CHM 224- Reaction Kinetics

and Reactor
Lecture 06
Reversible reactions [Link]#sible
Reversible reaction happens occurs in two directions (at the same time).

A⇌B+C
In a reversible reaction two reaction are happening at the same time.
1. Forward reaction A→B+C
A is converting (decomposing) to B and C
2. Backward/reverse reaction B+C→A
B and C are converting (combining) to A

2
 R =p
rate ∝ concentration of reactant
Chemical equilibrium
Initially:
R P Rate of forward reaction is high, since [R] is high.
Rate of reverse reaction is zero. [P] is zero initially.

R P After while:
Rate of forward reaction drops a bit as [R] drops. R is consumed as a
result of forward reaction
Rate of reverse reaction increases a bit as [P] increases. P is produced
as a result of forward reaction
R P A point in time comes when:
Rate of forward reaction = rate of reverse reaction
This state is called dynamic equilibrium

Note: Size of the arrow refers to the magnitude of the rate

Reaction does not stop .

At equilibrium →
3
 co
litfnin .

-4

s*
-
H
J€E > serpin .

to
Ymir
.

Dynamic .
Chemical equilibrium
Chemical equilibrium is a dynamic equilibrium.
Forward and reverse reactions do not stop at equilibrium.
Rate of forward reaction = rate of reverse reaction
As a result the concentration do not change any more

R .

4
Reversible reactions never go to completion!!
● Since an equilibrium is established in a reversible reaction, they would
never go to completion.
● Completion of reaction means the reactants are 100% converted to
products.

A → B
-
A- FB .

#
he
Eme .
Equilibrium constant Nu t 3
He ← 2
NHI
AI .

3315 c

Consider the reaction, where, a, b, c, d are stoichiometric coefficients in the

balanced chemical equation.
At 3 B f z C
aA + bB ⇌ cC + dD
Equilibrium constant is the ratio of product (×) of the concentration of the
products, each raised to the power given by the coefficient in the balanced
chemical equation, to the product (×) of the concentrations of the reactants,
each raised to the power given by the coefficient in the balanced chemical
equation.
Cate Klee
[ B) ee [D) ee

6
 3 H I 2 NH
I Nzt ,
,

[ Nike
[ Hide
( NH ) BY
z

[ NH Deg
keg = -

[ Nieg [ Hiley
s
 Nat 3
Hz → 2MHz
f
Remember
Nat 3 Hz .

Hy →
R 2N
In the example below:
N2 (g) + 3 H2 (g) ⇌ 2 NH3 (g)

When forward reaction •Reactants (N2 and H2 ) are consumed

happens •[N2] and [H2] would decrease; assuming constant V
•Products (NH3) is produced
•[NH3] would increase; assuming constant V

When reverse reaction •Reactants (N2 and H2 ) are produced

happens •[N2] and [H2] would increase; assuming constant V
•Products (NH3) is consumed
•[NH3] would decrease; assuming constant V

7
 4
- -

Remember R
f
2MHz
Nats Hz
→
-92MHz
Nat 3 Ha .

In the example below: a- T .

N2 (g) + 3 H2 (g) ⇌ 2 NH3 (g)

When forward reaction Total number of molecules (moles) in the reaction mixture would decrease
happens 4 moles of (N2 and H2 ) would convert to 2 moles of NH3
When reverse reaction Total number of molecules (moles) in the reaction mixture would increase
happens 2 moles of NH3 would convert to 4 moles of (N2 and H2 )
Ideal gas law PV = nRT;
P ∝ n (at constant V) and T
'

Larger the n (number of moles of gases) larger would be pressure

When forward reaction As n increases, P would increase
happens nt ; Pt .

When reverse reaction As n decreases, P would decrease

happens mt ; PT .

8
 3h Exo
f Nat → 2N Hz -

Remember
-
,

Nats Hz
-
DH : +92
R 2MHz → .

wknd
-

In the example below: Always for forward reaction .

N2 (g) + 3 H2 (g) ⇌ 2 NH3 (g) ∆H = -92 kJ/mol

-

Forward reaction Is exothermic; ∆H = -92 kJ/mol

Reverse reaction Is endothermic; ∆H = +92 kJ/mol
(Law of conservation of energy)
When forward reaction Exothermic;
happens Heat is released resulting in increase in T of reaction mixture

When reverse reaction Endothermic;

happens Heat is absorbed resulting in decrease in T of reaction mixture

9
Le Chatelier's Principle
If a dynamic equilibrium is disturbed by changing the conditions, the position of
equilibrium moves to reverse (suppress) the change

10
Reactant added to system at equilibrium
N2 (g) + 3 H2 (g) ⇌ 2 NH3 (g)
Suppose additional nitrogen (N2) was added to the system.

