Department of Chemistry

Indian Institute of Technology Madras

CY 102 Chemistry II Assignment I
Thermodynamics (First and second laws thermodynamics)



Jan 27, 2004



1. Two moles of N
2
gas at 25
0
C and 1 atm pressure are expanded reversibly
and isothermally to a pressure of 0.5 atm.
a) Calculate the work done (including the sign).
b) Calculate the heat change and the internal energy change involved in
the process.
c) Calculate the work done in expansion against a constant external
pressure of 0.5 atm (final state is 0.5 atm as in a). What is your
inference of the result in comparison with the result of a) ?

Ans: a) Isothermal (reversible) expansion:
Class formula: w = -nRT ln V
2
/V
1
.
= -2 mol x 8.3145 JK
-1
mol
-1
x 298.15 K. x 2.303 log P
1
/P
2
as PV = Constant
at constant temperature.

= -2 x 8.3145 x 298.15 x 2.303 log 2 J
= -3437.2 J

b) Heat Change and the internal energy change.
Internal energy change is zero for an ideal gas undergoing process at
constant temperature E = 0.

Heat change = - work done by the gas.
= 3437.2 J.
(This much heat is absorbed by the system to do the work)

c) Work done in expansion against a constant pressure of 0.5 atm.
= -PV.

To Calculate V, calculate V
1
and V
2
.
V
1
= nRT/P
1
= 2 mol x 0.082 L atm K
-1
mol
-1
x 298.15 K/1 atm.
= 48.09 L
V
2
= 2V
1
as P
2
= P
1
.

w = -PV = 0.5 atm x 48.90 L
= 24.45 L atm.
= 2479.1 J.

Observation: Expansion against constant pressure is NOT a reversible
process. Therefore, the work done by the gas is not the maximum possible
work done, but less than the maximum. It is a path-dependent quantity.

2. An ideal gas expands reversibly and isothermally from 20 atm to 1 atm at
300 K. What are the values for
a) work done by the gas per mole ?
b) heat absorbed by the gas per mole ?
c) E per mole and
d) H per mole ?

Ans: a) Reversible isothermal expansion from 20 atm to 1 atm at 300K.
a) w = -nRT ln P
1
/P
2
.
b) Q = -w
c) E = 0
d) H = q as the work done is reversible, under isothermal conditions.

Ans: w = -7473.8 j.


3. The heat capacity of a gas is represented by the formula
2
p
T
C T

== + +
For O
2
, = 29.96 J K
-1
, = 0.00418 J K
-2
and = -1.67 x 10
-5
J K.
Calculate the amount of heat required to heat the gas from 300 K to
1000K.

Ans: H =
T1
T2
C
P
(T) dT
= T
1
T2
( + T + /T
2
) dT
= (T
2
T
1
) + /2 (T
2
2
T
1
2
) - (1/T
2
1/T
1
)
For O
2
= 29.96 JK
-1
.
= 0.00418 JK
-2
.
= -1.67 x 10
5
JK
T
1
= 300 K T
2
= 1000 K.

Substitute: Answer H = 23.26 kJ
(T
2
T
1
) = 20.97 kJ
/2 (T
2
2
T
1
2
) = 1.90 kJ.
-(1/T
2
1/T
1
) = 0.39 kJ.

4. An ideal monatomic gas is expanded by a reversible adiabatic process
from an initial pressure of 1 atm to a final pressure of 0.3 atm. The initial
temperature of the gas is 300 K. Calculate the work done, internal energy
change and the final temperature of the gas.

Ans: Reversible adiabatic expansion.
q = 0, E = q + w = w
For adiabatic processes,
PV

= constant = C
P
/C
v
= 5/3 for an ideal monatomic gas.
Also PV = nRT for all ideal gases.
(V
1
/V
2
) = P
2
/P
1
and (V
1
/V
2
) = (T
1
/T
2
) (P
2
/P1)
or (T
1
/T
2
) = (P
2
/P
1
)
1-/

substitute the values T
1
, P
1
and P
2
.
T
2
is calculated as 185.3 K.
Work done = C
v
T = -1.43 kJ (T
2
< T
1
, work done is done by the gas, hence
negative).
Internal energy charge E = -1.43 kJ.


