ENG 115

Mid-Term Examination

Fall, 2014

348 HMMB

Wednesday, October 15, 2014

5:00 pm 6:30 pm

This is a closed book examination; no equation sheets are allowed.

PLEASE READ THE PAPER CAREFULLY.

Please answer Questions 1 and the other question. For Questions 1, you need answer only
5 of the 10 parts and for Questions 2 and 3 you only need to answer (a) or (b). The time
that you should invest in each question is indicated in parentheses. The total time is 90
minutes.

Question 1: Please answer five of the following (50 minutes):

1. Define reversible and irreversible processes in terms of the causative and

opposing forces and indicate what condition must be met for a change in a
property to be path-independent.

A reversible process occurs when the causative force is only infinitesimally

greater that the opposing force. Thus a macroscopic reversible change can be
viewed as occurring via an infinite number of infinitesimally-closely spaced
equilibrium states. The condition for path independence is that the function be an
exact differential.

2. Define the First Law of Thermodynamics and carefully explain the meanings of
all symbols contained therein. Combine the First and Second Laws to produce the
differential forms of the first auxiliary function.

dE = q w, where dE is the change in the internal energy, q is the heat

received by the system from the surroundings, w is the work done by the system
on the surroundings, d indicates a path-independent exact differential, and
indicates a path-dependent in-exact differential.

3. State the Second Law of Thermodynamics for changes that occur in an isolated
system. Differentiate between reversible and irreversible change.

The change in the state function entropy is defined as: dS = q/T. For a closed
system and surroundings within lying within an adiabatic boundary (perhaps at

1
 infinity), the Second Law states that: dSsyst + dSsurr 0, where the = sign
indicates a reversible process and > indicates an irreversible process.

4. State the Third Law of Thermodynamics and briefly explain why it is so

important and how it is used to predict changes in Gibbs energy with temperature.

The Third Law of Thermodynamics states the entropy for a perfectly-ordered

substance at 0 K is zero. It is important, because we may calculate the absolute
value of entropy at any temperature from the measured heat capacity, cP, and the
changes in enthalpy of all phase transitions between 0 K and T K as:

where Sconfig is the configurational entropy at 0 K. This may then be used to

calculate the Gibbs energy of a substance at any temperature T, G(T), from the
enthalpy, H(T), using G(T) = H(T) TS(T) where the enthalpy is given as:
T
H (T )=H ( T 0 ) + c P dT .
T0

5. State the thermodynamic equation of state and using one of Maxwells equations,
explain briefly how (U/V)T can be measured experimentally.

The Thermodynamic equation of state is: ( U

V )T
=(
S
V )
P
T
. However,

because we do not have an entropy meter we cannot evaluate ( V S )

T

directly. We therefore use the Maxwell relationship, ( V S ) =( TP )

T V
to write

( U T
P
V ) (T )
= P
V
. Because ( PT )
V
can be measured experimentally, or
may be calculated from the coefficient of thermal expansion and the
U
compressibility, we are then able to determine the internal pressure,
V T ( )
without having to deal with the entropy of the system.

6. State van der Vaals equation of state for a non-ideal gas and define all parameters
contained therein.

Van der Waals equation of state is given as ( P+ Va )( V b) =RT

2 , where P is
the pressure, V is the volume, T is the temperature, a is the inter-molecular
interaction parameter, and b is the volume excluded by the molecules.

2
7. Define the mean molal activity coefficient for an electrolyte, M pXq in terms of the
activity coefficients of the individual ions and state the extended Debye-Huckel
equation for estimating the single ion activity coefficient. Carefully define the
terms contained therein.

The mean molal activity coefficient for a dissolved salt MpXq pMn+ + qXm-,
where pn-qm = 0 is dictated by electro-neutrality, is given by

ln A | z1 z2 | I / 1 Ba I
, where I is the ionic strength, A and B are the
Debeye-Huckel coefficients, a is the distance of closest approach of the cation and
anion, and z1 = n and z2 = m are the charges on the cation and anion, respectively.

+
+
The mean-molal activity coefficient is defined as where and


=

are the respective single-ion activity coefficients for the cation and anion.

8. Starting with the definition of chemical potential, derive the change in Gibbs
energy of an ideal gas mixture in terms of the composition and then derive the
change of the entropy of mixing.

