Universidad Autónoma del Estado de México

Facultad de Ingeniería
UNIDAD DE APRENDIZAJE

QUÍMICA/ QUÍMICA GENERAL

CINÉTICA QUÍMICA

Rosa María Fuentes Rivas

CONTENIDO
OBJETIVO
INTRODUCCIÓN
1. Velocidad de Reacción Química
2. Factores que afectan la velocidad de reacción
2.1. Naturaleza de los reactantes
2.2. Concentración de los reactantes: expresión de la ley de velocidad
2.3. Concentración versus tiempo : Ecuación integrada de la velocidad,
vida media.
2.4.Temperatura : Ecuación de Arrhenius
2.5. Catalizadores
3. RESUMEN
4. SERIE DE EJERCICIOS
5. REFERENCIAS BIBLIOGRÁFICAS
 OBJETIVO

Al término del tema el alumno adquiere y aplica

conocimientos de cinética química y velocidad de
reacción; así como, reconoce y entiende los factores que
la afectan.
INTRODUCCIÓN

LA CINÉTICA QUÍMICA

Es el estudio de la velocidad de una reacción

química, los factores que la afectan y los
mecanismos de reacción.
16-1 The Rate of a Reaction 649

(a)
Figure 16-1 (a) Blue dye is
 ments were made, the rate-law expression for
648 order of the
CHAPTER reaction,
16: Chemical consistent
Kinetics

with converting the product of

1.
rate !VELOCIDAD
1.5 M #s [A] [B]
"2 "1 W
DE REACCIÓN
2
See the Saunders Interactive
General Chemistry CD-ROM,
Screen 6.3, Thermodynamics and
Kinetics, and Screen 20.2, Reaction
Spontaneity (Thermodynamics and
concentrations
e are all familiar with processes in which some quantity changes with time
a car on the
travels right
at 40 to a faucet delivers water at 3 gallons/minute,
miles/hour,
a factory produces 32,000 tires/day. Each of these ratios is called a rate. T
concentration/time
rate of a reaction describeson thehow left. For any
fast reactants are used up and products are form
Chemical kinetics is the study of rates of chemical reactions, the factors that affect re
Kinetics).
reaction that
tion rates, is third
and the mechanismsorder overall,
(the series the
of steps) by which reactions occur.
om one of the other sets of data. Our experience tells us that different chemical reactions occur at very different rat
units of k are
For instance, M"2 # time
combustion "1—
reactions . such as the burning of methane, CH , in natural g
4
and the combustion of isooctane, C H , in gasoline — proceed very rapidly, sometim
8 18
even explosively.
CH4(g) ! 2O2(g) 88n CO2(g) ! 2H2O(g)
2C8H18(g) ! 25O2(g) 88n 16CO2(g) ! 18H2O(g)

to Use the Rate of Reaction The rusting of iron is a complicated

process. It can be represented in
On the other hand, the rusting of iron occurs only very slowly.
In our study of thermodynamics, we learned to assess whether a particular reaction w
simplified form as favorable. The question of whether substantial reaction would occur in a certain tim
period is addressed by kinetics. If a reaction is not thermodynamically favored, it will n
ive the dependence of the rate of reaction on
4Fe(s) ! 3O2(g) 88n 2Fe2O3(s)
occur appreciably under the given conditions. Even though a reaction is thermodynam
cally favored, it might not occur at a measurable rate.
g calculation describe the rate of formation of The reactions of strong acids with strong bases are thermodynamically favored a
This is one of the reactions that occurs occur at very rapid rates. Consider, for example, the reaction of hydrochloric acid so
balanced equation is one, so inantacid
the rate
a human of reac-
digestive system when an
containing relatively insoluble
tion with solid magnesium hydroxide. It is thermodynamically spontaneous at standa
state conditions, as indicated by the negative "G 0 rxn value. It also occurs rapidly.
C. If the coefficient of the measured substance
magnesium hydroxide neutralizes
excess stomach acid. 2HCl(aq) ! Mg(OH)2(s) 88n MgCl2(aq) ! 2H2O(!) "G 0
rxn # $97 kJ/mol

lysis we should have divided each value of the The reaction of diamond with oxygen is also thermodynamically spontaneous.
Recall that the units kJ/mol refer to C(diamond) ! O2(g) 88n CO2(g) "G 0
rxn # $397 kJ/mol
he initial rate of reaction. For instance,
the numbers ofsuppose
moles of reactants and
products in the balanced equation. However, we know from experience that diamonds exposed to air, even over long perio

n the reaction do not react to form carbon dioxide. The reaction does not occur at an observable r
near room temperature.
The reaction of graphite with oxygen is also spontaneous, with a similar value of "G 0
r
$394 kJ/mol. Once it is started, this reaction occurs rapidly. These observations of re

2 88n 2AB tion speeds are explained by kinetics, not thermodynamics.

16-1 THE RATE OF A REACTION

Rates of reactions are usually expressed in units of moles per liter per unit time. If
1
"
know the chemical equation for a reaction, its rate can be determined by following t

! % (rate of formation of AB) change in concentration of any product or reactant that can be detected quantitative
To describe the rate of a reaction, we must determine the concentration of a reacta
2 or product at various times as the reaction proceeds. Devising effective methods for t
is a continuing challenge for chemists who study chemical kinetics. If a reaction is sl
enough, we can take samples from the reaction mixture after successive time intervals a
rate changes as we change the concentrations then analyze them. For instance, if one reaction product is an acid, its concentration c
be determined by titration (Section 11-2) after each time interval. The reaction of eth
acetate with water in the presence of a small amount of strong acid produces acetic ac
A methane flame is a rapid reaction. The extent of the reaction at any time can be determined by titration of the acetic ac

When heated in air, steel wool glows

but does not burn rapidly, due to the
low O2 concentration in air (about
 0.656
0.586
rate ! ## !
0.328
$t
0.293
" $t ! $t "5
! "# # ! "# ## ! " ##
2 0.035 3
6$t
! " ! "
1. ¿VELOCIDAD DE UNA REACCIÓN QUÍMICA?
ction 0.530 0.265
0.028
7
0.023
entire 0.484 0.242 8
La velocidad de una reacción describe que tan rápido
Consider as a specific
se consumen loschemical example
reactivos y sethe forman
gas-phase reaction that occurs when we
los productos
mix 1.000 mole of hydrogen and 2.000 moles of iodine chloride at 230°C in a closed
1.000-liter container.
Concentración de reactivos y productos

