Chemical Equilibrium PDF

Estudiantes Graduandos
Clases de Afianzamiento
Química General
Virgilio Bárcenas Semper
Tutorías y Clases de Afianzamiento
Clases Magistrales Clases Prácticas
Chemistry Content
Chemical Equilibrium
Content
• The concepto of Equilibrium

• Equilibrium Constant
• Equilibrium Constant Expression
• Equilibrium Constant Calculation
• Predicting the Direction of a Reaction
• Factors that affect Chemical Equilibrium
Módulo Digital
• LeChatelier’s Principle
Para mayor información:

Virgilio Bárcenas Semper
Cel: (507) 6679-3925.

Chemical Equilibrium 1 of 26
Clases de Afianzamiento de Química Chemical Equilibrium
Chemical Equilibrium
Chemical Equilibrium is achieved when the rates of the forward and reverse reactions are equal and de concentrations of the reactants and
products remain constant.
Important Details
• Reactants transform into products

• Products transform into reactants
• No observable changes as time goes by.
phosgene
[0cg)t C 12cg) # C O D 2cg)
carbon chlorine
monoxide g a s
1 Virgilio Bárcenas Semper

Equilibrium Constant
Ratio of reactant and product concentrations at Equilibrium conditions
Law of Mass Action Equilibrium Constant magnitude
Favors the products
[Products] High K values
[Reactants]
• a, b, c and d are the stoichiometric coefficients for reacting species A, B, C, D

Equilibrium will lie to the right
• Defined by a quotient.
• Multiplying together the equilibrium concentrations of the products, each raised to
a power equal to its stoichiometric coefficient in the balance reaction, at the
numerator applying the same procedure to the equilibrium concentrations of
Low K values
reactants at the denominator
Equilibrium will
Favors the reactants lie to the left
Equilibrium Constant Expressions
Homogeneus Equilibrium Relation Bet ween Kp and Kc

• All reacting species are in
the same phase (physical
state)
Kc = Concentration Constant Kp = Pressure Constant

1 Write expressions for Kc and Kp if applicable, for the following reversible reactions at equilibrium:
a ) K c :C H E E € ¥ H s ]
g k e=
[HE] [citycooligOH]
b)lhp:(PN0z)2
TRIPOD
2 Write expressions for Kc and Kp for the decomposition of dinitrogen pentoxide:

3 Write expressions for Kc and Kp if applicable, for the following reversible reactions at equilibrium:

4 The following equilibrium process has been studied at 230 ºC:
In one experiment, the concentrations of the reacting species at equilibrium are found to be [NO] = 0,0542M, [O2] = 0,127 M, and
[NO2] = 15,5 M. Calculate the equilibrium constant (Kc) of the reaction at this temperature.
2N0Cg) t 02cg)#218021g)
0.0 5 4 2 M 0.1 2 7 M # 15,5M
Kc : ¥[Norco.jp#o.amT--6.44×105
2
A n= L- 3 = - 1
Kpikfo-0821T)""
Kip:(6.44×105/(0.0821×503)" T : 23014273
F - 503K
kp= 15594--6
Mp?1.56×104

J : 741 + 2 73
5 Carbonyl chloride (COCl2) describes an equilibrium reaction as follows:
F . 347K
I 1 I AM: I - 2
A n : - 1
The equilibrium concentrations for the reaction between carbon monoxide and molecular chlorine to form carbonyl chloride at 74 ºC
are [CO] = 1,2 x 10-2 M, [Cl2] = 0,054 M and [COCl2] = 0,14 M. Calculate the equilibrium constant Kc.
(0cg) t Clacg) # C O C l z c g l Kp=kc(0.0821T)"

I-2×10-214 0.0 5 4 M 0.1 4 M hp:(2.2×102/(0.0821×341)''
the:#I 0.14M Hp: 7 . 7

[CO][Clif: 7×0=110.05414/2
K c : 2 1 6.0 5
K c : 2.2×102

Pclscg, # P C I3cg, t Clacg) Mp: 1.0 5

0 . 8 7 5a t m
0.463ohm t X
kp.lt#??g1
I-05=10.4631×1
(O-875atm)
405710.87kt = ×
(O-463a t m )
1 . 9 8a t m : x

kp.lt#P0z-
(PNOz)2-
158=l-270atm)2X
(0.400)2
1 5 8(O-40012
= X
¥0atm2
3 4 6 .7 7 = X
347atm: x

(emoltzmol)
(Rt)-n A N = enrol -
the= 1 0.5 14ps K c n . emol - 3h01
T:220°C = - 2 n d
(10,5/[4193×0.08217]-2
Kip:? Hp=
T: 2 2 0 ° C+ 2 7 3 Hp:6.41×10-3
5=49319

Consider t h e following equilibrium a t 7 0 0 .C
242cg,t 52cg) I 2125cg)
Analysisshows that there a r e 2 .s o mole,o f Hz, I-35×10-5mole o f 5 2

a n d 8 . 7 0mol o f H i s present i na 12.0L f l a s k . Calculate t h e equilibrium
constantK c a n d reaction
lapf o r t h e
in:f÷

