CINÉTICA METALÚRGICA Y DISEÑO DE

REACTORES -- MET-332
Martes14:00 - 15:30 (P-212)
Miércoles 09:45 -11:15 (LPRO) Lab/Ay/Rec
Jueves 09:45 -11:15 (P-208)

Marco A Vera
marco.verar@usm.cl

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2
Calculate half-life for first-order reaction if 68% of a substance is
reacted within 66 s.

Solution:

1) 68% reacted means 32% remains:

ln A = -kt + ln Ao
ln 0.32 = - k (66 s) + ln 1

k = 0.0172642 s-1

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2) for the half-life:

ln 0.5 = - (0.0172642 s-1) (t) + ln 1

t = 40. s

or:

t1/2 = (ln 2) / k
t1/2 = (ln 2) / 0.0172642 s-1

t1/2 = 40. s

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A certain first order reaction is 45.0% complete in 65 s. Determine the
rate constant and the half-life for this process.
Solution:
1) Integrated form of first-order rate law:

ln A = -kt + ln Ao
2) 45% complete means 55% remains:

ln 0.55 = - k (65 s) + ln 1
k = 0.0091975 s-1 (I kept a few guard digits for the next calculation.)

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3) for the half-life:

ln 0.5 = - (0.0091975 s-1) (t) + ln 1

t = 75.4 s

You can alse use this:

t1/2 = (ln 2) / k
to calculate the half-life.

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A certain reaction is first order, and 540 seconds after initiation of the
reaction, 32.5% of the reactant remains. What is the rate constant for
this reaction? At what time after initiation of the reaction of the
reaction will 10.0% of the reactant remain?

Solution:

1) Integrated form of first-order rate law:

ln A = -kt + ln Ao
ln 0.325 = - (k) (540. s) + ln 1.00

k = 0.002081352 s-1
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k = 0.00208 s-1.

Note that the problem specified the amount remaining, not the
amount decomposed.

2) Integrated form of first-order rate law:

ln A = -kt + ln Ao
ln 0.100 = - (0.002081352 s-1) (t) + ln 1.00

t = 1106 s

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A reaction of the form

a A  Product

ln[A]
Slope

Time (s)

gives a plot of ln[A] vs time in seconds which is a straight line with a

slope of -7.35 x10-3. Assuming 0.0100 M, calculate the time in
seconds required for the reaction to reach 80.5 percent completion.
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Solution:

80.5% complete means 19.5% remaining. 19.5% of 0.0100 M equals 0.00195 M

ln A = -kt + ln Ao

ln 0.00195 = - (7.35 x10-3) (t) + ln 0.01

-6.24 = - (7.35 x10-3) (t) + (-4.6052)

1.6348 = (7.35 x10-3) (t)

t = 222.42 s

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The reactant concentration in a first-order reaction was 7.30 x 10-2 M after 45.0 s
and 8.70 x 10-3 M after 65.0 s . What is the rate constant for this reaction?

Solution:

Set the first concentration to be Ao and the second to be A. The time will be 20.
seconds.

ln A = -kt + ln Ao
ln 8.70 x 10-3 = - (k) (20. s) + ln 7.30 x 10-2

-4.74443 = - (k) (20. s) + (-2.61730)

2.12713 = (k) (20. s)

k = 0.106 s-1
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A certain first-order reaction is 75% complete in 69.8 min. What is its rate constant
in s-1?

Solution:

75% complete means 25% of A remains.

ln A = -kt + ln Ao

ln 0.25 = - (k) (517.5 s-1) + ln 1

k = 2.68 x 10-3 s-1

517.5 comes from 69.8 min times 60 sec / min.

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The decomposition of aqueous hydrogen peroxide to gaseous oxygen and water is a
first-order reaction. If it takes 6.5 hours for the concentration of H2O2 to decrease
from 0.70 to 0.35, how many hours are required for the concentration to decrease
from 0.40 to 0.10 ?

Solution:
1) Find the rate constant:

ln A = -kt + ln Ao
ln 0.35 = - (k) (6.5 hr) + ln 0.70

-1.0498 = - (k) (6.5 hr) - 0.356675

-0.693125 = - k (6.5 hr)

k = 0.1066346 hr-1
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2) Solve for time:

ln A = -kt + ln Ao
ln 0.10 = - (0.1066346 hr-1) (t) + ln 0.40

-2.3026 = - (0.1066346 hr-1) (t) - 0.9163

-1.3863 = - (0.1066346 hr-1) (t)

t = 13 hr

Solution (specific to this problem):

