Problem Set #10

Assigned November 8, 2013 Due Friday, November 15, 2013

Please show all work for credit

To Hand in

1.

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 2.

A least squares fit of ln P versus 1/T gives the result H vaporization = 25.28 kJ mol1.

3.

Assuming constant pressure and temperature, and that the surface area of the protein is
reduced by 25% due to the hydrophobic interaction:
G 0.25 N A 4 r 2 Convert to per mole, determine size per molecule
4 3
r V2 M 2 N A 0.73mL / g 60000 g / mol (6.02 10 23 )
3
r 2.52 10 9 m
G 0.25 N A 4 r 2 0.0720 N / m 0.25 6.02 10 23 / mol ( 4 ) ( 2.52 10 9 m) 2 865kJ / mol

We think this is a reasonable approach, but the value seems high

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 4. The vapor pressure of an unknown solid is approximately given by ln(P/Torr) = 22.413
2035(K/T), and the vapor pressure of the liquid phase of the same substance is
approximately given by ln(P/Torr) = 18.352 1736(K/T).
a. Calculate Hvaporization and Hsublimation.
b. Calculate Hfusion.
c. Calculate the triple point temperature and pressure.
a) Calculate H vaporization and H sublimation .

From Equation (8.16)

d ln P H sublimation

dT RT 2
d ln P d ln P dT d ln P H sublimation
T 2

1 dT
1 dT R
d d
T T
For this specific case
H sublimation
2035 H sublimation 16.92 103 J mol 1
R
Following the same proedure as above,
H vaporization
1736 H vaporization 14.43 103 J mol 1
R

b. Calculate H fusion .

H fusion H sublimation H vaporization

16.92 103 J mol 1 14.43 103 J mol 1
2.49 103 J mol 1

c. Calculate the triple point temperature and pressure. At the triple point, the vapor pressures
of the solid and liquid are equal. Therefore,
K K
22.413 2035 18.352 1736
Ttp Ttp
K
4.061 299
Ttp
Ttp 73.62 K
Ptp 2035
ln 22.413 5.22895
Torr 73.62
Ptp 5.36 103 Torr

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 5. The UV absorbance of a solution of a double-stranded DNA is monitored at 260 nm as a
function of temperature. Data appear in the following table. From the data determine
the melting temperature.
Temperature (K) 343 348 353 355 357 359 361 365 370
Absorbance (260 nm) 0.30 0.35 0.50 0.75 1.22 1.40 1.43 1.45 1.47

Plotting the relative absorbance versus temperature yields:

1.6
1.4
Relative Absorbance

1.2
1.0

0.8
0.6
0.4
Tm 355.9C
0.2
0.0
340 350 360 370
T [degree Celsius]

The plot indicates a melting temperature of approximately 355.9C.

6. For the formation of a self-complementary duplex DNA from single strands H = 177.2 kJ
mol1, and Tm = 311 K for strand concentrations of 1.00 104M. Calculate the equilibrium
constant and Gibbs energy change for duplex formation at T = 335 K. Assume the enthalpy
change for duplex formation is constant between T = 311 K and T = 335 K.

first calculate equilibrium constant at 311 K, the melting

temperature, where f = 0.5: 4
( )
f
K , K311 K 0.5
10000
2 1 - 0.5 1.0 10-4 M
4
2(1 - f) 2 C 2 2 ( )
Then we can calculate the equilibrium constant at 335 K:
K H 1 1 ,
ln 2
,

K1 R T2 T1

( 4 )
( ) ( )
5
( )

And finally we can calculate the Gibbs energy at 335 K:

( ) ( ( )

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 7. At 47C, the vapor pressure of ethyl bromide is 10.0Torr and that of ethyl chloride is 40.0
Torr. Assume that the solution is ideal. Assume there is only a trace of liquid present and
the mole fraction of ethyl chloride in the vapor is 0.80 and then answer these questions:
a. What is the total pressure and the mole fraction of ethyl chloride in the liquid?
b. If there are 5.00 mol of liquid and 3.00 mol of vapor present at the same pressure as in
part (a), what is the overall composition of the system?
(a) what is the overall composition of the system?

