NORTH CAROLINA STATE UNIVERSITY

Department of Chemistry Name________________________________

CH 431 Practice Final Exam

Physical Chemistry I

Given: R = 8.314 J mol-1 K-1 = 0.08206 L atm mol-1 K-1

1 atm = 1.01325 x 105 Nm-2 = 760 Torr
3/2
qN
q = 2πmkT V , Q = q N
, Q = ,S=U + k ln Q , dP = ∆S
h 2 N! T dT ∆V

∂ln Q ∂ln Q ∂ E
P = kT , E =– , Cv = ,β= 1
∂V ∂β ∂T kT
Please show your work in the space allocated for each problem if possible.
Use addition space on the back and mark it clearly.
I. Short Answer (120 points total)
1. The diagram below shows a plot of the molar free energy vs. temperature for a pure
substance.
µ

Temperature (K)
A. Identify the thermodynamic quantity that represents the slope of the three lines on
the diagram below, i.e. what is (∂µ/∂t)? (4 points)

The slope (∂µ/∂t) = ___________-S______________.

B. Label the phases solid, liquid, and vapor on the diagram. (6 points)

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 Blue- solid, Purple – liquid, Red - vapor

C. Draw a line that represents the molar free energy of the liquid if a small amount of
solute is added. Please sketch and label the line in the diagram above. (5 points)

D. Describe the effect of solute on the chemical potential of the solvent. Include an
equation that describes mathematically how the chemical potential of a solvent is
affected by the addition of solute. (5 points)

The chemical potential of the solvent (here called component 1) is lowered.

µ1 = µ1 * + RT ln x1

2. The diagram below shows a plot of the free energy vs. extent of reaction.
G(ξ)

0.0 0.2 0.4 0.6 0.8 1.0

ξ

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 A. Identify the position where equilibrium occurs and give a mathematical
expression of the equilibrium condition. Please label the point on the diagram
above. (5 points)

B. If the total pressure on the system is increased, how will the curve shown in the
Figure change? To illustrate this you may draw a new diagram as needed. (5
points)

The position of the extent of reaction, ξ, at which the minimum occurs depends on
the stoichiometry of the reaction. If the net number of moles of gas is greater for
the products then increasing the pressure will shift toward the reactants and ξ will
get smaller. Alternatively, if the net numeber of moles of gas of products is
smaller than for the reactants then an increase in pressure will result in larger ξ.

3. A. You are given a partition function for a non- ideal gas. What formula would you
use to derive an equation of state from this partition function? (5 points)

∂ln Q
P = k BT
∂V

B. As an example, please outline the derivation of the ideal gas equation of state.
(5 points)

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 3/2
qN 2π M k BT 3/2
Q= , q= V = 2πM V
hβ
2 2
N! h
ln Q = N ln q – ln N !
∂ln Q ∂ln q
=N = N ∂ln V = N
∂V ∂V ∂V V
∂ln Q Nk BT
P = k BT = ⇒ PV = Nk BT
∂V V

4. Consider the statement: "The internal energy depends only on the temperature."

A. What formula would you use to calculate the internal energy for an ideal gas from
a known partition function. What is the relevant partition function? (5 points)

∂ln Q
E=–
∂β
For an ideal gas the partition function is the translational partition function used above. Thus,

3/2 3/2
2πM k BT
q= V = 2πM V
hβ
2 2
h
E = 3 Nk BT
2

B. Is this statement true for non-ideal gases? Give a reason for your answer.
(5 points)

If the non- ideality arises from intermolecular interactions such as those from
induced-dipole – induced-dipole interactions then the partition function will contain
temperature dependent terms that will give contributions to the energy. In other words,
terms like exp{βa/V2 } in the partition function for a van der Waal’s gas may give rise to
terms in the energy that do not depend on temperature.

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5. Give an expression for the relative amount of liquid and vapor present using the tie
line in the phase diagram below. Express the result as a ratio in terms of the lengths
A and B indicated. (10 points)
Vapor Pressure (Torr)

liquid
120
A B
100

80 vapor

0.2 0.3 0.4 0.5 0.6 0.7

zbenzene

Using the lever rule we can write

n liquid B
n vapor = A

6. What is residual entropy? (5 points)

Residual entropy is the entropy of an imperfect crystalline solid at T = 0 K. The third law
states that the entropy of perfect crystalline solids is zero at 0 K. However, a solid such
as CO may have configurations in which the CO molecules are flipped (OC instead of
CO) because their dipole moment is small enough that the energy of stabilization does
not force all dipoles to be aligned in an alternating anti-parallel fashion. For N CO
molecules the total number of such configurations is 2N.