Disturbance Addition of reactant (N2)

Change Concentration of N2 increased; (assume V is constant)
Equilibrium System would try to reverse this change- decrease [N2]
response Equilibrium would shift to right i.e. forward reaction would be
favored to decrease [N2]
Remember: forward reaction consumes N2

11
Product removed from system at equilibrium

N2 (g) + 3 H2 (g) ⇌ 2 NH3 (g)

Suppose some (NH3) was removed from system at equilibrium.

Disturbance Removal of product (NH3)

Change Concentration of NH3 decreased
Equilibrium Equilibrium would try to reverse this change –increase NH3
response Equilibrium would shift to right i.e. forward reaction would be
favored to increase [NH3]
Remember: forward reaction produces NH3

12
Reactant removed from system at equilibrium

N2 (g) + 3 H2 (g) ⇌ 2 NH3 (g)

Suppose some nitrogen (N2) is removed from system at equilibrium.

Disturbance Removal of reactant (N2)

Change Concentration of N2 decreased
Equilibrium System would try to reverse this change – increase [N2]
response Equilibrium would shift to left i.e. reverse reaction would be
favored to increase [N2]
Remember: reverse reaction produces N2

13
Increasing pressure of a system at equilibrium

N2 (g) + 3 H2 (g) ⇌ 2 NH3 (g)

Suppose P is increased of a system at equilibrium.

Disturbance Increase in pressure

Change Pressure of reaction mixture increased – increased P
Equilibrium System would try to reverse this change- decrease P
response Equilibrium would shift to right i.e. forward reaction would be
favored to decrease number of moles (n) and hence P
Remember: P ∝ n; (at constant V)

14
Decreasing pressure of a system at equilibrium
f. a pinta
.

N2 (g) + 3 H2 (g) ⇌ 2 NH3 (g)

- -

Suppose P is decreased on a system at equilibrium.

Disturbance decrease in pressure

Change Pressure of reaction mixture decreased – decreased P
Equilibrium System would try to reverse this change – - increase P
response Equilibrium would shift to left i.e. reverse reaction would be
favored to increase number of moles (n) and hence P
Remember: P ∝ n; (at constant V)

15
Increasing T of a system at equilibrium
N2 (g) + 3 H2 (g) ⇌ 2 NH3 (g) ∆H = -92 kJ/mol
Suppose T is increased of a system at equilibrium.

Disturbance Increase of T
Change T of reaction mixture has increased – increased T
Equilibrium System would try to reverse this change – decrease T
response Equilibrium would shift to left i.e. reverse reaction would be
favored to decrease T
Remember: Reverse reaction is endothermic

16
Adding a catalyst to a system at equilibrium

N2 (g) + 3 H2 (g) ⇌ 2 NH3 (g) ∆H = -92 kJ/mol

Suppose a catalyst is added to a system at equilibrium.

● Catalyst would not disturb the equilibrium.

● It would only enhance rate of reaction and enable the system to reach
equilibrium faster

17
 forward is tri
Shift to
right →

Question → reverse
Rx is
shift tr
left favored .

Consider the gas-phase equilibrium system represented by the equation:

2H2O(g) ⇌ 2H2(g) + O2(g) DH z t ve .

Given that the forward reaction is endothermic.

In which direction the equilibrium shifts if we add more oxygen?

'

COIT
Change →

Coit
→
system response to the left
Quillen would shift
.

18
Question
Consider the gas-phase equilibrium system represented by the equation:
2H2O(g) ⇌ 2H2(g) + O2(g)
Given that the forward reaction is endothermic.

In which direction the equilibrium shifts if we add more steam?

CHAT
change →
CHOI te
→
system response to RIGHT
.

Shula shift
qui libri
.

19
Question

= I
Consider the gas-phase equilibrium system represented by the equation:
2H2O(g) ⇌ 2H2(g) + O2(g)
Given that the forward reaction is endothermic.

In which direction the equilibrium shifts if we increase the pressure?