The chemical potential of a substance is defined as: i= ( G

n )
i T , P ,n j j i
where G
is the Gibbs energy of the system. In terms of composition, the chemical
= s RT ln s X s
0
potential is defined as s , where s is the standard state
value for component s when s X s =1 . Thus, for the formation of an ideal
gas mixture of gas A and gas B, for which s is 1, we have:
Gm =X A A + X B BX A 0A X B 0B . Thus,
m
G =RT ( X A ln ( X A ) + X B ln ( X B ) ) . The entropy of mixing is:
Gm
m
S = ( T )
=R ( X A ln ( X A ) + X B ln ( X B ) ) , because the mole fractions, XA
and XB are independent of temperature.

9. Define what is meant by a regular solution.

A regular solution is a mixture for which H m =GXS = X A X B=RT X A X B ,

where H m is the enthalpy of mixing, G XS is the excess Gibbs energy, and
and are interaction parameters. For an ideal (Raoultian) mixture,
and are zero (no inter-molecular interactions), so that
H =G = V m =0 .
m XS

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10. State Raoults law and Henrys law for a completely miscible binary mixture and
illustrate these laws for systems that display positive and negative deviations from
Raoultian behavior. Why do these deviations occur?

Raoults law relates the partial pressure of the solvent in a mixture A-B, where A
0
is considered to be the solvent and B is the solute as: p A =X A P A , where
P0A is the partial pressure of pure solvent. Henrys law relates the partial
pressure of the solute to the mole fraction of the solute as: pB =k B X A , where
k B is known as Henrys constant. Real systems exhibit positive or negative
deviations from these laws, as illustrated in Figures 9.2(a) and 90.2(b),
respectively. Positive deviations from Raoults and Henrys laws indicate that
energetically, the solvent A would rather be in the vapor phase rather than in
mixture with B. This is due to repulsive interaction with B. On the other hand, if
the interactions between A and B are more attractive than A with A and B with B
then A and B would rather exist in solution, giving rise to negative deviations
from ideality.

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Question 2: Please answer a) or b) (20 minutes)
a) Using heat transfer across a boundary and the definition of entropy, demonstrate
that the Second Law of Thermodynamics predicts that the entropy of the system
plus the surroundings must increase for irreversible heat transfer but remains
constant for reversible heat transfer. Using this expression, define the change in
the Gibbs energy of the system. What is meant by reversible heat transfer?

The change in the state function entropy is defined as: dS = q/T. For a closed
system and surroundings within an adiabatic boundary, and the Second Law states
that: dSsyst + dSsurr 0, where the = sign indicates a reversible process and >
indicates an irreversible process. Consider a system that receives an increment of
heat, q and for which the temperatures of the system and surroundings are Tsyst
and Tsurr, respectively. If the heat is received at constant pressure, we may write
dHsyst = q. Therefore, the changes in the entropy of the surroundings can be
written as dSsurr = -dHsyst/Tsurr. Substituting into the Second Law gives: dS = dSsyst
- dHsyst/Tsurr 0. For an infinitesimally small difference in temperature, Tsyst = Tsurr
=T, so that TdS = TdSsyst - dHsyst 0. Defining the Gibbs energy as G = H TS,
we then express the Second Law as dG 0. The importance of this expression is
that the Second Law is now expressed in terms of the properties of the system
alone and that the properties of the surroundings, which extend to infinity and
hence cannot be fully characterized, are eliminated. A reversible change occurs
for dG = 0, whereas an irreversible change occurs with dG < 0. Reversible heat
transfer from the surrounding to the system occurs when Tsurr is only
infinitesimally greater than Tsyst.

b) Sketch the P-V-T behavior of a non-ideal gas that follows the van der Waal
equation of state for temperatures above and below the critical point. How are the
critical parameters (Tcr, Pcr, and Vcr) defined from van der Waals equation of
state? For T < Tcr starting from a single gas phase, describe what you would
observe as you compress the system. Carefully note what parts of the isotherm
are physical and what parts are non-physical and explain why.