7. Give the appropriate condition for each process or state. Give an expression for an
important consequence of this condition. (5 points each)
Example: Constant volume heating: δw = 0. Consequence: dU = δq.

Adiabatic expansion: ___δq = 0_______. Consequence: ____dU = δw__________.

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 Isothermal expansion: ____dU = 0______. Consequence: ___δq = -δw _________.

Chemical equilibrium: ___δw = 0_____. Consequence: ___dU = δq________.

8. Sketch a Lennard-Jones potential. Label the well-depth, equilibrium distance, and

zero of energy. Please label the axes. (5 points)

9. Write out the molecular partition function for the three level system shown below.

3ε/2

The molecular partition function q = __1 + 3e-βε + e-5βε/2 _________. (5 points)

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 What is the magnitude of the partition function at T = 0 K? (5 points)

q=1

What is the magnitude of the partition function at T = ∞ K? (5 points)

q=5

10. Give a general formula for the equilibrium temperature if two substances X and Y at
initial temperatures TX and TY are brought together and allowed to equilibrate. You
may assume that the system (consisting of X and Y) is insulated from the
surroundings. There are nX moles of X with heat capacity Cp,X and nY moles of Y
with heat capacity Cp,Y. (10 points)

δq X = – δq Y
n X C p,X dTX = –n YC p,YdTY
n X C p,X Teq – TX = –n YC p,Y Teq – TY
n X C p,X TX + n YC p,YTY
Teq =
n X C p,X + n YC p,Y

11. A. Given dU = TdS - PdV, please give an expression for dG.

dG = dH – TdS – SdT
= dU + PdV + VdP– TdS – SdT
= TdS – PdV + PdV + VdP– TdS – SdT
= – SdT + VdP

dG = ___-SdT +VdP___________________. (5 points)

B. Derive an expression for the Maxwell relation for the total derivative
dA = -SdT -PdV.

∂A = – S , ∂A =P
∂T V ∂V T

– ∂S = ∂P
∂V T ∂T V

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 The Maxwell relation is _______________________________. (5 points)

II. Problems (180 points total)

1. Calculate the entropy change of the system, the surroundings, and the total entropy
change for a monatomic ideal gas for a constant pressure expansion of 0.1 moles of gas
against 0.492 atm of pressure at 300 K from an initial volume of 2.0 L. (17 points)

V2 = nRT/P = (0.1 moles)(0.082 L-atm/mole-K)(300K)/0.492 atm) = 5.0 L

∆S = nR ln(V2 /V1 ) = (0.1 moles)(8.314 J/mole-K) ln(5.0/2.0) = 0.76 J/K for the system

∆S = -P∆V/T = -(0.492 atm)(5.0 L - 2.0 L)/300 K = -0.498 J/K for the surroundings

∆Ssys = ___0.76 ____________ J/K. ∆Ssurr = _____-0.498 ____________ J/K.

∆Stotal = _____+0.262 _________ J/K.

2. Given the following data at 35 o C determine the activity and activity coefficient for
acetone (A) and chloroform (C) at a mole fraction of xA = 0.60.
xC PC (torr) PA (torr)
0 0 347
0.2 35 270
0.4 82 142
0.6 142 102
0.8 219 37
1.0 293 0
The Henry's law constants are KH,A = 175 torr and KH,C = 165 torr.

Henry's law standard state

Henry's law standard state

aA = 142/175 = 0.811 γA = 0.860/0.60 = 1.35
aC = 82/165 = 0.497 γC = 0.468/0.4 = 1.24 (6 points)

Raoult's law standard state

aA = 142/347 = 0.409 γA = 0.409/0.6 = 0.681
aC = 82/293 = 0.297 γC = 0.297/0.4 = 0.7425 (6 points)

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Using the data above for 25 o C and a mole fraction xA = 0.6, calculate the free energy and
entropy of mixing for a one mole of a regular solution of acetone and chloroform using
the Raoult's law standard state activity. Compare the ideal free energy of mixing with
non- ideal free energy of mixing.
Ideal

Ideal
∆mix Gm = RT(xA lnxA + xC lnxC) = (8.314 J/mol-K)(298 K)(0.6ln0.6 + 0.4ln0.4)
= 2477.57(-0.3065 - 0.3665) = -1667.4 J/mole (4 points)