PT
'

change
→
→
Pt .

system response the b⑦

to
Gail ibn shift 20
Question
Consider the gas-phase equilibrium system represented by the equation:
2H2O(g) ⇌ 2H2(g) + O2(g) AH = + Ve .

Given that the forward reaction is endothermic.

In which direction the equilibrium shifts if we decrease the temperature?

Tt
change →
- TT
system response
to uieu
Qui libre shift 21
Question
Consider the gas-phase equilibrium system represented by the equation:
2H2O(g) ⇌ 2H2(g) + O2(g)
Given that the forward reaction is endothermic.

In which direction the equilibrium shifts if we add a catalyst?

catalyst hes no a
Hat on
equilibria .

22
Question
Consider the gas-phase equilibrium system represented by the equation:
2H2O(g) ⇌ 2H2(g) + O2(g)
Given that the forward reaction is endothermic.

In which direction the equilibrium shifts if we remove hydrogen?

→
CHIT t .

Change [ Hrs ) T
'

→
system response [ HIT
'

world
shift to right 23
Equilibrium constant is a function of temperature
● The only factor which will affect the value of the equilibrium constant is
temperature.
● When an equilibrium constant is cited, the temperature at which that
constant holds true is also cited.
● Thus if the temperature is changed, the value of the equilibrium constant will
change too

O -
-

rate
th CA ) CB) 24
 4mA
Problem
=
4%1=4 M

When 4.0 mol of A and 4.0 mol of B are placed in a 1 liter container and
- -

allowed to come to equilibrium, the resulting mixture is found to contain 0.80

-

mol of D. What are the amounts of A, B, and C at equilibrium?

A(g) + 3B (g) ⇌ C (g) + D(g)
I Initial: 4.0 mol
-
4.0 mol
-
-
0 mol 0 mol
c Change:

E Equilibrium: _______ ________ _______ 0.80 mol

25
I C
,
E method .

I → Initial concentration
reactants / products
.

of
in concentration
C →
Change
of reactants/ products
to achieveequilibrium
E- →
Concentration of reactants
products at equilibrium
.
 D
At 313 T C 1-

[Link]
T .

time .

& C t D .

A t 313

4#÷
-

3am nM M
IM
n
C

Eetmnmi
-

M =
0.8 M
N

/n=O.8J
[A) I 4 -
n = 4-0.8
eq
Mr
= 3.2

¥08 )
[ B) I 4 3N-
=

ef 4 -
2 - 4
=

= irbm ,

0.8 M
[c) eye a =
-

[ D)
eg
= a =
0.8mi
 n
3M n
.

N
C t D .

A t 2B →

A is consumed .

I met of
must be consumed
3mL f B

1in of f
C must be
produced
I wel f D
must be
produced
Problem 1keg=KJ
0.60 mol of Br2 and 0.60 mol of Cl2 are placed in a 1.00 L flask and allowed to
-

reach equilibrium. (There is no BrCl at first.) After reaching equilibrium, the flask
is found to contain 0.28 mol of BrCl. What is the value of K for this reaction?
.

Br2(g) + Cl2(g) ⇌ 2 BrCl(g)

Initial: 0.6 mol 0.6 mol

Equilibrium: 0.28

Ans: Keq=0.37
-

26
 Br t Az = 2 Bra
,

I : 0.6M O -
6M ON

M 2x M
N M
.

N
C :

2km
(O a) M
.

(0.6 a) M G
E
-
-

: -

0.6 -0.14 0.28M .

O 46M
0.46 M
-

2N I 0-28 M

|N=O
-

( Breezy
keg
-
:

Gsr ] .
ef
Case

(0-28)<(0-46710.46)
-
( key 0.37 =
'

→
Problem
For the following reaction:
CO(g) + H2O(g) ⇌ CO2 (g) + H2 (g) Keq = 23.2 at 600 K
If the initial amounts of CO and H2O were both 0.100 M (at the start of the
-

reaction), what will be the amounts of each reactant and product at

equilibrium?
Ans: 0.017; 0.017; 0.083, 0.083 for reactants and products respectively.

