October 22, 2001
Reading: Chapter VIII
Homework: 8.1, 8.3, 8.5, 8.6, 8.7
Mixing of Ideal Gas under various conditions:
(1) At fixed P and T
nA, T, P
nC, T, P
nB, T, P
nD, T, P
(a) Mixing Gibbs free energy:
G 'initial = n A G A0 (T ) + n A RT ln P + n B G B0 (T ) + n B RT ln P
+ nC GC0 (T ) + nC RT ln P + n D G D0 (T ) + n D RT ln P
G ' final = n A G A0 (T ) + n A RT ln p A + n B G B0 (T ) + n B RT ln p B
+ nC GC0 (T ) + nC RT ln p C + n D G D0 (T ) + n D RT ln p D
Thus, the change in Gibbs free energy on mixing is
G ' mix = G ' final G ' initial
p
p
p
p
= n A RT ln A + n B RT ln B + nC RT ln C + n D RT ln D
P
P
P
P
= n A RT ln x A + n B RT ln x B + nC RT ln xC + n D RT ln x D
Also,
G ' final G ' initial = n A (G Af G Ai ) + n B (G Bf G Bi ) + nC (GCf GCi ) + n D (G Df G Di )
= G ' mix
(b) Mixing Enthalpy:
0
(G A / T )
ln p A
2 (G A / T )
H A = T
= T
T 2
T
T
T
So, H A = H A0
2
Thus, H Ai = H A0 , and H Af = H A0
H ' initial = n A H A0 + n B H B0 + nC H C0 + n D H D0
And, H ' final = n A H A0 + n B H B0 + nC H C0 + n D H D0
H ' mix = H ' final H ' initial = 0
(c) Mixing Entropy:
G
S A = A
= S A0 R ln p A
T P ,ni , n j ,...
So,
S Ai = S A0 R ln P
S Af = S A0 R ln p A
S ' initial = n A S A0 + n B S B0 + nC S C0 + n D S D0 R{n A ln P + n B ln P + nC ln P + n D ln P}
S ' final = n A S A0 + n B S B0 + nC S C0 + n D S D0 R{n A ln p A + n B ln p B + nC ln p C + n D ln p D }
S ' mix = S ' final S ' initial
= R{n A ln x A + n B ln x B + nC ln xC + n D ln x D }
Since,
pA
= xA ,
P
pB
= xB ,
P
pC
= xC ,
P
pD
= xD
P
Note that mixing was done at fixed T and P. So, the initial pressures of the individual
gases are identical, and equals to the final total pressure of the gas mixture.
(2) Fixed total volume and T
nA, T, PA
nC, T, PC
nB, T, PB
nD, T, PD
(a) Gibbs free energy:
G 'initial = n A G A0 + n A RT ln PA + n B G B0 + n B RT ln PB
+ nC GC0 + nC RT ln PC + n D G D0 + n D RT ln PD
G ' final = n A G A0 + n A RT ln p A + n B G B0 + n B RT ln p B
+ nC GC0 + nC RT ln p C + n D G D0 + n D RT ln p D
Where p A = x A P,
p B = x B P,
p C = x C P,
pD = xD P
With P=total pressure
The volume of the box is
n RT n B RT nC RT n D RT
V= A
+
+
+
PA
PB
PC
PD
The total moles in the box = n A + n B + nC + n D
So, the total pressure is
(n A + n B + nC + n D ) RT
P=
n A RT n B RT nC RT n D RT
+
+
+
PA
PB
PC
PD
n + n B + nC + n D
= A
n A n B nC n D
+
+
+
PA PB PC PD
ni
P
i
Gibbs free energy of mixing:
G ' mix = G ' final G ' initial
p
p
p
p
= n A RT ln A + n B RT ln B + nC RT ln C + n D RT ln D
PD
PB
PA
PC
Where
nA
nA
P =
n A n B nC n D
n A + n B + nC + n D
+
+
+
PA PB PC PD
Similar equations for p B , p C , p D
pA = xAP =
(b) Enthalpy:
(G ' mix / T )
H ' mix = T 2
T
P ,comp
p
d pA
+ ln B
ln
dT PA
PB
I.e. the enthalpy of mixing is zero.
= RT 2
p
p
+ ln C + ln D
PD
PC
= 0
(c) Entropy:
(G ' mix )
S ' mix =
P ,comp
p
p
p
= R n A ln A + n B ln B + nC ln C
PB
PA
PC
+ n D ln D
PD
Note that the entropy of mixing is no longer simply related to terms like R ni ln xi .
i
The above also includes thermal entropy (Discuss problem 4.1 in the context of the above
equation).
S ' mix S ' mix + R ni ln P R ni ln P
i
= R ni ln p i + R ni ln Pi + R ni ln P R ni ln P
i
P
= R ni ln xi R ni ln
P
i
i
14
4
244
3 144
244
3i
conf .
thermal
(3) Under adiabatic condition and at a fixed volume:
n A , T A , PA
nC, TC, PC
n B , T B , PB
nD, TD, PD
G 'initial = n A G A0 (T A ) + n A RT A ln PA + n B G B0 (TB ) + n B RTB ln PB
+ nC GC0 (TC ) + nC RTC ln PC + n D G D0 (TD ) + n D RTD ln PD
G ' final = n A G A0 (T ) + n A RT ln p A + n B G B0 (T ) + n B RT ln p B
+ nC GC0 (T ) + nC RT ln p C + n D G D0 (T ) + n D RT ln p D
Mixing at fixed volume and under adiabatic condition,
w = 0, q = 0, U = q w = 0
(G 'initial / T )
H ' initial = T 2
= n A H A0 (T A ) + n B H B0 (TB ) + nC H C0 (TC ) + n D H D0 (TD )
T
G
(
'
final / T )
H ' final = T 2
= n A H A0 (T ) + n B H B0 (T ) + nC H C0 (T ) + n D H D0 (T )
T
Now, H A0 (T A ) H A0 (T ) , etc. But heat lost by one gas is heat gained by the other. Thus,
the net H must be zero. We could have carried out the process by first allowing heat
transfer to occur and then allowing the gases to mix. In such a case, change in state
functions remains the same.
Lets consider the heat transfer between two gases before mixing:
n A,
P A,
T A,
VA
n B,
P B,
T B,
VB
n A,
PA,
T,
VA
n B,
PB,
T,
VB
n A RT A
n RT
, PB = B B
VA
VB
n RT
n RT
Final: P' A = A
, P' B = B
VA
VB
Initial: PA =
H A = U Af + P ' A V A U Ai PAV A
H B = U Bf + P ' B V B U Bi PBV B
n RT n A RT A
= n A (C v + R)(T T A )
H A = n A C v (T T A ) + V A A
V A
VA
Similarly,
H B = n B (C v + R )(T TB )
H A + H B = n A (C v + R )(T T A ) + n B (C v + R )(T TB )
= (C v + R ){n A (T T A ) + n B (T TB )}
But,
C v {n A (T T A ) + n B (T TB )} = U = 0
So, H A + H B = 0
Now, in the second step H (mixing ) = 0 . Thus, H ' mix is again zero for mixing at fixed
V and adiabatic conditions. Also, we can obtain
G ' final
G ' initial
T
T
This will be different from either the first case (fixed P and T) or the second case (mixing
at fixed V and T).
S ' mix = S ' final S ' initial =