Spring 2008

INSTRUCTIONS:

1.

Chemistry 2000 Practice Test #2

____/ 45 marks

1) You should have 5 pages of questions and two pages of

data/formulas/periodic table.
2) If your work is not legible, it will be given a mark of zero.
3) Marks will be deducted for improper use of significant figures and for
missing or incorrect units.
4) Show your work for all calculations.
Answers without supporting
calculations will not be given full credit.
5) You may use a calculator.
6) You have 90 minutes to complete this test.

Carbon disulfide is a liquid at room temperature while carbon dioxide is a gas. What is the
most important cause of this difference?
[3 marks]

..
O
..

..

O
..

..
S
..

..
S
..

Both carbon dioxide and carbon disulfide are nonpolar molecules (linear and symmetric). As
such, the only intermolecular forces they experience are induced dipole-induced dipole forces.
Because sulfur is a larger atom than oxygen (and therefore CS2 is a larger molecule than CO2),
CS2 is more polarizable than CO2. This means that the induced dipoles for CS2 are larger and
therefore the induced dipole-induced dipole forces are stronger.
2.
(a)

(b)

BF3 and NH3 are both gases at room temperature.

[5 marks]
Which gas will have a higher root mean square speed at room temperature? Justify your
answer.
NH3 (M = 17.0304 g/mol) has a smaller molar mass than BF3 (M = 67.806 g/mol). Since root
mean square speed is inversely proportional to molar mass, NH3 will have molecules with a
higher root mean square speed.
Which gas will condense at a higher temperature? (assume equal pressures) Justify your
answer.
.. ..F ..
..
N
H
H
B ..
..
H
..F
.
..
..F .
A gas will condense at the corresponding liquids boiling point. Since NH3 is a polar molecule,
the strongest intermolecular forces in a sample of liquid NH3 will be dipole-dipole attractions.
Since BF3 is a nonpolar molecule, the strongest intermolecular forces in a sample of liquid BF3
will be induced dipole-induced dipole forces (aka London dispersion forces). Since dipoledipole forces are generally stronger than induced dipole-induced dipole forces, NH3 will have a
higher boiling point than BF3. Therefore, NH3 gas will condense at a higher temperature than
BF3 gas.

FYI (NOT expected in answer) At 1 atm, NH3 condenses at -33 C while BF3 condenses at -100 C.

3.

Benzene (C6H6) has an enthalpy of vaporization of 30.7 kJ/mol and a normal boiling point of
80.10 C. The receiving flask of a typical vacuum filtration is at a pressure of 0.025 bar at room
temperature. Will benzene boil under these conditions? Justify your answer by calculating the
boiling point of benzene at 0.025 bar.
[10 marks]
Yes, benzene will boil under these conditions. Its boiling point at 0.025 bar is -12 C, well
below room temperature:
C6H6(l)

aC6H6 ( g ) =

aC6H6 ( l ) = 1

K=

aC6H 6 ( g )
aC6H 6 ( l )

C6H6(g)

PC6H6
P

PC6H 6 / 1 bar
1

rH = 30.7 kJ/mol
rH = 3.07 104 J/mol

PC6H6
1 bar

PC6H 6
1 bar

Since the normal boiling point of benzene is 80.10 C (T1 = 80.10 C = 353.25 K), the vapour
pressure at that temperature is 1 atm = 1.01325 bar. Thus, K1 = 1.01325.
We want to know at what temperature the vapour pressure of benzene is 0.025 bar.
i.e. What is T2 for K2 = 0.025?
K H 1 1

ln 2 = r
R T1 T2
K1
J
0.025
mol
ln
=
1.01325 8.3145 J
mol K
3.07 10 4

1
1

353.25K T2

8.3145

1
1
0.025
mol K

= ln

353.25K T2
1.01325 3.07 10 4 J

mol

8.3145

1
1
0.025
mol K
=
ln

T2 353.25K
1.01325 3.07 10 4 J

mol

1
1
= 0.00383
T2
K
T2 = 261K = 12C

4.
(a)

(b)
(c)

[5 marks]
Explain what is meant by the term supercritical fluid. How/when is one formed?
A supercritical fluid is formed when the temperature and pressure both exceed a substances
critical point. It has the density of a liquid (due to the high pressure) but the high-energy
particles of a gas (due to the high temperature).
Sketch a phase diagram and clearly label the region where a supercritical fluid is found. Make
sure to label the axes on your sketch.
Label the triple point and the critical point on your phase diagram.

supercritical fluid

critical point
Pressure

solid

liquid
gas

triple point
Temperature

5.
(a)
(b)

Carbonic acid (H2CO3) is a diprotic acid.