∆mix Sm = -R(xA lnxA + xC lnxC) = -8.314(-0.3065 - 0.3665) = +5.59 J/mole-K (4 points)

Non-ideal
∆mix Gm = -RT(xA lnaA + xC lnaC ) = (8.314 J/mol-K)(298 K)(0.6ln0.409 + 0.4ln0.279)
=2477.57(-0.5364 -0.4856) = -2532.0 J/mole (4 points)

∆mix Sm = same as ideal for a regular solution. (4 points)

3. A worker at the patent office opens a sealed envelope and reads a new patent
disclosure form. The patent describes an engine that can run at 99% efficiency. The
patent review scientist scribbles some numbers on a sheet of paper. Her calculation
assumes that the engine is an ideal reversible Carnot cycle. After completing the
calculation, she shakes her head, smiles, and stamps REJECT on the application.
A. Given that exhaust temperature of the engine must be approximately 300 K, what
is the thermodynamic temperature required for the expansion cycle of the engine?

η = (Thot - Tcold)/Thot => ηThot = (Thot - Tcold) => (1 - η)Thot = Tcold => Thot =
Tcold/(1 - η) = 300/(1-0.99) = 300/0.01 = 30,000 K!!!

Thot = ___30,000______ K. (5 points)

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 B. How much work would be derived for every kJ of heat expelled into the
environment by this engine?

|w| = ____0.99_________ kJ. (5 points)

4. At 90 o C, the vapor pressure of toluene is 400 torr and that of o-xylene is 150 torr.
What is the composition of the liquid when the liquid mixture boils at 90 o C with a
total vapor pressure of 340 torr in an enclosed container? What is the composition of
the vapor produced?

Ptol* = P1*= 400 torr , P xyl* = P 2* = 150 torr

If the vapor pressure at boiling is 240 torr then the mole fraction in the liquid
is:
Ptotal – P2* 340 – 150
x1 = * = = 0.76
P1 – P2* 400 – 150
Obviously, x2 = 1 - x1 = 0.63. Thus, the composition of the liquid is
determined. The composition of the vapor is given by Dalton's law.
P x P * (0.76)400 torr
y1 = 1 = 1 1 = = 0.894 , y2 = 0.106
Ptotal Ptotal 340 torr
Note that the more volatile component (toluene) has a larger mole fraction in
the vapor than it does in the liquid as out intuition suggests.

xtoluene = __0.76__________ xo-xylene = _____0.24______ (5 points)

ytoluene = _0.894__________ yo-xylene = ____0.106______ (5 points)

5. Nitrogen tetroxide, which is present in the equilibrium N2 O4 (g) ⇔ 2 NO2 (g), is

18.46 percent dissociated at 25 o C and 1.00 bar. Calculate (a) K, (b) ∆rGo , (c) ∆ rG for
the production of NO2 (g) at 1.00 bar from N2 O4 at 10.0 bar and 25 o C, (d) K at 100
o
C given that ∆rHo = + 57.2 kJ/mol over the temperature range (you may neglect the
temperature dependence of ∆rH and ∆rS over the temperature range).

Solution: Set up a table

N2O4 2 NO2 Total

Equilibrium Moles 1–x 2x 1+x
Equilibrium (1 – x)/(1 + x) 2x/(1 + x) 1

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Mole fraction

a. The equilibrium constant is:

2
2
2x 2
PNO2 1+x 4x 2 4(0.1846)
K= = = = = 0.1363
PN 2O4 1–x 1 – x 2 1 – (0.1846) 2
1+x
b. The standard free energy is:
∆Go = – RT ln K = – (8.31 J / mol – K)(298 K)ln 0.1363 = 4935 J /mol = 4.935 kJ/mol
c. The free energy for the condition where the N2 O4 partial pressure is 10 atm is:
∆G = ∆G o + RT ln Q = 4.935 kJ/mol + (8.31 J/mol–K)(298 K)ln (0.1) = – 767 J/mol
d. To obtain the free energy at 100 o C we first calculate the standard entropy change.
∆G o = ∆H o – T∆S o
∆S o = ∆H – ∆G = 57200 J/mol – 4935 J/mol = 175 J /mol–K
o o

T 298 K
Then substitute in the temperature:
∆G o = ∆H o – T∆S o = 59200 J /mol – (373 K)175 J /mol–K = – 6075 J /mol
= – 6.075 kJ/mol

6. An animal rights group protests against a circus act that involves a 500 kg. skating
gorilla. Their expert claims that the melting point of ice will drop below 240 K
underneath the mass of gorilla and this is unsafe. Given that the surface area of the
skates is 10-4 m2 calculate the melting point of ice underneath the skates. Is the
group's expert correct about the melting temperature of ice under the skating gorilla?