( )

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b) We use the lever rule.
tot
nliq Z B xB nvap
tot
yB Z B
Z B xB 1 Z A 1 x A x A Z A
yB zB 1 y A 1 z A Z A y A

Therefore,

yEC Z EC 5
tot
nliq

ntot
vap Z EC xEC 3

we know that xEC = 0.50 and yEC = 0.80

5
0.80 Z EC Z EC 0.50
3
Z EC 0.613
Z EB 1 Z EC 0.387

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8. 1.053 g of beef heart myoglobin dissolved in 50.0 ml of water at T = 298 K generates sufficient
osmotic pressure to support a column of solution of height d. If the molar mass of
myoglobin is 16.9 kg per mole, calculate d.
We set the osmotic pressure equal to the pressure of the column:
n RT
solutes gh
V
We can now solve for the height, h:
msolutes RT
n solutes RT M solutes
h
V g V g
1.053 g

-1 8.314472 J K mol-1 298 K
16900 g mol
0.315 m
0.00005 m3 1000 kg m-3 9.81 m s-2

9. Calculate the change in the freezing point of water if 0.0053 g of a protein with molecular
weight 10083 g mol1 is dissolved in 100. mL of water.

Tf K f msolute K f
m protein / M protein
1860 K g mol-1
0.0053 g / 10083 g mol
-1

msolute 100 g
9.78 106 K

10.

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11.

12.

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13.

( ) (2 )
( )

2

Assume we have 5g cholesterol dissolved in 95g Dipalmitoyl phosphatidylcholine.

( )

(2 2 ) 2 ( 22 )

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Extra practice for exam, do not hand in

Phase equilibrium

1. Use the vapor pressures for C2N2 given in the following table to estimate the
temperature and pressure of the triple point and also the enthalpies of fusion,
vaporization, and sublimation.
Phase T (C) P (Torr)
Solid 62.7 40.0
Solid 51.8 100.
Liquid 33.0 400.
Liquid 21.0 760.
P 100 Torr
R ln 2 8.314 J mol 1 K 1 ln
P1 40.0 Torr
H sublimation 32.6 kJ mol 1
1 1 1 1

T T
210.5 K 221.4 K

1 2

760 Torr
8.314 J mol 1 K 1 ln
400 Torr
H vaporization 26.9 kJ mol 1
1 1

240.2 K 252.2 K
H fusion 32.6 26.9 kJ mol 1 5.6 kJ mol 1

To calculate the triple point temperature, take

Tsolid ,ref 221.4 K Psolid ,ref 100 Torr

Tliquid ,ref 240.2 K Pliquid ,ref 400 Torr

1 1 32.6 103 J mol 1 26.9 103 J mol 1

Ttp 32.6 26.9 103 J mol-1 221.4 K 240.2 K
100 Torr
+ 8.314 J mol 1 K 1 ln
400 Torr
1
0.00416 K 1 , Ttp 240.3 K
Ttp
32.6 103 J mol 1 1 1
Ptp 100 Torr exp 402 Torr
1
8.314 J mol K
1
221.4 K 240.3 K

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 2. Use the vapor pressures of Cl2 given in the following table to calculate the enthalpy of
vaporization using a graphical method or a least-squares fitting routine.
T (K) P (atm) T (K) P (atm)
227.6 0.585 283.15 4.934
238.7 0.982 294.3 6.807
249.8 1.566 305.4 9.173
260.9 2.388 316.5 12.105
272.0 3.483 327.6 15.676

A least squares fit of ln P versus 1/T gives the result H vaporization = 20.32 kJ mol1.

3. It has been suggested that the surface melting of ice plays a role in enabling speed
skaters to achieve peak performance. Carry out the following calculation to test this
Hfusion = 6010 J mol1, the density
of ice is 920 kg m3, and the density of liquid water is 997 kg m3.
a. What pressure is required to lower the melting temperature by 5.0C?
b. Assume that the width of the skate in contact with the ice has been reduced by
sharpening to 25 103 cm, and that the length of the contact area is 15 cm. If a skater of
mass 85 kg is balanced on one skate, what pressure is exerted at the interface of the skate
and the ice?

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 c. What is the melting point of ice under this pressure?
d. If the temperature of the ice is 5.0C, do you expect melting of the ice at the iceskate
interface to occur?
a)

dP Smfusion Smfusion 22.0 J mol 1K 1

dT fusion Vm
fusion
M

M 18.02 10 3 kg 18.02 103 kg

H O ,l
2
H O ,l
2
997 kg m 3 920 kg m 3
1.44 10 Pa K 144 bar K
7 1 1

The pressure must be increased by 720 bar to lower the melting point by 5.0C.

F 85 kg 9.81 ms 2
b) P = 2.2 107 Pa = 2.2 102 bar
A 15 10 m 25 10 m
2 5

dT 1C
c) T P 2.20 102 bar 1.5 C ; Tm = 1.5C
dP fusion 144 bar

d) No, because the lowering of the melting temperature is less than the temperature of the ice.