H2(g) % 2ICl(g) 88n I2(g) % 2HCl(g)

Concentrations of reactants and products

2.000 M
The coefficients tell us that one mole of H2 disappears for every two moles of ICl that
disappear and for every one mole of I2 and two moles of HCl that are formed. In other
[HCl]
terms, the rate of disappearance of moles of H2 is one-half the rate of disappearance of
moles of ICl, and so on. So we write the rate of reaction as

1.000 M
[I2]

rations
ersus [ICl]
M H2 [H2]
om 0
more 0 5 10 15
Time (s)
Tiempo (s)
VELOCIDAD DE REACCIÓN: Cambio de la concentración
de reactivos o productos respecto al tiempo.
1. VELOCIDAD DE UNA REACCIÓN QUÍMICA

¿Cómo se describe la velocidad de una reacción?

A+B C+D

La velocidad puede O bien a la velocidad con la

expresarse en términos de la que aparecen los productos.
velocidad con la que
desaparecen los reactivos.

𝚫𝑪 𝚫𝑫
𝚫𝑨 𝚫𝑩 𝒗= =
𝒗=− =− 𝚫𝒕 𝚫𝒕
𝚫𝒕 𝚫𝒕
1. VELOCIDAD DE UNA REACCIÓN QUÍMICA
La expresión de la velocidad de una reacción a
partir de una reacción química.

aA + bB cC + Dd a,b,c,d
𝟏𝚫 𝑨 𝟏𝚫 𝑩 𝟏𝚫 𝑪 𝟏𝚫 𝑫
𝒗=− =− 𝒗= =
𝒂 𝚫𝒕 𝒃 𝚫𝒕 𝒄 𝚫𝒕 𝒅 𝚫𝒕

EJEMPLO: Exprese la velocidad de reacción en términos de la rapidez

de cambio de cada reactivo y producto de la reacción siguiente:
2NO (g) + Br2(g) ----→ 2NOBr(g)

𝟏 𝚫 𝑵𝑶 𝚫 𝑩𝒓𝟐 𝟏 𝚫 𝑵𝑶𝑩𝒓
𝒗=− =− =
𝟐 𝚫𝒕 𝚫𝒕 𝟐 𝚫𝒕
EJEMPLO: CÁLCULO DE LA VELOCIDAD DE UNA REACCIÓN
La siguiente ecuación muestra la producción de NO y H2O por oxidación
del amoniaco NH3. A un cierto tiempo, NH3 reacciona a una velocidad de
1.10 M/s. A ese mismo tiempo, ¿Cual es la velocidad a la cual los otros
reactivos y cada producto están cambiando?

4𝑁𝐻! + 5 𝑂! → 4 𝑁𝑂 + 6 𝐻! 𝑂

𝟏 𝚫 !"! 𝟏 𝚫 !! 𝟏 𝚫 𝑵𝑶 𝟏 𝚫 !! !
𝒗=− =− = =
𝟒 𝚫𝒕 𝟓 𝚫𝒕 𝟒 𝚫𝒕 𝟔 𝚫𝒕

1.10 𝑚𝑜𝑙 𝑁𝐻3 5 𝑚𝑜𝑙 𝑂! 1.37 𝑚𝑜𝑙𝑂!

=−
𝐿. 𝑠 4 𝑚𝑜𝑙𝑁𝐻! 𝐿. 𝑠

1.10 𝑚𝑜𝑙 𝑁𝐻3 4 𝑚𝑜𝑙 𝑁𝑂 1.10 𝑚𝑜𝑙 𝑁𝑂

=
𝐿. 𝑠 4 𝑚𝑜𝑙𝑁𝐻! 𝐿. 𝑠
EJEMPLO: VELOCIDAD DE UNA REACCIÓN
4𝑁𝐻! + 5 𝑂! → 4 𝑁𝑂 + 6 𝐻! 𝑂

𝟏 𝚫 !"! 𝟏 𝚫 !! 𝟏 𝚫 𝑵𝑶 𝟏 𝚫 !! !
𝒗=− =− = =
𝟒 𝚫𝒕 𝟓 𝚫𝒕 𝟒 𝚫𝒕 𝟔 𝚫𝒕

1.10 𝑚𝑜𝑙 𝑁𝐻3 6 𝑚𝑜𝑙 𝐻2𝑂 1.65 𝑚𝑜𝑙 𝐻2𝑂

=
𝐿. 𝑠 4 𝑚𝑜𝑙𝑁𝐻! 𝐿. 𝑠

1 Δ NH! 1 mol mol

v=− = − 1.10 = 0.275
4 Δt 4 L. s L. s

𝟏 𝚫 𝐻! 𝑂 1 mol mol
v= = 1.65 = 0.275
𝟔 𝚫𝒕 6 L. s L. s
2. FACTORES QUE AFECTAN LA VELOCIDAD
DE REACCIÓN
 or, in logarithmic form, 0.656 0.328
0.035
5
! 0.148 M%s#1 0.586 0.293 6

2. ¿FACTORES QUE INFLUYEN EN E LA VELOCIDAD DE UNA

0.028
This does not mean that the reaction 0.530 0.265 7
0.023
proceeds at this rate during the entire 0.484 a0.242 8
ln k " ln A # $$
REACCIÓN QUÍMICA?
interval.
RT
In this expression, A is a constant having the same units as the rate constant. It is equal
to the fraction of collisions with the proper2.000
orientations when all reactant concentrations

Concentrations of reactants and products

M
are one molar. R is the universal gas constant, expressed with the same energy units in its [HCl]
numerator as are used for Ea. For instance, when Ea is known in J/mol, the value R "
Fosforo blanco

