CHE 3161 Chemistry & Chemical Thermodynamics

Test 1 Solution

Date: 23/03/2011 Total Marks: 30 marks

The exam is open book and notes.

1) Read carefully and determine whether the following statements are true or false and indicate
your thermodynamic reasoning. If you claim that a statement is false, you may state that it
violates a law of thermodynamics, or you may employ a physical counter-example or any
plausible reason. You may wish to amend any false statement with a clarifying phrase that
makes the statement true.
(a) A system comprised of ethanol, methanol and helium exists as a two-phase vapor/liquid
system at 300 K and 80 kPa. After the addition of some pure methanol, the system can be
returned to two-phase equilibrium at the initial T and P while all other parameters change.

True

The phase rule yields: F = 2 – π + N = 2 −2 + 3 = 3. With only T and P fixed, one degree of
freedom remains. Thus changes in the phase compositions are possible for the given T and
P. If methanol is added in a quantity that allows T and P to be restored to their initial values,
the methanol distributes itself between the phases so as to form new equilibrium phase
compositions and altered amounts of the vapor and liquid phases. Nothing remains the same
except T and P.

(b) The work done on a closed system during an irreversible process cannot be calculated.

False

Work done can be calculated through measurement of forces and displacement.

However, the expression dW = - P dV cannot be applied.

(c) A process fluid enters a condenser such that the temperature decreases from 400 K to 300 K
at constant pressure. Hence, the molar heat capacity of the fluid is not a state property
because the heat exchanged in the cooling process depends on the path.

False

Cp = dH / dT is always a state properties regardless of the path

(d) The PV diagram in Figure 1 below shows 2 different reversible processes performed on an
ideal gas. The temperature of the gas in process A→B decreases while temperature of the
gas in adiabatic process A→C increases.
 Figure 1

False

The ideal gas E.O.S PV= RT can be applied.

A→B isobaric
Hence T increases with increasing V

A→C adiabatic TVγ-1 = constant

Hence T decreases with increasing V

(8 marks)

2) (a) Calculate Z and V for ethane at 330 K and 20 bar by applying the truncated viral
equation with a value of B from the generalized Pitzer correlation.

From Appendix B:
Tc = 305.3 K Pc = 48.72 bar ω = 0.100

Tr = T / Tc
= 1.081

Pr = P / Pc
= 0.411

Viral Equation:
Z = 1 + B’ P

Introduce Pitzer correlation : B Pc / R Tc = B0 + ω B1

 Hence,
Z = 1 + B0 Pr / Tr + ω B1 Pr / Tr

B0 = 0.083 – 0.422 / Tr1.6

= - 0.29

B1 = 0.139 – 0.172 / Tr4.2

= 0.015

Hence,
Z = 0.89

V = ZRT / P
= 1221 cm3 / mol
(b) Is the V obtained for part (a) the molar volume of liquid phase or vapor phase? Explain.

Vapor phase since T > Tc

(c) Comment on the accuracy of the V obtained by the same method in part (a) if the
pressure increases to 100 bar while the temperature remains the same.

Inaccurate

Pitzer correlation was developed based on the linear equation. When Pr = 2.053 and Tr
= 1.081, linear relationship between Z0 and Pr does not exist according to Figure 3.14.
(7 marks)

3) An ideal gas initially at 500 K and 10 bar undergoes a four steps mechanically reversible
cycle in a closed system. In step 1→2, pressure decreases isothermally to 3 bar; in step
2→3, pressure decreases at constant volume to 2 bar; in step 3→4 volume decreases at
constant pressure; and in step 4→1, the gas returns adiabatically to its initial state.
Data: Cp = (7/2) R and Cv = (5/2) R

(a) Sketch the cycle on a PV diagram.

(b) Determine (where unknown) both T and V for states 1, 2, 3 and 4.
(c) Calculate Q, W, ΔU and ΔH for each step of the cycle.

( 15 marks)