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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: w = -7473.8 j.
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.
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
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.
CV = - ∂E ∂V
∂V T ∂T E
From the expression for the total differential of E (T, V).
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.
Also P1T1 V
Form cyclic partial derivatives.
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.
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.
Ans:
Logarithmic. c
a
S
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.
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
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.
Process 2:
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
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.
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