5. An ideal monatomic gas at 1 atm pressure with a heat capacity at
constant volume C
v
=3R/2 is expanded adiabatically against a constant
external pressure of 0.5 atm. Calculate q, w, Eand H (per mole)

Ans: For T use the same formula as above
T
1
= 300 k, T
2
= 227.3 k.
E = -PV = -642.5 J
H = C
p
T = 5/2R x 72.7 J.

6. Determine whether the following are exact differentials.

a) xy
2
dx x
2
ydy b)
2
dx x
dy
y y

b). Verify that dq = dE +Pdv = C
V
dT + RTd ln V is not an exact
differential but that


dq
C
T
=
v
d ln T + R d ln V is an exact differential.

Ans: a). Let xy
2
dx x
2
y dy = df
Then
2
f/xy =
2
f/yx must be satisfied.

It is NOT. Therefore xy
2
dx x
2
y is NOT an exact differential.

b) dq = C
v
dT + Rt d ln V.

2
q/VT = /V (C
V
) = for an ideal gas.

2
q/TV = [/T (RT/V)]
V
= R/V
2
q/VT.
Hence dq is NOT an exact differential.
dq/T = C
V
/T dT + R/v dV = df

2
f/VT = (/T[R/V])
V
= 0.

2
f/VT = (/V[C
V
/T])
T
= 0 =
2
f/TV.
Hence dq/T is an exact differential.


7. Derive the relation

C
V
= -
T

E
E V
V T
| | | |
| |

\ . \ .

From the expression for the total differential of E (T, V).

Ans: E, V, T follow the cyclic relation
(E/T)
v
(T/V)
E
(V/E)
T
= -1.
Or (E/T)
V
= -1/(T/V)
E
(V/E)
T
= -(V/T)
E
(E/V)
T

More elaborately:
E = E (V,T)
dE = (E/T)
v
dT + (E/V)
T
dV.
= C
V
dT + (E/V)
T
dV.
Express V as a function of E and T and substitute for dV in the above
expression.
dV = (V/E)
t
dE + (V/T)
E
dT.
dE = (E/V)
T
{(V/E)
T
dE + (V/T)
E
dT} + C
V
dT.
0 = {1-(E/V)
T
(V/E)
T
} dE + {C
v
+ (E/V)
T
(V/T)
E
}dT
The equality implies the coefficients of dE and de are zero, as two of the
three variables E, v, T are independent.
Hence: (E/V)
T
(V/E)
T
= 1,
C
V
= - (E/V)
T
(V/T)
E
.


8. Show that
C
p
C
v
=T
V P
P V
T T
| | | |
| |

\ . \ .

Using appropriate relations between partial derivatives, show also that

C
p
C
v
=
2
P
T
V
T
T
V
P
(
(

(
(

For water at 4
0
C, given that the density of water is maximum, what does the
above result indicate . Also evaluate (C
p
C
v
) for an ideal gas.

Ans: dE = (E/T)
v
dT + (E/V)
T
dV = C
v
dT +
T
dV.

T
internal pressure.
(E/T)
P
=
T
(V/T)
P
+ C
V
.
(E/T)
P
C
V
=
T
(V/T)
P
Also,
T
= T(P/T)
V
- P
C
P
C
V
= (H/T)
P
(E/T)
V
; H = E + PV.
= (E/T)
P
+ P (V/T)
P
(E/T)
V
.
= P(V/T)
P
+
T
(V/T)
P
.
= (
T
+ P) (V/T)
P
= T(P/T)
V
(V/T)
P
.

Also P
1
T
1
V
Form cyclic partial derivatives.
(P/T)
v
= -1/(T/V)
P
(V/P)
T
= - (V/T)
P
/(V/P)
T

C
P
C
V
= -T(V/T) [(V/T)
P
/(V/P)
T
].
For an ideal gas Pv = nRT
(V/T)
P
= nR/P.
(V/P)
T
= -nRT/P
2

C
P
C
V
= nR.

