Experimental Set up

Flow meter
between the cylinder
1. Fill carboy with a gas
and the inlet tube
thermally equilibrate (T1) h
Heat Capacity Ratios of Gases measure p1

2. Open/close stopper
(pressure= atm. press. = p2)

3. thermally equilibrate to (T1)

measure p3

I II I II
n’ Adiabatic Equilibrate n’ Adiabatic Equilibrate
expansion to T1 expansion to T1
p2, V2, T2 p2, V2, T2
n n n + n’ n n

p1, V1,T1 p3, V2, T1 T1 = Room Temperature p1, V1,T1 p3, V2, T1
V2 = Volume of the carboy
The gas leaving as the stopper is opened be n’ moles and the rest For n moles p1, V1,T1
I. Adiabatic expansion p2, V2, T2
of the gas moles be n. Consider this n moles here onwards.
nRT
As n’ moles (p1, V1,T1) leave the carboy n moles occupying dE  q  pdV dE   pdV ;adabatic dE   dV
V
expands into the volume of the carboy (V2, cooled down to T2)
dE  dT   molar constant volume heat capacity
adiabatically.  nCv  dE  nCv Cv
dT

Equating dE; dT   nRT dV

nC   dT   R dV
C
V V
v v
T
 Integrating the preceding,
p2  V
 RC
ln    v
 ln
2
p1 
T2
 dT   R dV
V2
 Cv  V1
Cv V
T
T1 V1
For an ideal gas; p  RC
C v
 ln T2   R ln V2
C  ln
T2 R V
  ln 2
v
T1 V1 T1  V
C
 V
v 1
p2 C
   ln 2
p
ln
p2V2 p1V1 T p V p1 C V
using ideal gas for n moles nR    ln 2  ln 2  ln 2  v 1
T2 T1 T1 p1 V1
T2 p R V V
equating ln we get, ln 2   ln 2  ln 2
T1 p1  V
C V1
v 1

p2  R  V
ln     1 ln 2

p1  Cv  V1

II Equilibrate to T1 n p1, V1,T1 p3, V2, T1 Cv = Energy (heat) absorbed or released per unit temperature increase
or decrease, respectively.
V2 p1 V2 p
Using IDE;   ln  ln 1
V1 p3 V1 p3 At low temperatures the heat exchanged is involved with translational,
rotational and vibrational motions of a molecule (particle).

V2 p2 C V
substitutefor ln in ln  
p
 ln 2 For a molecule with N atoms there are 3N total number of degrees of
V1 p1   V
C freedom. Of the N the degrees of freedom for translational motion are
 v  1
3, rotational motions are 3 for nonlinear and 2 for linear molecules;
p2 C p p for vibrational motions the # degrees of freedom are 3N-5 (for linear)
   ln 1   ln 1
p
ln
p1    and 3N-6 (for non-linear) molecules.
 Cv  p3 p2

C p ln( p1 / p2 ) Each quadratic term of energy (motional and potential) contributes
i.e.  = 
C ln( p / p ) kB 2per molecule or R/2 per mole of the substance.
v 1 3
 Each quadratic term in the (active) energy modes contribute
(R/2) J mol-1 K-1 amount of heat to the Cv of the substance.

Contribution for Cv
# atoms=N Contribution for Cv motion He(N=1) N2(N=2) CO2(N=3)
motion all linear non-linear translation 3(R/2) 3(R/2) 3(R/2)
translation 3(R/2) rotation 2(R/2) 2(R/2)
rotation 2(R/2) 3(R/2) vibration (6-5)R (9-5)R
vibration (3N-5)R (3N-6)R Total 1.5R 7.5R 9.5R

Note:
1. Start with He, fill the carboy with using b as the inlet.
2. Once He data are taken, using the tubing as shown in the figure
study nitrogen and carbon dioxide in that order (inlet a, outlet b).
b
a

1 hPa = 100 Pa

pressure(mmHg)
Density of Hg
= h(cm) × + atmospheric pressure(mmHg)
Density of liquid used