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Chemistry I -- Final Exam

2012/1/13

Periodic Table of Elements

Constants
R = 8.314 J / mol K 1 atm = 760 Torr = 1.01x10
5
Pa
= 0.0821 L atm / K mol c = 2.9910
8
m/s
= 8.314 L kPa / K mol h = 6.6310
-34
Js
Mass of e , m
e
= 9.10939 10
-31
kg k = 1.3810
-23
J/K

2
1. (10%) If 2.00 mol of an idea gas at 300K and 3.00 atm expands from 6.00 L to
18.00 L and has a final pressure of 1.00 atm, isothermally and reversibly, calculate
the w, q and U?

2. Benzoic acid has a known internal energy of combustion (-3251 kJ/mol). When a
bomb calorimeter was calibrated by burning 0.825 g of benzoic acid (C
6
H
5
COOH)
in oxygen, the temperature rose 1.94 C. A 0.727 g sample of the sugar D-ribose
(C
5
H
10
O
5
) was then burned in excess oxygen in the same calorimeter, forming
gaseous CO
2
and liquid H
2
O. The temperature of the calorimeter rose from
21.81C to 22.72C.
(a) (5%) Write a balanced equation for the combustion.
(b) (5%) Calculate heat capacity of bomb calorimeter.
(c) (5%) Calculate the internal energy change, U, for the combustion of 1.00 mol
ribose molecules.

3. (5%) The standard molar heat of combustion of the isomers m-xylene and p-xylene
are -4553.9 kJ/mol and -4556.8 kJ/mol, respectively. Use the data, together with
Hesss Law, to calculate the value of H
r
for the isomerization reaction
m-xylene p-xylene.

4. (10%) An idea gas mixture consists of N and N
2
. At room temperature, only
translational and rotational motion contribute to heat capacity of the mixture, C
v
, is
found to be 9R (translation) and 4R (rotational), respectively. Find the mole
fraction of N
2
.

5. (10%) Given the following standard reaction enthalpies:
O
2
(g) 2O(g) H = +498.4 kJmol
1

NO(g) + O
3
(g) NO
2
(g) + O
2
(g) H = 200.0 kJmol
1

And the standard enthalpy of formation of ozone, +142.7 kJmol
1
, calculate the
standard reaction enthalpy for the reaction
NO(g) + O(g) NO
2
(g)

6. (8%) (a) Define statistical entropy and explain it; (b) Which would you expect to
have a higher molar entropy at 0 K, single crystals of BF
3
or of COF
2
? Why?
3

7. (8%) List the following substances in order of increasing molar entropy at 298 K:
H
2
O(l), H
2
O(g); H
2
O(s), C(s, diamond). Explain your reasoning.

8. (8%) Show that if two metal blocks with different temperatures, T
1
, T
2
and T
1
< T
2
,
are placed in contact, then the direction of spontaneous change is toward the
equalization of temperatures. Assume that the temperatures of the blocks remain
constant individually.

9. (10%) (a) Verify the Clausius inequality, S

. (b) Use the change in free

energy to explain how an endothermic reaction can be spontaneous.

10. (6%) Calculate the standard Gibbs free energy of formation of HI(g) at 25C.
Given: AH
f
(HI, g) = 26.48 kJ mol
-1
; S
m
(in J K
-1
mol
-1
): H
2
(g) = 130.7, I
2
(s) =
116.1, HI(g)= 206.6.

11. (10%) Show that the change in Gibbs free energy for a process is equal to the
maximum nonexpansion work that the system can do at constant temperature and
pressure, i.e. dG = d
,
or G =
,
.

4
1. isothermally T=0
U = C
v
T = C
v
0 = 0. (2%)
w = nRTln(v
f
/v
i
) = -28.314300ln(18/6) = 5480J = 5.48 kJ. (4%)
q =U-w = +5.48 kJ. (4%)
.
2. (a) (5%)
(b) benzoic acid ,

Heat released on combustion of 0.825g:

heat capacity of bomb calorimeter, C =

=
21.96
1.94
= 11.32
1

(5%)
(c) D-ribose, , molecular mass = 150.13 g mol
1

Bomb calorimeter is a fixed volume. AU = q + w = q
Heat released by reaction, q
(released)
= heat gained by calorimeter, q
(gained)

On combustion of 0.727g (or ) of D-ribose

Per mole of D-ribose,
(5%)
(l) 2 2(g) 2 5 10 5
O 5H 5CO 5O O H C + +
C
6
H
5
COOH
1
mol . g 12 . 122

0.825g
122.12 g. mol
1
= 6.755 10
3
mol
kJ 96 . 21
) mol . kJ 3251 )( mol 10 755 . 6 (
1 3
=
=

q
5 10 5
O H C

0.727 g
150.13 g. mol
1
= 4.842 10
3
mol
0 (gained) (released) = + q q
kJ 30 . 10
) C 81 . 21 C 72 . 22 )( C . kJ 32 . 11 (
1
) gained ( ) released (
=
=
A =
=

T C
q q
mol 10 842 . 4
3

kJ 30 . 10 ) released ( = = A q U
mol 10 842 . 4
kJ 30 . 10
3

= AU

= 2127.5 kJ. mol
1
5
3. m-xylene combustion products H
r
= -4553.9 kJ
+ combustion products p-xylene H
r
= +4556.8 kJ
=> m-xylene p-xylene H
r
= + 2.9 kJ