9. For n moles of a Van der Waals gas, whose equation of state is given by
2
2
n a
P
V
(
+
(

( V - nb) = nRT calculate the expression for the entropy change for
the system from an initial state T
1
, V
1
to the final state T
2
, V
2
.

Ans: Use: du = tDs PdV [i.e. u u(s,v)]
= C
V
dT + [T(P/T)
V
P] dV [u u(T,V)]
Also, from ds = (S/T)
V
dT + S/V)
T
dV and the firstline,
(S/T)
V
= C
V
/T; (S/V)
T
= (P/T)
V
P/T + P/T = (P/T)
V.


Thus the equation for entropy change you need to use is dS = C
v
dT/T +
(P/T)
V
dV.
For a van der waals gas.
(P + n
2
a/V
2
)(V nb) = nRT,
P = nRT/V nb n
2
a/V
2


(P/T)
v
= nR/V nb
dS = C
v
dT/T + nR/ V nb dV.
S =
T1V1
T2V2
ds
=
T1
T2
C
V
/dT +
V1
V2
nR/V-nb dV
= C
V
ln T
2
/T
1
nR ln V
2
nb/V
1
nb if C
v
is independent of temperature.

10. Without doing explicit calculations, predict the signs of
, , , P V T Hand S for one mole of an ideal gas taken through each of
the following four steps of a Carnot cycle. Assume C
p
and C
v
Constants.

Step (a): Isothermal reversible expansion P
1
V
1
T
1
P
2
V
2
T
1
Step (b): Adiabatic reversible expansion P
2
V
2
T
1
P
3
V
3
T
2

Step (c): Isothermal reversible compression P
3
V
3
T
2
P
4
V
4
T
2

Step (d): Adiabatic reversible compression P V T P
1
V
1
T
1



Text book material.

11. On a single entropy versus temperature diagram, draw the curves for the
following reversible processes for an ideal gas ( the initial state is the
same foe all processes).
(a) isothermal expansion,
(b) adiabatic expansion and
(c) isochoric process in which heat is added.

Ans:










a) Isothermal expansion. T- constant
b) adiabatic expansion. q = 0. s = 0
c) Isochoric with heat added.
S = C
v
ln T
2
/T
1
.
T
1
is an initial point.
So, S(T
2
) = S
0
(at T
1
) + C
v
ln T
2
C
v
ln T
1
.

12. Sketch diagrams for the reversible Carnot cycle of an ideal gas with
constant C and C ; P Vs S; E Vs P; T Vs P; H Vs P; V Vs T; S Vs V; V Vs
E; V Vs H; E Vs T; H Vs T, T Vs S, E Vs H and H Vs S.

Ans: discuss three cases. The others are similar.

a) P. vs. S







T
S
a
b
Logarithmic. c
I
II
III
IV
S
P




I Isothermal expansion.
II adiabatic exp.
III Isothermal compression.
IV adiabatic compression.


b) c)











Others can be constructed similarly.

13. One mole of water at 0
0
C is brought into contact with a large heat
reservoir at 100
0
C. When the water reaches 100
0
C calculate the entropy
change of water, the reservoir and the universe(which consists of water and
the reservoir). If the water was brought into contact with a heat reservoir at
75
0
C first and then water at 75
0
C is brought into contact with the reservoir at
100
0
C so that the final state of the water is 100
0
C, calculate the net entropy
change of water, the reservoir and the universe. Assume that the heat
capacity of water to be constant at 1.0 cal g
-1
K
-1.

Ans: For a body at temp T
1
in contact with a reservoir at T
2
with T
1
< T
2
.
S for the body
(for a suitable reversible path by which T
1
T
2
) = nC
v
ln T
2
/T
1
.

