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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 N2 gas at 250 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 V2/V1.
= -2 mol x 8.3145 JK-1 mol-1 x 298.15 K. x 2.303 log P1/P2 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.


= -P∆V.
To Calculate ∆V, calculate V1 and V2.
V1 = nRT/P1 = 2 mol x 0.082 L atm K-1 mol-1 x 298.15 K/1 atm.
= 48.09 L
V2 = 2V1 as P2 = ½ P1.

∴w = -P∆V = 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 P1/P2.
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
C p == α + β T + Tγ2

For O2, α = 29.96 J K-1, β = 0.00418 J K-2 and γ = -1.67 x 10-5 J K.


Calculate the amount of heat required to heat the gas from 300 K to
1000K.

Ans: ∆H = ∫T1T2CP(T) dT
= ∫T1T2 (α + βT + γ/T2) dT
= α (T2 – T1) + β/2 (T22 – T12) - γ (1/T2 – 1/T1)
For O2 α = 29.96 JK-1.
β = 0.00418 JK-2.
γ = -1.67 x 105 JK
T1 = 300 K T2 = 1000 K.

Substitute: Answer ∆H = 23.26 kJ


α(T2 – T1) = 20.97 kJ
β/2 (T22 – T12) = 1.90 kJ.
-γ(1/T2 – 1/T1) = 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,
PVγ = constant γ = CP/Cv = 5/3 for an ideal monatomic gas.
Also PV = nRT for all ideal gases.
∴(V1/V2) = P2/P1 and (V1/V2) = (T1/T2) (P2/P1)
or (T1/T2) = (P2/P1)1-γ/γ
substitute the values T1, P1 and P2.
T2 is calculated as 185.3 K.
Work done = Cv ∆T = -1.43 kJ (T2 < T1, 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 Cv=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


T1 = 300 k, T2 = 227.3 k.
∆E = -P∆V = -642.5 J
∆H = Cp ∆T = 5/2R x 72.7 J.
6. Determine whether the following are exact differentials.

dx x
a) xy2dx –x2ydy b) − dy
y y2
b). Verify that dq = dE +Pdv = CVdT + RTd ln V is not an exact
differential but that

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

Ans: a). Let xy2 dx – x2y dy = df


Then ∂2f/∂x∂y = ∂2f/∂y∂x must be satisfied.

It is NOT. Therefore xy2dx – x2y is NOT an exact differential.

b) dq = Cv dT + Rt d ln V.
∂2q/∂V∂T = ∂/∂V (CV) = for an ideal gas.
∂2q/∂T∂V = [∂/∂T (RT/V)]V = R/V ≠ ∂2q/∂V∂T.
Hence dq is NOT an exact differential.
dq/T = CV/T dT + R/v dV = df
∂2f/∂V∂T = (∂/∂T[R/V])V = 0.
∂2f/∂V∂T = (∂/∂V[CV/T])T = 0 = ∂2f/∂T∂V.
Hence dq/T is an exact differential.

7. Derive the relation

CV = -  ∂E   ∂V 
 ∂V T  ∂T  E
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.
= CV 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} + CV dT.
⇒ 0 = {1-(∂E/∂V)T (∂V/∂E)T} dE + {Cv + (∂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,
CV = - (∂E/∂V)T (∂V/∂T)E.

8. Show that
∂P ∂V
Cp – Cv=T    
 ∂T V  ∂T  P
Using appropriate relations between partial derivatives, show also that

 ∂V  2
 ∂T 
Cp – Cv = T   P
 ∂V 
 ∂P 
T

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

Ans: dE = (∂E/∂T)v dT + (∂E/∂V)T dV = Cv dT + πT dV.


πT → internal pressure.
∴(∂E/∂T)P = πT(∂V/∂T)P + CV.
⇒ (∂E/∂T)P – CV = πT(∂V/∂T)P Also, πT = T(∂P/∂T)V - P
CP – CV = (∂H/∂T)P – (∂E/∂T)V; H = E + PV.
= (∂E/∂T)P + P (∂V/∂T)P – (∂E/∂T)V.
= P(∂V/∂T)P + πT(∂V/∂T)P.
= (πT + P) (∂V/∂T)P = T(∂P/∂T)V (∂V/∂T)P.

Also P1T1 V
Form cyclic partial derivatives.

(∂P/∂T)v = -1/(∂T/∂V)P (∂V/∂P)T = - (∂V/∂T)P/(∂V/∂P)T


∴ CP – CV = -T(∂V/∂T) [(∂V/∂T)P/(∂V/∂P)T].
For an ideal gas Pv = nRT
(∂V/∂T)P = nR/P.
(∂V/∂P)T = -nRT/P2
∴CP – CV = nR.