The P-V-T properties of a real gas that follows van der Waals equation of state,
a
( )
P+ 2 ( V b ) =RT
V
is displayed in Figure 8.1. At sufficiently high
temperature (T1), the gas behaves ideally, but as the temperature is lowered to T3,
a small deviation from ideal behavior appears in the isotherm. On lowering the
temperature to Tcr, this deviation develops into a mathematical inflexion for which
2 P
we may write ( ) P
V T
cr
=0 and
( ) V 2 T
cr
=0 . These partial differentials

define the critical point (Pcr, Vcr, Tcr). Accordingly, from van der Waals equation
and the application of these first and second differentials we obtain:
a 8a
Pcr = , V cr =3 b , T cr = . At temperatures below Tcr , there appears an
27 b 2
27 bR

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ever expanding region of co-existence of a liquid phase and a vapor phase as the
temperature is lowered further, and as is represented by the broken line. If the
isotherms are predicted from the van der Waal equation, however, the results are
shown in Figure 8.7. It is seen that at temperatures below Tcr the isotherm
displays a maximum and a minimum in the two-phase, co-existence region. Since
P
( )
V T
<0 (i.e., the volume of a system must always decrease with increasing
pressure) the region J to F (Figure 8.7) is mechanically and thermodynamically
non-physical and cannot exist, but N to J and F to A are in compliance with this
condition. Thus, starting at A and by increasing the pressure (decreasing the
volume), B is reached and the system transitions to J by condensing vapor in the
two phase region B-J and a further decrease in volume results from compression
of the liquid from J to N. At a temperature above Tcr (Point O) the system is a
single fluid phase.

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Question 3: Please answer a) or b) (20 minutes)
a) Derive Maxwells equations from the definition of an exact differential. Why are
Maxwells equations so valuable in computational thermodynamics?

Let Z(x,y) be a state function with x and y being the independent variables.
Accordingly, the complete differential may be written as:

Z Z
dZ dx dy
x y y x
Z / x y Z / y x
Noting that the partial derivative and are also functions of x and
y, we may write:

dZ Ldx Mdy

Accordingly, we may write:

Z L

y x y x y x
and
Z M

x y x y x y

Because Z is a state function, the change in Z is independent of the order of

differentiation, so that:

Z Z 2Z

y x y x x y x y
xy

Therefore,

L M
y
x x y

For a closed system, from the First and Second Laws of Thermodynamics and the
definitions of the state functions H, A, and G, we write

dU TdS PdV

dH TdS VdP

dA SdT PdV
 And

dG SdT VdP

Thus, application of the Identity yields the Maxwell equations as:

T P
V
S S V

T V
P
S S P

S P
V
T T V

and

S V
P
T T P

The relations that require that the entropy be measured or be held constant, are not
very useful, because there is no practical way of measuring S (no entropy meter) or
of ensuring that the entropy be held constant during a thermodynamic process.
However, the last two equations are enormously useful, because their right sides do
not involve entropy and because the conditions of constant P and V are
experimentally realizable.

b) Sketch the phase diagram for water and using the Gibbs phase rule indicate the
number of degrees of freedom along all boundaries, within each phase, and at the
triple point and the critical point of water. What is meant by a degree of freedom
and why can the triple point be used as the same temperature standard on Earth and
on Mars. Why can a person skate on ice?

The phase diagram for water as a single component system is displayed in Figure
7.11. The diagram comprises one component (H2O) and three phases [liquid water, ice
(solid water), and vapor (steam)]. According to Gibbs phase rule, f = C - P +2,
where C is the number of components (C = 1), P is the number of phases, and the
number of degrees of freedom is the number of independent variables (p,T) that may
be varied independently while maintaining the phase relationship. Because C = 1 for
a single component system, the phase rule reduces to f = 3 P.
 For any point within a single phase (e.g. A, B, C), P = 1 and hence f = 2, so that T
and p may be varied independently while maintaining the single phase of interest. On
the lines OA, OB, and OC, two phases are in equilibrium, so that P = 2 and hence f =
1. In this case, either p or T may be varied, but in doing so T and p, respectively, are
fixed by the need to maintain equilibrium between the two phases. At Point O, three
phases are in equilibrium, and hence f = 0, such that the triple point is invariant with
respect to either pressure or temperature. That is why it is the came on Earth as it is
on Mars. Further, the slope of OA is negative, which means that the melting
temperature of ice decreases with increasing pressure. When a person skates, the
blade exerts a high pressure on the ice, causing the ice to melt locally, which provides
liquid water as a lubricant.

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