S for the reservoir: heat is supplied at T
2
to heat a body from T
1
to T
2
with
a constant heat capacity C
v
.
I
II
III
IV S
P
I
II
III
IV
S
T

s = -nC
V
(T
2
T
1
)/T
2
.
s
universe
= nC
V
ln T
2
/T
1
nC
V
(T
2
T
1
)/T
2
.
> 0 if T
2
> T
1
.
= 0 if T
2
= T
1
. (obvious).
Apply this for each of the cases mentioned in the problem.
T
1
= 273 k, T
2
= 373 k. C
V
= 18.0 cal mol
-1
k
-1

S = 18[2.303 log373/273 100/373] = 0.7938 cal.
Please understand the underlying assumption. Reservoir is so huge that the
process of heat transfer is assumed to be reversible! Otherwise S heat/T.

Process 2:

S
universe
is calculated for two processes.
T
1
= 273 k. T
2
= 348 k
And T
1
= 348 k, T
2
= 373 k.
S = 18 [2.303 log 348/273 75/348] + [2.303 log 373/348 25/373]
= 0.5346 cal.
What does this tell you?
If you divide this further and further, (i.e. infinitely many such intermediate
temperatures and attain equilibrium at each stage, what will be the value of
S
universe
? [zero, in the end!].

14. A mass m of liquid at temp T
1
is mixed with an equal mass of the same
liquid at a temperature T
2
. If the system is isolated show that the entropy
change of the universe is



1 2
1 2
( ) / 2
2 ln
p
T T
mC
TT
(
+
(
(



Where C
p
is the specific heat capacity of the liquid and is assumed to be
constant over the temperature range.

Ans: Heat capacity of the liquid is mC
P
.
Let T
1
> T
2
, T be an intermediate temp. (equilibrium).
Then:
mC
P
(T
1
T) = mC
P
(T T
2
).
Heat lost by the hot liquid. Heat gained by the hot liquid.
T
1
T = T T
2
or T = T
1
+ T
2
. It is also trivially true.
Entropy change in the liquid.
(hot) = m C
P
ln (T
1
+ T
2
)/2/T
1

Entropy change in the cold liquid = mC
P
ln (T
1
+ T
2
)/2/T
2
.
Total entropy change = 2m C
P
ln [(T
1
+ T
2
)/2 / T
1
T
2
]
Always positive. So long as T
1
and T
2
are different.


15. Two moles of an ideal gas are expanded isothermally at 298 K from a
volume V to a final volume of 2.5 V. Find the value of
gas
S and
total
S
for the following:
a) Reversible expansion
b) Irreversible expansion in which the heat absorbed is 400 J mol
-1
less
than the reversible expansion and
c) Free expansion.

Ans: Reversible expansion.
s
gas
= nR ln V
2
/V
1
= 2 x 8.314 ln 2.5
= 15.24 JK
-1
.
S
surr
= -15.24 JK
-1
as the heat transfer takes places reversibly from
surroundings at the same temperature.
S
tot
= 0.

b) S
gas
= 15.24 JK
-1
. Remember the initial and final states of the gas are
exactly the same as in the previous case, therefore S
gas
= 15.24 only still.
S
surr
= -(nRT ln V
2
/V
1
400)/T!
= -13.90 JK
-1
.
S
tot
= 1.34 JK
-1
> 0. (irreversible path).

c) free expansion: system does not draw any heat from the surroundings.
S
surr
= 0.
S
tot
= 15.24 JK
-1
.

16. The molar entropy of an ideal gas at 298 K is 146 J K
-1
Mol
-1
. Find the
value of entropy of the gas at 500 K when its pressure is kept constant.

Ans: Missing statement: (C
P
of the gas is a constant and is 20.97 JK
-1
mol
-1
.)
use this to calculate.
S
500
= S
298
+ C
P
ln T
2
/T
1

= 146 + 20.97 x 2.303 x log 500/298.
= 156.85 JK
-1
mol
-1
.

17. How much does the entropy of an ideal gas increase when one mole is
heated from 298 K to 1000 K at a constant pressure and then expanded to
five times the volume at the higher temperature ?
C = 20.9 J K
-1
mol
-1


Ans: S = C
P
ln T
2
/T
1
+ R ln V
2
/V
1
.
= 2.9 x 2.303 log 1000/298 + 8.314 x 2.303 x log 5
= 25.3 + 13.4 = 38.7 JK
-1
mol
-1
.