8.314 J/mol%K is appropriate. Here the unit “mol” is interpreted as “mole of reaction,”
as described in Chapter 15. One important1.000 point
M
is the following: The greater the value [I2]
Ea, the
ofFigure smaller the value of k and the slower the reaction rate (other factors being equal).
16-2 Plot of concentrations
of all reactants and products versus [ICl]
CHAPTER
time in 16:
the Chemical
reaction
Fosforo rojo Kinetics
of 1.000 M H2 [H2]
with 2.000 M ICl at 230°C, from 0
data in Table 16-1 (and a few more 0 5 10 15
Naturaleza de los reactivos
points). ConcentraciónTime
de(s) los reactivos
ntial energy
e effect of a
Fracción de moléculas con una energía cinética dada.
Fraction of molecules with

Fraction of molecules with

provides a T2 ! T1
T1
a given kinetic energy

corresponding a given kinetic energy

thway, for the Ea′ < Ea
Ea
ducts. A forward
T2 Ea Ea′
pically occurs reverse Ea′
with its own reverse
Energy

Energy
forward
Derecha Inversa
ll energy
action, Ea#, is
he uncatalyzed ∆Erxn ∆Erxn
ue of $Erxn
states of the Ea1 Ea2
Ea
Energía Cinética
ts, so it is the
Kinetic energy
Temperatura Progress of Kinetic energyProgress
Presencia de Catalizadores
of
2.1. NATURALEZA DE LOS REACTIVOS
El fosforo se encuentra en dos formas alotrópicas

El fosforo blanco reacciona

violentamente con el oxígeno
del aire.

Fosforo blanco

Fosforo rojo

Fosforo rojo es inerte.

2.1. NATURALEZA DE LOS REACTIVOS

La velocidad de reacción
depende del área superficial o
del grado de subdivisión.

El grado máximo de subdivisión

hace posible que todas las
moléculas o átomos y iones
reaccionen en cualquier
momento.

El gis pulverizado reacciona más rápido con HCl debido

a que hay una mayor área superficial.
 NO ! N2O 88n NO2 ! N2
2.2. CONCENTRACIÓN DE LOS REACTIVOS

La LEY DE VELOCIDAD describe

la manera en que van
cambiando las concentraciones
conforme pasa el tiempo de
reacción.

𝒗𝒆𝒍𝒐𝒄𝒊𝒅𝒂𝒅 = 𝒌 𝑨 𝒙 𝑩 𝐲

Donde:
K= constante de velocidad a una temperatura.
x, y= orden de reacción respecto a A y B -”se determina experimentalmente”
Orden general de la reacción = x+y
EJEMPLO EXPRESIÓN LEY DE VELOCIDAD

Inicial Inicial Velocidad de

Experimento [B] Formación [C]
[A]
1 1x10 -2 M 1x10 -2 M 1.5x10 -6 M.s-1
2 1x10 -2 M 2x10 -2 M 3.0x10 -6 M.s-1
3 2x10 -2 M 1x10 -2 M 6.0x10 -6 M.s-1

𝒗𝒆𝒍𝒐𝒄𝒊𝒅𝒂𝒅 = 𝒌 𝑨 𝒙 𝑩 𝐲
Relación Velocidad = (Relación B)y

relación relación

Relación Relación
velocidad velocidad

𝒗𝒆𝒍𝒐𝒄𝒊𝒅𝒂𝒅 = 𝑲 𝑨 𝟐 𝑩 orden general = x+y = 3

2.2. CONCENTRACIÓN DE LOS REACTIVOS

¿Qué cantidad de reactivo existe

después de un determinado tiempo?

CONCENTRACIÓN VERSUS TIEMPO

Ecuación integrada de la velocidad y el tiempo

de vida media.
2.2. CONCENTRACIÓN DE LOS REACTIVOS

aA Productos orden cero en A

ORDEN CERO

Expresión de la ley de
velocidad pendiente
V = k k= M. tiempo-1

Ecuación de velocidad
integrada
𝐴 = 𝐴 0 - akt

Tiempo de vida media

!!
𝑡 1⁄2 = Tiempo
!"#
 2.2. CONCENTRACIÓN DE LOS REACTIVOS
me: The Integrated Rate Equation 673
aA Productos Características
Primer orden en A
n products thatPRIMER
follows ORDEN
first-
ght line would confirm that First order
Expresión de la ley de velocidad ln [A]0
is, rate " k[A]. The slope is
𝑣 = 𝑘 𝐴 𝑘 = 𝑡𝑖𝑒𝑚𝑝𝑜 _1
pe of the line is always
e units (time)!1. The slope
Pendiente = – ak
s for concentrations less than
Ecuación de velocidad integrada

ln [A]
𝐴0 𝐴0 𝑎𝑘𝑡
𝑙𝑛 = akt ó 𝑙𝑜𝑔 =
[𝐴] [𝐴] 2.303

Tiempo de vida media

t can be interpreted
𝑙𝑛2as m. The
0.693
𝑡1/2 = and
r each experiment, = ln [A]
𝑎𝑘 𝑎𝑘 0
or a first-order reaction would Tiempo
pe of the line equal to !ak and Time
 however, if the reaction times used are
he2.2. CONCENTRACIÓN
reaction followed zero-order DE too short.
LOS In practice, all three lines
REACTIVOS
ne. But if the reaction followed might seem to be straight; we should
a straight line whose slope could then suspect that we need to observe
aA Productos theSegundo
reaction for aorden en A
longer time.
e second order in A and second
ht line, but a plot of 1/[A] versus
expected scatter due to experi-
correct orderSEGUNDO ORDEN
(rate law) for the 1
Second order
can graphical tests for rate-law [#]
Expresión de la ley de velocidad
are subjects for2 more advanced
𝑣 = 𝑘 𝐴 𝑘 = M −1. tiempo−1
strated in the following example.
slope
Pendiente = ak

l![A]
Ecuación de velocidad integrada
1 1
− = akt
n products that
[𝐴] follows𝐴0 a
ves a straight line would
d order overall,
Tiempothat is, rate
de vida "
media l![A]0
ve numbers, the slope of1 the
egative, 1/[A] 𝑡is1/2always
=
𝑎𝑘 positive,
𝐴
0 Tiempo
Time
2.2. EJEMPLO CONCENTRACIÓN DE LOS REACTIVOS

A partir de los siguientes datos determine el orden de la reacción y escriba la

expresión de la ley de velocidad. A B + C

Tiempo (min) [A] mol/L Ln [A] 1/[A]