You may need the following data

∆fusV = -0.00168 L/mole ∆vap V = 24.4 L/mole
∆fusH = 6,000 J/mole ∆vap H = 40,650 J/mole
Tfus = 273.15 K Tvap = 373.15 K

P = (500 kg)(9.8 m/s2 )/10-4 m2 = 483.6 atm

∆P = P - P* = 483.6 atm - 1 atm = 482.6 atm
T = T* exp{∆P ∆V/∆H }
T = (273.15 K)exp{(482.6 atm)(-0.00168 L/mole)(101.325 J/L-atm)/6,000J/mole}
T = (273.15 K) (0.986) = 269.4 K

Temperature of fusion of ice under the gorilla = ______269.4 K_____. (15 points)

7. A column of air rises adiabatically up the side of Mt. Kilimanjaro. If the initial
temperature was 40 o C calculate the temperature at 6000 m assuming that the pressure
at that elevation is 0.5 atm and that air can be treated as a diatomic ideal gas.
(15 points)

Solution: Derivation of temperature/volume relationship for an adiabatic expansion.

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Adiabatic δq = 0
dU = δw
nCvdT = – PdV = –nRT dV
V
T2 V2

nCv dT = –nR dV
T1 T V1 V
T2 V
nCvln = –nRln 2
T1 V1

R 2
T2 V Cv V 5
= 1 = 1
T1 V2 V2
2
V 5
T2= T1 1
V2

_________________________________. (Partial Credit 8 points)

We have used the fact that Cv = 5/2R for a diatomic gs.Recall that P1 V1 γ = P2 V2 γ for an
adiabatic expansion, where γ = Cp /Cv is the heat capacity ratio. For a diatomic gas γ =
7/5. Thus,
2
P2 7
T2= T1
P1

_________________________________. (Partial Credit 13 points)

or in the present problem:
2

T2= (313 K) 0.5 atm = 256.8 K

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1 atm

Numerical answer: T = ___________________ K. (Full Credit)

8. Given the thermodynamic data below:

Compound ∆f Ho (kJ mol-1 ) So (J K-1 mol-1 ) Cp (J K-1 mol-1 )
Pb (s) 0 64.8 26.44
PbO (s, red) -218.99 66.5 45.81
PbO (s, yellow) -217.32 68.7 45.77
PbO2 -277.4 68.6 64.64
CO (g) -110.53 197.67 29.14
CO2 (g) -393.51 213.74 37.11

Calculate the standard Gibbs energy and the equilibrium constant at 400 K for the
reaction PbO(s, red) + CO (g) ¾ Pb (s) + CO2 (g).

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 ∆Go = ______________________. (15 points)

K = ________________________. (5 points)

9. The vapor pressure of a 500 g. sample of benzene was 400 torr at 60.6 o C, but it fell
to 386 torr when 19.0 g. of an involatile compound was dissolved in it. Treating
benzene as an ideal solvent, calculate the molar mass of the compound. (15 points)

Solution: Since benzene is an ideal solvent we can use Raoult’s law to calculate the mole
fraction of benzene in the solution.
P
x b = b* = 386 = 0.965
Pb 400
The mass fraction of the unknown is:
As = 19 = 0.0366
19 + 500
Using the relationship between mass fraction and mole fraction:
x sM s
As =
xs M s + xb M b
and solving for Ms we find:
A s xs M s + x bM b = xs M s
xs M s 1 – A s = xb M b
x bM b 0.965(78 g / mol)
Ms = = = 2232 g / mol
xs 1 – A s 0.035(1 – 0.0366)

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10. Calculate the temperature of boiling water in equilibrium with the liquid in a pressure
cooker at 10 atm. The boiling point of water is 373.15 K and the enthalpy of
vaporization is ∆vapHo = 40,650 J/mole. (15 points)

Solution: Use the Clausius-Clapeyron equation.

∆H 1 – 1 = ln P2
R T1 T2 P1
1 = 1 – R ln P2
T2 T1 ∆H P1
T1
T2 =
RT1 P
1– ln 2
∆H P1
The numerical answer is:
T2 = 373.15 K = 452.7 K
(8.31)(373.15) 10
1– ln
40650 1

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