Advanced Physical Chemistry

Problem Set 7
Due Wednesday, November 18, 2021
Name:
Fay Dosunmu
1. (10 points) The half-life for the first-order radioactive decay of 14C is 5730 years (it emits ß-rays with
an energy of 0.16 MeV). An archeological sample contained wood that had only 72% of the 14C found in
living trees. What is its age?

2. (20 points) The rate constant for the first-order decomposition of N2O5 in the reaction 2N2O5 -> 4NO2
+ O2 is k = 3.38 x 10-5 s-1 at 25 C.

(a) What is the half-life of N2O5?

(b) What will be the partial pressure of N2O5, initially 500 Torr, (a) 100 s, (b) 100 min after the initiation
of the reaction?

(3) (10 points) The composition of a liquid-phase reaction 2A -> B was followed spectroscopically with
the following results:

t (min) 0 10 20 30 40 infinity
[B] (M) 0 0.089 0.153 0.200 0.230 0.312

Determine the order of the reaction and its rate constant.

(4) (10 points) The enzyme-catalyzed conversion of a substrate at 25 C has a Michaelis constant of 0.035
M. The rate of the reaction is 1.15 x 10-3 M/s when the substrate concentration is 0.110 M. What is the
maximum velocity?

(5) (20 points) The condensation reaction of acetone (CH3)2CO (denoted AH) in aqueous solution is
catalyzed by base B, which react reversibly to form the carbanion A -. The carbanion then reacts with a
molecule of A to give the product P. A simplified mechanism is given by:

AH + B -> BH+ + A-
A- + BH+ -> AH + B
A- + AH -> P

(a) Use the steady-state approximation to find an expression for the concentration of A-.

(b) Derive the rate equation for the concentration of the product.

(6) (30 points) The reaction Cl2 + CO -> COCl2 is believed to proceed by the following mechanism:

Cl2 <-> 2Cl k1 (forward), k-1 (reverse)

half life =
5730 yrs

in
1¥.ee
-
-

0-693
K =

-5730
=
1.209 > 10-4 yrs -1

[ C) o
e
100

[ C]
= 23

In [ C) =
In [C) k +
-

In 123)
=
In 11001 - (1.209×10^4) t

t
12,152 yrs
=
2.
first order

(a)
1h12 )

£1,2
=

is

t ,, =
in
,
3- 38 7) 0-5

=
507 313s =
20 ,
-

5. 696 hrs

(b)
Pin , he 1
=
500 torr

PV =
n RT

Cimini %
=
¥-1 =

o¥Y! 298
= 0 - 02688
In C C f. )
= In lcimhell -
k 't
no ,

In ( Cfme , ) In 10-02688 )
-
=

13-38>10-5 ) Nov)

C f. not =
0.02678M

P final
=

cf.n.FR -1 =

• 298
0.02678*62-4
=

498.152 torr
b)

In ( China ) =
In 10.026882 -

15.38>10-5/1100×6)

( final =
0.021946 M

*
RT
lf.no,
e

Pfnol
=

0.021946*62-40298
= 408.482 torr
3.
data and
use the
following
plot it on a spreadsheet
CAT
Kt = -
in 1 I
↳ , f- first order
,

linear At
-1
-1
[ AT CA ] ,
-

Kt =

order,
↳ if second

I > near ft
we see
by excusing graph
first order
it is
0 033612×1
0018955
-

+
111 =
0 .
i. thus the stupe is

V. 03361

but since this is 9

2A → p reaehnn

rate =

-1,2%1,3 = KCA ]

In [ A]
-2kt
2

If
-1
2K = 0.0336 man

keo.co/68min-#
4.
Vo
= Vm]
kmtcs ]

km __ 0-035

V0
= 1.15>10-3
[ ST = 0.110

Vmex ?
-110
Vme > do
1. 15×10-3 =

T.E.nu

Vmax =
1.52×10-3 Mls
5.

steady state approximation for A- :

AHTCBT.kz
=0 =
K, [

[A T [ 131T£ ]
-

Ks [ A- T.CH ]
-
A

[ Tss k , CAH ] (B)

A =

k CHA]
Kz [ Bitt ] t
z

d¥dYtJ= kiksCAB]
kz [ BHT ] t ks CHA ]
6.
overall rate low

Rate =kzEcoc1][ Cle ]

Ss anpnx for intermediate

[ cool] :

d[÷?=o=kzauTEc1 ]
-
k -
z[ ( Oct ]
-
Kz [ fuel ] ( Cle]

k< [ co ][ CI ]
[ ( UC] =

k z
- t K3[Ck ]
S S
- . approximation for cel ]

OCCI]
= 0 =
Ki [ Cle ] -

Ky Ccl ]2
Jf
-
kz [ CO ][ a ]
1- K -
z [ ( VCI] t

ks cruel ][ C) z]

'
K , [ Clz ] - k -
,
CCI ] - 0

¥ Cais )
"
[ a] '

=/ ,

overall role :

" "
rate = Ks
/¥ / , 4¥ ,,,
Cascais
graph :

last stop 's RDS so

activation energy
highest

.¥Ñ
C- > Ea Eez
-
-

as ,

A
Fcz

:| steal
progress
step 2

of
reaction
step]

nxn :

cuurdinele