0 2.000 0.693 0.5000
2 1.107 0.102 0.9033
4 0.612 -0.491 1.60
6 0.338 -1.085 2.95
8 0.187 -1.677 5.35
10 0.103 -2.273 9.71
us time, as shown in Figure 16-8d.
2.2. EJEMPLO CONCENTRACIÓN DE LOS REACTIVOS
ar from the answer to part (b) that the plot of ln [A] versus time gives a straight
CONCENTRACIÓN
tells VERSUS
us that the reaction is first order in TIEMPO
[A].
ormAofpartir de los siguientes
a rate-law expression,datos determine
the answer el orden
to part de larate
(d) gives reacción y escriba la
" k[A].
expresión de la ley de velocidad. A B + C

ORDEN CERO
2.5
[A] ln [A] 1![A]
Tiempo (min) [A] mol/L
2.0
2.000 0
0.693 2.000
0.5000

[A] Mol/L
2 1.107 1.5

[A]
1.107 0.102 0.9033
4 0.612
1.0
0.612 –0.491
6 1.63 0.338

8 0.5
0.338 –1.085 2.95 0.187
10 0.103 0
0.187 –1.677 5.35 0 2 4 6 8 10

0.103 –2.273 9.71 Tiempo (min)

Time (min)
Example 16-10. (b) Example 16-10(a).
 0
2.2.
0.187 EJEMPLO
–1.677 CONCENTRACIÓN 0DE LOS
5.35 2 4REACTIVOS
6 8 10

CONCENTRACIÓN
0.103 –2.273 9.71 VERSUS TIEMPO Time (min)
Example 16-10.
A partir (b) Example
de los siguientes datos determine 16-10(a).
el orden de la reacción y escriba la
expresión de la ley de velocidad. A B + C

SEGUNDO ORDEN
P 12
Tiempo (min) 1/[A] 10
0 0.5000 8

1/1/[A]
[A]
2 0.9033
6
4 Q 1.60
4
6 2.95
8 5.35 2
2 6 8 10 12
10 9.71 0
1.5 8.5 0 2 4 6 8 10
Time (min) Tiempo (min)
Time (min)
ple 16-10(b). (d) Example 16-10(c).
 6.00 0.338 –1.085 2.95
2.2. EJEMPLO CONCENTRACIÓN
8.00 DE LOS –1.677
0.187 REACTIVOS
5.35
ure 16-8 Data conversion and
ts CONCENTRACIÓN
for Example 16-10. (a) TheVERSUS10.00 TIEMPO 0.103 –2.273 9.71
a areA used
partirtode
calculate the twodatos determine
los siguientes (a) Dataelfororden de 16-10.
Example la reacción y escriba la
umns ln [A] and
expresión de1/[A].
la ley(b)
de Test
velocidad. A B + C
zero-order kinetics: a plot of [A]
sus time. The nonlinearity
PRIMER ORDEN of this 1
t shows that the reaction does not P
0.5
ow zero-order kinetics. (c)
Tiempo (min) Ln Test
[A]
0.2
0
first-order kinetics: a plot of ln
0 0.693 – 0.5

ln [A]
versus time. The observation
2
t this plot gives a straight0.102
line –1
icates that the4 reaction follows
-0.491 –1.5 Q
–1.83 –2
t-order kinetics.
6 (d) Test -1.085
for
ond-order kinetics:
8 a plot-1.677
of 1/[A] –2.5
sus time. If the reaction had –3
0 2 6 8 10 12
10 -2.273
owed second-order kinetics, this 1.5 8.5
t would have resulted in a Tiempo (min)
aight line and the plot in part (c) Time (min)
uld not. (c) Example 16-10(b).
𝒗𝒆𝒍𝒐𝒄𝒊𝒅𝒂𝒅 = 𝒌 𝑨
2.2. CONCENTRACIÓN DE LOS REACTIVOS

TEORIA DE LAS COLISIONES

Para que una reacción ocurra, las moléculas deben colisionar

Al aumentar la concentración de los reactivos se favorecen las

colisiones. Sin embargo no todas dan lugar a reacción.

Para que una colisión sea efectiva, las especies deben:

1. Poseer la energía mínima necesaria para romper y formar

enlaces nuevos

2. Tener la orientación adecuada en el momento de la colisión.

2.2. CONCENTRACIÓN DE LOS REACTIVOS

NO NO →O
+ N2+O N NO→
2 +NO
N2 + N
2 2 2

n
n
Orientación
Efectiva de
Colisión

Reaction
occurs Reaction
occurs

Reactants Collision Products

Reactantes Colisión Productos
Reactants Collision Pro
 2.2. CONCENTRACIÓN DE LOS REACTIVOS
Reactants Collision Products
NO + N2O → NO2 + N2
ive
eion
on
ion
on
Orientación
Inefectiva de
Colisión

No reaction Reaction
occurs

Reactantes
Reactants Colisión
Collision Reactantes
Reactants
Reactants Collision P
 2.3. TEMPERATURA 16-8 Temperature: The Arrhenius Equation
16-8 Temperature: The Arrhenius Equation

Antimony
ntimony powder
powder
El antimonio reacts
reacts with
reacciona with bromine
bromine
con Bromo moremore
más rapidly
rapidly aat75
at 75°C
fuertemente 75°C (left)
(left) thanthan atque
at 25°C
oC (Izquierda) 25°C (right).
(right).
a 25 oC (Derecha)
 2.3. TEMPERATURA

ARRHENIUS
Fracción de moléculas con una energía cinética dada.
Fraction of molecules with

Fraction of molecules with

T1 T2 ! T1
a given kinetic energy

a given kinetic energy

T2
A mayor temperatura
(T2) habrá una mayor
fracción de moléculas
que tenga la energía
de activación necesaria
(Ea), para que la
Energía Cinética Ea reacción proceda, a
Kinetic energy comparación de una Kineti
temperatura mas baja.
Figure 16-13 (Left) The effect of temperature on the number of mo
2.3. TEMPERATURA

La ecuación de Arrhenius relaciona la velocidad de reacción

(mediante su k) con una temperatura (T) para una misma energía
de activación (Ea).