[12 marks]
Calculate the Ka for dissociation of the first proton of H2CO3(aq) at 25.00 C.
Would the strength of this acid increase or decrease with temperature? Explain briefly.

(a)

H2CO3(aq)

r G = f G H

+
( aq )

H+(aq)

) + G(HCO

3 ( aq )

HCO3-(aq)

) G(H CO
2

3 ( aq )

K = Ka =

aH + aHCO
( aq )

3 ( aq )

aH2CO3 ( aq )

kJ
kJ
kJ
r G = 0
+ 586.8
623.1

mol
mol
mol
kJ
r G = 36.3
mol

r G = RT ln K
kJ
mol
kJ

8.314510 3
(298.15 K )
mol

36.3

Ka = e
(b)

r G
RT

=e

= 4.37 10 7

r H = f H H (+aq ) + f H HCO3( aq ) f H H 2CO3( aq )

kJ
kJ
kJ
r H = 0

699.7
+ 689.9
mol
mol
mol
kJ
r H = 9 .8
mol
Since rH > 0, this reaction is endothermic, so increasing the temperature will favour the
forward reaction. This corresponds to an increase in the equilibrium constant (Ka) and a
strengthening of the acid (since more H+ is present at equilibrium).
This can be demonstrated mathematically:
K H 1 1

ln 2 = r
R T1 T2
K1
K2
=e
K1

r H 1 1

R T1 T2

K 2 = K 1e

r H 1 1

R T1 T2

Let us define T1 as 298.15 K. This makes K1 equal to the Ka for carbonic acid at 25.00 C.
If T2 > T1 then T1-1 T2-1 > 0.
If T1-1 T2-1 > 0 and rH > 0 then rH(T1-1 T2-1)/R > 0.
The exponential of any positive number is greater than one, so K2 > K1.
If K2 > K1 then acid 2 is stronger than acid 1. Here, acid 2 is carbonic acid at higher
temperature while acid 1 is carbonic acid at 25.00 C.

6.

(a)

(b)

(c)

You wish to prepare oxygen difluoride (a gas). You are considering two methods for
preparation of oxygen difluoride:
Reaction of molecular oxygen with molecular fluorine (Method A)
Reaction of molecular oxygen with atomic fluorine (Method B)
Due to equipment limitations, you must perform your reaction under standard conditions.
[10 marks]
Write a balanced reaction equation for each method.
Method A
O2(g) + F2(g) OF2(g)
Method B
O2(g) + 2 F(g) OF2(g)
For each method, indicate whether you would expect the reaction to have a positive or negative
entropy change. Justify your answers.
I would expect both reactions to have negative entropy changes. In Method A, 1.5 moles of gas
react to form 1 mole of gas. In Method B, 2.5 moles of gas react to form 1 mole of gas. Since
gases have large entropy values, reactions which have more moles of gaseous reactants than
gaseous products generally have negative entropy changes.
For each method, indicate whether or not the reaction will be spontaneous under standard
conditions.
Method A

r G = f G(OF2( g ) ) = 41.9

kJ
mol

This reaction has a positive standard molar free energy change, so it is not spontaneous under
standard conditions.
Method B

r G = f G(OF2( g ) ) f G(O2( g ) ) + 2 f G(F( g ) )

2

kJ 1 kJ
kJ

r G = 41.9
0
+ 2 61.91

mol 2 mol
mol

r G = 81.9

kJ
mol

This reaction has a negative standard molar free energy change, so it is spontaneous under
standard conditions.