4. Consider the transition between two forms of solid tin, Sn(s, gray) Sn(s, white).
The two phases are in equilibrium at 1 bar and 18C. The densities for gray and white tin
are 5750 and 7280 kg m3 Htransition = 8.8 J K1 mol1. Calculate the
temperature at which the two phases are in equilibrium at 200 bar.
In going from 1 atm, 18 C to 200 atm, and the unknown temperature T
G gray Vmgray P S gray T
G white Vmwhite P S white T
At equilibrium
G gray G white 0 Vmgray Vmwhite P S gray S white T
1 1
M Sn P
T
V m V
gray
m
white
P


gray white
S gray S white Stransition
1 1
118.71 103 kg mol 1 3
3
199 x105 Pa
5750 kg m 7280 kg m 9.8 C
8.8 J K 1mol 1
T f 8.2 C

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5. A protein has a melting temperature of Tm = 335 K. At T = 315 K, UV absorbance
determines that the fraction of native protein is fN = 0.965. At T = 345. K, fN = 0.015.
Assuming a two-state model and assuming also that the enthalpy is constant between T
= 315 and 345 K, determine the enthalpy of denaturation. Also, determine the entropy
of denaturation at T = 335 K. By DSC, the enthalpy of denaturation was determined to
be 251 kJ mol1. Is this denaturation accurately described by the two-state model?
We first calculate the equilibrium constants at 315 K and 345 K:

f D 1 - f N 1 - 0.965
K315 K 0.036
fN fN 0.965

f D 1 - f N 1 - 0.015
K345 K 65.67
fN fN 0.015

K 345 K 65.67
ln R ln 8.314472 J mol K
-1 -1

K 315 K 0.036
H 226.2 kJ mol-1
1 1 1 1

T2 T1 345 K 315 K

This result deviates from the DSC result, indicating that the denaturation process is not

accurately described by a two-state model.

6. Suppose a DNA duplex is not self-complementary in the sense that the two
polynucleotide strands composing the double helix are not identical. Call these strands
A and B. Call the duplex AB. Consider the association equilibrium of A and B to form
duplex AB

Assume the total strand concentration is C and, initially, A and B have equal concentrations;
that is, CA,0 = CB,0 = C/2. Obtain an expression for the equilibrium constant at a point where
the fraction of the total strand concentration C that is duplex is defined as f. If the strand
concentration is 1.00 104 M, calculate the equilibrium constant at the melting
temperature.

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We make the table of concentrations:
Cinitial Cequilibrium
AB 0 fC
A=B C/2 C/2 2f C
The equilibrium constant at the melting temperature with f = 0.5 is given by:
C AB fC 2
K 2

CACB C C
2 f C
2
And for C = 1.00 104 M:
2 2
K 20000

C 1 10 4 M
Ideal and Real Solutions
1. Predict the ideal solubility of lead in bismuth at 280C given that its melting point is
327C and its enthalpy of fusion is 5.2 kJ mol1.

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2. The vapour pressure of 2-propanol is 50.00 kPa at 338.8C, but it fell to 49.62 kPa when
8.69 g of an involatile organic compound was dissolved in 250 g of 2-propanol. Calculate
the molar mass of the compound.

3. The addition of 5.00 g of a compound to 250 g of naphthalene lowered the freezing

point of the solvent by 0.780 K. Calculate the molar mass of the compound.

4. The osmotic pressure of an aqueous solution at 288 K is 99.0 kPa. Calculate the freezing
point of the solution.

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5. The molar mass of an enzyme was determined by dissolving it in water, measuring the
osmotic pressure at 20C, and extrapolating the data to zero concentration. The
following data were obtained:

c/(mg cm3) 3.221 4.618 5.112 6.722

h/cm 5.746 8.238 9.119 11.990

Calculate the molar mass of the enzyme.

6. a

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7. a

16
8. a

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9. A and B form an ideal solution. At a total pressure of 0.900 bar, yA = 0.450 and xA =
0.650. Using this information, calculate the vapor pressure of pure A and of pure B.

Ptotal x A Pa* yB Ptotal

Ptotal yB Ptotal 0.900 barx 1 0.550
Pa* 0.623 bar
xA 0.650
y A PB*
xA
Pa* PB* PA* y A
0.450 PB*
0.650
PA* 0.450 PB* PA*
PB* 0.650 1 0.450
2.27
PA* 0.450 1 0.650
PB* 1.414 bar

10. The heat of fusion of water is 6.008 103 J mol1 at its normal melting point of 273.15 K.
Calculate the freezing point depression constant Kf.

8.314 J mol 1K 1 18.02 103 kg mol 1 273.15 K

2 2
RM solventT fusion
Kf
H fusion 6.008 103J mol 1
K f 1.86 K kg mol 1

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12.

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