!!"/!"
𝑘 = 𝐴 𝑒
!"
ln𝑘 = 𝑙𝑛𝐴 −
!"
K La
Si T Ea/RT - Ea /RT exp (-Ea/RT) reacción
aumenta Disminuye Aumenta Aumenta se
Aumenta acelera
2.3. TEMPERATURA
La ecuación de Arrhenius relaciona la velocidad de reacción
(mediante su k) con una temperatura (T) para una misma energía
de activación (Ea).

Pendiente

!! !
ln𝑘 = − + ln A
! !

La ecuación de Arrhenius para dos

diferentes temperaturas.

!! !! ! !
ln! = − ! !!
−
!!
!
 C2H5I 88n C2H4 # HI
E2.3.
XAMPLE 16-12 Activation
EJEMPLO CON Energy
ECUACIÓN DEtheARRHENIUS
600. K, the value of k is 1.60 ! 10"5 s"1. When temperature is raised to 700. K, th
The gas-phase decomposition of ethyl iodide to give ethylene parahydrogen
and iodide isya yoduro
first-
ue La
of kdescomposición
increases to en fase
6.36 ! gaseosa
10"3 s"1del yodurois de
. What theetilo
activationproducir
energyetileno
for this reaction?
order reaction. se comporta como una reacción de primer orden.
de hidrógeno,
n C2H5I 88n C2H4 # HI
know k at two different temperatures. We solve the two-temperature forms of the Arrh
AtA600.
600K,K the value of
el valor lais constante
1.60 ! 10 k=
dekevaluate. "5 s 1.6x10
"1. When-5sthe
-1. temperature is raised to 700.
Cuando la temperatura K, thelos
alcanza
s equation for Ea and
value
700ofK k, increases to 6.36
el valor de se10
la k ! s . What
"3 "1
incrementa is the activation
a 6.36x10 energy
-3s-1 . ¿Cuál es laforenergía
this reaction?
de activación
ution
de la reacción?
Plan
We know k at two different
"5 s"1temperatures. We solve the two-temperature
"3forms
"1 of the Arrhe-
k 1 $ 1.60
nius equation ! 10 at T
for Ea and evaluate. 1 $ 600. K k 2 $ 6.36 ! 10 s at T2 $ 700. K
R $ 8.314 J/mol % K
Solution Ea $ _?_
k1!$ 1.60 !!10"5 s!"1 at T
!1 $ 600. K k2 $ 6.36 ! 10"3 s"1 at T2 $ 700. K
= −J/mol
lnR $ 8.314
! !
− Ea $ _?_
!! ! %!K ! ! !

Despejando Ea y sustituyendo valores

!" !
! !" !.!"# (!.!")
!" !"#.!
Ea= ! ! = = 2.09x105 J/mol
! !.!"#$% !! ! !!
!! !!
 2.4. PRESENCIA DEKinetics
CHAPTER 16: Chemical CATALIZADOR
Los catalizadores abaten la
gy
fa
Ea permitiendo que la
reacción
a CHAPTER se lleve
16: Chemical a cabo más
Kinetics
nding
r the
rápido. Ea′ < Ea
Ea
forward Ea
curs Ea′ Ea′

Energía →
reverse reverse
own
Energy

Energy
forward
Derecha Inversa

a#,is
lyzed ∆Erxn Ea′ < ∆E
Earxn
Ea
xn forward
Derecha Ea
Energía →

the Ea′ Ea′

the reverse
Inversa reverse
Energy

Energy
forward
Progress of Inversa Progress of
Progreso de una reacción catalizada
uncatalyzed reaction catalyzed reaction

∆Erxn ∆Erxn
No toma parte en la
reacción, por lo que no
aparece Progress en laof ecuación
olecules with

Progreso de una reacción no catalizada

Progress of
etic energy

uncatalyzed reaction Minimumbalanceada. catalyzed reaction

kinetic energy
for catalyzed reaction
 Homogeneous
Section 11-8). Catalysis
For example, Ce4! oxidizes thallium(I) ions in solution
2.4. PRESENCIA
A homogeneous
alyzed by the additionDE CATALIZADOR
catalyst exists in the same phase as the reactants. Ceric ion, Ce4!, at
of a very small amount of a soluble salt
one time was an important laboratory oxidizing agent that was used in many redox
(II) ions,
titrations Mn2!
Un catalizador
(Section . The
11-8). For Mn2!Ceacts
homogéneo
example, as athallium(I)
4! oxidizes
existe homogeneous
en la misma fasecatalyst.
ions in solution; quereac-
this los
tion is catalyzed by the addition of a very small amount of a soluble salt containing
reactivos.
manganese(II) ions, Mn2!. The Mn2! acts as 2!
Mna homogeneous catalyst.
2Ce4! ! Tl! Mn
8888n
2! 2Ce3! ! Tl3!
2Ce4! ! Tl! 8888n 2Ce3! ! Tl3!
onThis
is reaction
thought to proceed
is thought to proceed by the
by the following
following sequencesequence
of elementary of elementary
steps.

4! Ce4! ! Mn2! 88n Ce3! ! Mn3!

2!
Ce ! Mn 88n Ce3! ! Mn 3!
step 1
step 1
Ce4! ! Mn3! 88n Ce3! ! Mn4! step 2
Ce4! Mn
!4!Mn 3! 88n Ce
! Tl! 88n
3! ! Mn4!
Mn2! ! Tl3! step 3 step 2
4!2Ce4! ! !
Tl! 88n 2Ce3! !2!
Tl3! 3!
Mn ! Tl 88n Mn ! Tloverall step 3
Some of the Mn2! catalyst reacts in step 1, but an equal amount is regenerated in step 3
2Ce4!to !
and is thus available Tlagain.
react ! The 88n two 2Ce 3! !inTl
ions shown 3!Mn3! and
blue, overall
Mn4!, are
reaction intermediates. Mn3! ions are formed in step 1 and consumed in an equal amount
step2!
2; similarly, Mn 4! ions are formed in step 2 and consumed in an equal amount in
e Mn catalyst reacts in step 1, but an equal amount is regenerate
in
step 3.
available
We can now tosummarize
react again. The
the species two
that can ions
appear in ashown in blue, Mn3! and
reaction mechanism.
rmediates. Mn3! ions are formed in step 1 and consumed in an equ
milarly, Mn 4! ions are formed in step 2 and consumed in an equal
1. Reactant: More is consumed than is formed.
2.4. PRESENCIA DE CATALIZADOR
Un catalizador heterogéneo esta presente en una fase distinta a
la de los reactivos.