Heterogeneus Equilibrium
8
• Reversible reaction involving
reactants and products that are in
different phases (Physical states)
• Solids and liquids should not be

included in the Equilibrium
constant Expression

Xp: Roz Hp: K c (Rt)-n

2 . 68×10-3
143=0.236atm (¥¥=kc
[%?%ItI# ""

Review Problems
1 4
5 Methanol is commercially produced by the catalyzed

2
reaction between carbon monoxide and hydrogen gas as
follows:
CO2 (g) + 2H2 (g) <——> CH3OH.
The analysis found a mixture in equilibrium conditions in

a 2.00 L flask containing 0,0406 moles of CH3OH; 0,170
moles of CO and 0,302 moles of H2 at 500 K. Calculate
3
Kp and Kc at this temperature.

Predicting The Direction of a Reaction
Reaction Quotient (Qc) Chemical Ratio between initial concentrations
Qc < Kc Qc = Kc Qc > Kc
9 The equilibrium constant Kc for the formation of hydrogen iodide from molecular hydrogen and molecular iodine in the gas phase
is 54.3 at 430 ºC
"" " '"
Suppose that in a certain experiment we place 0,243 mole of H2; 0,146 mole of I2 and 1,98 moles of HI in a 1,00 L
container at 430 ºC. Will there be a net reaction to form more H2 and I2 or more HI?
Hach t I
2cg) # 2 H I Cg) %=[H¥ Qc= t .fi?
0.24310' t o o l e # 1 . 9 8 m L
[ H , ]L I , ] [it,]ofI,]j 8I%2co.14bM)
1 L u e l
0.243M t 0.14614 I n 1.98M a i ". Reaction shifts t o t h e left
15 Q , > 4 , Virgilio Bárcenas Semper

Predicting The Direction of a Reaction
10

Calculating Equilibrium Concentrations
ICE Chart Method
11 Lets consider the following system involving two organic compounds, cis-stilbene a non polar hydro-carbon solvent:
The equilibrium constant (Kc) for this system is 24,0 at 200ºC. Suppose that initially only cis-
stilbene is present at a concentration of 0,850 mol/L. Calculate the concentrations of cis-stilbene
and trans-stilbene at equilibrium
cis-stilbene # t r a n s . stibene K c : 2 4 . 0
initial: 0.850M¥ ① µ,:[trans.se/ilbene1-
change: - X ¥ X [c i s - stilbene]
Equilibrium: 0.850M X ← ×
2 4 . 0 : - X
-
0.850M-0.81614 0.850M-x
[Cis-stibene]eq: 0.850M-X:
so.@16,50034M 24.010.85014-x) = X
[trans-stalbene]eq:X
2 0 . 4 M - 2 4x = x
20.4M: x t 2 4 x
2 0 . 4 M :2 s x
20.24¥:X
0.816M:X

ICE Chart Method
12

ICE Chart Method
13 For the same reaction as the problem No. 12; suppose that the inicial concentrations of H2, I2 and HI are 0,00623 M;
0,00414 M and 0,0224 M, respectively. Calculate the concentrations of these species at equilibrium.
'H2cg)
t 12cg) #241cg) "" ' " "3
initial 0.0 0 6 2 3 M t 0.00414M I 0.0224M 1. 4×10-3M 0.563×454.3×2=0
-
¥
2x.su#io4m:o::9::Is4EI.o
X X
change t -
-
Equilibrium (0.0062314-×) t (0.00414M-×) E (O-022414+2×7

8. 9824×10-4
Qc.-to ¥4142 the, [ H ¥ A×2tbxtc=0

[ H , ][ I z ] C--8.9824×10-4
[µ,]-[Izzo: (0.0062314)(0.00414M) A--543 13=-0-6526
Qc--19,45 54.3:
µ4Mt§}oy,,#
(O-00623-X
X,-0.0114
Xz=l.565Xµ
Qc < K c 54.3: ftp.t#9I.ooimx+xz
-
54.3: 5.0176×1=0.0896×+4×2
[Hz]eq:O-00623M-X 2.579×10-s - 0.01037×4×2-
:O-00623M-1.565×10-3
(54-3)( 2.579×10-s- 0.01037×4×2): 5.0176×10-4+0.0896×+4×2
f t p : / /
1 .4×10-314 - 0.563×454.3×2=5.0176×10-4+0.0896×+4×2
[12]eg:O-0041414-I-565×10-3
0.022414+24.565×10-3M)
[I2Jeq=2.58×1O-3- [HI]l4:
[HI]eq¥255µ 19 Virgilio Bárcenas Semper
ICE Chart Method
Dissociation Percentage Reactant percentage which dissociates in a equilibrium reaction of dissociation
14 Consider the equilibrium: Br2 (g) <——> . 2Br (g) at 1600ºC. When 1,05 moles of Br2 are put in a 0,980 L flask, 1,20% of
Br2 undergoes dissociation. Calculate the equilibrium constant Kc for the reaction.
dissocil-201.
Brzeg, → 2Br 1.
I-Osmol -/.dissoc: , 1001'
¥ µ x
-0.980L 1001'
1.201. =
1 ¥ x
'initial 1 . 0 7 M ¥ 0
2 × t.mil?fo!j?#=x Kc: ¥ 2
Change - × = L [Brz]"
Equilibrium1 . 0 7 M -X # 2 × 10.0128M¥ Kc: 1,982¥44
[Braley--1.07M-X [Brief:2×
= 1.07M-0.0128M = 210.0128M) K c= 6.2×10-4
[Braley.-i. o g , [Br]eq=0 . 0 2 5 6
ICE Chart Method
15 A 2,50 mole quantity of nitrosyl chloride, NOCl, was initially in a 1,50 L reaction chamber at 400 ºC. After equilibrium was
stablished, it was found that 28,0 % of the NOCl had dissociated. Calculate the equilibrium constant Kc for the reaction:

