Physical chemistry Exam

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Physical chemistry Exam

© All Rights Reserved

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(20 Points) For each statement or question in the left column, find the appropriate response in

the right column and place the letter of the response in the blank line provided in the left column.

1.
For
a
multi-component
system,
since
the
Gibbs
Free
Energy
is
an

extensive
state
function,
we
can
derive
the
following
relation
that
couples

the
total
extensive
Gibbs
Free
Energy
of
the
system
to
the
individual

component
chemical
potentials:
_____________e________________

2.
Under
conditions
of
constant
pressure
and
entropy,
what

thermodynamic
state
function
reaches
an
extremum?
__________i_________

3.
The
entropy
change
for
an
adiabatic,
irreversible
process
of
an
isolated

system
is
______________l_________.

4.
The
enthalpy
of
isothermal
mixing
of
ideal
gases
is

____________k____________.

5.
Entropy
is
a
quantifiable
statistical
property
as
well
as
an
absolute

measure
of
the
chaos
content
of
a
system.
True
or
False?
____False________

6.
The
chemical
potential
of
a
species
in
a
multi-phase
system
at

equilibrium
is
constant
and
equal
throughout
the
system.
True
or
False?

____True___

7.
For
water
at
its
triple
point,
the
number
of
degrees
of
freedom
is
___k__.

a.
entropy

b.
U
and
V

c.
intensive

d.
3

e.
G = n i i

i

f.
equal

g.
Le
Chatelier

h.
all
the
above

i.
enthalpy

j.
true

k.
zero

l.
positive

m.
false

n.
not

calculable

8.
The
natural
variables
for
entropy
are
____________b______________.

o.
diffusion

p.
P
and
T

9.
Partial
molar
properties
are
_______c___________.

q.
2

r.
4

10.
The
equilibrium
constant
contains
information
regarding
the
entropy
s.
Equipartition

of
mixing
of
reaction
components.
True
or
False?
______TRUE______

t.
Joule

2. (25 Points) Based on your knowledge of thermodynamics, demonstrate that the enthalpy of

an ideal gas is only temperature dependent. Maxwell relations may be useful.

Solution:

If we consider the internal energy in a general sense to depend on temperature, T, and

volume, V, then the total differential of the internal energy in the most general case is:

H

H

dH(T,P) = dT + dP

T P

P T

By definition, the temperature partial derivative is the constant volume heat capacity, which in

general can be treated as temperature dependent.

H

dH(T,P) = CP dT + dP

P T

The trick is to determine what the second partial derivative is. We can start with the combined

First and Second Laws to write the fundamental equation as:

dH = TdS + VdP

Taking the partial derivative of both sides with respect to volume at constant temperature, we

obtain:

H

S

= T + V

P T

P T

The entropy partial derivative is determined from a Maxwell Relation,

S

V

=

P T

T P

Thus,

H

V

= T + V

P T

T P

For an ideal gas:

S

V

nR

= =

P T

T P

P

giving for the final relation for dH(T,P) of an ideal gas:

nRT

dH(T,P) = CP dT +

+ V dP

P

dH(T,P) = CP dT + 0

dH(T) = CP dT

3. (20 Points) A. Determine a general expression for the following partial differential in terms of

partial derivatives of an Equation of State (Maxwell Relations might be useful):

S

V T

Solution:

This is a partial derivative involvingS, V, and T. We can think of starting with a thermodynamic

function that depends on V and T. This is the Helmholtz Free Energy.

A

A

dA = dV + dT

V T

T V

dA = pdV SdT

Since A is a state function, we can make use of the Maxwell Relations:

S p

=

V T T V

This gives us the general relation between the given derivative and partial derivatives of an

Equation of State.

1). An ideal gas

pV = nRT

nRT

S p V

nR

=

=

=

V T T V T

V

V

2) for a Van der Waals gas.

p=

nRT

an 2

+ 2

V nb V

nRT

an 2

+

S p V nb V 2

nR

=

= =

V T T V

T

V nb

4. (10 Points) We have seen that the Carnot cycle on a pressure-Volume, P-V, diagram looks

like the following:

What would the Carnot cycle drawn on a temperature-entropy, T-S, diagram look like? Use

temperature for the y-axis and entropy for the x-axis.

Solution:

Since the Carnot cycle involves reversible processes, the adiabatic steps are isentropic

(constant entropy).

5.(25 Points). A. For the following chemical reaction at 298.15K, compute the equilibrium

constant, KP, using available information and making any necessary assumptions:

ln(K P ) =

1

0

Grxn

RT

1

G 0f (CO2 ,gas) + G 0f (H 2 ,gas) G 0f (H 2O,liquid) G 0f (CO,gas)

RT

1

=

394400Jmol 1K 1 + 0 + 237100Jmol 1K 1 +137200Jmol 1K 1 )

(

1 1

(8.314Jmol K )(298.15K)

= 8.1087

K P = 3320 >> 1

=

B. Based on your value of KP above, what are the primary components of the reaction mixture

at equilibrium?

Because KP is so much greater than 1, the reaction mixture will consist mostly of products,

hydrogen and carbon dioxide gas, at equilibrium.

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