Etapas de proceso:

1.- Adsorción
2.- Activación del reactivo
adsorbido
3.- Reacción
4.- Desorción
3. RESUMEN
Velocidad de reacción

𝟏𝚫 𝑨 𝟏𝚫 𝑩 𝟏𝚫 𝑪 𝟏𝚫 𝑫
𝒗=− =− 𝒗= =
𝒂 𝚫𝒕 𝒃 𝚫𝒕 𝒄 𝚫𝒕 𝒅 𝚫𝒕

Expresión de la ley de Velocidad de reacción

𝒗𝒆𝒍𝒐𝒄𝒊𝒅𝒂𝒅 = 𝑲 𝑨 𝒙 𝑩 𝐲

Factores que influyen en la Velocidad de reacción

Naturaleza de Concentración Temperatura Catalizadores

los reactivos de los reactivos
3. RESUMEN Ecuaciones integradas
ORDEN CERO PRIMER ORDEN SEGUNDO ORDEN
Expresión de la ley de Expresión de la ley de
Expresión de la ley de velocidad
velocidad
velocidad 𝑣 = 𝑘 𝐴 𝑘 = M−1. tiempo−1
2
𝑣 = 𝑘 𝐴 𝑘 = 𝑡𝑖𝑒𝑚𝑝𝑜 _1
V = k k= M. tiempo-1
Ecuación de velocidad Ecuación de velocidad
Ecuación de velocidad
integrada integrada
integrada
𝐴0 1 1
𝐴 = 𝐴 0 - akt 𝑙𝑛 = akt − = akt
[𝐴] [𝐴] 𝐴0
𝐴0 𝑎𝑘𝑡
Tiempo de vida media 𝑙𝑜𝑔 =
!! [𝐴] 2.303 Tiempo de vida media
𝑡 1⁄2 =
!"# 1
Tiempo de vida media
𝑙𝑛2 0.693 𝑡1/2 =
𝑎𝑘 𝐴 0
𝑡1/2 = =
𝑎𝑘 𝑎𝑘

Ecuación de Arrhenius

!! ! !! !! ! !
ln𝑘 = − + ln A ln =− −
! ! !! ! !! !!
 4. SERIE DE EJERCICIOS Exercises 699
Exercises 699
*08. Express the rate of reaction in terms of the rate of change t
1.- Exprese la velocidad de reacción en términos del cambio deofcada eachreactivo y producto
reactant and para in
each product cada
the una de las
following. i
siguientes
of the rate reacciones.
of change *08. Express
tion ofthe
O2 rate of reaction
is doubled. in terms
The initial rate inof
thethe rate exper-
second of change (a) 3ClOtion of O88n
!(aq) 2 is doubled.
ClO3!The
(aq) initial
" 2Clrate in the second exper-
!(aq)
the following. of each
imentreactant and each
will be ______ timesproduct
that of thein first.
the following. (b) 2SOiment will be ______ times that of the first.
2(g) " O2(g) 88n 2SO3(g)
Cl!(aq) (a) 3ClO!(aq) 88n ClO3!(aq) " 2Cl!(aq) (c) C2H4(g) " Br2(g) 88n
2NO " O 88n 2NO
(b) 2SO2(g) " O2(g) 88n 2 2SO3(g) 2 2NO C "2O H4Br
2 88n 2(g)2NO2 *15. T
(g) *15.
*09. At a given time, N2 is reacting with H2 at a rate of 0.25 t
(c) The
C2Hrate-law expression for the following reaction is found
4(g) " Br2(g) 88n C2H4Br2(g) *15. toThe rate-lawNH expression for the following reaction is found
H2 at a rate of 0.25 to be rate # k [N2O5]. What is the overall reaction order? M/min produce 3. At that same time, what is the
me time, what is the *09. At a given time, N2 is reacting with H2 at a rate of 0.25 rate at which to be rate # k [N O
the other 2reactant
5 ]. What is ischanging
the overallandreaction order?
the rate
hanging2.- andAthe M/min to produce
2N O NH
(g) . At that
4NO (g)
un tiempo dado, N2 reacciona con H2 a una razón de 0.25atM/min same O time,
(g) what is the
which para producir NH3 . Al mismo tiempo, ¿Cuál
rate 2 5 88n
3 2 " 2
the product 2Nis changing?
rateUse
at times
whichexpressed
the other reactant is changing and the rate 2O5(g) 88n 4NO2(g) " O2(g) *16. U
es la razón de700cambio
*16.
at which a laproduct
the cual loschanging?
in reactivos
seconds to give
CHAPTER y producto
the units of the están
rate
16: Chemical cambiando?.
Kinetics
for reactionsis that *16. Use timesN c
2 " 3H2in88n 2NH
H3 constant are overall (a) first order; (b) expressed seconds to give
3 the units of the rate
second order; (c) third order; (d) of order 1$12$. s
oduction of NO and *17. were N 2 " 3H 88nfor2NH constant for reactions that are overall (a) first order; (b)
given 3.-
time,Los
NH3datos
is paraRatela data
siguiente obtained
reacción at2 25°C fueron the 3following
obtenidos reac-a*10.
Initial Rate 25*25.
ºC,
The ¿Cuál
following
Given es la expresión de la ley
second order; (c) third order; (d) of order of
the equation
following data for shows
the the
reaction A de
production
# B n velocidad
C, write11$2$. NOlaand *17. R
tion.
Expt.What[A]is the rate-law expression
(mol/L) [B]0 (mol/L) for this ofreaction?
Reaction
hat same time, which *10. The following equation shows the production of NO and H2O
reacción? 0 the byRate
oxidation
rate-law
*17. of ammonia.
expression.
data were obtained atAt 25°C a given time,
for the NH3 reac-
following is t
is changing and the H2O by oxidation A of" 2B
ammonia.
88n C At
" 2D
a given time, NH is reacting at a rate of 1.10 M/min. At that same time, which
1 0.10 0.10 0.0090 M!s "1
3 tion. Initial
What is theInitial
rate-law expression for this reaction?
Initial Rate of
g? reacting2 at a rate0.20 of 1.10 M/min. At that same time, which
[A] [B]
0.10 Vel. 0.0360
Inicial
Initial Rate
M!s
deof
"1 is the rate
Expt. at which
[A] the other
[B] reactant is changing
Formation of C and the
" 6H2O is the rate
3
Expt. at which0.10
[mol/L] the other
[mol/L] reactant
0.20 is changing
0.0180
Formación de
Formation of C M!s
C and
"1 the
rate at which each product A " is 2B 88n
changing? C " 2D
rate at4which each 0.10product is changing?0.30 0.0270 M!s"1 1 0.25 0.15 8.00 $ 10"5 M/s
ore slowly than finely 0.25 "[A]
1 0.10 0.10 3.0 % 10!4 M&min!1 2 4NH 3 5O20.3088n [B] 4NO
3.20 "$ 106H 2O
Initial Rate of
"4 M/s
E
2 4NH0.303 " 5O2 0.3088n 4NO 9.0 "
% 106H2O
!4 M&min !1
3 Expt. 0.50 [mol/L]0.60 [mol/L] 5.12 $ 10"3 Formation
M/s of C
the burning of mag- (a)
3 What is0.30 the rate-law0.10expression
3.0 for
% 10this reaction?
!4 M&min !1
*11. Why do large crystals of sugar burn more slowly than finely
might be constructed *11. Why(b)
zes of the pieces of 4doDescribe
large crystals
0.40 of of
the order sugar
0.20 burn 6.0
the reactionmore
with
% 10slowly
respect than
to
!4 M&min !1finely
each
ground sugar?1 0.10 0.10 3.0 % 10!4 M&min!1
ground sugar?
reactant and to the overall order. *26. Given the following data for the reaction A # B n C, write !4
d you expect to occur *12. Some 2
fireworks are 0.30
bright because 0.30of the burning
9.0 % 10 of M&min
mag- !1
d? Too4.- *12. *22.
Los siguientes
small? SomeRate
datos
data wereare
fireworks
fueron
collected
brightforbecause
the following
recolectados
reaction
of para
the at a par-
burning
la the rate-law
of mag- reacción
siguiente a expression.
una temperatura en particular.
*18. ticular
Rate datatemperature.
were obtained for fireworks
the following reaction 3
nesium. Speculate 0.30
on how fireworks 0.10 might3.0be%constructed
10!4 M&min!1
nesium. Speculate on how might be at 25°C.
constructed
What is the rate-law" expression for the reaction?
88n the sizes of the pieces of using magnesium. 4 Initial How might 0.20
0.40 Initial the Initial
sizesRate
of the
6.0 % 10pieces of !1
of !4 M&min
using2ClOmagnesium.
2(aq) # 2OH How
(aq) might
Expt. [A] [B] Formation of C
2A " B "ClO expect2 to occur magnesium be important? What would you expect to occur
"(aq) # ClO "(aq) # H O(!)
magnesium be important? 2CWhat
3 88n D " 2E
would you
2

