝐶𝑂2 = 𝑀𝐶𝑂2 𝑁𝐶𝑂2 = (44.01 ) 4.89 𝑘𝑚𝑜𝑙𝑒 = 215.209 𝑘𝑔
𝑘𝑚𝑜𝑙𝑒

𝑘𝑔
𝑚𝑂2 = 𝑀𝑂2 𝑁𝑂2 = (31.999 ) 12.2 𝑘𝑚𝑜𝑙𝑒 = 390.388 𝑘𝑔
𝑘𝑚𝑜𝑙𝑒

𝑘𝑔
𝑚𝐻2𝑂 = 𝑀𝐻2𝑂 𝑁𝐻2𝑂 = (18.015 ) 6.50 𝑘𝑚𝑜𝑙𝑒 = 117.098 𝑘𝑔
𝑘𝑚𝑜𝑙𝑒

𝑘𝑔
𝑚𝑁2 = 𝑀𝑁2 𝑁𝑁2 = (28.013 ) 76.41 𝑘𝑚𝑜𝑙𝑒 = 2140.5 𝑘𝑔
𝑘𝑚𝑜𝑙𝑒

The average molar mass of the mixture is calculated using

(215.209 + 390.388 + 117.098 + 2140.5)𝑘𝑔 2863.2 𝑘𝑔

𝑀𝑚 = = = 28.632 𝑘𝑔/𝑘𝑚𝑜𝑙𝑒
100 𝑘𝑚𝑜𝑙𝑒 100 𝑘𝑚𝑜𝑙𝑒

The specific heat of the mixture can now be calculated using

 𝑘

𝐶𝑝,𝑚 = ∑ 𝑚𝑓𝑖 𝐶𝑝,𝑖

𝑖=1

We need mfs and Cps of the gas constituents.

𝑚𝐶𝑂2 215.209
𝑚𝑓𝐶𝑂2 = = = 0.0752
𝑚𝑚 2863.2

𝑚𝑂2 390.388
𝑚𝑓𝑂2 = = = 0.1363
𝑚𝑚 2863.2

𝑚𝐻2𝑂 117.098
𝑚𝑓𝐻2𝑂 = = = 0.0409
𝑚𝑚 2863.2

𝑚𝑁2 2140.5
𝑚𝑓𝑁2 = = = 0.7476
𝑚𝑚 2863.2

The Cps at 600 K are found from Table A-2b.

𝑘𝐽
𝐶𝑝,𝐶𝑂2 = 1.075
𝑘𝑔. 𝐾

𝑘𝐽
𝐶𝑝,𝑂2 = 1.003
𝑘𝑔. 𝐾

𝑘𝐽
𝐶𝑝,𝑁2 = 1.075
𝑘𝑔. 𝐾

For water, use the equation in Table A-2C.

𝑘𝐽
𝐶̅ 𝑝𝐻2𝑂 = 32.24 + 0.1923𝑒 −2 𝑇 + 1.055𝑒 −5 𝑇 2 − 3.595𝑒 −9 𝑇 3 ( )
𝑘𝑚𝑜𝑙𝑒. 𝐾

𝑘𝐽
̅̅̅̅𝐻2𝑂 = 32.24 + 0.1923𝑒 −2 (600) + 1.055𝑒 −5 6002 − 3.595𝑒 −9 6003 = 36.415
𝐶𝑝
𝑘𝑚𝑜𝑙𝑒. 𝐾

̅̅̅̅
𝐶𝑝𝐻2𝑂 36.415 𝑘𝐽
𝐶𝑝,𝐻20 = = = 2.021
𝑀𝐻2𝑂 18.015 𝑘𝑔. 𝐾

Now
 𝑘

𝐶𝑝,𝑚 = ∑ 𝑚𝑓𝑖 𝐶𝑝,𝑖

𝑖=1
= (0.0752)(1.075) + (0.1363)(1.003) + (0.0409)((2.021) + (0.7476)(1.075)
𝑘𝐽
= 1.1039
𝑘𝑔. 𝐾

