Ideal Gasses

The question: U(P,T) = ?, (P,T)= N/V(P,T) = ?

Here: only for special substances: ideal gasses

Interactions between moleculesneglected

Range of interactions: much shorter than distance between molecules
HW
2.5
2.9
Due 9/11

PV =NRT
R = 8.314 J mol
-1
K
-1


U
IG
= NU
IG
(T)
N number of molecules
U
IG
(T) kinetic, rotational and vibrational energy of molecules
No potential energy no interactions
Heating of ideal gas in a container
with rigid walls: V = const

dU
IG
= / dQ= NC
V
IG
dT
/ dW = Fdx
0

C
V
IG

dU
IG
dT
Heat capacity at constant volume

C
V
IG
=3R/2 (monoatomic gases)
Only translational degrees of freedom: no rotational, no vibrational

Each degree of freedom contributes R/2 to C
v
:
C
v
IG
= 5R/2 (linear molecules)

C
V

U
T

V
For interacting molecules:
high density, molecules feel each others presence
Units of C
v
: J mol
-1
K
-1


C
P
IG

dH
IG
dT
=
d
dT
U
IG
+PV

=
d
dT
U
IG
+RT

= C
V
IG
+R
Heating of ideal gas at constant
pressure: P = const

U =Q P V Q= (U+PV)= H

dW = -Fdx = -PAdx = -PdV
For any system:

C
P
=
1
N
H
T

N,P
=
H
T

P
Adiabatic expansion of ideal gasses

dU = PdV NC
V
IG
dT = NPdV = NPd
RT
P

C
V
IG
dT = PdV = RdT +
RT
P
dP


dQ = 0
Three variables: P, T, and V
Eliminating P

C
V
IG
dT = PdV C
V
IG
dT =
RT
V
dV C
V
IG
dT
T
= R
dV
V


T
T
0
=
V
V
0

R
C
V
IG
=
V
V
0

1 g
=
V
V
0

1 g
R
V
V
V
V
C
IG
V
T
T
IG
V
T
T
IG
V
V
V
V
V
R V R
V
dV
R
T
T
T
T
C T C
T
dT
C
IG
V

|
|
.
|

\
|
= = =
}

|
|
.
|

\
|
= = =
}
0 0
0 0
ln ln ) ln(
ln ln ) ln(
0
0
0
0
= C
p
/C
V
= (C
v
IG
+ R)/C
V
IG
= 1 + R/C
V
IG

Eliminating V

C
V
IG
dT = RdT +
RT
P
dP (C
V
IG
+R)
dT
T
= R
dP
P
C
P
IG
dT
T
= R
dP
P


T
T
0
=
P
P
0

R
C
P
IG
=
P
P
0

g 1
g
Eliminating T

PdV =C
V
IG
dT =
C
V
IG
R
d(PV)=
C
V
IG
R
(PdV +VdP)

C
V
IG
R
VdP =
C
V
IG
+R
R
PdV C
V
IG
dP
P
=C
P
IG
dV
V

P
P
0
=
V
V
0

g
=
V
V
0

g
PV
g
= const.
Summary: Adiabatic expansion of ideal
gasses

T
T
0
=
V
V
0

R
C
V
IG
=
V
V
0

1 g
=
V
V
0

1 g

T
T
0
=
P
P
0

R
C
P
IG
=
P
P
0

g 1
g

P
P
0
=
V
V
0

g
=
V
V
0

g
PV
g
= const.

U = Q +WW= NC
V
IG
T
Example:
N
i
moles of ideal gas at temperature T
i
are held in volume V.
Same gas at temperature T
in
is pumped in until N
f
.
No heat transfer.

T
f
= f(T
i
, T
in
,N
f
/N
i
,C
p
) = ?
Solution:
From first law:

dU = / dQ+ / dW+ H
in
dN
in
entering
streams

H
out
dN
out
leaving
streams

dU = H
in
dN
in

d(U N)= H
in
dN
in

U dN+ NdU = H
in
dN
in
= H
in
dN
Solution: continued
U(T) = U
o
(T
o
) + C
v
(T T
o
)
H(T) = H
o
(T
o
) + C
p
(T T
o
) H
o
(T
o
) = U
o
(T
o
) + RT
o

U and H known to within a constant:
Assume T
o
= 0 and U
o
= 0

U(T) = C
v
T and H(T) = C
p
T
We get from

U dN+ NdU = H
in
dN

C
v
TdN + NC
V
dT = C
p
T
in
dN
NC
V
dT = (C
p
T
in
C
v
T)dN
) (
ln ln
i in
f
i
in f
i in
f in
i
f
T
T in
N
N
T T
N
N
T T
T T
T T
N
N
T T
dT
N
dN
f
i
f
i
=

=
}

=
}

What if T
in
= T
i
?
(
(

+ =
(
(

=
=
f
i
f
i
i f
f
i
i f
i i
f
i
i f
N
N
N
N
T T
N
N
T T
T T
N
N
T T



) 1 (
) (
1
1
, 1 0
>
(
(

+
>
+
= =
< < <
f
i
f
i
V
V
V
p
f
i
f
i
N
N
N
N
C
RT C
C
C
N
N
N
N

If N
f
>>N
i,
T
f
> T
i

If N
f
~ N
i
, T
f
~ T
i

T
f
> T
i

Problem 2.9
A container with N
2
at P
i
= 5 bar and T
i
= 300 K is quickly filled
from a much larger cylinder with P = 10 bar and T = 300 K;
P
f
= 10 bar. T
f
= ?
Air
water
2.10. Water gun. Air: 750 cm
3
, P = 2.5 bar, T = 30
o
C
Water pumped at 8 m/s for 5 s through 2 mm ID tube
T
f
= ?, P
f
= ?