if pieces that were too large were used? Vel.

TooInicial
small? if pieces
1 that0.10
were
M too large
0.10 Mwere used? Too
2.00 $ 10 small?
"4 M/s
Initial
[ClO Initial
] Initial
[OH "] Initial Rate
Initial ofde
Rate *18. Rate0.20
dataMwere obtained for the following reaction at 25°C. *18. R
2 0 0 2 0.10 M 8.00 $ 10"4 M/s
Expt.
Expt. [A](mol/L)[B] [C]
(mol/L) of reacción
Formation of D
Reaction What0.40
is the W
3 M rate-law expression
0.20 M 2.56 for
$ 10the reaction?
"2 M/s

11 0.10 M 0.20
0.012 M 0.10 M
0.012 5.02.07
% 10 10M&min
$!4 "4 M!s!1
"1
2A " B " 2C 88n D " 2E
22 0.20 M 0.20
0.024 M 0.30 M
0.012 1.58.28
% 10$ 10M&min
!3 "4 M!s"1
!1
*27. Consider a chemical reaction between compounds A and
33 0.30 0.012
M 0.20 M 0.024
0.10 M 5.04.14
% 10 10M&min
$!4 "4 M!s!1
"1
Initial Initial Initial
B that is first order in A and first order in B. From Initial
the Rate of
44 0.40 0.024
M 0.60 M 0.024
0.30 M 4.51.66
% 10 10M&min
$!3 "3 M!s!1
"1
Expt.shown[A]
information here, fill in[B] [C]
the blanks. Formation of D E
a) ¿Cuál es *19.
la expresión
(a)
(a)A What
de la ley
certainisreaction is zero
the rate-law
deexpression
velocidad
order in reactantparaand esta
sec- reacción?
for thisA reaction?
Expt. 1 Rate0.10 M) 0.20 M[A] 0.10 M
(M!s"1 5.0
[B] % 10!4 M&min!1
b) Describe el orden
ond respecto
order
(b) Describe in the deofB.cada
reactant
order If the
the uno de respect
los reactivos
concentrations
reaction with oftoboth
each y el orden
1 general
2 0.24 de la reacción.
0.20 M 0.20 M 0.30 M
0.20 M
1.5 % 10!3 M&min!1
0.050 M
reactants
reactant are
and doubled, what order.
to the overall happens to the reaction rate? !4 !1
 What is the rate constant for this first-order decomposi- 14.00 Exercises
0.168
tion?
4. SERIE DE EJERCICIOSA 88n B # C
16.00 0.180
18.00 0.190
*53. For a gas-phase reaction, E ! 103 kJ/mol, and the rate
a of ammonia at high tempera-
*59.20.00
Biological reactions
0.199 nearly always occur
*43. The thermal
5.- La descomposición térmica decomposition
constant del amoniaco
is 0.0850 min"1aataltas
273 temperaturas
K. Find the ratefue estudiado en presencia
constant enzymes de un gas inerte.
as catalysts. Los catala
The enzyme
tures was studied in the presence of inert gases. Data at
datos de un solo experimento a 2000K
at 3232000
K. son:
K are given for a single experiment.
peroxides,
(a) Plot reduces
[Cl2] versus the[SO
t. (b) Plot Ea 2for
Cl2]the reactio
versus t. (c)
*54. The rate constant of a reaction is tripled when the tem- mine(uncatalyzed)
the rate law fortothis
28 reaction.
kJ/mol (catalyzed).
(d) What is thB
perature is increased NH 3 88n
from NHto
298 K 2# H K. Find E .
308 a
withthe reaction
units, rate increase
for the specific at at
rate constant normal
320°C? b(
*55. The rate constant for the decomposition of N O long37.0°C,
would it take
for for
the95%
sameof the original (peroxid
reactant SO2Cl2 t
t (horas)
t (hours) [NH3] (mol/L) 2
*46. At some temperature, the rate constant
Assume that the collision factor, A, for the de
rem
2N O(g) 88n 2N (g) # O (g) sition of HI on a gold surface is 0.080 M & s . "1
00 2 8.000 ! 10"7 2 2 *60. The enzyme carbonic anhydrase catalyze
is 2.6 $ 25
10"11 s"16.750 ! 10"7
at 300°C and 2.1 $ 10"10 s"1 at 330°C. carbon dioxide.
2HI(g) 88n H2(g) # I2(g)