9. For n moles of a Van der Waals gas, whose equation of state is given by
 n2a 
 P +  ( V - nb) = nRT calculate the expression for the entropy change for
 V2 
the system from an initial state T1, V1 to the final state T2, V2.

Ans: Use: du = tDs – PdV [i.e. u ≡ u(s,v)]


= CV 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 = CV/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 = CvdT/T +
(∂P/∂T)V dV.
For a van der waals gas.
(P + n2a/V2)(V – nb) = nRT,
P = nRT/V – nb – n2a/V2

(∂P/∂T)v = nR/V – nb
∴dS = CvdT/T + nR/ V – nb dV.
∴∆S = ∫T1V1T2V2 ds
= ∫T1T2 CV/dT + ∫V1V2 nR/V-nb dV
= CV ln T2/T1 – nR ln V2 – nb/V1 – nb if Cv 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 Cp and Cv Constants.

Step (a): Isothermal reversible expansion P1 V1 T1 → P2 V2 T1


Step (b): Adiabatic reversible expansion P2 V2 T1 → P3 V3 T2
Step (c): Isothermal reversible compression P3 V3 T2 → P4 V4 T2
Step (d): Adiabatic reversible compression P V T → P1 V1 T1

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:

Logarithmic. c
a
S

a) Isothermal expansion.T T- constant


b) adiabatic expansion. q = 0. ∆s = 0
c) Isochoric with heat added.
∆S = Cv ln T2/T1.
T1 is an initial point.
So, S(T2) = S0 (at T1) + Cv ln T2 – Cv ln T1.

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

II

I
S III

IV

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

b) c) II
I

II III I
S IV S

III IV

P T

Others can be constructed similarly.

13. One mole of water at 00C is brought into contact with a large heat
reservoir at 1000C. When the water reaches 1000C 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
750C first and then water at 750C is brought into contact with the reservoir at
1000C so that the final state of the water is 1000C, 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-1K-1.

Ans: For a body at temp T1 in contact with a reservoir at T2 with T1 < T2.
∆S for the body
(for a suitable reversible path by which T1 → T2) = nCv ln T2/T1.

∆S for the reservoir: heat is supplied at T2 to heat a body from T1 to T2 with


a constant heat capacity Cv.
∴∆s = -nCV (T2 – T1)/T2.
∆suniverse = nCV ln T2/T1 – nCV (T2 – T1)/T2.
> 0 if T2 > T1.
= 0 if T2 = T1. (obvious).
Apply this for each of the cases mentioned in the problem.
T1 = 273 k, T2 = 373 k. CV = 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:

∆Suniverse is calculated for two processes.


T1 = 273 k. T2 = 348 k
And T1 = 348 k, T2 = 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
∆Suniverse? [zero, in the end!].

14. A mass m of liquid at temp T1 is mixed with an equal mass of the same
liquid at a temperature T2. If the system is isolated show that the entropy
change of the universe is

 (T + T ) / 2 
2mC p ln  1 2 
 T1T2 

Where Cp 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 mCP.


Let T1 > T2, T be an intermediate temp. (equilibrium).
Then:
mCP (T1 – T) = mCP (T – T2).
Heat lost by the hot liquid. Heat gained by the hot liquid.
T1 – T = T – T2 or T = T1 + T2. It is also trivially true.
Entropy change in the liquid.
(hot) = m CP ln (T1 + T2)/2/T1
Entropy change in the cold liquid = mCP ln (T1 + T2)/2/T2.
∴Total entropy change = 2m CP ln [(T1 + T2)/2 / √T1T2]
Always positive. So long as T1 and T2 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 ∆S gas and ∆Stotal
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.


∆sgas = nR ln V2/V1 = 2 x 8.314 ln 2.5
= 15.24 JK-1.
∆Ssurr = -15.24 JK-1 as the heat transfer takes places reversibly from
surroundings at the same temperature.
∴∆Stot = 0.

b) ∆Sgas = 15.24 JK-1. Remember the initial and final states of the gas are
exactly the same as in the previous case, therefore ∆Sgas = 15.24 only still.
∆Ssurr = -(nRT ln V2/V1 – 400)/T!
= -13.90 JK-1.
∴∆Stot = 1.34 JK-1 > 0. (irreversible path).

c) free expansion: system does not draw any heat from the surroundings.
∴ ∆Ssurr = 0.
∆Stot = 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: (CP of the gas is a constant and is 20.97 JK-1 mol-1.)
use this to calculate.
S500 = S298 + CP ln T2/T1
= 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-1mol -1

Ans: ∆S = CP ln T2/T1 + R ln V2/V1.


= 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.