̅
To get 𝐶𝑝,𝑚 in kJ/kmol. K,

𝑘𝐽 𝑘𝑔 𝑘𝐽
̅
𝐶𝑝,𝑚 = 𝐶𝑝,𝑚 𝑀𝑚 = 1.1039 ( ) 28.632 ( ) = 31.6069
𝑘𝑔. 𝐾 𝑘𝑚𝑜𝑙 𝑘𝑚𝑜𝑙. 𝐾

b) The partial pressure of each constituent can be calculated using

𝑝𝑖 𝑁𝑖
= = 𝑦𝑖
𝑝𝑚 𝑁𝑚

So
𝑁𝑖
𝑝𝑖 = 𝑝𝑚
𝑁𝑚

Hence

4.89
𝑝𝐶𝑂2 = 200 𝑘𝑃𝑎 = 9.780 𝑘𝑃𝑎
100
12.20
𝑝𝑂2 = 200 𝑘𝑃𝑎 = 24.4 𝑘𝑃𝑎
100
76.41
𝑝𝑁2 = 200 𝑘𝑃𝑎 = 152.82 𝑘𝑃𝑎
100

6.50
𝑝𝐻2𝑂 = 200 𝑘𝑃𝑎 = 13 𝑘𝑃𝑎
100

Q7) A piston-cylinder device contains a mixture of 0.5 kg of H2 and 1.6 kg of N2 at 100 kPa and
300 K. Heat is now transferred to the mixture at constant pressure until the volume is doubled.
Assuming constant specific heats at the average temperature, determine:

a) The final temperature, K and (ans. 600 K)

b) The heat transfer, kJ (ans. 2679 kJ)
c) The work produced, kJ (ans. 761 kJ)
d) The entropy change of the mixture, kJ. (ans. 6.189 kJ/K)
Solution:
The assumption. Under the specified conditions both N2 and H2 can be treated as ideal gases
throughout the process, and hence the mixture can also be treated as ideal gas. You should be able
to prove this by confirming their reduced pressures are << 1 or reduced temperatures > 2 as in the
earlier questions. The second assumption is that within the temperature range of the process the
variation of specific heats of N2 and H2 are negligible. Therefore specific heats are assumed
constant.

a) Noting that P2 = P1 = 100 kPa and V2 = 2 V1

Using ideal gas equation of state and the fact that the quantity m R is
constant,

𝑝𝑉
𝑚𝑅 =
𝑇

hence

𝑝1 𝑉1 𝑝2 𝑉2
𝑚𝑅= =
𝑇1 𝑇2

Noting that P2 = P1, we have

𝑉2
𝑇2 = 𝑇
𝑉1 1

Noting V2 = 2 V1 we have

2 𝑉1
𝑇2 = 𝑇 = 2 𝑇1 = 2 (300 𝐾 ) = 600 𝐾
𝑉1 1

b) The second assumption is within the temperature range of the process (300 K and 600 K) the
variation of specific heats of N2 and H2 are small < 5%. Therefore constant specific heats are
assumed constant.

𝐶𝑝,𝐻2@600𝐾 − 𝐶𝑝,𝐻2@300𝐾 14.546 − 14.307

𝑥 100% = 𝑥 100% = 1.67%
𝐶𝑝,𝐻2@300𝐾 14.307

𝐶𝑝,𝑁2@600𝐾 − 𝐶𝑝,𝑁2@300𝐾 1.075 − 1.039

𝑥 100% = 𝑥 100% = 3.46%
𝐶𝑝,𝑁2@300𝐾 1.039

𝑘𝐽 𝑘𝐽
Let us then adopt 𝐶𝑝,𝐻2@450𝐾 = 14.501 𝑘𝑔.𝐾 and 𝐶𝑝,𝑁2@450𝐾 = 1.049 𝑘𝑔.𝐾

From the closed system energy balance relation

 𝐸𝑖𝑛 − 𝐸𝑜𝑢𝑡 = ∆𝐸𝑠𝑦𝑠𝑡𝑒𝑚

𝑄𝑖𝑛 − 𝑊𝑜𝑢𝑡 = ∆𝑈

Wout and U can be combine as H for quasi-equilibrium constant pressure processes.

𝑄𝑖𝑛 − (𝑃2 𝑉2 − 𝑃1 𝑉1 ) = 𝑈2 − 𝑈1

𝑄𝑖𝑛 = (𝑈2 + 𝑃2 𝑉2 ) − (𝑈1 + 𝑃1 𝑉1 ) = ∆𝐻

𝑄𝑖𝑛 = 𝑊𝑜𝑢𝑡 + ∆𝑈 = ∆𝐻

Next

𝑄𝑖𝑛 = ∆𝐻 = ∆𝐻𝐻2 + ∆𝐻𝑁2

= [𝑚 𝐶𝑝 (𝑇2 − 𝑇1) ] + [𝑚 𝐶𝑝 (𝑇2 − 𝑇1) ]