Calculate50the activation
5.840 !energy
10"7
for this reaction. Prepare (a) What is the order of
CO the #
reaction?
H O 88n(b) How
Hlon
C
75 5.150 ! 10"7
a reaction coordinate diagram like Figure 16-10 using take for the concentration2of HI 2to drop from 21.5
"164.1 kJ/mol as the %Erxn. 0.30This
M? reaction is involved in the transfer o
*56. For a Plot
particular
a) Traza la gráfica de la expresión deappropriate
the concentración %E 0 !apropiada
reaction, concentration
51.51expressions
kJ/mol, ! 8.0 $
k against
en función tiempo to
delActivation paratheobtener
Energy,
lungs via el the bloodstream.
orden
Temperature,
6
de
and
One
laCatalysts
reacción. b) Determina la10 constante
"7 stimeatto0.0°C,
"1
find andorder
the
de velocidadk ! 8.9 $la10
ofdethe "4 s at
"1
reaction.
reacción 50.0°C.
Find Pre-
the rate
a partir de la pendiente hydrates 10 molecules
de la línea y utiliza of
losCO2 per se
pare aconstant
reaction coordinate
of the diagram
reaction from likeofFigure
the slope the line.16-10
Use thefor *47. Draw kilograms
typical of CO
reaction 2 are
energy hydrated
diagrams for in one
one-ste
datos que se dan y la ecuación integrada de velocidad para verificar
given data and the appropriate integrated rate equation to
tu respuesta. tions that release
1.0 $ 10 M enzyme?
"6 energy and that absorb
this reaction.
check your answer. Distinguish between the net energy change, 'E, f
*57. You are given the rate constant as a function of tempera- *61. The following gas-phase reaction fo
*44. The following data were obtained from a study of the kind of reaction and the activation energy. Indicate
6.- Los datos de la constante
ture fordethe
velocidad
exchangeen función de la temperatura de la reacción
reaction de intercambio son:
kinetics.
tial energies of products and reactants for both k
decomposition of a sample of HI on the surface of a gold
wire.(CH
(a) Plot the#data to find reactions.
Mn(CO) 3CN) # NC Hthe order of the reaction, the
5 88n(b) Calculate the HI
ClO F 88n ClOF # O
*48. Use graphs to illustrate how 2the presence of a cata
rate5constant, and the rate5 equation.
Mn(CO) (NC5H5)# # CH3CN
concentration in mmol/L at 600. 5s. affectThe
the activation
rate of a reaction.
energy of this reaction is
*49. How do homogeneous catalysts and heterogeneou
T (K)t (seconds)
k (min"1[HI]
) value of k at 322°C is 6.76 $ 10"4 s"1
(mmol/L) lysts differ?
be the
*50. (a) Why value
should oneof k foranthis
expect reaction
increase at 2
in tempera
298 000.0.0409 5.46 temperature
increase would
the initial rate this reaction
of reaction? (b) Why shohav
308 250.0.0818 4.10 3.00
expect $ 10"2insthe
a reaction "1?gaseous state to be faster t

500.0.157 2.73 *62.

sameThe following
reaction gas-phase
in the solid state? reaction is firs
318 *51. What is the activation energy for a reaction if its ra
750. 1.37
stant is found to triple whenN2Othe5 88n NO2 #
temperature NO
is rais
300 K to 310 K?
a) (a) del
Calcule la Ea a partir Calculate
grafico from
Ea del logaofK
plot of1/T
VsCl log k versus 1/T. (b) Use *52. What The activation
is the activation energy ofathis
energy for reaction
reaction if its ra
*45. The decomposition SO 2 2 in the gas phase,
Use el gráfico parathe graph to predictde
the Kvalue
a 311ofK.k at 311 K. (c) What is stantvalue
is foundof tok triple
at 0°Cwhenis the
9.16temperature
$ 10 s"1 . (a
is rais
"3
b) predecir el valor
the numerical value SO Cl2 collision
88n SO # Cl2 600 the
K tovalue
610 K?
c) ¿Cuál es el valor numérico del factor de frecuencia2frequency
of 2the factor, A, in
de colisión (A) en la ecuación de Arrhenius? of k for this reaction at room te
the Arrhenius equation? (b) At what temperature would this react
*58. The rearrangement of cyclopropane to propene described of 3.00 $ 10"2 s"1?
in Exercise 40 has been studied at various temperatures.
5. REFERENCIAS BIBLIOGRÁFICAS

1.- Química. Raymond Chang. Ed. Mc Graw Hill. 11a edición.

México (2013).

2.- Química General. Kenneth W. Whitten. Ed. Cengage

Learning. 8 a edición. México (2008).

3.- Química. Jerome L. Rosenberg, Lawrence M. Epstein y

Peter J. Krieger. Ed. Mc Graw Hill. 9a edición. México (2009).

4.- Problemas de Química y Como Resolverlos. Paul Frey. Ed.

CECSA. México (2000).