0.70 to 0.35 is one half-life and 0.40 to 0.10 is two half-lives. Since one half-life
equals 6.5 hrs, two half-lives would take 13.0 hrs.
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The half-life for a first-order reaction is 32.0 s. What was the original concentration
if, after 2.00 minutes, the reactant concentration is 0.062 M?
Solution:
1) Find k:

k = (ln 2) / 32.0 s = 0.021661 s-1

2) Find Ao:

ln A = -kt + ln Ao
ln 0.062 = - (0.021661 s-1) (120. s) + ln Ao

-2.78062 = -2.59932 + ln Ao

ln Ao = -0.1813

Ao = 0.834 M 15
El pentoxido de nitrogeno (N2O5) se
descompone en dioxido de nitrogeno
(NO2) y oxigeno molecular (O2) a 3
relativamente baja temperature de Tiempo (s) · 10 [N2O5] (M)
0.0 0.0365
acuerdo a la siguiente reacción:
0.6 0.0274
1.2 0.0206
2N2O5(soln)  4NO2(soln) + O2(g) 1.8 0.0157
2.4 0.0117
3.0 0.0086
Esta reacción se lleva a cabo en una
3.6 0.0064
solución de de cloroformo (C Cl4) a
45°C.
La concentración de N2O5 en
function del tiempo se presenta en
la siguiente tabla: 16
Graficar:

• [N2O5] versus tiempo

• ln[N2O5] versus tiempo
• 1/[N2O5] versus tiempo

Escribir la ley de velocidad

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Tiempo (s) · 103 [N2O5] (M) ln[N2O5] 1/[N2O5]
0.0 0.0365 -3.3104 27.40
0.6 0.0274 -3.5972 36.50
1.2 0.0206 -3.8825 48.54
1.8 0.0157 -4.1541 63.69
2.4 0.0117 -4.4482 85.47
3.0 0.0086 -4.7560 116.28
3.6 0.0064 -5.0515 156.25

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Tiempo (s) · 103 [N2O5] (M)
0.0 0.0365 Intercepto 0.0328
0.6 0.0274 Pendiente -8.14E-06
1.2 0.0206 Coeficiente de regresión al cuadrado 0.9478
1.8 0.0157
2.4 0.0117
3.0 0.0086
3.6 0.0064

Tiempo (s) · 103 ln[N2O5]

0.0 -3.3104 Intercepto -3.3029
0.6 -3.5972 Pendiente -4.83E-04
1.2 -3.8825 Coeficiente de regresión al cuadrado 0.9997
1.8 -4.1541
2.4 -4.4482
3.0 -4.7560
3.6 -5.0515

Tiempo (s) · 103 1/[N2O5]

0.0 27.40 Intercepto 13.8347
0.6 36.50 Pendiente 3.47E-02
1.2 48.54 Coeficiente de regresión al cuadrado 0.9354
1.8 63.69
2.4 85.47
3.0 116.28
3.6 156.25 19
Azometano (CH3N2CH3) se descompone a 600 K
produciendo C2H6 y N2. Determinar el orden del proceso
descomposicion, la constante cinetica, y el tiempo de vida
media.

Tiempo (s) P (atm)

0 8.20E-02
2000 3.99E-02
4000 1.94E-02

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 Tiempo (s) P (atm) lnP 1/P
0 8.20E-02 -2.501036 1.22E+01
2000 3.99E-02 -3.221379 2.51E+01
4000 1.94E-02 -3.942482 5.15E+01

.
½ = = .
.

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Tritium (3H) es un isotopo radioactivo usado rutinariamente
en aplicaciones bioquimicas.

½ = 12.32 ñ

• Calcular la constant de decaimiento radioactivo para 3H.

• Determinar la masa de 3H que todavia esta presente en 5
g de una muestra de NaB3H4 que tiene 17.57 años de
antiguedad.

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El acido salicilico es la substancia que alivia la fiebre y las
inflamaciones. Se ha hecho mucha investigacion en
entender la reaccion de hidrolisis para evaluar la cinetica
del proceso farmacologico.

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Tiempo (h) [Aspirina] (M)
0 5.55E-03 Determinar el orden de la
2 5.51E-03 reaccion, constant
5 5.45E-03 cinetica, y vida media.
10 5.35E-03
20 5.15E-03
30 4.96E-03
40 4.78E-03
50 4.61E-03
100 3.83E-03
200 2.64E-03
300 1.82E-03

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 Determinar el orden de la
reaccion, constant
cinetica, y vida media.

.
½ = = .
.
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La enzima ureasea contiene dos atomos de nickel que cataliza la
hidrolisis de urea de la siguiente forma:

+ · +
Ureasea es un catalizador muy poderoso. Baja en forma considerable
la energia de activacion ( ) del proceso de hidrolisis de la urea.

• Sin enzima, la hidrolisis necesita sobrepasar una =

• Con enzima, la hidrolisis necesita sobrepasar una =

Calcular la razon de la velocidad de reaccion para el proceso

catalizado en relacion al proceso NO catalizado a 37°C. Asumir que
el factor de frecuencia es el mismo para ambos casos. 27
Una proceso de Orden Cero es el cual es INDEPENDIENTE
de la cantidad de material que define la velocidad del
proceso (concentracion).

∆
= − = · = · =
∆

La ley de velocidad integrada integrada de cero orden es:

= − ·

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Una proceso de Orden Cero es el cual es INDEPENDIENTE
de la cantidad de material que define la velocidad del
proceso (concentracion).

∆
= − = · = · =
∆

La ley de velocidad integrada integrada de cero orden es:

= − ·

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