Factors that Affects Chemical Equilibrium
Le Chatelier’s If an external stress is applied to a system at equilibrium, the system adjust in such a way that te stress is
Principle partially offset as the system reaches a new equilibrium position
Left Right
Reactants Product
To offset the stress, added Reactant converts to

Reactants Equilibrirum shifts from left to right
Product to consume the excess in reactants
To offset the stress, added Product converts back

Products Equilibrirum shifts from Right to Left
to Reactant to consume the excess in products
Reactants To offset the stress, equilibrium shifts to restore

Equilibrirum shifts from Right to Left
back the amount of reactant decreased.
Products To offset the stress, equilibrium shifts to restore Equilibrirum shifts from left to right
back the amount of product decreased.

Left Right
Reactants Product
Favors the net reaction that decrease the total

Pressure Volume
amount of moles of gases
Pressure Volume Favors the net reaction that increase the total
amount of moles of gases
Reactions with no change in the number of moles of gases a pressure or volume change has no effect on the position of equilibrium.

Left Right
Reactants Product
Temperature Adds heat to the system, favors the endothermic direction of the reaction
Temperature Removes heat from the system, favors the Exothermic direction of the reaction

16


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Estudiantes Graduandos

Clases Magistrales Clases Prácticas

• The concepto of Equilibrium

Para mayor información:

Cel: (507) 6679-3925.

• Reactants transform into products

1 Virgilio Bárcenas Semper

Ratio of reactant and product concentrations at Equilibrium conditions

Law of Mass Action Equilibrium Constant magnitude

Favors the products

[Products] High K values

• a, b, c and d are the stoichiometric coefficients for reacting species A, B, C, D

Homogeneus Equilibrium Relation Bet ween Kp and Kc

Kc = Concentration Constant Kp = Pressure Constant

3 Virgilio Bárcenas Semper

2 Write expressions for Kc and Kp for the decomposition of dinitrogen pentoxide:

4 Virgilio Bárcenas Semper

5 Virgilio Bárcenas Semper

4 The following equilibrium process has been studied at 230 ºC:

6 Virgilio Bárcenas Semper

(0cg) t Clacg) # C O C l z c g l Kp=kc(0.0821T)"

the:#I 0.14M Hp: 7 . 7

7 Virgilio Bárcenas Semper

Pclscg, # P C I3cg, t Clacg) Mp: 1.0 5

8 Virgilio Bárcenas Semper

9 Virgilio Bárcenas Semper

the= 1 0.5 14ps K c n . emol - 3h01

10 Virgilio Bárcenas Semper

Consider t h e following equilibrium a t 7 0 0 .C

242cg,t 52cg) I 2125cg)

Analysisshows that there a r e 2 .s o mole,o f Hz, I-35×10-5mole o f 5 2

11 Virgilio Bárcenas Semper

• Solids and liquids should not be

12 Virgilio Bárcenas Semper

Xp: Roz Hp: K c (Rt)-n

13 Virgilio Bárcenas Semper

5 Methanol is commercially produced by the catalyzed

CO2 (g) + 2H2 (g) <——> CH3OH.

The analysis found a mixture in equilibrium conditions in

14 Virgilio Bárcenas Semper

Reaction Quotient (Qc) Chemical Ratio between initial concentrations

0.243M t 0.14614 I n 1.98M a i ". Reaction shifts t o t h e left

15 Q , > 4 , Virgilio Bárcenas Semper

16 Virgilio Bárcenas Semper

ICE Chart Method

17 Virgilio Bárcenas Semper

ICE Chart Method

18 Virgilio Bárcenas Semper

ICE Chart Method

Equilibrium (0.0062314-×) t (0.00414M-×) E (O-022414+2×7

Qc.-to ¥4142 the, [ H ¥ A×2tbxtc=0

ICE Chart Method

Dissociation Percentage Reactant percentage which dissociates in a equilibrium reaction of dissociation

ICE Chart Method

21 Virgilio Bárcenas Semper

To offset the stress, added Reactant converts to

To offset the stress, added Product converts back