27
 CO t H2O = CO
,
t H,

IM OM OM
I : O IM-
O -

NM NM NM
C : N M

nm
a) @ I a) M nm
E @ M
-

l
-

:
-
-

keg =
Cloister
[ Why [ Hike

key Kang
=

( ) . , - a) 0.1 - d -

A- "

Cbtc)
2

M a
23.2 =

¥1
-
'

@ -
l -
N )2 "

f@÷,j
-

23.2 =

d- E 4.817 -

O -
I -
N
 In 4.817
'

O . I - N

0.4817 - 4.817N .

n =

5. 8.172 = 0.4817 -

a = 0.4817/5.817

1nI0.083.J@Iegn_o.i x =
0.1 -
O -
.

083

= 0.017 At
-

0.1 H
( Hooley
-

= 0.017in

0.083mi
wifey [
Iffy
a
[
=
=
=
 U = 4.817 .

u =
aI ( El
-

ze) .

0.4817 9.8172 .

N =
-

←
4.817N + x = 0.481-7

0.4817
.

5- 817N =

U =

0.48175-817 -
Problem

Determine the mole fractions of all gas components at equilibrium for

the equilibrium reaction:

choosing a feed mixture containing 1 mole of N2 and 3 moles of H2 and

the total pressure of the system is 20 atm. The equilibrium conversion
of nitrogen is 40%. Assume a constant volume reactor of 1 liter.
-

28
 Nz t 3 Ha ← 2 N Hz .

O M
I l M 3M
.

'
.

O 8 M
1.2 M
-

C : 0.4M

O 8 M .

l 8 M
-

O 6 M
-

E :
-

mixture contains
Equilibrium
0.6M of Nz
1. 8M of Hz

0<8 M
of MHz .

¥cm castration .

0-61
syn
'
cruel fraction of Nz ,
3.2M
=

end fraction of Ha =
THE ¥2 .

and
fraction of
NH
,
=
You ,
=
0-83-2
=
0.25 .
Problem
If the water gas shift reaction:
CO(g) + H2O(g) ⇌ CO2 (g) + H2 (g)
proceeds to equilibrium. The equilibrium constant Keq = 1 at a temperature of
1100 K. The total pressure of the system is 1 atm.
Determine the molar composition (mole fractions) of the gas components at
equilibrium for a feed mixture of 1 mole CO and 2 mole H2O.

29
 K ,
=
East
Problem
Derive the rate law that is consistent with the proposed mechanism in the
formation of phosgene from Cl2 and CO.
i. Cl2 ⇌ 2 Cl fast equilibrium, K1) Cag
ii. Cl + CO ⇌ ClCO (fast equilibrium, K2)
Kz =
Ca) Coo)

iii. ClCO + Cl2 Cl2CO + Cl (slow, k3)

The overall reaction is m n

Cl2 + CO Cl2CO rate = k Cas) Cco ) .

30
 absence mechanism and
In the
of
date ; rate law
experimental
can

be written as

rate = K Cco Taiji ④

Rate law can be derived from

+

the reaction mechanism

based
is
always
on
Rate law
+

determining step
.

the rate

slowest in the mechanism

+ step
is the rate determining step .

in the mechanism
+ 3rd step
Sl
-

Fp the slow

g [a co ] Cad → ④

compare ⑦
and ⑤
 reactants
+
only
can
appear
in the rate law

is reactant if
+ Az a

Cleo is not a reactant xx .

is Cleo ? ?
+
what

a co is an
intermediate -

+
and
formed
in
step 2
consumed in
step 9 .

fix ⑨ now ??
+ How can we

+ we will try to
express
Cda ) and
[ Cleo) in terms
of
reactants )
[ cod ( the
.

.
 From
step ② we can

write
Ccl co )
.

Kz =

ep F .

rate =
kg [ a co ] Caa) → ④
[ a co ) = Kz [a ] [co) .

Now eq ④ becomes .

crate = k Ks [a ] Eco] Cuz ] → ②

,

② acceptable
.

is cq

acceptable
.

not
+ ② is

[ da ) are reactant
+ Cco ) and

concentration ✓✓
i

[ a] is not a reactant .

is an
intermediate ;
+ a

step ①
in and
formed
in step ②
-

consumed
+ we will
try to
express
in terms reactant
Ccl ] of
[ Az ) and [ co ]

①
Using step
we can
+

write .

K =
CAI
, Cai .

'
K, Celal
[ AT
.

kik cask
.

Cate =

Insert this nice ②

crate = k Ks [a ] Eco] Cuz ] → ②

,

ki cash cooked
'
rate .
.

Coo ] Cash
.

rate = K
where k = K, Kiki 't i