4. N is atom, C
v
= 3/2 R. (2%)
N
2
is diatomic molecule, C
v
= 5/2 R. (2%)
Assume x moles of N, y moles of N
2

Translational: 3/2 R (x+y) = 9R (2%)
Rotational: yR = 4R (2%)
y = 4, and x = 2
mole fraction of N = 1/3, mole fraction of N
2
= 2/3 (2%)

5. NO(g) + O
3
(g) NO
2
(g) + O
2
(g) H = 200.0 kJmol
1
(2%)
3/2 O
2
(g) O
3
(g) H = +142.7 kJmol
1
(2%)
O(g) O2

(g) H = - 249.2 kJmol
1
(2%)
NO(g) + O(g) NO
2
(g) H = -306.5 kJmol
1
(4%)
6. (a) S = k lnW, (2%)
k: Boltzmann constant (1%)
W 3 (2%)
W
W: the number of ways that the atoms or molecules in the sample can be
arranged and yet still give rise to the same total energy
W: the number of different microstates that correspond to the same energy
(b) COF
2
. (2%)
(2%)
COF
2
and BF
3
are both trigonal planar molecules, but it would be possible for
the molecule to be disordered with the fluorine and oxygen atoms occupying
the same locations. Because all the groups attached to boron are identical, such
disorder is not possible.
6
W(COF
2
)=3 and W(BF
3
)=1,
W(COF
2
) > W(BF
3
) COF
2
has a higher molar entropy.

7. C(s, diamond) < H
2
O(s) < H
2
O(l) < H
2
O(g) (4%)
It is easy to order
2
H O in its various phases because entropy will increase when
going from a solid to a liquid to a gas. (
H
2
O(s) < H
2
O(l) < H
2
O(g)) (2%)
(2%)
The main question concerns where to place C(s, diamond) in this order, and
that will essentially become a question of whether C(s, diamond) should have
more or less entropy than
2
H O(s) , because we would automatically expect
C(s, diamond) to have less entropy than any liquid. Because water is a
molecular substance held together in the solid phase by weak hydrogen bonds,
and in C(s, diamond) the carbon is more rigidly held in place and will have less
entropy.
DiamondCHO
W(H
2
O, solid) > W(C, diamond)

8.
Assume the transfer of energy as heat is reversible. The change in entropy for each
block (block 1 and block 2) are:
1 2
1 2
1 2
and
q q
S S
T T
A = A = (2%)
Energy is transferred, then the change in entropy for the system is:
2
2
1
1
2 1
T
q
T
q
S S S + = A + A = A (2%)

Only when energy is transferred from hot to cold block,
7
q
1
> 0, q
2
< 0 and q
1
= -q
2
, (2%)
AS = q
1
/T
1
q
1
/T
2
> 0, (2%)
the process is spontaneous.
Assume the transfer of energy as heat is reversible and the heat is assigned as q,
where q>0. If the energy is transferred from hot (T
2
) to cold block (T
1
), the
change in entropy for each block (block 1 and block 2) are:

1
=

(4%)
Then, the change in entropy for the total system is:
|
|
.
|

\
|
= +
+
= A + A = A
2 1
1 2
2 1
2 1
-
S S S
T T
T T
q
T
q
T
q
(2%)

T
2
> T
1
and q>0

|
|
.
|

\
|
= A
2 1
1 2
S
T T
T T
q > 0, (2%)
The process for the energy transferred from hot (T
2
) to cold block (T
1
) is
spontaneous.

9. (a) (5%) Clausius inequality AS > q/T. For reversible processes, AS = q/T. For
irreversible processes, q
rev
> q
irrev
. AS = q
rev
/T > q
irrev
/T.
(b) (5%) If
r
AG < 0, (
r
AG is negative); the process is spontaneous.
A = A A
r r r
G H T S If a reaction is endothermic
r
AH is positive, then the
reaction will be spontaneous only if A
r
T S is larger than
r
AH . So, effectively, a
reaction that is endothermic can be spontaneous only if the entropy change in the
system outweighs the enthalpy changes effect on the entropy of the surroundings.

10. H
2
(g) + I
2
(s) HI(g)
AH = 1 mol AH
f
(HI, g) = 1 mol (+26.48) kJ mol
-1
; = +26.48 kJ (2%)
AS = S
m
(HI, g) {0.5 S
m
(H
2
, g) +0.5 S
m
(I
2
, s)}
8
= 1 mol 206.6 J K
-1
mol
-1
{ 0.5 mol 130.7 + 0.5 mol 116.1} J K
-1
mol
-1

= +83.2 J K
-1
. (2%)
AG = AH -TAS = 26.48+298*83.2/1000 = +51.27 kJ (2%)

11.
w
rev,e
w
rev,non
(nonnon-expansion work)
d
therefore do, can system at the on work th nonexpansi maximun the is Because
(1%)
into and Insert
(1%)
(1%)
(1%)
process reverdible a For
(1%)
(2%) pressure and emperature constant t at
(1%) pressure constant at
(1%) emperature constant t at
e
e
e
e expansion
rev,e
rev
rev
rev
rev rev rev
rev
dw
dw dG
TdS PdV dw PdV TdS dG
dG dw dq
dw PdV dw
dw dw dw dw
TdS dq dq
TdS PdV dw dq dG
TdS PdV dU dG
PdV dU dH
TdS dH dG

=
+ + =
+ =
+ = =
= =
+ + =
+ =
+ =
=
dG = dw
e, max
at constant T and P (1%)