𝐻2 𝑁2

𝑘𝐽 𝑘𝐽
= [(0.5 𝑘𝑔)(14.501 ) (600 − 300)𝐾] + [(1.6 𝑘𝑔) (1.049 )(600 − 300)𝐾]
𝑘𝑔. 𝐾 𝐻2
𝑘𝑔. 𝐾 𝑁2

= 2678.7 𝑘𝐽

c) The work produced can be calculated

𝑊𝑜𝑢𝑡 = ∆𝐻 − ∆𝑈
𝑘𝐽 𝑘𝐽
To calculate U, let us adopt 𝐶𝑣,𝐻2@450𝐾 = 10.377 𝑘𝑔.𝐾 and 𝐶𝑣,𝑁2@450𝐾 = 0.752 𝑘𝑔.𝐾

∆𝑈 = [𝑚 𝐶𝑣 (𝑇2 − 𝑇1) ] + [𝑚 𝐶𝑣 (𝑇2 − 𝑇1) ]

𝐻2 𝑁2

𝑘𝐽 𝑘𝐽
= [(0.5 𝑘𝑔)(10.377 ) (600 − 300)𝐾] + [(1.6 𝑘𝑔) (0.752 )(600 − 300)𝐾]
𝑘𝑔. 𝐾 𝐻2
𝑘𝑔. 𝐾 𝑁2

= 1917.5 𝑘𝐽

So

𝑊𝑜𝑢𝑡 = 2678.7 − 1917.5 = 761.2 𝑘𝐽

Alternatively
 𝑊𝑜𝑢𝑡 = 𝑃 (𝑉2 − 𝑉1 )

Here we need to know V1, which can be found using the equation of state applied to the mixture.

𝑚𝑚 𝑅𝑚 𝑇𝑚
𝑉1 = [ ]
𝑝𝑚 1

We need to find

𝑅𝑢
𝑅𝑚 =
𝑀𝑚

Where

𝑚𝐻2 + 𝑚𝑁2
𝑀𝑚 =
𝑁𝐻2 + 𝑁𝑁2

𝑚𝐻2 + 𝑚𝑁2
𝑀𝑚 = 𝑚 𝑚
(𝑀𝐻2 ) + ( 𝑁2 )
𝐻2 𝑀𝑁2
0.5 + 1.6
𝑀𝑚 = = 6.8823 𝑘𝑔/𝑘𝑚𝑜𝑙
0.5 1.6
(2.016) + (28.013)

So

𝑅𝑢 8.31447 𝑘𝐽
𝑅𝑚 = = = 1.2081
𝑀𝑚 6.8823 𝑘𝑚𝑜𝑙. 𝐾

And

𝑚𝑚 𝑅𝑚 𝑇𝑚 (0.5 + 1.6)(1.2081)(300)
𝑉1 = [ ] = = 7.611 𝑚3
𝑝𝑚 1
100

𝑊𝑜𝑢𝑡 = 𝑃 (𝑉2 − 𝑉1) = 100 (7.611) = 761.1 𝑘𝐽

d) The entropy change of the mixture is

 𝑘

∆𝑆𝑚 = ∑ 𝑚𝑖 ∆𝑠𝑖
𝑖=1

∆𝑆𝑚 = 𝑚𝐻2 ∆𝑠𝐻2 + 𝑚𝑁2 ∆𝑠𝑁2

Each of these terms are calculated as follow

∆𝑠𝐻2 = [(𝑠2 − 𝑠1 )]𝐻2

𝑇2 𝑃2 600 100
= [𝐶𝑝 𝑙𝑛 − 𝑅 𝑙𝑛 ] = [14.501𝑙𝑛 − 𝑅 𝑙𝑛 ] = 10.0513𝑘𝐽/𝑘𝑔
𝑇1 𝑃1 𝐻2 300 100 𝐻2

∆𝑠𝑁2 = [(𝑠2 − 𝑠1 )]𝑁2

𝑇2 𝑃2 600 100
= [𝐶𝑝 𝑙𝑛 − 𝑅 𝑙𝑛 ] = [1.049 𝑙𝑛 − 𝑅 𝑙𝑛 ] = 0.7271 𝑘𝐽/𝑘𝑔
𝑇1 𝑃1 𝑁2 300 100 𝑁2

So

∆𝑆𝑚 = 𝑚𝐻2∆𝑠𝐻2 + 𝑚𝑁2∆𝑠𝑁2 = 0.5 (10.0513) + 1.6 (0.7271) = 6.189 𝑘𝐽/K